[[pp. 18703-18751]] National Emission Standards for Hazardous Air Pollutants for

Note: EPA no longer updates this information, but it may be useful as a reference or resource.

[Federal Register: April 15, 1998 (Rules and Regulations)]
[Page 18703-18751]
From the Federal Register Online via GPO Access [wais.access.gpo.gov]
[DOCID:fr15ap98-23]

[[pp. 18703-18751]] National Emission Standards for Hazardous Air Pollutants for
Source Category: Pulp and Paper Production; Effluent Limitations
Guidelines, Pretreatment Standards, and New Source Performance
Standards: Pulp, Paper, and Paperboard Category

[[Continued from page 18702]]

[[Page 18703]]

Subpart I
[Facilities where newsprint is produced]
[NSPS]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 6.0 3.2 1.7
TSS...................................................................... 12.0 6.3 3.3
pH....................................................................... (^{1) (^{1) (^{1)
----------------------------------------------------------------------------------------------------------------

Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
pounds per
1,000 lb) Milligrams/liter
of product
Pentachlorophenol......................................... 0.0030 (0.044)(16.2)/y
Trichlorophenol........................................... 0.0010 (0.015)(16.2)/y
y = wastewater discharged in kgal per ton at all times.
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Sec. 430.96 Pretreatment standards for existing sources (PSES).

(a) Except as provided in 40 CFR 403.7 and 403.13, any existing
source subject to this subpart that introduces pollutants into a
publicly owned treatment works must comply with 40 CFR part 403 and
achieve the following pretreatment standards for existing sources
(PSES) if it uses chlorophenolic-containing biocides. Permittees not
using chlorophenolic-containing biocides must certify to the permit-
issuing authority that they are not using these biocides. PSES must be
attained on or before July 1, 1984:

Subpart I
[Facilities where fine or tissue paper is produced]
----------------------------------------------------------------------------------------------------------------
PSES
-----------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Pollutant or pollutant property Kg/kkg (or
pounds per
Milligrams/liter (mg/l) 1,000 lb)
of product
----------------------------------------------------------------------------------------------------------^{a-----
Pentachlorophenol................................... (0.032)(24.4)/y.............................. 0.0033
Trichlorophenol..................................... (0.082)(24.4)/y.............................. 0.0084
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass equivalent limitations.

Subpart I
[Facilities where newsprint is produced]
----------------------------------------------------------------------------------------------------------------
PSES
-----------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Pollutant or pollutant property Kg/kkg (or
pounds per
Milligrams/liter (mg/l) 1,000 lb)
of product
----------------------------------------------------------------------------------------------------------^{a-----
Pentachlorophenol................................... (0.032)(24.4)/y.............................. 0.0033
Trichlorophenol..................................... (0.010)(24.4)/y.............................. 0.0010
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass equivalent limitations.

[[Page 18704]]

Sec. 430.97 Pretreatment standards for new sources (PSNS).

(a) Except as provided in 40 CFR 403.7, any new source subject to
this subpart that introduces pollutants into a publicly owned treatment
works must comply with 40 CFR part 403 and achieve the following
pretreatment standards for new sources (PSNS) if it uses
chlorophenolic-containing biocides. Permittees not using
chlorophenolic-containing biocides must certify to the permit-issuing
authority that they are not using these biocides:

Subpart I
[Facilities where fine paper is produced]
----------------------------------------------------------------------------------------------------------------
PSNS
-----------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Pollutant or pollutant property Kg/kkg (or
pounds per
Milligrams/liter (mg/l) 1,000 lb)
of product
----------------------------------------------------------------------------------------------------------^{a-----
Pentachlorophenol................................... (0.049)(15.9)/y.............................. 0.0033
Trichlorophenol..................................... (0.126)(15.9)/y.............................. 0.0084
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass equivalent limitations.

Subpart I
[Facilities where tissue paper is produced]
----------------------------------------------------------------------------------------------------------------
PSNS
-----------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Pollutant or pollutant property Kg/kkg (or
pounds per
Milligrams/liter (mg/l) 1,000 lb)
of product
----------------------------------------------------------------------------------------------------------^{a-----
Pentachlorophenol................................... (0.040)(19.5)/y.............................. 0.0033
Trichlorophenol..................................... (0.103)(19.5)/y.............................. 0.0084
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass equivalent limitations.

Subpart I
[Facilities where newsprint is produced]
----------------------------------------------------------------------------------------------------------------
PSNS
-----------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Pollutant or pollutant property Kg/kkg ( or
pounds per
Milligrams/liter (mg/l) 1,000 lb)
of product
----------------------------------------------------------------------------------------------------------^{a-----
Pentachlorophenol................................... (0.048)(16.2)/y.............................. 0.0033
Trichlorophenol..................................... (0.015)(16.2)/y.............................. 0.0010
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass equivalent limitations.

Subpart J--Secondary Fiber Non-Deink Subcategory

Sec. 430.100 Applicability; description of the secondary fiber non-
deink subcategory.

The provisions of this subpart are applicable to discharges
resulting from the production of: paperboard from wastepaper; tissue
paper from wastepaper without deinking at secondary fiber mills; molded
products from wastepaper without deinking at secondary fiber mills; and
builders' paper and roofing felt from wastepaper.

Sec. 430.101 Specialized definitions.

For the purpose of this subpart:
(a) Except as provided below, the general definitions,
abbreviations, and methods of analysis set forth in 40 CFR part 401 and
Sec. 430.01 of this part shall apply to this subpart.
(b) Noncorrugating medium furnish subdivision mills are mills where
recycled corrugating medium is not used in the production of
paperboard.
(c) Corrugating medium furnish subdivision mills are mills where
only recycled corrugating medium is used in the production of
paperboard.

[[Page 18705]]

Sec. 430.102 Effluent limitations representing the degree of effluent
reduction attainable by the application of the best practicable control
technology currently available (BPT).

(a) Except as provided in 40 CFR 125.30 through 125.32, any
existing point source subject to this subpart must achieve the
following effluent limitations representing the degree of effluent
reduction attainable by the application of the best practicable control
technology currently available (BPT):

Subpart J
[BPT effluent limitations for secondary fiber non-deink facilities where
paperboard from wastepaper is produced--noncorrugating medium finish
subdivision]
------------------------------------------------------------------------
Kg/kkg (or pounds per
1,000 lb) of product
-------------------------
Average of
Pollutant or pollutant property daily
Maximum for values for
any 1 day 30
consecutive
days
------------------------------------------------------------------------
BOD5.......................................... 3.0 1.5
TSS........................................... 5.0 2.5
pH............................................ (\1\) (\1\)
------------------------------------------------------------------------
\1\ 1Within the range of 6.0 to 9.0 at all times.

Subpart J
[BPT effluent limitations for secondary fiber non-deink facilities where
paperboard from wastepaper is produced--corrugating medium finish
subdivision]
------------------------------------------------------------------------
Kg/kkg (or pounds per
1,000 lb) of product
-------------------------
Average of
Pollutant or pollutant property daily
Maximum for values for
any 1 day 30
consecutive
days
------------------------------------------------------------------------
BOD5.......................................... 5.7 2.8
TSS........................................... 9.2 4.6
pH............................................ (\1\) (\1\)
------------------------------------------------------------------------
\1\ Within the range of 6.0 to 9.0 at all times.

Subpart J
[BPT effluent limitations for secondary fiber non-deink facilities where
builders' paper and roofing felt from wastepaper are produced]
------------------------------------------------------------------------
Kg/kkg (or pounds per
1,000 lb) of product
-------------------------
Average of
Pollutant or pollutant property daily
Maximum for values for
any 1 day 30
consecutive
days
------------------------------------------------------------------------
BOD5.......................................... 5.0 3.0
TSS........................................... 5.0 3.0
pH............................................ (\1\) (\1\)
Setteable Solids.............................. (\2\) (\2\)
------------------------------------------------------------------------
\1\ Within the range of 6.0 to 9.0 at all times.
\2\ Not to exceed 0.2 ml/l.

(b) Except as provided in 40 CFR 125.30 through 125.32, any
existing point source subject to this subpart must achieve the
following effluent limitations representing the degree of effluent
reduction attainable by the application of the best practicable control
technology currently available (BPT), except that non-continuous
dischargers shall not be subject to the maximum day and average of 30
consecutive days limitations but shall be subject to annual average
effluent limitations:

[[Page 18706]]

Subpart J
[BPT effluent limitations for secondary fiber non-deink facilities where tissue from wastepaper is produced
without deinking]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
-------------------------- Non-
Pollutant or pollutant property Average of continuous
daily dischargers
Maximum for values for (annual
any 1 day 30 average
consecutive days)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 13.7 7.1 4.0
TSS...................................................................... 17.05 9.2 5.1
pH....................................................................... (\1\) (\1\) (\1\)
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Subpart J
[BPT effluent limitations for secondary fiber non-deink facilities where molded products from wastepaper are
produced without deinking]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
-------------------------- Non-
Pollutant or pollutant property Average of continuous
daily dischargers
Maximum for values for (annual
any 1 day 30 average
consecutive days)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 4.4 2.3 1.3
TSS...................................................................... 10.8 5.8 3.2
pH....................................................................... (\1\) (\1\) (\1\)
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Sec. 430.103 Effluent limitations guidelines representing the degree
of effluent reduction attainable by the application of the best
conventional pollutant control technology (BCT).

(a) Except as provided in 40 CFR 125.30 through 125.32, any
existing point source subject to this subpart shall achieve the
following effluent limitations representing the degree of effluent
reduction attainable by the application of the best conventional
pollutant control technology (BCT): The limitations shall be the same
as those specified for conventional pollutants (which are defined in 40
CFR 401.16) in Sec. 430.102 of this subpart for the best practicable
control technology currently available (BPT).
(b) For secondary fiber non-deink facilities where paperboard from
wastepaper is produced, non-continuous dischargers shall not be subject
to the maximum day and average-of-30-consecutive-days limitations, but
shall be subject to annual average effluent limitations determined by
dividing the average-of-30-consecutive-days limitations for BOD5 and
TSS by 1.77 and 2.18.
(c) For secondary fiber non-deink facilities where builders' paper
and roofing felt from wastepaper are produced, non-continuous
dischargers shall not be subject to the maximum day and average-of-30-
consecutive-days limitations, but shall be subject to annual average
effluent limitations determined by dividing the average-of-30-
consecutive-days limitations for BOD5 and TSS by 1.90 and 1.90.

Sec. 430.104 Effluent limitations representing the degree of effluent
reduction attainable by the application of the best available
technology economically achievable (BAT).

Except as provided in 40 CFR 125.30 through 125.32, any existing
point source subject to this subpart where chlorophenolic-containing
biocides are used must achieve the following effluent limitations
representing the degree of effluent reduction attainable by the
application of the best available technology economically achievable
(BAT). Non-continuous dischargers shall not be subject to the maximum
day mass limitations in kg/kkg (lb/1000 lb) but shall be subject to
concentration limitations. Concentration limitations are only
applicable to non-continuous dischargers. Permittees not using
chlorophenolic-containing biocides must certify to the permit-issuing
authority that they are not using these biocides:

[[Page 18707]]

Subpart J
[BAT effluent limitations for secondary fiber non-deink facilities where paperboard from wastepaper is produced]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
1,000 lb) Milligrams/liter
of product
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol......................................... 0.00087 (0.029)(7.2)/y
Trichlorophenol........................................... 0.00030 (0.010)(7.2)/y
y = wastewater discharged in kgal per ton of product.
----------------------------------------------------------------------------------------------------------------

Subpart J
[BAT effluent limitations for secondary fiber non-deink facilities where builders' paper and roofing felt from
wastepaper are produced]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
1,000 lb) Milligrams/liter
of product
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol......................................... 0.0017 (0.029)(14.4)/y
Trichlorophenol........................................... 0.00060 (0.010)(14.4)/y
y = wastewater discharged in kgal per ton of product.
----------------------------------------------------------------------------------------------------------------

Subpart J
[BAT effluent limitations for secondary fiber non-deink facilities where tissue from wastepaper is produced
without deinking]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
1,000 lb) Milligrams/liter
of product
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol......................................... 0.0030 (0.029)(25.2)/y
Trichlorophenol........................................... 0.0011 (0.010)(25.2)/y
y = wastewater discharged in kgal per ton of product.
----------------------------------------------------------------------------------------------------------------

Subpart J
[BAT effluent limitations for secondary fiber non-deink facilities where molded products from wastepaper are
produced without deinking]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
1,000 lb) Milligrams/liter
of product
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol......................................... 0.0026 (0.029)(21.1)/y
Trichlorophenol........................................... 0.00088 (0.010)(21.1)/y
y = wastewater discharged in kgal per ton of product.
----------------------------------------------------------------------------------------------------------------

Sec. 430.105 New source performance standards (NSPS).

Any new source subject to this subpart must achieve the following
new source performance standards (NSPS), except that non-continuous
dischargers shall not be subject to the maximum day and average of 30
consecutive days effluent limitations for BOD5 and TSS, but shall be
subject to annual average effluent limitations. Also, for non-
continuous dischargers, concentration limitations (mg/l) shall apply,
where provided. Concentration limitations will only apply to non-
continuous dischargers. Only facilities where chlorophenolic-containing
biocides are used shall be subject to pentachlorophenol and
trichlorophenol limitations. Permittees not using chlorophenolic-
containing biocides must certify to the permit-issuing authority that
they are not using these biocides:

[[Page 18708]]

Subpart J
[NSPS for secondary fiber non-deink facilities where paperboard from wastepaper is produced--noncorrugating
medium furnish subdivision]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 2.6 1.4 0.73
TSS...................................................................... 3.5 1.8 0.95
pH....................................................................... (\1\) (\1\) (\1\)
----------------------------------------------------------------------------------------------------------------

Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
pounds per
1,000 lb) Milligrams/liter
of product
Pentachlorophenol......................................... 0.00087 (0.065)(3.2)/y
Trichlorophenol........................................... 0.00030 (0.023)(3.2)/y
y = wastewater discharged in kgal per ton at all times.
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Subpart J
[NSPS for secondary fiber non-deink facilities where paperboard from wastepaper is produced--corrugating medium
finish subdivision]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 3.9 2.1 1.1
TSS...................................................................... 4.4 2.3 1.2
pH....................................................................... (\1\) (\1\) (\1\)
----------------------------------------------------------------------------------------------------------------

Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
pounds per
1,000 lb) Milligrams/liter
of product
Pentachlorophenol......................................... 0.00087 (0.065)(3.2)/y
Trichlorophenol........................................... 0.00030 (0.023)(3.2)/y
y = wastewater discharged in kgal per ton at all times.
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Subpart J
[NSPS for secondary fiber non-deink facilities where builders' paper and roofing felt from wastepaper are
produced]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 1.7 0.94 0.49
TSS...................................................................... 2.7 1.40 0.74

[[Page 18709]]

pH....................................................................... (\1\) (\1\) (\1\)
----------------------------------------------------------------------------------------------------------------

Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
pounds per
1,000 lb) Milligrams/liter
of product
Pentachlorophenol......................................... 0.0017 (0.155)(2.7)/y
Trichlorophenol........................................... 0.00060 (0.053)(2.7)/y
y = wastewater discharged in kgal per ton at all times.
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Subpart J
[NSPS for secondary fiber non-deink facilities where tissue from wastepaper is produced without deinking]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 4.6 2.5 1.3
TSS...................................................................... 10.2 5.3 2.8
pH....................................................................... (\1\) (\1\) (\1\)
----------------------------------------------------------------------------------------------------------------

Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
pounds per
1,000 lb) Milligrams/liter
of product
Pentachlorophenol......................................... 0.0030 (0.045)(16.3)/y
Trichlorophenol........................................... 0.0011 (0.015)(16.3)/y
y = wastewater discharged in kgal per ton at all times.
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Subpart J
[NSPS for secondary fiber non-deink facilities where molded products from wastepaper are produced without
deinking]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 2.1 1.1 0.58
TSS...................................................................... 4.4 2.3 1.21
pH....................................................................... (\1\) (\1\) (\1\)
----------------------------------------------------------------------------------------------------------------

[[Page 18710]]

Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
pounds per
1,000 lb) Milligrams/liter
of product
Pentachlorophenol......................................... 0.0026 (0.107)(5.7)/y
Trichlorophenol........................................... 0.00088 (0.037)(5.7)/y
y = wastewater discharged in kgal per ton at all times.
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Sec. 430.106 Pretreatment standards for existing sources (PSES).

Except as provided in 40 CFR 403.7 and 403.13, any existing source
subject to this subpart that introduces pollutants into a publicly
owned treatment works must: comply with 40 CFR part 403; and achieve
the following pretreatment standards for existing sources (PSES) if it
uses chlorophenolic-containing biocides. Permittees not using
chlorophenolic-containing biocides must certify to the permit-issuing
authority that they are not using these biocides. PSES must be attained
on or before July 1, 1984:

Subpart J
[PSES for secondary fiber non-deink facilities where paperboard from wastepaper is produced]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb)
of product^{a
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol................................... (0.032)(7.2)/y............................... 0.00096
Trichlorophenol..................................... (0.010)(7.2)/y............................... 0.00030
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

Subpart J
[PSES for secondary fiber non-deink facilities where builders' paper and roofing felt from wastepaper are
produced]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb) of
product ^{a
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol................................... (0.032)(14.4)y.............................. 0.0019
Trichlorophenol..................................... (0.010)(14.4)y.............................. 0.00060
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

Subpart J
[PSES for secondary fiber non-deink facilities where tissue from wastepaper is produced without deinking]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb)
of product
^{a
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol................................... (0.032)(25.2)y............................... 0.0034
Trichlorophenol..................................... (0.010)(25.2)/y.............................. 0.0011
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

[[Page 18711]]

Subpart J
[PSES for secondary fiber non-deink facilities where molded products from wastepaper are produced without
deinking]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb)
of product
----------------------------------------------------------------------------------------------------------^{a-----
Pentachlorophenol................................... (0.032)(21.1)y............................... 0.0028
Trichlorophenol..................................... (0.010)(21.1)y............................... 0.00088
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

Sec. 430.107 Pretreatment standards for new sources (PSNS).

Except as provided in 40 CFR 403.7, any new source subject to this
subpart that introduces pollutants into a publicly owned treatment
works must: comply with 40 CFR part 403; and achieve the following
pretreatment standards for new sources (PSNS) if it uses
chlorophenolic-containing biocides. Permittees not using
chlorophenolic-containing biocides must certify to the permit-issuing
authority that they are not using these biocides:

Subpart J
[PSNS for secondary fiber non-deink facilities where paperboard from wastepaper is produced]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb)
of product
----------------------------------------------------------------------------------------------------------^{a-----
Pentachlorophenol................................... (0.072)(3.2)/y............................... 0.00096
Trichlorophenol..................................... (0.023)(3.2)/y............................... 0.00030
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

Subpart J
[PSNS for secondary fiber non-deink facilities where builders' paper and roofing felt from wastepaper are
produced]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb) of
product ^{a
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol................................... (0.171)(2.7)/y.............................. 0.0019
Trichlorophenol..................................... (0.053)(2.7)/y.............................. 0.00060
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

Subpart J
[PSNS for secondary fiber non-deink facilities where tissue from wastepaper is produced without deinking]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb)
of product
----------------------------------------------------------------------------------------------------------^{a-----
Pentachlorophenol......................................................... (0.049)(16.3)/y 0.0034
Trichlorophenol........................................................... (0.015)(16.3)/y 0.0011
y = wastewater discharged in kgal per ton of product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

[[Page 18712]]

Subpart J
[PSNS for secondary fiber non-deink facilities where molded products from wastepaper are produced without
deinking]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb) of
product ^{a
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol................................... (0.118)(5.7)/y.............................. 0.0028
Trichlorophenol..................................... (0.037)(5.7)/y.............................. 0.00088
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

Subpart K--Fine and Lightweight Papers from Purchased Pulp
Subcategory

Sec. 430.110 Applicability; description of the fine and lightweight
papers from purchased pulp subcategory.

The provisions of this subpart are applicable to discharges
resulting from the production of: fine paper at nonintegrated mills;
and lightweight paper at nonintegrated mills.

Sec. 430.111 Specialized definitions.

For the purpose of this subpart:
(a) Except as provided in paragraphs (b) and (c) of this section,
the general definitions, abbreviations, and methods of analysis set
forth in 40 CFR part 401 and Sec. 430.01 of this part shall apply to
this subpart.
(b) Cotton fiber furnish subdivision mills are those mills where
significant quantities of cotton fibers (equal to or greater than 4
percent of the total product) are used in the production of fine
papers.
(c) Wood fiber furnish subdivision mills are those mills where
cotton fibers are not used in the production of fine papers.

Sec. 430.112 Effluent limitations representing the degree of effluent
reduction attainable by the application of the best practicable control
technology currently available (BPT).

Except as provided in 40 CFR 125.30 through 125.32, any existing
point source subject to this subpart must achieve the following
effluent limitations representing the degree of effluent reduction
attainable by the application of the best practicable control
technology currently available (BPT), except that non-continuous
dischargers shall not be subject to the maximum day and average of 30
consecutive days limitations but shall be subject to annual average
effluent limitations:

Subpart K
[BPT effluent limitations for non-integrated mills where fine paper is produced from purchased pulp--wood fiber
furnish subdivision]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 8.2 4.25 2.4
TSS...................................................................... 11.0 5.9 3.2
pH....................................................................... (\1\) (\1\) (\1\)
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Subpart K
[BPT effluent limitations for non-integrated mills where fine paper is produced from purchased pulp--cotton
fiber furnish subdivision]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 17.4 9.1 5.1
TSS...................................................................... 24.3 13.1 7.2

[[Page 18713]]

Subpart K
[BPT effluent limitations for non-integrated mills where lightweight papers are produced from purchased pulp]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 24.1 13.2 7.37
TSS...................................................................... 21.6 10.6 6.0
pH....................................................................... (\1\) (\1\) (\1\)
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Subpart K
[BPT effluent limitations for non-integrated mills where lightweight papers are produced from purchased pulp--
electrical grade papers subdivision
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 38.0 20.9 11.7
TSS...................................................................... 34.2 16.7 9.5
pH....................................................................... (\1\) (\1\) (\1\)
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Sec. 430.113 Effluent limitations guidelines representing the degree
of effluent reduction attainable by the application of the best
conventional pollutant control technology (BCT).

Except as provided in 40 CFR 125.30 through 125.32, any existing
point source subject to this subpart shall achieve the following
effluent limitations representing the degree of effluent reduction
attainable by the application of the best conventional pollutant
control technology (BCT): The limitations shall be the same as those
specified for conventional pollutants (which are defined in 40 CFR
401.16) in Sec. 430.102 of this subpart for the best practicable
control technology currently available (BPT).

Sec. 430.114 Effluent limitations representing the degree of effluent
reduction attainable by the application of the best available
technology economically achievable (BAT).

[[Page 18714]]

Subpart K
[BAT effluent limitations for non-integrated mills where fine paper is produced from purchased pulp--wood fiber
furnish subdivision]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
1,000 lb) of Milligrams/liter
product
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol......................................... 0.0018 (0.029)(15.2)/y
Trichlorophenol........................................... 0.00064 (0.010)(15.2)/y
y = wastewater discharged in kgal per ton of product.
----------------------------------------------------------------------------------------------------------------

Subpart K
[BAT effluent limitations for non-integrated mills where fine paper is produced from purchased pulp--cotton
fiber furnish subdivision]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
1,000 lb) Milligrams/liter
of product
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol......................................... 0.0051 (0.029)(42.3)/y
Trichlorophenol........................................... 0.0018 (0.010)(42.3)/y
y = wastewater discharged in kgal per ton of product.
----------------------------------------------------------------------------------------------------------------

Subpart K
[BAT effluent limitations for non-integrated mills where lightweight papers are produced from purchased pulp]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
1,000 lb) Milligrams/liter
of product
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol......................................... 0.0059 (0.029)(48.7)/y
Trichlorophenol........................................... 0.0020 (0.010)(48.7)/y
y = wastewater discharged in kgal per ton of product.
----------------------------------------------------------------------------------------------------------------

Subpart K
[BAT effluent limitations for non-integrated mills where lightweight papers are produced from purchased pulp--
electrical grade papers subdivision]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
1,000 lb) Milligrams/liter
of product
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol......................................... 0.0093 (0.029)(76.9)/y
Trichlorophenol........................................... 0.0032 (0.010)(76.9)/y
y = wastewater discharged in kgal per ton of product.
----------------------------------------------------------------------------------------------------------------

Sec. 430.115 New source performance standards (NSPS).

[[Page 18715]]

Subpart K
[NSPS for non-integrated mills where fine paper is produced from purchased pulp--wood fiber furnish subdivision]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (Annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 3.5 1.9 1.0
TSS...................................................................... 4.4 2.3 1.2
pH....................................................................... (^{1) (^{1) (^{1)
----------------------------------------------------------------------------------------------------------------

Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
pounds per
1,000 lb) of Milligrams/liter
product
Pentachlorophenol......................................... 0.0018 (0.047)(9.4)/y
Trichlorophenol........................................... 0.00064 (0.016)(9.4)/y
y=wastewater discharged in kgal per ton at all times.
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Subpart K
[NSPS for non-integrated mills where fine paper is produced from purchased pulp--cotton fiber furnish
subdivision]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 7.8 4.2 2.2
TSS...................................................................... 9.5 4.9 2.6
pH....................................................................... (\1\) (\1\) (\1\)
----------------------------------------------------------------------------------------------------------------

Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
pounds per
1,000 lb) Milligrams/liter
of product
Pentachlorophenol......................................... 0.0051 (0.039)(31.1)/y
Trichlorophenol........................................... 0.0018 (0.014)(31.1)/y
y = wastewater discharged in kgal per ton at all times.
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Subpart K
[NSPS for non-integrated mills where lightweight papers are produced from purchased pulp]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 13.7 6.7 4.5
TSS...................................................................... 12.0 5.2 3.2
pH....................................................................... (\1\) (\1\) (\1\)
----------------------------------------------------------------------------------------------------------------

[[Page 18716]]

Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
pounds per
1,000 lb) Milligrams/liter
of product
Pentachlorophenol......................................... 0.0059 (0.037)(38.2)/y
Trichlorophenol........................................... 0.0020 (0.013)(38.2)/y
y = wastewater discharged in kgal per ton at all times.
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Subpart K
[NSPS for non-integrated mills where lightweight papers are produced from purchased pulp--electrical grade
papers subdivision]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 24.1 11.7 7.9
TSS...................................................................... 21.1 9.2 5.6
pH....................................................................... (\1\) (\1\) (\1\)
----------------------------------------------------------------------------------------------------------------

Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
pounds per
1,000 lb) Milligrams/liter
of product
Pentachlorophenol......................................... 0.0093 (0.033)(66.8)/y
Trichlorophenol........................................... 0.0032 (0.012)(66.8)/y
y = wastewater discharged in kgal per ton at all times.
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Sec. 430.116 Pretreatment standards for existing sources (PSES).

Subpart K
[PSES for non-integrated mills where fine paper is produced from purchased pulp--wood fiber furnish subdivision]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb) of
product^{a
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol................................... (0.032)(15.2)/y............................. 0.0020
Trichlorophenol..................................... (0.010)(15.2)/y............................. 0.00064
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

Subpart K
[PSES for non-integrated mills where fine paper is produced from purchased pulp--cotton fiber furnish
subdivision]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb) of
product^{a
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol................................... (0.032)(42.3)/y............................. 0.0056

[[Page 18717]]

Trichlorophenol..................................... (0.010)(42.3)/y............................. 0.0018
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

Subpart K
[PSES for non-integrated mills where lightweight papers are produced from purchased pulp]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb)
of product
----------------------------------------------------------------------------------------------------------^{a-----
Pentachlorophenol................................... (0.032)(48.7)/y.............................. 0.0065
Trichlorophenol..................................... (0.010)(48.7)/y.............................. 0.0032
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

Subpart K
[PSES for non-integrated mills where lightweight papers are produced from purchased pulp--electrical grade
papers subdivision]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb) of
product ^{a
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol................................... (0.032)(76.9)/y............................. 0.010
Trichlorophenol..................................... (0.010)(76.9)/y............................. 0.0032
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

Sec. 430.117 Pretreatment standards for new sources (PSNS).

Subpart K
[PSNS for non-integrated mills where fine paper is produced from purchased pulp--wood fiber furnish subdivision]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb) of
product ^{a
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol................................... (0.052)(9.4)/y.............................. 0.0020
Trichlorophenol..................................... (0.016)(9.4)/y.............................. 0.0064
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

[[Page 18718]]

Subpart K
[PSNS for non-integrated mills where fine paper is produced from purchased pulp--cotton fiber furnish
subdivision]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb)
of product
----------------------------------------------------------------------------------------------------------^{a-----
Pentachlorophenol................................... (0.044)(31.1)/y.............................. 0.0056
Trichlorophenol..................................... (0.014)(31.1)/y.............................. 0.0018
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

Subpart K
[PSNS for non-integrated mills where lightweight papers are produced from purchased pulp]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb)
of product
----------------------------------------------------------------------------------------------------------^{a-----
Pentachlorophenol................................... (0.041)(38.2)/y.............................. 0.0065
Trichlorophenol..................................... (0.013)(38.2)/y.............................. 0.0020
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

Subpart K
[PSNS for non-integrated mills where lightweight papers are produced from purchased pulp--electrical grade
papers subdivision]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb) of
product ^{a
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol................................... (0.037)(66.8)/y............................. 0.010
Trichlorophenol..................................... (0.012)(66.8)/y............................. 0.0032
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

Subpart L--Tissue, Filter, Non-Woven, and Paperboard From Purchased
Pulp Subcategory

Sec. 430.120 Applicability; description of the tissue, filter, non-
woven, and paperboard from purchased pulp subcategory.

The provisions of this subpart are applicable to discharges
resulting from the production of tissue papers at non-integrated mills,
filter and non-woven papers at non-integrated mills, and paperboard at
non-integrated mills. The production of electrical grades of board and
matrix board is not included in this subpart.

Sec. 430.121 Specialized definitions.

For the purpose of this subpart, the general definitions,
abbreviations, and methods of analysis set forth in 40 CFR part 401 and
Sec. 430.01 of this part shall apply to this subpart.

Sec. 430.122 Effluent limitations representing the degree of effluent
reduction attainable by the application of the best practicable control
technology currently available (BPT).

[[Page 18719]]

Subpart L
[BPT effluent limitations for non-integrated mills where tissue papers are produced from purchased pulp]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 11.4 6.25 3.49
TSS...................................................................... 10.25 5.0 2.84
pH....................................................................... (\1\) (\1\) (\1\)
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Subpart L
[BPT effluent limitations for non-integrated mills where filter and non-woven papers are produced from purchased
pulp]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 29.6 16.3 9.1
TSS...................................................................... 26.6 13.0 7.4
pH....................................................................... (\1\) (\1\) (\1\)
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Subpart L
[BPT effluent limitations for non-integrated mills where paperboard is produced from purchased pulp]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Non-continuous
dischargers (Annual
average)
Pollutant or pollutant property -------------------------
Continuous Average of
dischargers daily
Maximum for values for
any 1 day 30
consecutive
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 6.5 3.6 2.0
TSS...................................................................... 5.8 2.8 1.6
pH....................................................................... (\1\) (\1\) (\1\)
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Sec. 430.123 Effluent limitations guidelines representing the degree
of effluent reduction attainable by the application of the best
conventional pollutant control technology (BCT).

Except as provided in 40 CFR 125.30 through 125.32, any existing
point source subject to this subpart shall achieve the following
effluent limitations representing the degree of effluent reduction
attainable by the application of the best conventional pollutant
control technology (BCT): The limitations shall be the same as those
specified for conventional pollutants (which are defined in 40 CFR
401.16) in Sec. 430.122 of this subpart for the best practicable
control technology currently available (BPT).

Sec. 430.124 Effluent limitations representing the degree of effluent
reduction attainable by the application of the best available
technology economically achievable (BAT).

[[Page 18720]]

Subpart L
[BAT effluent limitations for non-integrated mills where tissue papers are produced from purchased pulp]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
1,000 lb) of Milligrams/liter
product
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol......................................... 0.0028 (0.029)(22.9)/y
Trichlorophenol........................................... 0.00096 (0.010)(22.9)/y
y = wastewater discharged in kgal per ton of product.
----------------------------------------------------------------------------------------------------------------

Subpart L
[BAT effluent limitations for non-integrated mills where filter and non-woven papers are produced from purchased
pulp]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
1,000 lb) Milligrams/liter
of product
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol......................................... 0.0072 (0.029)(59.9)/y
Trichlorophenol........................................... 0.0025 (0.010)(59.9)/y
y = wastewater discharged in kgal per ton of product.
----------------------------------------------------------------------------------------------------------------

Subpart L
[BAT effluent limitations for non-integrated mills where paperboard is produced from purchased pulp]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
1,000 lb) of Milligrams/liter
product
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol......................................... 0.0016 (0.029)(12.9)/y
Trichlorophenol........................................... 0.00054 (0.010)(12.9)/y
y = wastewater discharged in kgal per ton of product.
----------------------------------------------------------------------------------------------------------------

Sec. 430.125 New source performance standards (NSPS).

Subpart L
[NSPS for non-integrated mills where tissue papers are produced from purchased pulp]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 7.0 3.4 2.3
TSS...................................................................... 6.0 2.6 1.6
pH....................................................................... (\1\) (\1\) (\1\)
----------------------------------------------------------------------------------------------------------------

[[Page 18721]]

Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
pounds per
1,000 lb) of Milligrams/liter
product
Pentachlorophenol......................................... 0.0028 (0.035)(19.1)/y
Trichlorophenol........................................... 0.00096 (0.012)(19.1)/y
y = wastewater discharged in kgal per ton at all times.
----------------------------------------------------------------------------------------------------------------
\1\ Within the range of 5.0 to 9.0 at all times.

Subpart L
[NSPS for non-integrated mills where filter and non-woven papers are produced from purchased pulp]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 17.1 8.3 5.6
TSS...................................................................... 15.0 6.6 4.0
pH....................................................................... (^{1) (^{1) (^{1)
----------------------------------------------------------------------------------------------------------------

Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
pounds per
1,000 lb) Milligrams/liter
of product
Pentachlorophenol......................................... 0.0072 (0.037)(47.5)/y
Trichlorophenol........................................... 0.0025 (0.013)(47.5)/y
y = wastewater discharged in kgal per ton at all times.
----------------------------------------------------------------------------------------------------------------
^{1 Within the range of 5.0 to 9.0 at all times.

Subpart L
[NSPS for non-integrated mills where paperboard is produced from purchased pulp]
----------------------------------------------------------------------------------------------------------------
Kg/kkg (or pounds per 1,000 lb) of
product
--------------------------------------
Continuous dischargers
--------------------------
Pollutant or pollutant property Average of Non-
daily continuous
Maximum for values for dischargers
any 1 day 30 (annual
consecutive average)
days
----------------------------------------------------------------------------------------------------------------
BOD5..................................................................... 4.0 1.9 1.3
TSS...................................................................... 3.5 1.5 0.9
pH....................................................................... (^{1) (^{1) (^{1)
----------------------------------------------------------------------------------------------------------------

Maximum for any 1 day
-----------------------------------------------------
Kg/kkg (or
pounds per
1,000 lb) of Milligrams/liter
product
Pentachlorophenol......................................... 0.0016 (0.033)(11.2)/y
Trichlorophenol........................................... 0.00054 (0.012)(11.2)/y
y = wastewater discharged in kgal per ton at all times.
----------------------------------------------------------------------------------------------------------------
(^{1) Within the range of 5.0 to 9.0 at all times.

Sec. 430.126 Pretreatment standards for existing sources (PSES).

[[Page 18722]]

containing biocides must certify to the permit-issuing authority that
they are not using these biocides. PSES must be attained on or before
July 1, 1984:

Subpart L
[PSES for non-integrated mills where tissue papers are produced from purchased pulp]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb) of
product ^{a
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol................................... (0.032)(22.9)/y............................. 0.0031
Trichlorophenol..................................... (0.010)(22.9)/y............................. 0.00096
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

Subpart L
[PSES for non-integrated mills where filter and non-woven papers are produced from purchased pulp]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb)
of product
----------------------------------------------------------------------------------------------------------^{a-----
Pentachlorophenol................................... (0.032)(59.9)/y.............................. 0.0080
Trichlorophenol..................................... (0.010)(59.9)/y.............................. 0.0025
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

Subpart L
[PSES for non-integrated mills where paperboard is produced from purchased pulp]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb) of
product ^{a
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol................................... (0.032)(12.9)/y............................. 0.0017
Trichlorophenol..................................... (0.010)(12.9)/y............................. 0.00054
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

Sec. 430.127 Pretreatment standards for new sources (PSNS).

Subpart L
[PSNS for non-integrated mills where tissue papers are produced from purchased pulp]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb) of
product ^{a
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol................................... (0.038)(19.1)/y............................. 0.0031
Trichlorophenol..................................... (0.012)(19.1)/y............................. 0.00096
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

[[Page 18723]]

Subpart L
[PSNS for non-integrated mills where filter and non-woven papers are produced from purchased pulp]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb)
of product
----------------------------------------------------------------------------------------------------------^{a-----
Pentachlorophenol................................... (0.040)(47.5)/y.............................. 0.0080
Trichlorophenol..................................... (0.013)(47.5)/y.............................. 0.0025
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

Subpart L
[PSNS for non-integrated mills where paperboard is produced from purchased pulp]
----------------------------------------------------------------------------------------------------------------
Maximum for any 1 day
-----------------------------------------------------------
Kg/kkg (or
Pollutant or pollutant property pounds per
Milligrams/liter (mg/l) 1,000 lb) of
product ^{a
----------------------------------------------------------------------------------------------------------------
Pentachlorophenol................................... (0.037)(11.2)/y............................. 0.0017
Trichlorophenol..................................... (0.012)(11.2)/y............................. 0.00054
y = wastewater discharged in kgal per ton of
product.
----------------------------------------------------------------------------------------------------------------
^{a The following equivalent mass limitations are provided as guidance in cases when POTWs find it necessary to
impose mass effluent limitations.

Appendix A to Part 430--Methods 1650 and 1653

Method 1650--Adsorbable Organic Halides by Adsorption and Coulometric
Titration

1.0 Scope and Application

1.1 This method is for determination of adsorbable organic
halides (AOX) associated with the Clean Water Act; the Resource
Conservation and Recovery Act; the Comprehensive Environmental
Response, Compensation, and Liability Act; and other organic halides
amenable to combustion and coulometric titration. The method is
designed to meet the survey and monitoring requirements of the
Environmental Protection Agency (EPA).
1.2 The method is applicable to the determination of AOX in
water and wastewater. This method is a combination of several
existing methods for organic halide measurements (References 1
through 7).
1.3 The method can be used to measure organically-bound halides
(chlorine, bromine, iodine) present in dissolved or suspended form.
Results are reported as organic chloride (Cl^-). The
detection limit of the method is usually dependent on interferences
rather than instrumental limitations. A method detection limit (MDL;
Reference 8) of 6.6 g/L, and a minimum level (ML; Section
18) of 20 g/L, can be achieved with no interferences
present.
1.4 This method is for use by or under the supervision of
analysts experienced in the use of a combustion/micro-coulometer.
Each laboratory that uses this method must demonstrate the ability
to generate acceptable results using the procedures described in
Section 9.2.
1.5 Any modification of the method beyond those expressly
permitted (Section 9.1.2) is subject to application and approval of
an alternate test procedure under 40 CFR 136.4 and 136.5.

2.0 Summary of Method

2.1 Sample preservation: Residual chlorine that may be present
is removed by the addition of sodium thiosulfate. Samples are
adjusted to a pH < 2 and maintained at 0 to 4 deg.C until analysis.
2.2 Sample analysis: Organic halide in water is determined by
adsorption onto granular activated carbon (GAC), washing the
adsorbed sample and GAC to remove inorganic halide, combustion of
the sample and GAC to form the hydrogen halide, and titration of the
hydrogen halide with a micro-coulometer, as shown in Figure 1.
2.3 Micro-coulometer.
2.3.1 This detector operates by maintaining a constant silver-
ion concentration in a titration cell. An electric potential is
applied to a solid silver electrode to produce silver ions in the
cell. As hydrogen halide produced from the combustion of organic
halide enters the cell, it is partitioned into an acetic acid
electrolyte where it precipitates as silver halide. The current
produced is integrated over the combustion period. The electric
charge is proportional to the number of moles of halogen captured in
the cell (Reference 6).
2.3.2 The mass concentration of organic halides is reported as
an equivalent concentration of organically bound chloride
(Cl^-).

3.0 Definitions

3.1 Adsorbable organic halides is defined as the analyte
measured by this method. The nature of the organo-halides and the
presence of semi-extractable material will influence the amount
measured and interpretation of results.
3.2 Definitions for terms used in this method are given in the
glossary at the end of the method (Section 18).

4.0 Interferences

4.1 Solvents, reagents, glassware, and other sample processing
hardware may yield elevated readings from the micro-coulometer. All
materials used in the analysis shall be demonstrated to be free from
interferences under the conditions of analysis by running method
blanks initially and with each sample batch (samples started through
the adsorption process in a given eight-hour shift, to a maximum of
20 samples). Specific selection of reagents and purification of
solvents may be required.
4.2 Glassware is cleaned by detergent washing in hot water,
rinsing with tap water and distilled water, capping with aluminum
foil, and baking at 450 deg.C for at least one hour. For some
glassware, immersion in a chromate cleaning solution prior to
detergent washing may be required. If blanks from glassware without
cleaning or with fewer cleaning steps show no detectable organic
halide, the cleaning steps that do not eliminate organic halide may
be omitted.
4.3 Most often, contamination results from methylene chloride
vapors in laboratories that perform organic extractions. Heating,
ventilating, and air conditioning systems that are shared between
the extraction laboratory and the laboratory in which organic halide
measurements are performed transfer the methylene chloride vapors to
the air in the organic halide laboratory. Exposure of the activated
carbon

[[Page 18724]]

used in the analysis results in contamination. Separate air handling
systems, charcoal filters, and glove boxes can be used to minimize
this exposure.
4.4 Activated carbon.
4.4.1 The purity of each lot of activated carbon must be
verified before each use by measuring the adsorption capacity and
the background level of halogen (Section 9.5). The stock of
activated carbon should be stored in its granular form in a glass
container that is capped tightly. Protect carbon at all times from
sources of halogen vapors.
4.4.2 Inorganic substances such as chloride, chlorite, bromide,
and iodide will adsorb on activated carbon to an extent dependent on
their original concentration in the aqueous solution and the volume
of sample adsorbed. Treating the activated carbon with a solution of
nitrate causes competitive desorption of inorganic halide species.
However, if the inorganic halide concentration is greater than 2,000
times the organic halide concentration, artificially high results
may be obtained.
4.4.3 Halogenated organic compounds that are weakly adsorbed on
activated carbon are only partially recovered from the sample. These
include certain alcohols and acids such as chloroethanol and
chloroacetic acid that can be removed from activated carbon by the
nitrate wash.
4.5 Polyethylene gloves should be worn when handling equipment
surfaces in contact with the sample to prevent transfer of
contaminants that may be present on the hands.

5.0 Safety

5.1 The toxicity or carcinogenicity of each reagent used in
this method has not been precisely determined; however, each
chemical substance should be treated as a potential health hazard.
Exposure to these substances should be reduced to the lowest
possible level. The laboratory is responsible for maintaining a
current awareness file of OSHA regulations regarding the safe
handling of the chemicals specified in this method. A reference file
of material safety data sheets (MSDSs) should be made available to
all personnel involved in the chemical analysis. Additional
information on laboratory safety can be found in References 9
through 11.
5.2 This method employs strong acids. Appropriate clothing,
gloves, and eye protection should be worn when handling these
substances.
5.3 Field samples may contain high concentrations of toxic
volatile compounds. Sample containers should be opened in a hood and
handled with gloves that will prevent exposure.

6.0 Equipment and Supplies

Note: Brand names, suppliers, and part numbers are for
illustrative purposes only. No endorsement is implied. Equivalent
performance may be achieved using apparatus and materials other than
those specified here, but demonstration of equivalent performance
that meets the requirements of this method is the responsibility of
the laboratory.
6.1 Sampling equipment.
6.1.1 Bottles: 100- to 4000-mL, amber glass, sufficient for all
testing (Section 8.2). Detergent water wash, chromic acid rinse,
rinse with tap and distilled water, cover with aluminum foil, and
heat to 450 deg.C for at least one hour before use.
6.1.2 PTFE liner: Cleaned as above and baked at 100 to
200 deg.C for at least one hour.
6.1.3 Bottles and liners must be lot certified to be free of
organic halide by running blanks according to this method.
6.2 Scoop for granular activated carbon (GAC): Capable of
precisely measuring 40 mg (5 mg) GAC (Dohrmann Measuring
Cup 521-021, or equivalent).
6.3 Batch adsorption and filtration system.
6.3.1 Adsorption system: Rotary shaker, wrist action shaker,
ultrasonic system, or other system for assuring thorough contact of
sample with activated carbon. Systems different from the one
described below must be demonstrated to meet the performance
requirements in Section 9 of this method.
6.3.1.1 Erlenmeyer flasks: 250- to 1500-mL with ground-glass
stopper, for use with rotary shaker.
6.3.1.2 Shake table: Sybron Thermolyne Model LE ``Big Bill''
rotator/shaker, or equivalent.
6.3.1.3 Rack attached to shake table to permit agitation of 16
to 25 samples simultaneously.
6.3.2 Filtration system (Figure 2).
6.3.2.1 Vacuum filter holder: Glass, with fritted-glass support
(Fisher Model 09-753E, or equivalent).
6.3.2.2 Polycarbonate filter: 0.40 to 0.45 micron, 25-mm
diameter (Micro Separations Inc, Model K04CP02500, or equivalent).
6.3.2.3 Filter forceps: Fisher Model 09-753-50, or equivalent,
for handling filters. Two forceps may better aid in handling
filters. Clean by washing with detergent and water, rinsing with tap
and deionized water, and air drying on aluminum foil.
6.3.2.4 Vacuum flask: 500- to 1500-mL (Fisher 10-1800, or
equivalent).
6.3.2.5 Vacuum Source: A pressure/vacuum pump, rotary vacuum
pump, or other vacuum source capable of providing at least 610 mm
(24 in.) Hg vacuum at 30 L/min free air displacement.
6.3.2.6 Stopper and tubing to mate the filter holder to the
flask and the flask to the pump.
6.3.2.7 Polyethylene gloves: (Fisher 11-394-110-B, or
equivalent).
6.4 Column adsorption system.
6.4.1 Adsorption module: Dohrmann AD-2, Mitsubishi TXA-2, or
equivalent with pressurized sample and nitrate-wash reservoirs,
adsorption columns, column housings, gas and gas pressure
regulators, and receiving vessels. For each sample reservoir, there
are two adsorption columns connected in series. A small steel funnel
for filling the columns and a rod for pushing out the carbon are
also required. A schematic of the column adsorption system is shown
in Figure 3.
6.4.2 Adsorption columns: Pyrex, 5 0.2 cm long x
2 mm ID, to hold 40 mg of granular activated carbon (GAC).
6.4.3 Cerafelt: Johns-Manville, or equivalent, formed into
plugs using stainless steel borer (2 mm ID) with ejection rod
(available from Dohrmann or Mitsubishi) to hold 40 mg of granular
activated carbon (GAC). Caution: Handle Cerafelt with gloves.
6.4.4 Column holders: To support adsorption columns.
6.5 Combustion/micro-coulometer system: Commercially available
as a single unit or assembled from parts. At the time of the writing
of this method, organic halide units were commercially available
from the Dohrmann Division of Rosemount Analytical, Santa Clara,
California; Euroglas BV, Delft, the Netherlands; and Mitsubishi
Chemical Industries, Ltd., Tokyo, Japan.
6.5.1 Combustion system: Older systems may not have all of the
features shown in Figure 4. These older systems may be used provided
the performance requirements (Section 9) of this method are met.
6.5.1.1 Combustion tube: Quartz, capable of being heated to 800
to 1000 deg.C and accommodating a boat sampler. The tube must
contain an air lock for introduction of a combustion boat,
connections for purge and combustion gas, and connection to the
micro-coulometer cell.
6.5.1.2 Tube furnace capable of controlling combustion tube in
the range of 800 to 1000 deg.C.
6.5.1.3 Boat sampler: Capable of holding 35 to 45 mg of
activated carbon and a polycarbonate filter, and fitting into the
combustion tube (Section 6.5.1.1). Some manufacturers offer an
enlarged boat and combustion tube for this purpose. Under a time-
controlled sequence, the boat is first moved into an evaporation
zone where water and other volatiles are evaporated, and then into
the combustion zone where the carbon and all other organic material
in the boat are burned in a flowing oxygen stream. The evolved gases
are transported by a non-reactive carrier gas to the micro-
coulometer cell.
6.5.1.4 Motor driven boat sampler: Capable of advancing the
combustion boat into the furnace in a reproducible time sequence. A
suggested time sequence is as follows:
A. Establish initial gas flow rates: 160 mL/min CO2;
40 mL/min O2.
B. Sequence start.
C. Hold boat in hatch for five seconds to allow integration for
baseline subtraction.
D. Advance boat into vaporization zone.
E. Hold boat in vaporization zone for 110 seconds.
F. Establish gas flow rates for combustion: 200 mL/min
O2; 0 mL/min CO2; advance boat into pyrolysis
zone (800 deg.C).
G. Hold boat in pyrolysis zone for six minutes.
H. Return gas flow rates to initial values; retract boat into
hatch to cool and to allow remaining HX to be swept into detector
(approximately two minutes).
I. Stop integration at 10 minutes after sequence start.

Note: If the signal from the detector does not return to
baseline, it may be necessary to extend the pyrolysis time.The
sequence above may need to be optimized for each instrument.

6.5.1.5 Absorber: Containing sulfuric acid to dry the gas
stream after combustion to

[[Page 18725]]

prevent backflush of electrolyte is highly recommended.
6.5.2 Micro-coulometer system: Capable of detecting the
equivalent of 0.2 g of Cl^- at a signal-to-noise
ratio of 2; capable of detecting the equivalent of 1 g of
Cl^- with a relative standard deviation less than 10%, and
capable of accumulating a minimum of the equivalent of 500
g of Cl^- before a change of electrolyte is
required.
6.5.2.1 Micro-coulometer cell: The three cell designs presently
in use are shown in Figure 1. Cell operation is described in Section
2.
6.5.2.2 Cell controller: Electronics capable of measuring the
small currents generated in the cell and accumulating and displaying
the charge produced by hydrogen halides entering the cell. A strip-
chart recorder is desirable for display of accumulated charge.
6.6 Miscellaneous glassware: nominal sizes are specified below;
other sizes may be used, as necessary.
6.6.1 Volumetric flasks: 5-, 10-, 25-, 50-, 100-, and 1000-mL.
6.6.2 Beakers: 100-, 500-, and 1000-mL.
6.6.3 Volumetric pipets: 1- and 10-mL with pipet bulbs.
6.6.4 Volumetric micro-pipets: 10-, 20-, 50-, 100-, 200-, and
500-L with pipet control (Hamilton 0010, or equivalent).
6.6.5 Graduated cylinders: 10-, 100-, and 1000-mL.
6.7 Micro-syringes: 10-, 50-, and 100-L.
6.8 Balances.
6.8.1 Top-loading, capable of weighing 0.1 g.
6.8.2 Analytical, capable of weighing 0.1 mg.
6.9 pH meter.
6.10 Wash bottles: 500- to 1000-mL, PTFE or polyethylene.
6.11 Strip-chart recorder: suggested but not required--useful
for determining end of integration (Section 11.4.2).

7.0 Reagents and Standards

7.1 Granular activated carbon (GAC): 75 to 150 m (100
to 200 mesh); (Dohrmann, Mitsubishi, Carbon Plus, or equivalent),
with chlorine content less than 1 g Cl^- per
scoop (< 25 g Cl^- per gram), adsorption capacity
greater than 1000 g Cl^- (as 2,4,6-
trichlorophenol) per scoop (>25,000 g/g), inorganic halide
retention of less than 1 g Cl^- per scoop in the
presence of 10 mg of inorganic halide (< 20 g
Cl^- per gram in the presence of 2500 mg of inorganic
halide), and that meets the other test criteria in this method.
7.2 Reagent water: Water in which organic halide is not
detected by this method.
7.2.1 Preparation: Reagent water may be generated by:
7.2.1.1 Activated carbon: Pass tap water through a carbon bed
(Calgon Filtrasorb-300, or equivalent).
7.2.1.2 Water purifier: Pass tap water through a purifier
(Millipore Super Q, or equivalent).
7.2.2 pH adjustment: Adjust the pH of the reagent water to < 2
with nitric acid for all reagent water used in this method, except
for the acetic acid solution (Section 7.13).
7.3 Nitric acid (HNO3): Concentrated, analytical
grade.
7.4 Sodium chloride (NaCl) solution (100 g/mL of
Cl^-): Dissolve 0.165g NaCl in 1000 mL reagent water. This
solution is used for cell testing and for the inorganic halide
rejection test.
7.5 Ammonium chloride (NH4Cl) solution (100
g/mL of Cl^-): Dissolve 0.1509 g NH4Cl
in 1000 mL reagent water.
7.6 Sulfuric acid: Reagent grade (specific gravity 1.84).
7.7 Oxygen: 99.9% purity.
7.8 Carbon Dioxide: 99.9% purity.
7.9 Nitrate stock solution: In a 1000-mL volumetric flask,
dissolve 17g of NaNO3 in approximately 100 mL of reagent
water, add 1.4 mL nitric acid (Section 7.3) and dilute to the mark
with reagent water.
7.10 Nitrate wash solution: Dilute 50 mL of nitrate stock
solution (Section 7.9) to 1000 mL with reagent water.
7.11 Sodium thiosulfate
(Na2S2O3) solution (1 N): Weigh 79
grams of Na2S2O3 in a 1-L
volumetric flask and dilute to the mark with reagent water.
7.12 Trichlorophenol solutions.

Note: The calibration solutions in this section employ 100-mL
volumes. For determinations requiring a larger or smaller volume,
increase or decrease the size of the volumetric flasks
commensurately. For example, if a 1-L sample is to be analyzed, use
1000-mL flasks (Sections 7.12.3.1 and 7.12.4) and 10 times the
volume of reagent water (Sections 7.12.3.1 and 7.12.4). The volume
of stock solution added to the calibration solutions and precision
and recovery (PAR) test solution remain as specified (Sections
7.12.3.2 and 7.12.4) so that the same amount of chloride is
delivered to the coulometric cell regardless of the volume of the
calibration and PAR solutions.

7.12.1 Methanol: HPLC grade.
7.12.2 Trichlorophenol stock solution (1.0 mg/mL of
Cl^-): Dissolve 0.186 g of 2,4,6-trichlorophenol in 100 mL
of halide-free methanol.
7.12.3 Trichlorophenol calibration solutions.
7.12.3.1 Place approximately 90 mL of reagent water in each of
five 100-mL volumetric flasks.
7.12.3.2 Using a calibrated micro-syringe or micro-pipets, add
2, 5, 10, 30, and 80 L of the trichlorophenol stock
solution (Section 7.12.2) to the volumetric flasks and dilute each
to the mark with reagent water to produce calibration solutions of
2, 5, 10, 30, and 80 g Cl^- per 100 mL of
solution (20, 50, 100, 300, and 800 g/L).
7.12.3.3 Some instruments may have a calibration range that
does not extend to 800 g/L (80 g of
Cl^-). For those instruments, a narrower dynamic range may
be used. However, if the concentration of halide in a sample exceeds
that range, the sample must be diluted to bring the concentration
within the range calibrated.
7.12.4 Trichlorophenol precision and recovery (PAR) test
solution (10 g/L of Cl^-): Partially fill a 100-
mL volumetric flask, add 10 L of the stock solution
(Section 7.12.2), and dilute to the mark with reagent water.
7.13 Acetic acid solution: Containing 30 to 70% acetic acid in
deionized water, per the instrument manufacturer's instructions.

8.0 Sample Collection, Preservation, and Storage

8.1 Sample preservation.
8.1.1 Residual chlorine: If the sample is known or suspected to
contain free chlorine, the chlorine must be reduced to eliminate
positive interference that may result from continued chlorination
reactions. A knowledge of the process from which the sample is
collected may be of value in determining whether dechlorination is
necessary. Immediately after sampling, test for residual chlorine
using the following method or an alternative EPA method (Reference
12):
8.1.1.1 Dissolve a few crystals of potassium iodide in the
sample and add three to five drops of a 1% starch solution. A blue
color indicates the presence of residual chlorine.
8.1.1.2 If residual chlorine is found, add 1 mL of sodium
thiosulfate solution (Section 7.11) for each 2.5 ppm of free
chlorine or until the blue color disappears. Do not add an excess of
sodium thiosulfate. Excess sodium thiosulfate may cause
decomposition of a small fraction of the OX.
8.1.2 Acidification: Adjust the pH of aqueous samples to < 2
with nitric acid. Acidification inhibits biological activity and
stabilizes chemical degradation, including possible dehalogenation
reactions that may occur at high pH. Acidification is necessary to
facilitate thorough adsorption.
8.1.3 Refrigeration: Maintain samples at a temperature of 0 to
4 deg. C from time of collection until analysis.
8.2 Collect the amount of sample necessary for analysis
(Section 11) and all QC tests (Section 9) in an amber glass bottle
of the appropriate size (Section 6.1.1).
8.3 Analyze samples no less than three days nor more than six
months after collection.

9.0 Quality Control

9.1 Each laboratory that uses this method is required to
operate a formal quality assurance program. The minimum requirements
of this program consist of an initial demonstration of laboratory
capability, an ongoing analysis of standards and blanks as tests of
continued performance, and analysis of matrix spike and matrix spike
duplicate (MS/MSD) samples to assess accuracy and precision.
Laboratory performance is compared to established performance
criteria to determine if the results of analyses meet the
performance characteristics of the method.
9.1.1 The laboratory shall make an initial demonstration of the
ability to produce acceptable results with this method. This ability
is demonstrated as described in Section 9.2.
9.1.2 The laboratory is permitted to modify this method to
improve separations or lower the costs of measurements, provided
that all performance specifications are met. Each time a
modification is made to the method, the laboratory is required to
repeat the procedures in Sections 9.2.2 and 10 to demonstrate
continued method performance. If the detection limit of the method
will be affected by the modification, the laboratory should
demonstrate that the MDL (40 CFR

[[Page 18726]]

136, Appendix B) is less than or equal to the MDL in this method or
one-third the regulatory compliance level, whichever is higher.
9.1.3 The laboratory shall spike 10% of the samples with known
concentrations of 2,4,6-trichlorophenol to monitor method
performance and matrix interferences (interferences caused by the
sample matrix). This test is described in Section 9.3. When results
of these spikes indicate atypical method performance for samples,
the samples are diluted to bring method performance within
acceptable limits.
9.1.4 Analyses of blanks are required to demonstrate freedom
from contamination. The procedures and criteria for analysis of
blanks are described in Section 9.4.
9.1.5 The laboratory shall, on an ongoing basis, demonstrate
through the analysis of the precision and recovery (PAR) standard
that the analysis system is in control. These procedures are
described in Section 9.10.
9.1.6 The laboratory shall perform quality control tests on the
granular activated carbon. These procedures are described in Section
9.5.
9.1.7 Samples are analyzed in duplicate to demonstrate
precision. These procedures are described in Section 9.6.
9.2 Initial demonstration of laboratory capability.
9.2.1 Method Detection Limit (MDL): To establish the ability to
detect AOX, the laboratory should determine the MDL per the
procedure in 40 CFR 136, Appendix B using the apparatus, reagents,
and standards that will be used in the practice of this method. An
MDL less than or equal to the MDL in Section 1.3 should be achieved
prior to the practice of this method.
9.2.2 Initial precision and recovery (IPR): To establish the
ability to generate acceptable precision and recovery, the
laboratory shall perform the following operations:
9.2.2.1 Analyze four aliquots of the PAR standard (Section
7.12.4) and a method blank according to the procedures in Sections
9.4 and 11.
9.2.2.2 Using the blank-subtracted results of the set of four
analyses, compute the average percent recovery (X) and the standard
deviation of the percent recovery (s) for the results.
9.2.2.3 The average percent recovery shall be in the range of
81 to 114 g/L and the standard deviation shall be less than
8 g/L. If X and s meet these acceptance criteria, system
performance is acceptable and analysis of blanks and samples may
begin. If, however, s exceeds the precision limit or X falls outside
the range for recovery, system performance is unacceptable. In this
case, correct the problem and repeat the test.
9.3 Matrix spikes: The laboratory shall spike a minimum of 10%
of samples from a given matrix type (e.g., C-stage filtrate,
produced water, treated effluent) in duplicate (MS/MSD). If only one
sample from a given matrix type is analyzed, an additional two
aliquots of that sample shall be spiked.
9.3.1 The concentration of the analytes spiked into the MS/MSD
shall be determined as follows:
9.3.1.1 If, as in compliance monitoring, the concentration of
OX is being checked against a regulatory concentration limit, the
spiking level shall be at that limit or at one to five times higher
than the background concentration determined in Section 9.3.2,
whichever concentration is higher.
9.3.1.2 If the concentration of OX is not being checked against
a regulatory limit, the spike shall be at the concentration of the
precision and recovery standard (PAR; Section 7.12.4) or at one to
five times higher than the background concentration determined in
Section 9.3.2, whichever concentration is higher.
9.3.2 Analyze one sample out of each batch of 10 samples from
each site to determine the background concentration of AOX. If
necessary, prepare a solution of 2,4,6-trichlorophenol appropriate
to produce a level in the sample one to five times the background
concentration. Spike two additional sample aliquots with spiking
solution and analyze them to determine the concentration after
spiking.
9.3.2.1 Compute the percent recovery of each analyte in each
aliquot:
[GRAPHIC] [TIFF OMITTED] TR15AP98.018

9.3.2.2 Compute the relative percent difference (RPD) between
the two results (not between the two recoveries) as described in
Section 12.4.
9.3.2.3 If the RPD is less than 20%, and the recoveries for
the MS and MSD are within the range of 78 to 116%, the results are
acceptable.
9.3.2.4 If the RPD is greater than 20%, analyze two aliquots of
the precision and recovery standard (PAR).
9.3.2.4.1 If the RPD for the two aliquots of the PAR is greater
than 20%, the analytical system is out of control. In this case,
repair the problem and repeat the analysis of the sample batch,
including the MS/MSD.
9.3.2.4.2 If, however, the RPD for the two aliquots of the PAR
is less than 20%, dilute the sample chosen for the MS/MSD by a
factor of 2-10 (to remain within the working range of the analytical
system) and repeat the MS/MSD test. If the RPD is still greater than
20%, the result may not be reported for regulatory compliance
purposes. In this case, choose another sample for the MS/MSD and
repeat analysis of the sample batch.
9.3.2.5 If the percent recovery for both the MS and MSD are
less than 78% or greater than 116%, analyze the precision and
recovery (PAR) standard.
9.3.2.5.1 If the recovery of the PAR is outside the 78 to 116%
range, the analytical system is out of control. In this case, repair
the problem and repeat the analysis of the sample batch, including
the MS/MSD.
9.3.2.5.2 If the recovery of the PAR is within the range of 78
to 116%, dilute the sample, MS, and MSD by a factor of 2-10 (to
remain within the working range of the analytical system) and re-
analyze. If the results of the dilute analyses remain outside of the
acceptable range, these results may not be reported for regulatory
compliance purposes. In this case, choose another sample for the MS/
MSD and repeat the analysis of the sample batch.
9.4 Blanks.
9.4.1 Reagent water blanks: Analyzed to demonstrate freedom
from contamination.
9.4.1.1 Analyze a reagent water blank with each batch of
samples. The blank must be analyzed immediately preceding
calibration verification to allow for blank subtraction and to
demonstrate freedom from contamination and memory effects, and must
include all details of the procedure to be followed when analyzing
samples.
9.4.1.2 Prepare the reagent water blank using a volume of
reagent water equivalent to the volume used for sample preparation
(Section 11.1). If using the micro-column procedure, adsorb the
method blank using two columns, as described in Section 11. Combust
the GAC from each column separately, as described in Section 11.
9.4.1.3 If the result from the blank from the batch method or
the sum of the results from two columns is more than 20 g/
L, analysis of samples is halted until the source of contamination
is eliminated and a blank shows no evidence of contamination at this
level.
9.4.2 Nitrate-washed GAC blanks: Analyzed daily to demonstrate
that the GAC is free from contamination.
9.4.2.1 Nitrate-washed GAC blank for the batch procedure:
Analyze a batch nitrate-washed GAC blank by adding a scoop of dry
GAC to the assembled filter apparatus containing the polycarbonate
membrane and washing the GAC with the nitrate wash solution (Section
7.10) using the procedure in Section 11.2.6.
9.4.2.2 Nitrate-washed GAC blank for the column procedure:
Analyze a column nitrate-washed GAC blank by assembling two carbon
columns in series and washing the columns with the nitrate wash
solution (Section 7.10) using the procedure in Section 11.3.4.2.
Analyze the GAC in each column separately. The results of the second
analysis must be within 0.2 g Cl^- of
the first. A difference greater than 0.2 g Cl^-
indicates a lack of homogeneity in the GAC that could introduce
unacceptable variability. If the difference exceeds this amount, the
GAC should be replaced.
9.4.3 The result for the reagent water blank (Section 9.4.1)
shall not exceed the result for the nitrate wash blank (Section
9.4.2.1 or 9.4.2.2) by more than 0.5 g Cl^-.
9.5 Granular activated carbon (GAC) batch testing: Each lot
number or batch of activated carbon received from a supplier is
tested once before use to ensure adequate quality. Use only GAC that
meets the test criteria below.
9.5.1 Contamination test: Analyze a scoop of GAC. Reject carbon
if the amount of OX exceeds 1 g (25 g
Cl^-/g).
9.5.2 Inorganic chloride adsorption test: Attempt to adsorb
NaCl from 100 mL of a solution containing 100 mg/L in reagent water.
Wash with nitrate solution and analyze. The amount of halide should
be less than 1 g Cl^- larger than the blank. A
larger amount indicates significant uptake of inorganic chloride by
the carbon. Reject carbon if the 1 g level is exceeded.
9.6 Samples that are being used for regulatory compliance
purposes shall be analyzed in duplicate.

[[Page 18727]]

9.6.1 The procedure for preparing duplicate sample aliquots is
described in Section 11.5.
9.6.2 Calculate the RPD by following the same procedure
described in Section 12.4.
9.6.3 If the RPD is greater than 20%, the analyses must be
repeated.
9.6.4 If the RPD remains greater than 20%, the result may not
be reported for regulatory compliance purposes.
9.7 The specifications in this method can be met if the
apparatus used is calibrated properly and maintained in a calibrated
state. The standards used for calibration (Section 10), calibration
verification (Section 9.9), and for initial (Section 9.2.2) and
ongoing (Section 9.10) precision and recovery should be identical,
so that the most precise results will be obtained.
9.8 Depending on specific program requirements, field
duplicates may be collected to determine the precision of the
sampling technique.
9.9 At the beginning and end of each eight-hour shift during
which analyses are performed, system performance and calibration are
verified. Verification of system performance and calibration may be
performed more frequently, if desired.
9.9.1 If performance and calibration are verified at the
beginning and end of each shift (or more frequently), samples
analyzed during that period are considered valid.
9.9.2 If performance and calibration are not verified at both
the beginning and end of a shift (or more frequently), samples
analyzed during that period must be reanalyzed.
9.9.3 If calibration is verified at the beginning of a shift,
recalibration using the five standards described in Section 10.6 is
not necessary; otherwise, the instrument must be recalibrated prior
to analyzing samples (Section 10).
9.9.4 Cell maintenance and other changes to the analytical
system that can affect system performance may not be performed
during the eight-hour (or shorter) shift.
9.10 Calibration verification and ongoing precision and
recovery: Calibration and system performance are verified by the
analysis of the 100 g/L PAR standard.
9.10.1 Analyze a blank (Section 9.4) and analyze the PAR
standard (Section 7.12.4) immediately thereafter at the beginning
and end of each shift. Compute the concentration of organic halide
in the blank and in the PAR standard using the procedures in Section
12. The blank shall be less than 2 g Cl^- (20
g/L equivalent).
9.10.2 Subtract the result for the blank from the result of the
PAR standard using the procedures in Section 12, and compute the
percent recovery of the blank-subtracted PAR standard. The percent
recovery shall be in the range of 78 to 116%.
9.10.3 If the recovery is within this range, the analytical
process is in control and analysis of blanks and samples may
proceed. If, however, the recovery is not within the acceptable
range, the analytical process is not in control. In this event,
correct the problem and repeat the ongoing precision and recovery
test (Section 9.10), or recalibrate (Sections 10.5 through 10.6).
9.10.4 If the recovery is not within the acceptable range for
the PAR standard analyzed at the end of the eight-hour shift,
correct the problem, repeat the ongoing precision and recovery test
(Section 9.10), or recalibrate (Sections 10.5 through 10.6), and
reanalyze the sample batch that was analyzed during the eight-hour
shift.
9.10.5 If the recovery is within the acceptable range at the
end of the shift, and samples are to be analyzed during the next
eight-hour shift, the end of shift verification may be used as the
beginning of shift verification for the subsequent shift, provided
the next eight-hour shift begins as the first shift ends.
9.11 It is suggested but not required that the laboratory
develop a statement of data quality for AOX and develop QC charts to
form a graphic demonstration of method performance. Add results that
pass the specification in Section 9.10.2 to initial and previous
ongoing data. Develop a statement of data quality by calculating the
average percent recovery (R) and the standard deviation of percent
recovery (sr). Express the accuracy as a recovery
interval from R - 2sr to R + 2sr. For example,
if R=95% and sr=5%, the accuracy is 85 to 105%.

10.0 Calibration and Standardization

10.1 Assemble the OX system and establish the operating
conditions necessary for analysis. Differences between various makes
and models of instruments will require different operating
procedures. Laboratories should follow the operating instructions
provided by the manufacturer of their particular instrument.
Sensitivity, instrument detection limit, precision, linear range,
and interference effects must be investigated and established for
each particular instrument. Calibration is performed when the
instrument is first set up and when calibration cannot be verified
(Section 9.9).
10.2 Cell performance test: Inject 100 L of the sodium
chloride solution (10 g Cl^-; Section 7.4)
directly into the titration cell electrolyte. Adjust the instrument
to produce a reading of 10 g Cl^-.
10.3 Combustion system test: This test can be used to assure
that the combustion/micro-coulometer systems are performing properly
without introduction of carbon. This test should be used during
initial instrument setup and when instrument performance indicates a
problem with the combustion system.
10.3.1 Designate a quartz boat for use with the ammonium
chloride (NH4Cl) solution only.
10.3.2 Inject 100 L of the NH4Cl solution
(Section 7.5) into this boat and proceed with the analysis.
10.3.3 The result shall be between 9.5 and 10.5 g
Cl^-. If the recovery is not between these limits, the
combustion or micro-coulometer systems are not performing properly.
Check the temperature of the combustion system, verify that there
are no leaks in the combustion system, confirm that the cell is
performing properly (Section 10.2), and then repeat the test.
10.4 Trichlorophenol combustion test: This test can be used to
assure that the combustion/micro-coulometer systems are performing
properly when carbon is introduced. It should be used during
instrument setup and when it is necessary to isolate the adsorption
and combustion steps.
10.4.1 Inject 10 L of the 1 mg/mL trichlorophenol
stock solution (Section 7.12.2) onto one level scoop of GAC in a
quartz boat.
10.4.2 Immediately proceed with the analysis to prevent loss of
trichlorophenol and to prevent contamination of the carbon.
10.4.3 The result shall be between 9.0 and 11.0 g
Cl^-. If the recovery is not between these limits, the
combustion/micro-coulometer system shall be adjusted and the test
repeated until the result falls within these limits.
10.5 Background level of Cl^-: Determine the average
background level of Cl^- for the entire analytical system
as follows:
10.5.1 Using the procedure in Section 11 (batch or column) that
will be used for the analysis of samples, determine the background
level of Cl^- in each of three portions of reagent water.
The volume of reagent water used shall be the same as the volume
used for analysis of samples.
10.5.2 Calculate the average (mean) concentration of
Cl^- and the standard deviation of the concentration.
10.5.3 The sum of the average concentration plus two times the
standard deviation of the concentration shall be less than 20
g/L. If not, the water or carbon shall be replaced, or the
adsorption system moved to an area free of organic halide vapors,
and the test (Section 10.5) shall be repeated. Only after this test
is passed may calibration proceed.
10.6 Calibration by external standard: A calibration line
encompassing the calibration range is developed using solutions of
2,4,6-trichlorophenol.
10.6.1 Analyze each of the five calibration solutions (Section
7.12.3) using the procedure in Section 11 (batch or column) that
will be used for the analysis of samples, and the same procedure
that was used for determination of the system background (Section
10.5). Analyze these solutions beginning with the lowest
concentration and proceeding to the highest. Record the response of
the micro-coulometer to each calibration solution.
10.6.2 Prepare a method blank as described in Section 9.4.
Subtract the value of the blank from each of the five calibration
results, as described in Section 12.
10.6.3 Calibration factor (ratio of response to concentration)
Using the blank subtracted results, compute the calibration factor
at each calibration point, and compute the average calibration
factor and the relative standard deviation (coefficient of
variation; Cv) of the calibration factor over the calibration range.
10.6.4 Linearity: The Cv of the calibration factor shall be
less than 20%; otherwise, the calibration shall be repeated after
adjustment of the combustion/micro-coulometer system and/or
preparation of fresh calibration standards.
10.6.5 Using the average calibration factor, compute the
percent recovery at each calibration point. The recovery at each
calibration point shall be within the range of 80 to 111%. If any
point is not within this range, a fresh calibration standard shall
be

[[Page 18728]]

prepared for that point, this standard shall be analyzed, and the
calibration factor (Section 10.6.3) and calibration linearity
(Section 10.6.4) shall be computed using the new calibration point.
All points used in the calibration must meet the 80 to 111% recovery
specification.

11.0 Procedure

11.1 Sample dilution: Many samples will contain high
concentrations of halide. If analyzed without dilution, the micro-
coulometer can be overloaded, resulting in frequent cell cleaning
and downtime. The following guidance is provided to assist in
estimating dilution levels.
11.1.1 Paper and pulp mills that employ chlorine bleaching:
Samples from pulp mills that use a chlorine bleaching process may
overload the micro-coulometer. To prevent system overload, the
maximum volume suggested for paper industry samples that employ
halide in the bleaching process is 100 mL. An adsorption volume as
small as 25 mL may be used, provided the concentration of AOX in the
sample can be measured reliably, as defined by the requirements in
Section 9.11. To minimize volumetric error, an adsorption volume
less than 25 mL may not be used. If AOX cannot be measured reliably
in a 100-mL sample volume, a sample volume to a maximum of 1000 mL
must be used. The sample and adsorption volumes are suggested for
paper industry samples employing chlorine compounds in the bleaching
process:

------------------------------------------------------------------------
Sample
Paper or pulp mill stream volume Adsorption
(mL)* volume (mL)
------------------------------------------------------------------------
Evaporator condensate........................ 100.0 100
Process water................................ 100.0 100
Pulp mill effluent........................... 30.0 50
Paper mill effluent.......................... 10.0 25
Combined mill effluent....................... 5.0 25
Combined bleach effluent..................... 1.0 25
C-stage filtrate............................. 0.5 25
E-stage filtrate............................. 0.5 25
------------------------------------------------------------------------
* Assumes dilution to final volume of 100 mL. All sample aliquots
(replicates, diluted samples) must be analyzed using the same fixed
final volume (sample volume plus reagent water, as needed).

11.1.2 Sample dilution procedure.
11.1.2.1 Partially fill a precleaned volumetric flask with pH <
2 reagent water, allowing for the volume of sample to be added.
11.1.2.2 Mix sample thoroughly by tumbling or shaking
vigorously.
11.1.2.3 Immediately withdraw the required sample aliquot using
a pipet or micro-syringe.

Note: Because it will be necessary to rinse the pipet or micro-
syringe (Section 11.1.2.5), it may be necessary to pre-calibrate the
pipet or micro-syringe to assure that the exact volume desired will
be delivered.

11.1.2.4 Dispense or inject the aliquot into the volumetric
flask.
11.1.2.5 Rinse the pipet or syringe with small portions of
reagent water and add to the flask.
11.1.2.6 Dilute to the mark with pH < 2 reagent water.
11.1.3 All samples to be reported for regulatory compliance
monitoring purposes must be analyzed in duplicate, as described in
Section 11.5.
11.1.4 Pulp and Paper in-process samples: The concentration of
organic halide in in-process samples has been shown to be 20 to 30%
greater using the micro-column adsorption technique than using the
batch adsorption technique. For this reason, the micro-column
technique shall be used for monitoring in-process samples. Examples
of in-process samples include: combined bleach plant effluent, C-
stage filtrate, and E-stage filtrate.
11.2 Batch adsorption and filtration.
11.2.1 Place the appropriate volume of sample (diluted if
necessary), preserved as described in Section 8, into an Erlenmeyer
flask.
11.2.2 Add 5 mL of nitrate stock solution to the sample
aliquot.
11.2.3 Add one level scoop of activated carbon that has passed
the quality control tests in Section 9.
11.2.4 Shake the suspension for at least one hour in a
mechanical shaker.
11.2.5 Filter the suspension through a polycarbonate membrane
filter. Filter by suction until the liquid level reaches the top of
the carbon.
11.2.6 Wash the inside surface of the filter funnel with 25 mL
(5 mL) of nitrate wash solution in several portions.
After the level of the final wash reaches the top of the GAC, filter
by suction until the cake is barely dry. The time required for
drying should be minimized to prevent exposure of the GAC to halogen
vapors in the air, but should be sufficient to permit drying of the
cake so that excess water is not introduced into the combustion
apparatus. A drying time of approximately 10 seconds under vacuum
has been shown to be effective for this operation.
11.2.7 Carefully remove the top of the filter holder, making
sure that no carbon is lost. This operation is most successfully
performed by removing the clamp, tilting the top of the filter
holder (the funnel portion) to one side, and lifting upward.
11.2.8 Using a squeeze bottle or micro-syringe, rapidly rinse
the carbon from the inside of the filter holder onto the filter cake
using small portions of wash solution. Allow the cake to dry under
vacuum for no more than 10 seconds after the final rinse.
Immediately turn the vacuum off.
11.2.9 Using tweezers, carefully fold the polycarbonate filter
in half, then in fourths, making sure that no carbon is lost.
11.3 Column adsorption.
11.3.1 Column preparation: Prepare a sufficient number of
columns for one day's operation as follows:
11.3.1.1 In a glove box or area free from halide vapors, place
a plug of Cerafelt into the end of a clean glass column.
11.3.1.2 Fill the glass column with one level scoop
(approximately 40 mg) of granular activated carbon that has passed
the quality control tests in Section 9.
11.3.1.3 Insert a Cerafelt plug into the open end of the column
to hold the carbon in place.
11.3.1.4 Store the columns in a glass jar with PTFE lined
screw-cap to prevent infiltration of halide vapors from the air.
11.3.2 Column setup.
11.3.2.1 Install two columns in series in the adsorption
module.
11.3.2.2 If the sample is known or expected to contain
particulates that could prevent free flow of sample through the
micro-columns, a Cerafelt plug is placed in the tubing ahead of the
columns. If a measurement of the OX content of the particulates is
desired, the Cerafelt plug can be washed with nitrate solution,
placed in a combustion boat, and processed as a separate sample.
11.3.3 Adjusting sample flow rate: Because the flow rate used
to load the sample onto the columns can affect the ability of the
GAC to adsorb organic halides, the flow rate of the method blank is
measured, and the gas pressure used to process samples is adjusted
accordingly. The flow rate of the blank, which is composed of
acidified reagent water and contains no particulate matter, should
be greater than the flow rate of any sample containing even small
amounts of particulate matter.
11.3.3.1 Fill the sample reservoir with the volume of reagent
water chosen for the analysis (Section 9.4.1.2) that has been
preserved and acidified as described in Section 8. Cap the
reservoir.
11.3.3.2 Adjust the gas pressure per the manufacturer's
instructions. Record the time required for the entire volume of
reagent water to pass through both columns. The flow rate must not
exceed 3 mL/min over the duration of the time required to adsorb the
volume. If this flow rate is exceeded, adjust gas pressure, prepare
another blank, and repeat the adsorption.

[[Page 18729]]

11.3.3.3 Once the flow rate for the blank has been established,
the same adsorption conditions must be applied to all subsequent
samples during that eight-hour shift, or until another method blank
is processed, whichever comes first. To aid in overcoming
breakthrough problems, a lower gas pressure (and, therefore, flow
rate) may be used for processing of samples, if desired. If the
sample adsorption unit is disassembled or cleaned, the flow rate
must be checked before processing additional samples.
11.3.3.4 Elute the pair of columns with 2 mL of nitrate wash
solution. The flow rate of nitrate wash solution must not exceed 3
mL/min.
11.3.3.5 Separate the columns and mark for subsequent analysis.
11.3.4 The adsorption of sample volumes is performed in a
similar fashion. Fill the sample reservoir with the sample volume
chosen for the analysis (Section 11.1), that has been preserved as
described in Section 8. All analyses must be performed with this
volume (sample volume plus reagent water, as needed) in order to
maintain a flow rate no greater than that determined for the blank
(see Section 11.3.3).
11.3.4.1 Use the same gas pressure for sample adsorption as is
used for the blank.
11.3.4.2 Elute the columns with 2 mL of the nitrate wash
solution.
11.3.4.3 Separate the columns and mark for subsequent analysis.
11.3.5 If it is desirable to make measurements at levels lower
than can be achieved with the sample volume chosen, or if the
instrument response of an undiluted sample is less than three times
the instrument response of the blank (Section 12.6.3), a larger
sample volume must be used.
11.4 Combustion and titration.
11.4.1 Polycarbonate filter and GAC from batch adsorption.
11.4.1.1 Place the folded polycarbonate filter containing the
GAC in a quartz combustion boat, close the airlock, and proceed with
the automated sequence.
11.4.1.2 Record the signal from the micro-coulometer for a
minimum integration time of 10 minutes and determine the
concentration of Cl^- from calibration data, per Section
12.
11.4.2 Columns from column adsorption.
11.4.2.1 Using the push rod, push the carbon and the Cerafelt
plug(s) from the first column into a combustion boat. Proceed with
the automated sequence.
11.4.2.2 Record the signal from the micro-coulometer for a
minimum integration time of 10 minutes and determine the
concentration of Cl^- for the first column from
calibration data, per Section 12.
11.4.2.3 Repeat the automated sequence with the second column.
11.4.2.4 Determine the extent of breakthrough of organic
halides from the first column to the second column, as described in
Section 12.
11.4.3 The two columns that are used for the method blank must
be combusted separately, as is done for samples. 11.5 Duplicate
sample analysis: All samples to be reported for regulatory
compliance purposes must be analyzed in duplicate. This requirement
applies to both the batch and column adsorption procedures. In
addition, if it is necessary to dilute the sample for the purposes
of reducing breakthrough or maintaining the concentration within the
calibration range, a more or less dilute sample must be analyzed.
The adsorption volumes used for analysis of undiluted samples,
diluted samples, and all replicates must be the same as the volume
used for QC tests and calibration (Sections 9 and 10).
11.5.1 Using results from analysis of one sample volume
(Section 11.4) and the procedure in Section 11.1.2, determine if the
dilution used was within the calibration range of the instrument
and/or if breakthrough exceeded the specification in Section 12.3.1.
If the breakthrough criterion was exceeded or the sample was not
within the calibration range, adjust the dilution volume as needed.
If the breakthrough criterion was not exceeded and the sample
dilution was within the calibration range, a second volume at the
same dilution level may be used.
11.5.2 Adsorb the sample using the same technique (batch or
column) used for the first sample volume. Combust the GAC from the
second volume as described in Section 11.4, and calculate the
results as described in Section 12. Compare the results of the two
analyses as described in Section 12.4.
11.5.3 Duplicate analyses are not required for method blanks,
as different dilution levels are not possible.
11.5.4 Duplicate analyses of the PAR standard used for
calibration verification (Section 9.10) are not required.

12.0 Data Analysis and Calculations

12.1 Batch Adsorption Method: Calculate the blank-subtracted
concentration of adsorbable organic halide detected in each sample
(in micrograms of chloride per liter) using the following equation:
[GRAPHIC] [TIFF OMITTED] TR15AP98.019

Where:

C=g Cl^- from micro-coulometer for the sample
B=g Cl^- from micro-coulometer for the reagent
water blank (Section 9.4.1)
V = volume of sample in liters

This calculation is performed for each of the two dilution
levels analyzed for each sample.
12.2 Column Adsorption Method: Calculate the blank-subtracted
concentration of adsorbable organic halide detected in each sample
(in micrograms of chloride per liter) using the following equation:
[GRAPHIC] [TIFF OMITTED] TR15AP98.020

Where:

C1=g C1^- from micro-coulometer for
first column from the sample
C2=g C1^- from micro-coulometer for
second column from the sample
B1=g from micro-coulometer for first column from
the reagent water blank (Section 9.4.1)
B2=g C1^- from micro-coulometer for
second column from the reagent water blank (Section 9.4.1)
V=volume of sample in liters

12.3 Percent breakthrough: For each sample analyzed by the
column method, calculate the percent breakthrough of halide from the
first column to the second column, using the following equation:
[GRAPHIC] [TIFF OMITTED] TR15AP98.021

12.3.1 For samples to be reported for regulatory compliance
purposes, the percent breakthrough must be less than or equal to 25%
for both of the two analyses performed on each sample (see Section
11.5).
12.3.2 If the breakthrough exceeds 25%, dilute the affected
sample further, maintaining the amount of halide at least three
times higher than the level of blank, and reanalyze the sample.
Ensure that the sample is also analyzed at a second level of
dilution that is at least a factor of 2 different (and still higher
than three times the blank).
12.4 Relative percent difference (RPD): Calculate the relative
percent difference between the results of the two analyses of each
sample, using the following equation:
[GRAPHIC] [TIFF OMITTED] TR15AP98.022

12.5 High concentrations of AOX: If the amount of halide from
either analysis exceeds the calibration range, dilute the sample and
reanalyze, maintaining at least a factor of 2 difference in the
dilution levels of the two portions of the sample used.
12.6 Low concentrations of AOX: The blank-subtracted final
result from the batch procedure or the sum of the blank-subtracted
results from the two carbon columns should be significantly above
the level of the blank.
12.6.1 If the instrument response for a sample exceeds the
instrument response for the blank by a factor of at least 3, the
result is acceptable.
12.6.2 If the instrument response for a sample is less than
three times the instrument response for the blank, and the sample
has been diluted, analyze a less dilute aliquot of sample.
12.6.3 If the instrument response of an undiluted sample
containing AOX above the minimum level is less than three times the
instrument response for the blank, the result is suspect and may not
be used for regulatory compliance purposes. In this case, find the
cause of contamination, correct the problem, and reanalyze the
sample under the corrected conditions.
12.7 Report results that meet all of the specifications in this
method as the mean of the blank-subtracted values from Section 12.1
or 12.2 for the two analyses at different dilution levels, in
g/L of Cl^- (not as 2,4,6-trichlorophenol), to
three significant figures. Report the RPD of the two analyses. For
samples analyzed by the column procedure, also report the percent
breakthrough.

[[Page 18730]]

13.0 Method Performance

The specifications contained in this method are based on data
from a single laboratory and from a large-scale study of the pulp
and paper industry.

14.0 Pollution Prevention

14.1 The solvents used in this method pose little threat to the
environment when recycled and managed properly.
14.2 Standards should be prepared in volumes consistent with
laboratory use to minimize the volume of expired standards to be
disposed.

15.0 Waste Management

15.1 It is the laboratory's responsibility to comply with all
federal, state, and local regulations governing waste management,
particularly the hazardous waste identification rules and land
disposal restrictions, and to protect the air, water, and land by
minimizing and controlling all releases from fume hoods and bench
operations. Compliance with all sewage discharge permits and
regulations is also required.
15.2 Samples preserved with HCl or H2SO4
to pH <2 are hazardous and must be neutralized before being
disposed, or must be handled as hazardous waste. Acetic acid and
silver acetate solutions resulting from cell flushing must be
disposed of in accordance with all applicable federal, state, and
local regulations.
15.3 For further information on waste management, consult ``The
Waste Management Manual for Laboratory Personnel,'' and ``Less is
Better: Laboratory Chemical Management for Waste Reduction,'' both
available from the American Chemical Society's Department of
Government Relations and Science Policy, 1155 16th Street N.W.,
Washington, D.C. 20036.

16.0 References

16.1 ``Total Organic Halide, Methods 450.1--Interim,'' Prepared
by Stephen Billets and James J. Lichtenberg, USEPA, Office of
Research and Development, Physical and Chemical Methods Branch,
EMSL-Cincinnati, Cincinnati, OH 45268, EPA 600/4-81-056 (1981).
16.2 Method 9020, USEPA Office of Solid Waste, ``Test Methods
for Evaluating Solid Waste, SW-846,'' Third Edition, 1987.
16.3 ``Determination of Adsorbable Organic Halogens (AOX),''
``German Standard Methods for the Analysis of Water, Waste Water and
Sludge--General Parameters of Effects and Substances,'' Deutsche
Industrie Norm (DIN) Method 38 409, Part 14, DIN German Standards
Institute, Beuth Verlag, Berlin, Germany (1987).
16.4 ``Water Quality: Determination of Adsorbable Organic
Halogens (AOX),'' International Organization for Standard/Draft
International Standardization (ISO/DIS) Method 9562 (1988).
16.5 ``Organically Bound Chlorine by the AOX Method,'' SCAN-W
9:89, Secretariat, Scandinavian Pulp, Paper and Board Testing
Committee, Box 5604, S-11486, Stockholm, Sweden (1989).
16.6 Method 5320, ``Dissolved Organic Halogen,'' from
``Standard Methods for the Examination of Water and Wastewater,''
5320, American Public Health Association, 1015 15th St. NW,
Washington, DC 20005 (1989).
16.7 ``Canadian Standard Method for the Determination of
Adsorbable Organic Halides (AOX) in Waters and Wastewaters,''
Environment Canada and The Canadian Pulp and Paper Association
(1990).
16.8 40 CFR Part 136, Appendix B.
16.9 ``Working with Carcinogens,'' DHEW, PHS, CDC, NIOSH,
Publication 77-206, (Aug 1977).
16.10 ``OSHA Safety and Health Standards, General Industry''
OSHA 2206, 29 CFR 1910 (Jan 1976).
16.11 ``Safety in Academic Chemistry Laboratories,'' ACS
Committee on Chemical Safety (1979).
16.12 ``Methods 330.4 and 330.5 for Total Residual Chlorine,''
USEPA, EMSL-Cincinnati, Cincinnati, OH 45268, EPA-4-79-020 (March
1979).
16.13 ``Validation of Method 1650: Determination of Organic
Halide,'' Analytical Technologies Inc., ERCE Contract 87-3410,
November 15, 1990. Available from the EPA Sample Control Center,
DynCorp, 300 N. Lee St., Alexandria, VA 22314 (703-519-1140).

17.0 Figures

BILLING CODE 6560-50-P

[[Page 18731]]

[GRAPHIC] [TIFF OMITTED] TR15AP98.023

[[Page 18732]]

[GRAPHIC] [TIFF OMITTED] TR15AP98.024

[[Page 18733]]

[GRAPHIC] [TIFF OMITTED] TR15AP98.025

[[Page 18734]]

[GRAPHIC] [TIFF OMITTED] TR15AP98.026

BILLING CODE 6560-50-C

[[Page 18735]]

18.0 Glossary of Definitions and Purposes

These definitions and purposes are specific to this method but
have been conformed to common usage as much as possible.
18.1 Units of weight and measure and their abbreviations.
18.1.1 Symbols.

deg.C degrees Celsius
g microgram
L microliter
< less than
> greater than
% percent

18.1.2 Alphabetical characters.

cm centimeter
g gram
h hour
ID inside diameter
in inch
L liter
m meter
mg milligram
min minute
mL milliliter
mm millimeter
N normal; gram molecular weight of solute divided by hydrogen
equivalent of solute, per liter of solution
OD outside diameter
ppb part-per-billion
ppm part-per-million
ppt part-per-trillion
psig pounds-per-square inch gauge
v/v volume per unit volume
w/v weight per unit volume

18.2 Definitions and acronyms (in alphabetical order).
Analyte: AOX tested for by this method.
Calibration standard (CAL): A solution prepared from a secondary
standard and/or stock solution which is used to calibrate the
response of the instrument with respect to analyte concentration.
Calibration verification standard (VER): The mid-point
calibration standard (CS3) that is used to verify calibration.
Field blank: An aliquot of reagent water or other reference
matrix that is placed in a sample container in the laboratory or the
field, and treated as a sample in all respects, including exposure
to sampling site conditions, storage, preservation, and all
analytical procedures. The purpose of the field blank is to
determine if the field or sample transporting procedures and
environments have contaminated the sample.
IPR: Initial precision and recovery; four aliquots of the
diluted PAR standard analyzed to establish the ability to generate
acceptable precision and accuracy. An IPR is performed prior to the
first time this method is used and any time the method or
instrumentation is modified.
Laboratory blank: See Method blank.
Laboratory control sample (LCS): See Ongoing precision and
recovery sample (OPR).
Laboratory reagent blank: See Method blank.
May: This action, activity, or procedural step is neither
required nor prohibited.
May not: This action, activity, or procedural step is
prohibited.
Method blank: An aliquot of reagent water that is treated
exactly as a sample including exposure to all glassware, equipment,
solvents, reagents, internal standards, and surrogates that are used
with samples. The method blank is used to determine if analytes or
interferences are present in the laboratory environment, the
reagents, or the apparatus.
Minimum level (ML): The level at which the entire analytical
system must give a recognizable signal and acceptable calibration
point for the analyte. It is equivalent to the concentration of the
lowest calibration standard, assuming that all method-specified
sample weights, volumes, and cleanup procedures have been employed.
Must: This action, activity, or procedural step is required.
OPR: Ongoing precision and recovery standard; a laboratory blank
spiked with a known quantity of analyte. The OPR is analyzed exactly
like a sample. Its purpose is to assure that the results produced by
the laboratory remain within the limits specified in this method for
precision and recovery.
PAR: Precision and recovery standard; secondary standard that is
diluted and spiked to form the IPR and OPR.
Preparation blank: See Method blank.
Primary dilution standard: A solution containing the specified
analytes that is purchased or prepared from stock solutions and
diluted as needed to prepare calibration solutions and other
solutions.
Quality control check sample (QCS): A sample containing all or a
subset of the analytes at known concentrations. The QCS is obtained
from a source external to the laboratory or is prepared from a
source of standards different from the source of calibration
standards. It is used to check laboratory performance with test
materials prepared external to the normal preparation process.
Reagent water: Water demonstrated to be free from the analyte of
interest and potentially interfering substances at the method
detection limit for the analyte.
Relative standard deviation (RSD): The standard deviation
multiplied by 100, divided by the mean.
RSD: See Relative standard deviation.
Should: This action, activity, or procedural step is suggested
but not required.
Stock solution: A solution containing an analyte that is
prepared using a reference material traceable to EPA, the National
Institute of Science and Technology (NIST), or a source that will
attest to the purity and authenticity of the reference material.
VER: See Calibration verification standard.

Method 1653--Chlorinated Phenolics in Wastewater by In Situ Acetylation
and GCMS

1.0 Scope and Application

1.1 This method is for determination of chlorinated phenolics
(chlorinated phenols, guaiacols, catechols, vanillins,
syringaldehydes) and other compounds associated with the Clean Water
Act; the Resource Conservation and Recovery Act; and the
Comprehensive Environmental Response, Compensation, and Liability
Act; and that are amenable to in situ acetylation, extraction, and
analysis by capillary column gas chromatography/mass spectrometry
(GCMS). This method is based on existing methods for determination
of chlorophenolics in pulp and paper industry wastewaters
(References 1 and 2).
1.2 The chemical compounds listed in Table 1 may be determined
in waters and, specifically, in in-process streams and wastewaters
associated with the pulp and paper industry. The method is designed
to meet the survey and monitoring requirements of the Environmental
Protection Agency (EPA).
1.3 The detection limit of this method is usually dependent on
the level of interferences rather than instrumental limitations. The
method detection limits (MDLs) in Table 2 typify the minimum
quantity that can be detected with no interferences present.
1.4 The GCMS portions of this method are for use only by
persons experienced with GCMS or under the close supervision of such
qualified persons. Laboratories unfamiliar with analyses of
environmental samples by GCMS should run the performance tests in
Reference 3 before beginning.
1.5 Any modification of the method beyond those expressly
permitted is subject to the application and approval of alternative
test procedures under 40 CFR Parts 136.4 and 136.5.

2.0 Summary of Method

2.1 A 1000-mL aliquot of water is spiked with stable
isotopically labeled analogs of the compounds of interest and an
internal standard. The solution is adjusted to neutral pH, potassium
carbonate buffer is added, and the pH is raised to 9-11.5. The
chlorophenolics are converted in situ to acetates by the addition of
acetic anhydride. After acetylation, the solution is extracted with
hexane. The hexane is concentrated to a final volume of 0.5 mL, an
instrument internal standard is added, and an aliquot of the
concentrated extract is injected into the gas chromatograph (GC).
The compounds are separated by GC and detected by a mass
spectrometer (MS). The labeled compounds and internal standard serve
to correct the variability of the analytical technique.
2.2 Identification of a pollutant (qualitative analysis) is
performed by comparing the relative retention time and mass spectrum
to that of an authentic standard. A compound is identified when its
relative retention time and mass spectrum agree.
2.3 Quantitative analysis is performed in one of two ways by
GCMS using extracted ion-current profile (EICP) areas: (1) For those
compounds listed in Table 1 for which standards and labeled analogs
are available, the GCMS system is calibrated and the compound
concentration is determined using an isotope dilution technique; (2)
for those compounds listed in Table 1 for which authentic standards
but no labeled compounds are available, the GCMS system is
calibrated and the compound concentration is determined using an
internal standard technique.
2.4 Quality is assured through reproducible calibration and
testing of the extraction and GCMS systems.

[[Page 18736]]

3.0 Definitions

3.1 Chlorinated phenolics are the chlorinated phenols,
guaiacols, catechols, vanillins, syringaldehydes and other compounds
amenable to in situ acetylation, extraction, and determination by
GCMS using this method.
3.2 Definitions for other terms used in this method are given
in the glossary at the end of the method (Section 20.0).

4.0 Interferences

4.1 Solvents, reagents, glassware, and other sample processing
hardware may yield artifacts and/or elevated baselines, causing
misinterpretation of chromatograms and spectra. All materials used
in the analysis shall be demonstrated to be free from interferences
under the conditions of analysis by running method blanks initially
and with each sample batch (samples started through the extraction
process on a given eight-hour shift, to a maximum of 20). Specific
selection of reagents and purification of solvents by distillation
in all-glass systems may be required. Glassware and, where possible,
reagents are cleaned by using solvent rinse and baking at 450 deg.C
for a minimum of one hour.
4.2 Interferences co-extracted from samples will vary
considerably from source to source, depending on the diversity of
the site being sampled. Industry experience suggests that high
levels of non-chlorinated phenols may cause poor recovery of the
compounds of interest, particularly in samples collected in the
vicinity of a source of creosote, such as a wood-preserving plant
(Reference 1).
4.3 The internal standard, 3,4,5-trichlorophenol, has been
reported to be an anaerobic degradation product of 2,3,4,5-
tetrachlorophenol and/or pentachlorophenol (Reference 1). When an
interference with this or another compound occurs, labeled
pentachlorophenol or another labeled compound may be used as an
alternative internal standard; otherwise, the internal standards and
reference compounds must be used as specified in this method.
4.4 Blank contamination by pentachlorophenol has been reported
(Reference 1) to be traceable to potassium carbonate; it has also
been reported that this contamination may be removed by baking
overnight at 400 to 500 deg.C.
4.5 Catechols are susceptible to degradation by active sites on
injection port liners and columns, and are subject to oxidation to
the corresponding chloro-o-benzoquinones (Reference 2). A small
amount of ascorbic acid may be added to samples to prevent auto-
oxidation (Reference 2; also see Section 11.1.6). For pulp and paper
industry samples, ascorbic acid may be added to treated effluent
samples only.

5.0 Safety

5.1 The toxicity or carcinogenicity of each compound or reagent
used in this method has not been precisely determined; however, each
chemical compound should be treated as a potential health hazard.
Exposure to these compounds should be reduced to the lowest possible
level. The laboratory is responsible for maintaining a current
awareness file of OSHA regulations regarding the safe handling of
the chemicals specified in this method. A reference file of
materials safety data sheets (MSDSs) should be made available to all
personnel involved in these analyses. Additional information on
laboratory safety can be found in References 4 through 6.
5.2 Samples may contain high concentrations of toxic compounds,
and should be handled with gloves and a hood opened to prevent
exposure.

6.0 Equipment and Supplies

6.1 Sampling equipment for discrete or composite sampling.
6.1.1 Sample bottles and caps.
6.1.1.1 Sample bottle: Amber glass, 1000-mL minimum, with
screw-cap. If amber bottles are not available, samples shall be
protected from light.
6.1.1.2 Bottle caps: Threaded to fit sample bottles. Caps shall
be lined with PTFE.
6.1.1.3 Cleaning bottles: Detergent water wash, cap with
aluminum foil, and bake at 450 deg.C for a minimum of one hour
before use.
6.1.1.4 Cleaning liners: Detergent water wash, reagent water
(Section 7.4) and solvent rinse, and bake at approximately 200 deg.C
for a minimum of 1 hour prior to use.
6.1.1.5 Bottles and liners must be lot-certified to be free of
chlorophenolics by running blanks according to this method. If
blanks from bottles and/or liners without cleaning or with fewer
cleaning steps show no detectable chlorophenolics, the bottle and
liner cleaning steps that do not eliminate chlorophenolics may be
omitted.
6.1.2 Compositing equipment: Automatic or manual compositing
system incorporating glass containers cleaned per bottle cleaning
procedure above. Sample containers are kept at 0 to 4 deg.C during
sampling. Glass or PTFE tubing only shall be used. If the sampler
uses a peristaltic pump, a minimum length of compressible silicone
rubber tubing may be used in the pump only. Before use, the tubing
shall be thoroughly rinsed with methanol, followed by repeated
rinsing with reagent water (Section 7.4) to minimize sample
contamination. An integrating flow meter is used to collect
proportional composite samples.
6.2 Extraction apparatus.
6.2.1 Bottle or beaker: 1500-to 2000-mL capacity.
6.2.2 Separatory funnel: 500-to 2000-mL, glass, with PTFE
stopcock.
6.2.3 Magnetic stirrer: Corning Model 320, or equivalent, with
stirring bar.
6.3 Polyethylene gloves: For handling samples and extraction
equipment (Fisher 11-394-110-B, or equivalent).
6.4 Graduated cylinders: 1000-mL, 100-mL, and 10-mL nominal.
6.5 Centrifuge: Capable of accepting 50-mL centrifuge tubes and
achieving 3000 RPM.
6.5.1 Centrifuge tubes.
6.5.1.1 35-mL nominal, with PTFE-lined screw-cap.
6.5.1.2 15-mL nominal, conical graduated, with ground-glass
stopper.
6.6 Concentration apparatus.
6.6.1 Kuderna-Danish (K-D) concentrator tube: 10-mL,
graduated (Kontes K-570050-1025, or equivalent) with calibration
verified. Ground-glass stopper (size 19/22 joint) is used to prevent
evaporation of extracts.
6.6.2 Kuderna-Danish (K-D) evaporation flask: 1000-mL (Kontes
K-570001-1000, or equivalent), attached to concentrator tube with
springs (Kontes K-662750-0012).
6.6.3 Snyder column: Three-ball macro (Kontes K-503000-0232, or
equivalent).
6.6.4 Snyder column: Two-ball micro (Kontes K-469002-0219, or
equivalent).
6.6.5 Boiling chips: Approximately 10/40 mesh, extracted with
methylene chloride and baked at 450 deg.C for a minimum of one
hour.
6.6.6 Nitrogen evaporation apparatus: Equipped with a water
bath controlled at 35 to 40 deg.C (N-Evap, Organomation Associates,
Inc., South Berlin, MA, or equivalent), installed in a fume hood.
This device may be used in place of the micro-Snyder column
concentrator in Section 6.6.4 above.
6.7 Water bath: Heated, with concentric ring cover, capable
of temperature control ( 2 deg.C), installed in a
fume hood.
6.8 Sample vials: Amber glass, 1- to 3-mL, with PTFE-lined
screw-cap.
6.9 Balances.
6.9.1 Analytical: Capable of weighing 0.1 mg.
6.9.2 Top loading: Capable of weighing 10 mg.
6.10 pH meter.
6.11 Gas chromatograph: Shall have splitless or on-column
injection port for capillary column, temperature program with
50 deg.C hold, and shall meet all of the performance specifications
in Section 9.
6.12 Gas chromatographic column: 30 m (5 m) x
0.25 mm (0.02 mm) I.D. x 0.25 micron, 5% phenyl, 94%
methyl, 1% vinyl silicone bonded-phase fused-silica capillary column
(J & W DB-5, or equivalent).
6.13 Mass spectrometer: 70 eV electron impact ionization, shall
repetitively scan from 42 to 450 amu in 0.95 to 1.00 second, and
shall produce a unit resolution (valleys between m/z 441-442 less
than 10% of the height of the 441 peak), background-corrected mass
spectrum from 50 ng decafluorotriphenylphosphine (DFTPP) introduced
through the GC inlet. The spectrum shall meet the mass-intensity
criteria in Table 3 (Reference 7). The mass spectrometer shall be
interfaced to the GC such that the end of the capillary column
terminates within 1 cm of the ion source, but does not intercept the
electron or ion beams. All portions of the column which connect the
GC to the ion source shall remain at or above the column temperature
during analysis to preclude condensation of less volatile compounds.
6.14 Data system: Shall collect and record MS data, store mass-
intensity data in spectral

[[Page 18737]]

libraries, process GCMS data, generate reports, and compute and
record response factors.
6.14.1 Data acquisition: Mass spectra shall be collected
continuously throughout the analysis and stored on a mass storage
device.
6.14.2 Mass spectral libraries: User-created libraries
containing mass spectra obtained from analysis of authentic
standards shall be employed to reverse search GCMS runs for the
compounds of interest (Section 10.2).
6.14.3 Data processing: The data system shall be used to
search, locate, identify, and quantify the compounds of interest in
each GCMS analysis. Software routines shall be employed to compute
retention times, and to compute peak areas at the m/z's specified
(Table 4). Displays of spectra, mass chromatograms, and library
comparisons are required to verify results.
6.14.4 Response factors and multi-point calibrations: The data
system shall be used to record and maintain lists of response
factors (response ratios for isotope dilution) and multi-point
calibration curves (Section 10). Computations of relative standard
deviation (coefficient of variation) are used for testing
calibration linearity. Statistics on initial (Section 9.3.2) and
ongoing (Section 9.6) performance shall be computed and maintained.

7.0 Reagents and Standards

7.1 Reagents for adjusting sample pH.
7.1.1 Sodium hydroxide: Reagent grade, 6 N in reagent water.
7.1.2 Sulfuric acid: Reagent grade, 6 N in reagent water.
7.2 Reagents for sample preservation.
7.2.1 Sodium thiosulfate
(Na2S2O3) solution (1 N): Weigh 79
g Na2S2O3 in a 1-L volumetric flask
and dilute to the mark with reagent water.
7.2.2 Ascorbic acid solution: Prepare a solution of ascorbic
acid in reagent water at a concentration of 0.1 g/mL. This solution
must be prepared fresh on each day when derivatizations will be
performed. Therefore, do not prepare more than will be used that
day. (A 50-mL volume is sufficient for ten analyses).
7.3 Solvents: Hexane, acetone, and methanol. Distilled in glass
(Burdick and Jackson, or equivalent).
7.4 Reagent water: Water in which the compounds of interest and
interfering compounds are not detected by this method.
7.5 Reagents for derivatization.
7.5.1 Potassium carbonate (K2CO3).
7.5.1.1 Purification: Spread in a shallow baking dish, heat
overnight at 400 to 500 deg.C.
7.5.1.2 Solution: Dissolve 150 g purified
K2CO3 in 250 mL reagent water.
7.5.2 Acetic anhydride: Redistilled reagent grade.
7.6 Analytical standards.
7.6.1 Derivatization: Because the chlorinated phenolics are
determined as their acetate derivatives after in situ acetylation,
the method requires that the calibration standards be prepared by
spiking the underivatized materials into reagent water and carrying
the spiked reagent water aliquot through the entire derivatization
and extraction procedure that is applied to the field samples.
7.6.2 Standard solutions: Purchased as solutions or mixtures
with certification to their purity, concentration, and authenticity,
or prepared from materials of known purity and composition. If
chemical purity of a compound is 98% or greater, the weight may be
used without correction to compute the concentration of the
standard. When not being used, standards are stored in the dark at
-20 to -10 deg.C in screw-capped vials with PTFE-lined lids. A mark
is placed on the vial at the level of the solution so that solvent
evaporation loss can be detected. The vials are brought to room
temperature prior to use.
7.6.3 If the chemical purity of any standard does not meet the
98% requirement above, the laboratory must correct all calculations,
calibrations, etc., for the difference in purity.
7.7 Preparation of stock solutions: Prepare chlorovanillins and
chlorosyringaldehydes in acetone, as these compounds are subject to
degradation in methanol. Prepare the remaining chlorophenolics in
methanol. Prepare all standards per the steps below. Observe the
safety precautions in Section 5.
7.7.1 Dissolve an appropriate amount of assayed reference
material in a suitable solvent. For example, weigh 50 mg
(0.1 mg) of pentachlorophenol in a 10-mL ground-glass-
stoppered volumetric flask and fill to the mark with methanol. After
the pentachlorophenol is completely dissolved, transfer the solution
to a 15-mL vial with PTFE-lined cap.
7.7.2 Stock solutions should be checked for signs of
degradation prior to the preparation of calibration or performance
test standards and shall be replaced after six months, or sooner if
comparison with quality control check standards indicates a change
in concentration.
7.8 Labeled compound spiking solution: From stock solutions
prepared as above, or from mixtures, prepare one spiking solution to
contain the labeled chlorovanillin in acetone and a second spiking
solution to contain the remaining chlorophenolics, including the
3,4,5-trichlorophenol sample matrix internal standard (SMIS), in
methanol. The labeled compounds and SMIS are each at a concentration
of 12.5 g/mL.
7.9 Secondary standards for calibration: Using stock solutions
(Section 7.7), prepare one secondary standard containing the
chlorovanillins and chlorsyringaldehydes listed in Table 1 in
acetone and a second secondary standard containing the remaining
chlorophenolics in methanol. The monochlorinated phenol, guaiacol,
and catechol are included at a concentration of 25 g/mL;
the trichlorinated catechols, tetrachlorinated guaiacol and
catechol, pentachlorophenol, 5,6-dichlorovanillin, and 2,6-
dichlorosyringaldehyde are included at a concentration of 100
g/mL; and the remaining compounds are included at a
concentration of 50 g/mL, each in their respective
solutions.
7.10 Instrument internal standard (IIS): Prepare a solution of
2,2'-difluorobiphenyl (DFB) at a concentration of 2.5 mg/mL in
hexane.
7.11 DFTPP solution: Prepare a solution of DFTPP at 50
g/mL in acetone.
7.12 Solutions for obtaining authentic mass spectra (Section
10.2): Prepare mixtures of compounds at concentrations which will
assure authentic spectra are obtained for storage in libraries.
7.13 Preparation of calibration solutions.
7.13.1 Into five 1000-mL aliquots of reagent water, spike 50,
100, 200, 500 and 1000 L of each of the two solutions in
Section 7.9. Spike 1.00 mL of each of the two labeled compound
spiking solutions (Section 7.8) into each of the five aliquots.
7.13.2 Using the procedure in Section 11, derivatize and
extract each solution, and concentrate the extract to a final volume
of 0.50 mL. This will produce calibration solutions of nominal 5,
10, 20, 50, and 100 g/mL of the native chlorophenolics and
a constant concentration of 25 g/mL of each labeled
compound and the SMIS (assuming 100% derivatization and recovery).
As noted in Section 11.1.6, ascorbic acid is added to all samples of
final effluents to stabilize chlorocatechols, but is not added to
samples of pulp and paper in-process wastewaters. Therefore, it is
necessary to prepare separate sets of five initial calibration
standards with and without the addition of ascorbic acid. Also, in
the event that the laboratory is extracting final effluent samples
by both the stir-bar and separatory funnel procedures (see Section
11.3), initial calibration standards should be prepared by both
methods.
7.13.3 These solutions permit the relative response (labeled to
unlabeled) and the response factor to be measured as a function of
concentration (Sections 10.4 and 10.5).
7.13.4 The nominal 50 g/mL standard may also be used
as a calibration verification standard (see Section 9.6).
7.14 Ongoing precision and recovery (OPR) standard: Used for
determination of initial (Section 9.3.2) and ongoing (Section 9.6)
precision and recovery. This solution is prepared by spiking 500
L of each the two solutions of the secondary calibration
standards (Section 7.9) and 1 mL of each of the two labeled compound
spiking solutions (Section 7.8) into 1000 mL of reagent water.
7.15 Stability of solutions: All standard solutions (Sections
7.7 through 7.14) shall be analyzed within 48 hours of preparation
and on a monthly basis thereafter for signs of degradation.
Standards will remain acceptable if the peak area at the
quantitation m/z relative to the DFB internal standard remains
within 15% of the area obtained in the initial analysis
of the standard.

8.0 Sample Collection, Preservation, and Storage

8.1 Collect samples in glass containers (Section 6.1) following
conventional sampling practices (Reference 9). Aqueous samples are
collected in refrigerated bottles using automatic sampling
equipment.
8.2 Sample preservation.
8.2.1 Residual chlorine: If the sample contains residual
chlorine, the chlorine must be reduced to eliminate positive
interference resulting from continued chlorination reactions.
Immediately after sampling, test for residual chlorine using the
following

[[Page 18738]]

method or an alternative EPA method (Reference 10).
8.2.1.1 Dissolve a few crystals of potassium iodide in the
sample and add three to five drops of a 1% starch solution. A blue
color indicates the presence of residual chlorine.
8.2.1.2 If residual chlorine is found, add 1 mL of sodium
thiosulfate solution (Section 7.2.1) for each 2.5 ppm of free
chlorine or until the blue color disappears.
8.2.2 Acidification: Adjust pH of all aqueous samples to <2
with sulfuric acid (Section 7.1.2). Failure to acidify samples may
result in positive interferences from continued chlorination
reactions.
8.2.3 Refrigeration: Maintain sample temperature at 0 to 4
deg.C from time of collection until extraction, and maintain
extracts at a temperature of 0 to 4 deg. C from time of extraction
until analysis.
8.3 Collect a minimum of 2000 mL of sample. This will provide a
sufficient amount for all testing. Smaller amounts may be collected
if the stream is known to contain high levels of chlorophenolics.
8.4 All samples must be acetylated and extracted within 30 days
of collection, and must be analyzed within 30 days of acetylation.
If labeled compound recoveries for a sample do not meet the
acceptance criteria in Table 5 and the 30-day holding time is not
met, a new sample must be collected.

9.0 Quality Control

9.1 Each laboratory that uses this method is required to
operate a formal quality assurance program (Reference 8). The
minimum requirements of this program consist of an initial
demonstration of laboratory capability, analysis of samples spiked
with labeled compounds to evaluate and document data quality, and
analysis of standards and blanks as tests of continued performance.
Laboratory performance is compared to established performance
criteria to determine if the results of analyses meet the
performance characteristics of the method.
9.1.1 DFTPP spectrum validity shall be checked at the beginning
of each eight-hour shift during which analyses are performed. This
test is described in Section 9.2.
9.1.2 The laboratory shall make an initial demonstration of the
ability to generate acceptable results with this method. This
ability is established as described in Section 9.3.
9.1.3 The laboratory is permitted to modify this method to
improve separations or lower the costs of measurements, provided all
performance specifications are met. Each time a modification is made
to the method, the laboratory is required to repeat the procedures
in Sections 10.3 and 9.3.2 to demonstrate method performance. If the
detection limits for the analytes in this method will be affected by
the modification, the laboratory should demonstrate that each MDL
(40 CFR 136, Appendix B) is less than or equal to the MDL in this
method or one-third the regulatory compliance level, whichever is
higher.
9.1.4 The laboratory shall spike all samples with labeled
compounds and the sample matrix internal standard (SMIS) to monitor
method performance. This test is described in Section 9.4. When
results of these spikes indicate atypical method performance for
samples, the samples are diluted to bring method performance within
acceptable limits (Section 13).
9.1.5 Analyses of blanks are required to demonstrate freedom
from contamination. The procedures and criteria for analysis of a
blank are described in Section 9.5.
9.1.6 The laboratory shall, on an ongoing basis, demonstrate
through analysis of the ongoing precision and recovery standard
(Section 7.14) that the analysis system is in control. These
procedures are described in Section 9.6.
9.1.7 The laboratory shall maintain records to define the
quality of data that is generated. Development of accuracy
statements is described in Section 9.4.4 and 9.6.3.
9.2 DFTPP spectrum validity: Inject 1 L of the DFTPP
solution (Section 7.11) either separately or within a few seconds of
injection of the OPR standard (Section 9.6) analyzed at the
beginning of each shift. The criteria in Table 3 shall be met.
9.3 Initial demonstration of laboratory capability.
9.3.1 Method Detection Limit (MDL): To establish the ability to
detect the analytes in this method, the laboratory should determine
the MDL per the procedure in 40 CFR 136, Appendix B using the
apparatus, reagents, and standards that will be used in the practice
of this method. MDLs less than or equal to the MDLs in Table 2
should be achieved prior to the practice of this method.
9.3.2 Initial precision and recovery (IPR): To establish the
ability to demonstrate control over the analysis system and to
generate acceptable precision and accuracy, the laboratory shall
perform the following operations:
9.3.2.1 Derivatize, extract, concentrate, and analyze four
1000-mL aliquots of the ongoing precision and recovery standard
(OPR; Section 7.14), according to the procedure in Section 11.
Separate sets of IPR aliquots must be prepared with the addition of
ascorbic acid and without.
9.3.2.2 Using results of the four analyses, compute the average
percent recovery (X) and the relative standard deviation of the
recovery (s) for each compound, by isotope dilution for pollutants
with a labeled analog, and by internal standard for pollutants with
no labeled analog and for the labeled compounds and the SMIS.
9.3.2.3 For each compound, compare s and X with the
corresponding limits for initial precision and recovery in Table 5.
If s and X for all compounds meet the acceptance criteria, system
performance is acceptable and analysis of blanks and samples may
begin. If, however, any individual s exceeds the precision limit or
any individual X falls outside the range for recovery, system
performance is unacceptable for that compound. In this event,
correct the problem and repeat the test (Section 9.3.2).
9.4 Labeled compound recovery: The laboratory shall spike all
samples with labeled compounds and the sample matrix internal
standard (SMIS) to assess method performance on the sample matrix.
9.4.1 Analyze each sample according to the method beginning in
Section 11.
9.4.2 Compute the percent recovery (P) of the labeled compounds
and the SMIS using the internal standard method (Section 14.3) with
2,2'-difluorobiphenyl as the reference compound.
9.4.3 Compare the labeled compound and SMIS recovery for each
compound with the corresponding limits in Table 5. If the recovery
of any compound falls outside its warning limit, method performance
is unacceptable for that compound in that sample. Therefore, the
sample is complex. The sample is diluted and reanalyzed per Section
13.
9.4.4 As part of the QA program for the laboratory, it is
suggested, but not required, that method accuracy for samples be
assessed and records maintained. After the analysis of five samples
for which the labeled compounds pass the tests in Section 9.4.3,
compute the average percent recovery (P) and the standard deviation
of the percent recovery (sp) for the labeled compounds only. Express
the accuracy assessment as a percent recovery interval from P-2sp to
P + 2sp for each matrix. For example, if P = 90% and sp = 10%, the
accuracy interval is expressed as 70 to 110%. Update the accuracy
assessment for each compound on a regular basis (e.g., after each 20
to 30 new accuracy measurements).
9.5 Blanks: Reagent water blanks are analyzed to demonstrate
freedom from contamination.
9.5.1 Extract and concentrate a 1000-mL reagent water blank
with each sample batch (samples started through the extraction
process on the same eight-hour shift, to a maximum of 20 samples).
Blanks associated with samples to which ascorbic acid is added must
be prepared with ascorbic acid, and blanks associated with samples
to which ascorbic acid is not added must be prepared without
ascorbic acid. Analyze the blank immediately after analysis of the
OPR (Section 7.14) to demonstrate freedom from contamination.
9.5.2 If any of the compounds of interest (Table 1) or any
potentially interfering compound is found in an aqueous blank at
greater than 5g/L (assuming a response factor of one
relative to the sample matrix internal standard for compounds not
listed in Table 1), analysis of samples is halted until the source
of contamination is eliminated and a blank shows no evidence of
contamination at this level.
9.6 Calibration verification and ongoing precision and
recovery: At the beginning of each eight-hour shift during which
analyses are performed, analytical system performance is verified
for all compounds. Analysis of DFTPP (Section 9.2) and the nominal
50g/mL OPR (Section 11.1.5) is used to verify all
performance criteria. Adjustment and/or recalibration, per Section
10, shall be performed until all performance criteria are met. Only
after all performance criteria are met may samples and blanks be
analyzed.
9.6.1 Analyze the extract of the OPR (Section 11.1.5) at the
beginning of each eight-hour shift and prior to analysis of

[[Page 18739]]

samples from the same batch. Alternatively, a separate calibration
verification may be performed using an aliquot of the midpoint
calibration standard from Section 7.13 (with a nominal concentration
of 50 g/mL). This alternative may be used to check
instrument performance on failure of an OPR, or when samples
extracted with an OPR aliquot are not analyzed within the same
eight-hour analysis shift.
9.6.1.1 Retention times: The absolute retention time of 2,2'-
difluorobiphenyl shall be within the range of 765 to 885 seconds,
and the relative retention times of all pollutants and labeled
compounds shall fall within the limits given in Table 2.
9.6.1.2 GC resolution: The valley height between 4,6-
dichloroguaiacol and 3,4-dichloroguaiacol at m/z 192 shall not
exceed 10% of the height of the taller of the two peaks.
9.6.1.3 Multiple peaks: Each compound injected shall give a
single, distinct GC peak.
9.6.2 Compute the percent recovery of each pollutant (Table 1)
by isotope dilution (Section 10.4) for those compounds that have
labeled analogs. Compute the percent recovery of each pollutant that
has no labeled analog by the internal standard method (Section
10.5), using the 3,4,5-trichlorophenol (SMIS) as the internal
standard. Compute the percent recovery of the labeled compounds and
the SMIS by the internal standard method, using the 2,2'-
difluorobiphenyl as the internal standard.
9.6.2.1 For each compound, compare the recovery with the limits
for ongoing precision and recovery in Table 5. If all compounds meet
the acceptance criteria, system performance is acceptable and
analysis of blanks and samples may proceed. If, however, any
individual recovery falls outside of the range given, system
performance is unacceptable for that compound. In this event, there
may be a problem with the GCMS or with the derivatization/
extraction/concentration systems.
9.6.2.2 GCMS system: To determine if the failure of the OPR
test (Section 9.6.2.1) is due to instrument drift, analyze the
current calibration verification extract (Section 7.13.4), calculate
the percent recoveries of all compounds, and compare with the OPR
recovery limits in Table 5. If all compounds meet these criteria,
GCMS performance/stability is verified, and the failure of the OPR
analysis is attributed to problems in the derivatization/extraction/
concentration of the OPR. In this case, analysis of the sample
extracts may proceed. However, failure of any of the recovery
criteria in the analysis of a sample extract requires
rederivatization of that sample (Sections 13.3.1 and 13.3.2). If,
however, the performance/stability of the GCMS is not verified by
analysis of the calibration verification extract, the GCMS requires
recalibration and all extracts associated with the failed OPR must
be reanalyzed.
9.6.3 Add results that pass the specifications in Section
9.6.2.1 to initial and previous ongoing data for each compound.
Update QC charts to form a graphic representation of continued
laboratory performance. Develop a statement of laboratory accuracy
for each pollutant and labeled compound in each matrix type (reagent
water, C-stage filtrate, E-stage filtrate, final effluent, etc.) by
calculating the average percent recovery (R) and the standard
deviation of percent recovery (sr). Express the accuracy as a
recovery interval from R- 2sr to R + 2sr. For example, if R = 95%
and sr = 5%, the accuracy is 85 to 105%.
9.7 The specifications contained in this method can be met if
the apparatus used is calibrated properly, then maintained in a
calibrated state. The standards used for calibration (Section 10)
and for initial (Section 9.3.2) and ongoing (Section 9.6) precision
and recovery should be identical, so that the most precise results
will be obtained. The GCMS instrument in particular will provide the
most reproducible results if dedicated to the settings and
conditions required for the analyses of chlorophenolics by this
method.
9.8 Depending on specific program requirements, field
replicates may be collected to determine the precision of the
sampling technique, and spiked samples may be required to determine
the accuracy of the analysis when the internal standard method is
used.

10.0 Calibration and Standardization

10.1 Assemble the GCMS and establish the operating conditions
in Section 12. Analyze standards per the procedure in Section 12 to
demonstrate that the analytical system meets the minimum levels in
Table 2, and the mass-intensity criteria in Table 3 for 50 ng DFTPP.
10.2 Mass-spectral libraries: Detection and identification of
compounds of interest are dependent upon spectra stored in user-
created libraries.
10.2.1 Obtain a mass spectrum of the acetyl derivative of each
chlorophenolic compound (pollutant, labeled compound, and the sample
matrix internal standard) by derivatizing and analyzing an authentic
standard either singly or as part of a mixture in which there is no
interference between closely eluting components. That only a single
compound is present is determined by examination of the spectrum.
Fragments not attributable to the compound under study indicate the
presence of an interfering compound.
10.2.2 Adjust the analytical conditions and scan rate (for this
test only) to produce an undistorted spectrum at the GC peak
maximum. An undistorted spectrum will usually be obtained if five
complete spectra are collected across the upper half of the GC peak.
Software algorithms designed to ``enhance'' the spectrum may
eliminate distortion, but may also eliminate authentic m/z's or
introduce other distortion.
10.2.3 The authentic reference spectrum is obtained under DFTPP
tuning conditions (Section 10.1 and Table 3) to normalize it to
spectra from other instruments.
10.2.4 The spectrum is edited by removing all peaks in the m/z
42 to 45 range, and saving the five most intense mass spectral peaks
and all other mass spectral peaks greater than 10% of the base peak
(excluding the peaks in the m/z 42 to 45 range). The spectrum may be
further edited to remove common interfering m/z's. The spectrum
obtained is stored for reverse search and for compound confirmation.
10.3 Minimum level: Demonstrate that the chlorophenolics are
detectable at the minimum level (per all criteria in Section 14).
The nominal 5 g/mL calibration standard (Section 7.13) can
be used to demonstrate this performance.
10.4 Calibration with isotope dilution: Isotope dilution is
used when (1) labeled compounds are available, (2) interferences do
not preclude its use, and (3) the quantitation m/z (Table 4)
extracted ion-current profile (EICP) area for the compound is in the
calibration range. Alternative labeled compounds and quantitation m/
z's may be used based on availability. If any of the above
conditions preclude isotope dilution, the internal standard
calibration method (Section 10.5) is used.
10.4.1 A calibration curve encompassing the concentration range
is prepared for each compound to be determined. The relative
response (pollutant to labeled) vs. concentration in standard
solutions is plotted or computed using a linear regression. The
example in Figure 1 shows a calibration curve for phenol using
phenol-d5 as the isotopic diluent. Also shown are the
10% error limits (dotted lines). Relative response (RR)
is determined according to the procedures described below. A minimum
of five data points are employed for calibration.
10.4.2 The relative response of a pollutant to its labeled
analog is determined from isotope ratio values computed from
acquired data. Three isotope ratios are used in this process:

Rx = the isotope ratio measured for the pure pollutant.
Ry = the isotope ratio measured for the labeled compound.
Rm = the isotope ratio of an analytical mixture of
pollutant and labeled compounds.

The m/z's are selected such that Rx>Ry. If
Rm is not between 2Ry and 0.5Rx,
the method does not apply and the sample is analyzed by the internal
standard method.
10.4.3 Capillary columns sometimes separate the pollutant-labeled
pair when deuterium labeled compounds are used, with the labeled
compound eluted first (Figure 2). For this case,

[[Page 18740]]

[GRAPHIC] [TIFF OMITTED] TR15AP98.028

10.4.4 When the pollutant-labeled pair is not separated (as
occurs with carbon-13-labeled compounds), or when another labeled
compound with interfering spectral masses overlaps the pollutant (a
case which can occur with isomeric compounds), it is necessary to
determine the contributions of the pollutant and labeled compound to
the respective EICP areas. If the peaks are separated well enough to
permit the data system or operator to remove the contributions of
the compounds to each other, the equations in Section 10.4.3 apply.
This usually occurs when the height of the valley between the two GC
peaks at the same m/z is less than 70 to 90% of the height of the
shorter of the two peaks. If significant GC and spectral overlap
occur, RR is computed using the following equation:
[GRAPHIC] [TIFF OMITTED] TR15AP98.029

Where:

Rx is measured as shown in figure 3A,
Ry is measured as shown in figure 3B,
Rm is measured as shown in figure 3C.

For example, Rx = 46100/4780 = 9.644; Ry =
2650/43600 = 0.0608; Rm = 49200/48300 = 1.1019; thus, RR
= 1.114. 10.4.5 To calibrate the analytical system by isotope
dilution, analyze a 1-L aliquot of each of the calibration
standards (Section 7.13) using the procedure in Section 12. Compute
the RR at each concentration.
10.4.6 Linearity: If the ratio of relative response to
concentration for any compound is constant (less than 20%
coefficient of variation) over the five-point calibration range, an
averaged relative response/concentration ratio may be used for that
compound; otherwise, the complete calibration curve for that
compound shall be used over the five-point calibration range.
10.5 Calibration by internal standard: The method contains two
types of internal standards, the sample matrix internal standard
(SMIS) and the instrument internal standard (IIS), and they are used
for different quantitative purposes. The 3,4,5-trichlorophenol
sample matrix internal standard (SMIS) is used for measurement of
all pollutants with no labeled analog and when the criteria for
isotope dilution (Section 10.4) cannot be met. The 2,2'-
difluorobiphenyl instrument internal standard (IIS) is used for
determination of the labeled compounds and the SMIS. The results are
used for intralaboratory statistics (Sections 9.4.4 and 9.6.3).
10.5.1 Response factors: Calibration requires the determination
of response factors (RF) for both the pollutants with no labeled
analog and for the labeled compounds and the SMIS. The response
factor is defined by the following equation:
[GRAPHIC] [TIFF OMITTED] TR15AP98.030

Where:

As=the area of the characteristic mass for the compound
in the daily standard.
Ais=the area of the characteristic mass for the internal
standard.
Cis=the concentration of the internal standard
(g/mL).
Cs=is the concentration of the compound in the
calibration standard (g/mL).

When this equation is used to determine the response factors for
pollutant compounds without labeled analogs, use the area
(Ais) and concentration (Cis) of 3,4,5-
trichlorophenol (SMIS) as the internal standard. When this equation
is used to determine the response factors for the labeled analogs
and the SMIS, use the area (Ais) and concentration
(Cis) of 2,2'-difluorobiphenyl as the internal standard.
10.5.2 The response factor is determined for at least five
concentrations appropriate to the response of each compound (Section
7.13); nominally, 5, 10, 20, 50, and 100 g/mL. The amount
of SMIS added to each solution is the same (25 g/mL) so
that Cis remains constant. Likewise, the concentration of
IIS is constant in each solution. The area ratio (As/
Ais) is plotted versus the concentration ratio
(Cs/Cis) for each compound in the standard to
produce a calibration curve.
10.5.3 Linearity: If the response factor (RF) for any compound
is constant (less than 35% coefficient of variation) over the five-
point calibration range, an averaged response factor may be used for
that compound; otherwise, the complete calibration curve for that
compound shall be used over the five-point range.
10.6 Combined calibration: By using calibration solutions
(Section 7.13) containing the pollutants, labeled compounds, and the
internal standards, a single set of analyses can be used to produce
calibration curves for the isotope dilution and internal standard
methods. These curves are verified each shift (Section 9) by
analyzing the OPR standard, or an optional calibration verification
(VER) standard. Recalibration is required only if OPR criteria
(Section 9.6 and Table 5) cannot be met.

11.0 Sample Derivatization, Extraction, and Concentration

The procedure described in this section uses a stir-bar in a
beaker for the derivatization. The extraction procedures applied to
samples depend on the type of sample being analyzed. Extraction of
samples from in-process wastewaters is performed using a separatory
funnel procedure. All calibrations, IPR, OPR, and blank analyses
associated with in-process wastewater samples must be performed by
the separatory funnel procedure.
Extraction of samples of final effluents and raw water may be
performed using either the stir-bar procedure or the separatory
funnel procedure. However, all calibrations, IPR, OPR, blank, and
sample analyses must be performed using the same procedure. Both
procedures are described below.
11.1 Preparation of all sample types for stir-bar
derivatization.
11.1.1 Allow sample to warm to room temperature.
11.1.2 Immediately prior to measuring, shake sample vigorously
to insure homogeneity.
11.1.3 Measure 1000 mL (10 mL) of sample into a
clean 2000-mL beaker. Label the beaker with the sample number.
11.1.4 Dilute aliquot(s).
11.1.4.1 Complex samples: For samples that are expected to be
difficult to derivatize, concentrate, or are expected to overload
the GC column or mass spectrometer, measure an additional 100 mL
(1 mL) into a clean 2000-mL beaker and dilute to a final
volume of 1000-mL (50 mL) with reagent water. Label with
the sample number and as the dilute aliquot. However, to ensure
adequate sensitivity, a 1000-mL aliquot must always be prepared and
analyzed.
11.1.4.2 Pulp and paper industry samples: For in-process
streams such as E-stage and C-stage filtrates and other in-process
wastewaters, it may be necessary to prepare an aliquot at an
additional level of dilution. In this case, dilute 10 mL
(0.1 mL) of sample to 1000-mL (50 mL).
11.1.5 QC aliquots: For a batch of samples of the same type to
be extracted at the same time (to a maximum of 20), place two 1000-
mL (10 mL) aliquots of reagent water in clean 2000-mL
beakers. Label one beaker as the blank and the other as the ongoing
precision and recovery (OPR) aliquot. Because final effluent samples
are treated with ascorbic acid and in-process wastewater samples are
not (see Section 11.1.6), prepare an OPR aliquot and a blank for the
final effluent and a separate pair for the in-process samples. Treat
these QC aliquots in the same fashion as the associated samples,
adding

[[Page 18741]]

ascorbic acid to the pair associated with the final effluents, and
not adding ascorbic acid to the pair associated with the in-process
samples.
11.1.6 Ascorbic acid: Added to stabilize chlorocatechols.
However, for pulp and paper industry in-process streams and other
in-process wastewaters, the addition of ascorbic acid may convert
chloro-o-quinones to catechols if these quinones are present.
Separate calibration curves must be prepared with and without the
addition of ascorbic acid (Section 7.13.2).
11.1.6.1 Spike 5 to 6 mL of the ascorbic acid solution (Section
7.2.2) into each final effluent sample, and the associated
calibration standards, IPR and OPR aliquots, and blank.
11.1.6.2 For pulp and paper industry C-stage filtrates, E-stage
filtrates, and untreated effluents, omit the ascorbic acid to
prevent the conversion of chloro-o-quinones to catechols. Prepare
calibration standards, IPR and OPR aliquots, and blanks associated
with these samples without ascorbic acid as well.
11.1.7 Spike 1000 L of the labeled compound spiking
solution (Section 7.8) into the sample and QC aliquots.
11.1.8 Spike 500 L of the nominal 50 g/mL
calibration solution (Section 7.13.4) into the OPR aliquot.
11.1.9 Adjust the pH of the sample aliquots to between 7.0 and
7.1. For calibration standards, IPR and OPR aliquots, and blanks, pH
adjustment is not required.
11.1.10 Equilibrate all sample and QC solutions for
approximately 15 minutes, with occasional stirring.
11.2 Derivatization: Because derivatization must proceed
rapidly, particularly upon the addition of the
K2CO3 buffer, it is necessary to work with one
sample at a time until the derivatization step (Section 11.2.3) is
complete.
11.2.1 Place a beaker containing a sample or QC aliquot on the
magnetic stirrer in a fume hood, drop a clean stirring bar into the
beaker, and increase the speed of the stirring bar until the vortex
is drawn to the bottom of the beaker.
11.2.2 Measure 25 to 26 mL of
K2CO3 buffer into a graduated cylinder or
other container and 25 to 26 mL of acetic acid into another.
11.2.3 Add the K2CO3 buffer to the sample
or QC aliquot, immediately (within one to three seconds) add the
acetic anhydride, and stir for three to five minutes to complete the
derivatization.
11.3 Extraction: Two procedures are described below for the
extraction of derivatized samples. The choice of extraction
procedure will depend on the sample type. For final effluent
samples, either of two procedures may be utilized for extraction of
derivatized samples. For samples of in-process wastewaters, the
separatory funnel extraction procedure must be used.

Note: Whichever procedure is employed, the same extraction
procedure must be used for calibration standards, IPR aliquots, OPR
aliquots, blanks, and the associated field samples.

11.3.1 Stir-bar extraction of final effluents.
11.3.1.1 Add 200 mL (20 mL) of hexane to the beaker
and stir for three to five minutes, drawing the vortex to the bottom
of the beaker.
11.3.1.2 Stop the stirring and drain the hexane and a portion
of the water into a 500-to 1000-mL separatory funnel. Allow the
layers to separate.
11.3.1.3 Drain the aqueous layer back into the beaker.
11.3.1.4 The formation of emulsions can be expected in any
solvent extraction procedure. If an emulsion forms, the laboratory
must take steps to break the emulsion before proceeding. Mechanical
means of breaking the emulsion include the use of a glass stirring
rod, filtration through glass wool, and other techniques. For
emulsions that resist these techniques, centrifugation is nearly
100% effective.
If centrifugation is employed to break the emulsion, drain the
organic layer into a centrifuge tube, cap the tube, and centrifuge
for two to three minutes or until the phases separate. If the
emulsion cannot be completely broken, collect as much of the organic
phase as possible, and measure and record the volume of the organic
phase collected.
If all efforts to break the emulsion fail, including
centrifugation, and none of the organic phase can be collected,
proceed with the dilute aliquot (Section 11.1.4.2). However, use of
the dilute aliquot will sacrifice the sensitivity of the method, and
may not be appropriate in all cases.
11.3.1.5 Drain the organic layer into a Kuderna-Danish (K-D)
apparatus equipped with a 10-mL concentrator tube. Label the K-D
apparatus. It may be necessary to pour the organic layer through a
funnel containing anhydrous sodium sulfate to remove any traces of
water from the extract.
11.3.1.6 Repeat the extraction (Section 11.3.1.1 through
11.3.1.5) two more times using another 200-mL of hexane for each
extraction, combining the extracts in the K-D apparatus.
11.3.1.7 Proceed with concentration of the extract, as
described in Section 11.4.
11.3.2 Separatory funnel extraction of either final effluents
or in-process wastewaters.
11.3.2.1 Transfer the derivatized sample or QC aliquot to a 2-L
separatory funnel.
11.3.2.2 Add 200 mL (20 mL) of hexane to the
separatory funnel. Cap the funnel and extract the sample by shaking
the funnel for two to three minutes with periodic venting.
11.3.2.3 Allow the organic layer to separate from the water
phase for a minimum of 10 minutes.
11.3.2.4 Drain the lower aqueous layer into the beaker used for
derivatization (Section 11.2), or into a second clean 2-L separatory
funnel. Transfer the solvent to a 1000-mL K-D flask. It may be
necessary to pour the organic layer through a funnel containing
anhydrous sodium sulfate to remove any traces of water from the
extract.
11.3.2.5 The formation of emulsions can be expected in any
solvent extraction procedure. If an emulsion forms, the laboratory
must take steps to break the emulsion before proceeding. Mechanical
means of breaking the emulsion include the use of a glass stirring
rod, filtration through glass wool, and other techniques. For
emulsions that resist these techniques, centrifugation may be
required.
If centrifugation is employed to break the emulsion, drain the
organic layer into a centrifuge tube, cap the tube, and centrifuge
for two to three minutes or until the phases separate. If the
emulsion cannot be completely broken, collect as much of the organic
phase as possible, and measure and record the volume of the organic
phase collected. If all efforts to break the emulsion, including
centrifugation, fail and none of the organic phase can be collected,
proceed with the dilute aliquot (Section 11.1.4.2). However, use of
the dilute aliquot will sacrifice the sensitivity of the method, and
may not be appropriate in all cases.
11.3.2.6 If drained into a beaker, transfer the aqueous layer
to the 2-L separatory funnel (Section 11.3.2.1). Perform a second
extraction using another 200 mL of fresh solvent.
11.3.2.7 Transfer the extract to the 1000-mL K-D flask in
Section 11.3.2.4.
11.3.2.8 Perform a third extraction in the same fashion as
above.
11.3.2.9 Proceed with concentration of the extract, as
described in Section 11.4.
11.4 Macro concentration: Concentrate the extracts in separate
1000-mL K-D flasks equipped with 10-mL concentrator tubes. Add one
to two clean boiling chips to the flask and attach a three-ball
macro-Snyder column. Prewet the column by adding approximately 1 mL
of hexane through the top. Place the K-D apparatus in a hot water
bath so that the entire lower rounded surface of the flask is bathed
with steam. Adjust the vertical position of the apparatus and the
water temperature as required to complete the concentration in 15 to
20 minutes. At the proper rate of distillation, the balls of the
column will actively chatter but the chambers will not flood. When
the liquid has reached an apparent volume of 1 mL, remove the K-D
apparatus from the bath and allow the solvent to drain and cool for
at least 10 minutes. Remove the Snyder column and rinse the flask
and its lower joint into the concentrator tube with 1 to 2 mL of
hexane. A 5-mL syringe is recommended for this operation.
11.5 Micro-concentration: Final concentration of the extracts
may be accomplished using either a micro-Snyder column or nitrogen
evaporation.
11.5.1 Micro-Snyder column: Add a clean boiling chip and attach
a two-ball micro-Snyder column to the concentrator tube. Prewet the
column by adding approximately 0.5 mL hexane through the top. Place
the apparatus in the hot water bath. Adjust the vertical position
and the water temperature as required to complete the concentration
in 5 to 10 minutes. At the proper rate of distillation, the balls of
the column will actively chatter but the chambers will not flood.
When the liquid reaches an apparent volume of approximately 0.2 mL,
remove the apparatus from the water bath and allow to drain and cool
for at least 10 minutes. Remove the micro-Snyder column and rinse
its lower joint into the concentrator tube with approximately 0.2 mL
of hexane. Adjust to a final volume of 0.5 mL.
11.5.2 Nitrogen evaporation: Transfer the concentrator tube to
a nitrogen evaporation

[[Page 18742]]

device and direct a gentle stream of clean dry nitrogen into the
concentrator. Rinse the sides of the concentrator tube with small
volumes of hexane, and concentrate the extract to a final volume of
0.5 mL.
11.6 Spike each extract with 10 L of the 2,2'-
difluorobiphenyl IIS (Section 7.10) and transfer the concentrated
extract to a clean screw-cap vial using hexane to rinse the
concentrator tube. Seal the vial with a PTFE-lined lid, and mark the
level on the vial. Label with the sample number and store in the
dark at -20 to -10 deg.C until ready for analysis.

12.0 GCMS Analysis

12.1 Establish the following operating conditions:

Carrier gas flow: Helium at 30 cm/sec at 50 deg.C
Injector temperature: 300 deg.C
Initial temperature: 50 deg.C
Temperature program: 8 deg.C/min to 270 deg.C
Final hold: Until after 2,6-dichlorosyringaldehyde elutes

Adjust the GC conditions to meet the requirements in Section
9.6.1.1 and Table 2 for analyte separation and sensitivity. Once
optimized, the same GC conditions must be used for the analysis of
all standards, blanks, IPR and OPR aliquots, and samples.
12.2 Bring the concentrated extract (Section 11.6) or standard
(Sections 7.13 and 7.14) to room temperature and verify that any
precipitate has redissolved. Verify the level on the extract
(Sections 7.13, 7.14, and 11.6) and bring to the mark with solvent
if required.
12.3 Inject a 1-L volume of the standard solution or
extract using on-column or splitless injection. For 0.5 mL extracts,
this 1-L injection volume will contain 50 ng of the DFB
internal standard. If an injection volume other than 1 L is
used, that volume must contain 50 ng of DFB.
12.4 Start the GC column temperature ramp upon injection. Start
MS data collection after the solvent peak elutes. Stop data
collection after the 2,6-dichlorosyringaldehyde peak elutes. Return
the column to the initial temperature for analysis of the next
sample.

13.0 Analysis of Complex Samples

Some samples may contain high levels (>1000 g/L) of the
compounds of interest, interfering compounds, and/or other phenolic
materials. Some samples will not concentrate to 0.5 mL (Section
11.5); others will overload the GC column and/or mass spectrometer;
others may contain amounts of phenols that may exceed the capacity
of the derivatizing agent.
13.1 Analyze the dilute aliquot (Section 11.1.4) when the
sample will not concentrate to 0.5 mL. If a dilute aliquot was not
extracted, and the sample holding time (Section 8.4) has not been
exceeded, dilute an aliquot of sample with reagent water, and
derivatize and extract it (Section 11.1.4). Otherwise, dilute the
extract (Section 14.7.3) and quantitate it by the internal standard
method (Section 14.3).
13.2 Recovery of the 2,2'-difluorobiphenyl instrument internal
standard: The EICP area of the internal standard should be within a
factor of two of the area in the OPR or VER standard (Section 9.6).
If the absolute areas of the labeled compounds and the SMIS are
within a factor of two of the respective areas in the OPR or VER
standard, and the DFB internal standard area is less than one-half
of its respective area, then internal standard loss in the extract
has occurred. In this case, analyze the extract from the dilute
aliquot (Section 11.1.4).
13.3 Recovery of labeled compounds and the sample matrix
internal standard (SMIS): SMIS and labeled compound recovery
specifications have been developed for samples with and without the
addition of ascorbic acid. Compare the recoveries to the appropriate
limits in Table 5.
13.3.1 If SMIS or labeled compound recoveries are outside the
limits given in Table 5 and the associated OPR analysis meets the
recovery criteria, the extract from the dilute aliquot (Section
11.1.4) is analyzed as in Section 14.7.
13.3.2 If labeled compound or SMIS recovery is outside the
limits given in Table 5 and the associated OPR analysis did not meet
recovery criteria, a problem in the derivatization/extraction/
concentration of the sample is indicated, and the sample must be
rederivatized and reanalyzed.

14.0 Data Analysis and Calculations

14.1 Qualitative determination: Identification is accomplished
by comparison of data from analysis of a sample or blank with data
stored in the mass spectral libraries. Identification of a compound
is confirmed when the following criteria are met:
14.1.1 The signals for m/z 43 (to indicate the presence of the
acetyl derivative) and all characteristic m/z's stored in the
spectral library (Section 10.2.4) shall be present and shall
maximize within the same two consecutive scans.
14.1.2 Either (1) the background corrected EICP areas, or (2)
the corrected relative intensities of the mass spectral peaks at the
GC peak maximum shall agree within a factor of two (0.5 to 2 times)
for all m/z's stored in the library.
14.1.3 The relative retention time shall be within the window
specified in Table 2.
14.1.4 The m/z's present in the mass spectrum from the
component in the sample that are not present in the reference mass
spectrum shall be accounted for by contaminant or background ions.
If the mass spectrum is contaminated, an experienced spectrometrist
(Section 1.4) shall determine the presence or absence of the
compound.
14.2 Quantitative determination by isotope dilution: By adding
a known amount of a labeled compound to every sample prior to
derivatization and extraction, correction for recovery of the
pollutant can be made because the pollutant and its labeled analog
exhibit the same effects upon derivatization, extraction,
concentration, and gas chromatography. Relative response (RR) values
for sample mixtures are used in conjunction with calibration curves
described in Section 10.4 to determine concentrations directly, so
long as labeled compound spiking levels are constant. For the phenol
example given in Figure 1 (Section 10.4.1), RR would be equal to
1.114. For this RR value, the phenol calibration curve given in
Figure 1 indicates a concentration of 27 g/mL in the sample
extract (Cex).
14.2.1 Compute the concentration in the extract using the
response ratio determined from calibration data (Section 10.4) and
the following equation:
[GRAPHIC] [TIFF OMITTED] TR15AP98.031

Where:

Cex = concentration of the pollutant in the extract.
An = area of the characteristic m/z for the pollutant.
Cl = concentration of the labeled compound in the
extract.
Al = area of the characteristic m/z for the labeled
compound.
RR = response ratio from the initial calibration.

14.2.2 For the IPR (Section 9.3.2) and OPR (Section 9.6),
compute the percent recovery of each pollutant using the equation in
Section 14.6. The percent recovery is used for the evaluation of
method and laboratory performance, in the form of IPR (Section
9.3.2) and OPR (Section 9.6).
14.3 Quantitative determination by internal standard: Compute
the concentration using the response factor determined from
calibration data (Section 10.5) and the following equation:
[GRAPHIC] [TIFF OMITTED] TR15AP98.032

Where:

Cex = concentration of the pollutant in the extract.
As = area of the characteristic m/z for the pollutant.
Cis = concentration of the internal standard in the
extract (see note below).
Ais = area of the characteristic m/z for the internal
standard.
RF = response factor from the initial calibration.

Note: When this equation is used to compute the extract
concentrations of native compounds without labeled analogs, use the
area (Ais) and concentration (Cis) of 3,4,5-
trichlorophenol (SMIS) as the internal standard.

For the IPR (Section 9.3.2) and OPR (Section 9.6), compute the
percent recovery using the equation in Section 14.6.

Note: Separate calibration curves will be required for samples
with and without the addition of ascorbic acid, and also for both
extraction procedures (stir-bar and separatory funnel) where
applicable.

14.4 Compute the concentration of the labeled compounds and the
SMIS using the equation in Section 14.3, but using the area and
concentration of the 2,2'-difluorobiphenyl as the internal standard,
and the area of the labeled compound or SMIS as As.
14.5 Compute the concentration of each pollutant compound in
the sample using the following equation:

[[Page 18743]]

[GRAPHIC] [TIFF OMITTED] TR15AP98.033

Where:

Cs = Concentration of the pollutant in the sample.
Cex = Concentration of the pollutant in the extract.
Vex = Volume of the concentrated extract (typically 0.5
mL).
Vo = Volume of the original sample in liters.

14.6 Compute the recovery of each labeled compound and the SMIS
as the ratio of concentration (or amount) found to the concentration
(or amount) spiked, using the following equation:
[GRAPHIC] [TIFF OMITTED] TR15AP98.034

These percent recoveries are used to assess method performance
according to Sections 9 and 13.
14.7 If the EICP area at the quantitation m/z for any compound
exceeds the calibration range of the system, three approaches are
used to obtain results within the calibration range.
14.7.1 If the recoveries of all the labeled compounds in the
original sample aliquot meet the limits in Table 5, then the extract
of the sample may be diluted by a maximum of a factor of 10, and the
diluted extract reanalyzed.
14.7.2 If the recovery of any labeled compound is outside its
limits in Table 5, or if a tenfold dilution of the extract will not
bring the pollutant within the calibration range, then extract and
analyze a dilute aliquot of the sample (Section 11). Dilute 100 mL,
10 mL, or an appropriate volume of sample to 1000 mL with reagent
water and extract per Section 11.
14.7.3 If the recoveries of all labeled compounds in the
original sample aliquot (Section 14.7.1) meet the limits in Table 5,
and if the sample holding time has been exceeded, then the original
sample extract is diluted by successive factors of 10, the DFB
internal standard is added to give a concentration of 50 g/
mL in the diluted extract, and the diluted extract is analyzed.
Quantitation of all analytes is performed using the DFB internal
standard.
14.7.4 If the recoveries of all labeled compounds in the
original sample aliquot (Section 14.7.1) or in the dilute aliquot
(Section 14.7.2) (if a dilute aliquot was analyzed) do not meet the
limits in Table 5, and if the holding time has been exceeded, re-
sampling is required.
14.8 Results are reported for all pollutants, labeled
compounds, and the sample matrix internal standard in standards,
blanks, and samples, in units of g/L.
14.8.1 Results for samples which have been diluted are reported
at the least dilute level at which the area at the quantitation m/z
is within the calibration range (Section 14.7).
14.8.2 For compounds having a labeled analog, results are
reported at the least dilute level at which the area at the
quantitation m/z is within the calibration range (Section 14.7) and
the labeled compound recovery is within the normal range for the
method (Section 13.3).

15.0 Method Performance

15.1 Single laboratory performance for this method is detailed
in References 1, 2, and 11. Acceptance criteria were established
from multiple laboratory use of the draft method.
15.2 A chromatogram of the ongoing precision and recovery
standard (Section 7.14) is shown in Figure 4.

16.0 Pollution Prevention

16.1 The solvents used in this method pose little threat to the
environment when recycled and managed properly.
16.2 Standards should be prepared in volumes consistent with
laboratory use to minimize the volume of expired standards to be
disposed.

17.0 Waste Management

17.1 It is the laboratory's responsibility to comply with all
federal, state, and local regulations governing waste management,
particularly the hazardous waste identification rules and land
disposal restrictions, and to protect the air, water, and land by
minimizing and controlling all releases from fume hoods and bench
operations. Compliance with all sewage discharge permits and
regulations is also required.
17.2 Samples preserved with HCl or H2SO4
to pH < 2 are hazardous and must be neutralized before being
disposed, or must be handled as hazardous waste.
17.3 For further information on waste management, consult ``The
Waste Management Manual for Laboratory Personnel'', and ``Less is
Better: Laboratory Chemical Management for Waste Reduction'', both
available from the American Chemical Society's Department of
Government Relations and Science Policy, 1155 16th Street N.W.,
Washington, D.C. 20036.

18.0 References

18.1 ``Chlorinated Phenolics in Water by In Situ Acetylation/
GC/MS Determination,'' Method CP-86.01, National Council of the
Paper Industry for Air and Stream Improvement, Inc., 260 Madison
Avenue, New York, NY 10016 (July 1986).
18.2 ``6240-Chlorinated Phenolics (Interim Standard),'' Draft
Version, U.S. Environmental Protection Agency, Manchester
Laboratory, Manchester, Washington.
18.3 ``Performance Tests for the Evaluation of Computerized Gas
Chromatography/Mass Spectrometry Equipment and Laboratories,''
USEPA, EMSL Cincinnati, OH 45268, EPA-600/4-80-025 (April 1980).
18.4 ``Working with Carcinogens,'' DHEW, PHS, CDC, NIOSH,
Publication 77-206 (August 1977).
18.5 ``OSHA Safety and Health Standards, General Industry,''
OSHA 2206, 29 CFR 1910 (January 1976).
18.6 ``Safety in Academic Chemistry Laboratories,'' ACS
Committee on Chemical Safety (1979).
18.7 ``Interlaboratory Validation of U. S. Environmental
Protection Agency Method 1625A, Addendum Report,'' SRI
International, Prepared for Analysis and Evaluation Division (WH-
557), USEPA, 401 M St. SW, Washington, DC 20460 (January 1985).
18.8 ``Handbook of Analytical Quality Control in Water and
Wastewater Laboratories,'' USEPA, EMSL, Cincinnati, OH 45268, EPA-
600/4-79-019 (March 1979).
18.9 ``Standard Practice for Sampling Water,'' ASTM Annual Book
of Standards, ASTM, Philadelphia, PA, 76 (1980).
18.10 ``Methods 330.4 and 330.5 for Total Residual Chlorine,''
USEPA, EMSL, Cincinnati, OH 45268, EPA 600/4-70-020 (March 1979).
18.11 ``Determination of Chlorophenolics, Special Analytical
Services Contract 1047, Episode 1886,'' Analytical Technologies,
Inc., Prepared for W. A. Telliard, Industrial Technology Division
(WH-552), USEPA, 401 M St. SW, Washington, DC 20460 (June 1990).
18.12 ``Determination of Chlorophenolics by GCMS, Development
of Method 1653,'' Analytical Technologies, Inc., Prepared for W. A.
Telliard, Industrial Technology Division (WH-552), USEPA, 401 M St.
SW, Washington, DC 20460 (May 1991).

19.0 Tables and Figures

[[Page 18744]]

Table 1.--Chlorophenolic Compounds Determined by GCMS Using Isotope Dilution and Internal Standard Techniques
----------------------------------------------------------------------------------------------------------------
Pollutant Labeled compound
Compound -----------------------------------------------------------------------------
CAS registry EPA-EGD Analog CAS registry EPA-EGD
----------------------------------------------------------------------------------------------------------------
4-chlorophenol.................... 106-48-9 1001
2,4-dichlorophenol................ 120-83-2 1002 d3 93951-74-7 1102
2,6-dichlorophenol................ 87-65-0 1003
2,4,5-trichlorophenol............. 95-95-4 1004
2,4,6-trichlorophenol............. 88-06-2 1005
2,3,4,6-tetrachlorophenol......... 58-90-2 1006
pentachlorophenol................. 87-86-5 1007 ^{13C6 85380-74-1 1107
4-chloroguaiacol.................. 16766-30-6 1008 ^{13C6 136955-39-0 1108
3,4-dichloroguaiacol.............. 77102-94-4 1009
4,5-dichloroguaiacol.............. 2460-49-3 1010
4,6-dichloroguaiacol.............. 16766-31-7 1011
3,4,5-trichloroguaiacol........... 57057-83-7 1012
3,4,6-trichloroguaiacol........... 60712-44-9 1013
4,5,6-trichloroguaiacol........... 2668-24-8 1014 ^{13C6 136955-40-3 1114
tetrachloroguaiacol............... 2539-17-5 1015 ^{13C6 136955-41-4 1115
4-chlorocatechol.................. 2138-22-9 1016
3,4-dichlorocatechol.............. 3978-67-4 1017
3,6-dichlorocatechol.............. 3938-16-7 1018
4,5-dichlorocatechol.............. 3428-24-8 1019 ^{13C6 136955-42-5 1119
3,4,5-trichlorocatechol........... 56961-20-7 1020
3,4,6-trichlorocatechol........... 32139-72-3 1021
tetrachlorocatechol............... 1198-55-6 1022 ^{13C6 136955-43-6 1122
5-chlorovanillin.................. 19463-48-0 1023 ^{13C6 136955-44-7 1123
6-chlorovanillin.................. 18268-76-3 1024
5,6-dichlorovanillin.............. 18268-69-4 1025
2-chlorosyringaldehyde............ 76341-69-0 1026
2,6-dichlorosyringaldehyde........ 76330-06-8 1027
trichlorosyringol................. 2539-26-6 1028

Sample matrix internal standard
(SMIS)

3,4,5-trichlorophenol............. 609-19-8 184

Instrument internal standard (IIS)

2,2'-difluorobiphenyl............. 388-82-9 164
----------------------------------------------------------------------------------------------------------------

Table 2.--Gas Chromatography and Method Detection Limits for Chlorophenolics
----------------------------------------------------------------------------------------------------------------
Minimum
Retention EGD ref level \4\ MDL \5\
EGD No.\1\ Compound time mean No. RRT window (g/ (g/
(sec) \2\ \3\ L) L)
----------------------------------------------------------------------------------------------------------------
1001.............. 4-chlorophenol........ 691 184 0.651-0.681 1.25 1.11
1003.............. 2,6-dichlorophenol.... 796 184 0.757-0.779 2.5 1.39
1102.............. 2,4-dichlorophenol-d3. 818 164 0.986-0.998
1202.............. 2,4-dichlorophenol.... 819 1102 0.997-1.006 2.5 0.15
164............... 2,2'-difluorobiphenyl 825 164 1.000
(I.S.).
1108.............. 4-chloroguaiacol-^{13C6. 900 164 1.077-1.103
1208.............. 4-chloroguaiacol...... 900 1108 0.998-1.002 1.25 0.09
1005.............. 2,4,6-trichlorophenol. 920 184 0.879-0.895 2.5 0.71
1004.............. 2,4,5-trichlorophenol. 979 184 0.936-0.952 2.5 0.57
1016.............. 4-chlorocatechol...... 1004 184 0.961-0.975 1.25 0.59
1011.............. 4,6-dichloroguaiacol.. 1021 184 0.979-0.991 2.5 0.45
1009.............. 3,4-dichloroguaiacol.. 1029 184 0.986-0.998 2.5 0.52
184............... 3,4,5-trichlorophenol 1037 164 1.242-1.272
(I.S.).
1010.............. 4,5-dichloroguaiacol.. 1071 184 1.026-1.040 2.5 0.52
1018.............. 3,6-dichlorocatechol.. 1084 184 1.037-1.053 2.5 0.57
1006.............. 2,3,4,6- 1103 184 1.050-1.078 2.5 0.38
tetrachlorophenol.
1123.............. 5-chlorovanillin-^{13C6. 1111 164 1.327-1.367
1223.............. 5-chlorovanillin...... 1111 1123 0.998-1.001 2.5 1.01
1013.............. 3,4,6- 1118 184 1.066-1.090 2.5 0.46
trichloroguaiacol.
1024.............. 6-chlorovanillin...... 1122 184 1.070-1.094 2.5 0.94
1017.............. 3,4-dichlorocatechol.. 1136 184 1.083-1.105 2.5 0.60
1119.............. 4,5-dichlorocatechol- 1158 164 1.384-1.424
^{13C6.
1219.............. 4,5-dichlorocatechol.. 1158 1119 0.998-1.001 2.5 0.24
1012.............. 3,4,5- 1177 184 1.120-1.160 2.5 0.49
trichloroguaiacol.
1114.............. 4,5,6- 1208 164 1.444-1.484
trichloroguaiacol-
^{13C6.
1214.............. 4,5,6- 1208 1114 0.998-1.002 2.5 0.25
trichloroguaiacol.
1021.............. 3,4,6- 1213 184 1.155-1.185 5.0 0.44
trichlorocatechol.
1025.............. 5,6-dichlorovanillin.. 1246 184 1.182-1.222 5.0 0.80

[[Page 18745]]

1026.............. 2-chlorosyringaldehyde 1255 184 1.190-1.230 2.5 0.87
1107.............. pentachlorophenol-^{13C6 1267 164 1.511-1.561
1207.............. pentachlorophenol..... 1268 1107 0.998-1.002 5.0 0.28
1020.............. 3,4,5- 1268 184 1.208-1.238 5.0 0.53
trichlorocatechol.
1115.............. tetrachloroguaiacol- 1289 164 1.537-1.587
^{13C6.
1215.............. tetrachloroguaiacol... 1290 1115 0.998-1.002 5.0 0.23
1028.............. trichlorosyringol..... 1301 184 1.240-1.270 2.5 0.64
1122.............. tetrachlorocatechol- 1365 164 1.630-1.690
^{13C6.
1222.............. tetrachlorocatechol... 1365 1122 0.998-1.002 5.0 0.76
1027.............. 2,6- 1378 184 1.309-1.349 5.0 1.13
dichlorosyringaldehyd
e.
----------------------------------------------------------------------------------------------------------------
\1\ Four digit numbers beginning with 10 indicate a pollutant quantified by the internal standard method; four
digit numbers beginning with 11 indicate a labeled compound quantified by the internal standard method; four
digit numbers beginning with 12 indicate a pollutant quantified by isotope dilution.
\2\ The retention times in this column are based on data from a single laboratory (reference 12), utilizing the
GC conditions in Section 11.
\3\ Relative retention time windows are estimated from EPA Method 1625.
\4\ The minimum level (ML) is defined as the level at which the entire analytical system must give a
recognizable signal and acceptable calibration point for the analyte. It is equivalent to the concentration of
the lowest calibration standard, assuming that all method-specified sample weights, volumes, and cleanup
procedures have been employed.
\5\ 40 CFR Part 136, Appendix B; from reference 2.

Table 3.--DFTPP Mass Intensity Specifications \1\
------------------------------------------------------------------------
Mass Intensity required
------------------------------------------------------------------------
51........................... 8 to 82% of m/z 198.
68........................... Less than 2% of m/z 69.
69........................... 11 to 91% of m/z 198.
70........................... Less than 2% of m/z 69.
127.......................... 32 to 59% of m/z 198.
197.......................... Less than 1% of m/z 198.
198.......................... Base peak, 100% abundance.
199.......................... 4 to 9% of m/z 198.
275.......................... 11 to 30% of m/z 198.
441.......................... 44 to 110% of m/z 443.
442.......................... 30 to 86% of m/z 198.
443.......................... 14 to 24% of m/z 442.
------------------------------------------------------------------------
\1\ Reference 7.

Table 4.--Characteristic M/Z's of Chlorophenolic Compounds
------------------------------------------------------------------------
Compound Primary m/z
------------------------------------------------------------------------
4-chlorophenol.......................................... 128
2,4-dichlorophenol...................................... 162
2,4-dichlorophenol-d3................................... 167
2,6-dichlorophenol...................................... 162
2,4,5-trichlorophenol................................... 196
2,4,6-trichlorophenol................................... 196
2,3,4,6-tetrachlorophenol............................... 232
pentachlorophenol....................................... 266
pentachlorophenol^{-13C6.................................. 272
4-chloroguaiacol........................................ 158
4-chloroguaiacol^{-13C6................................... 164
3,4-dichloroguaiacol.................................... 192
4,5-dichloroguaiacol.................................... 192
4,6-dichloroguaiacol.................................... 192
3,4,5-trichloroguaiacol................................. 226
3,4,6-trichloroguaiacol................................. 226
4,5,6-trichloroguaiacol................................. 226
4,5,6-trichloroguaiacol^{-13C6............................ 234
tetrachloroguaiacol..................................... 262
tetrachloroguaiacol^{-13C6................................ 268
4-chlorocatechol........................................ 144
3,4-dichlorocatechol.................................... 178
3,6-dichlorocatechol.................................... 178
4,5-dichlorocatechol.................................... 178
4,5-dichlorocatechol^{-13C6............................... 184
3,4,5-trichlorocatechol................................. 212
3,4,6-trichlorocatechol................................. 212

[[Page 18746]]

tetrachlorocatechol..................................... 248
tetrachlorocatechol^{-13C6................................ 254
5-chlorovanillin........................................ 186
5-chlorovanillin^{-13C6................................... 192
6-chlorovanillin........................................ 186
5,6-dichlorovanillin.................................... 220
2-chlorosyringaldehyde.................................. 216
2,6-dichlorosyringaldehyde.............................. 250
trichlorosyringol....................................... 256

Sample Matrix Internal Standard (SMIS)

3,4,5-trichlorophenol................................... 196

Instrument Internal Standard (IIS)

2,2'-difluorobiphenyl................................... 190
------------------------------------------------------------------------

Table 5.--Acceptance Criteria for Performance Tests \1\
----------------------------------------------------------------------------------------------------------------
Initial precision Labeled compound and
and recovery sec. SMIS recovery sec.
Test 9.3.2 (percent) Ongoing 9.4 and 14.6
conc.\3\ ---------------------- recovery ---------------------
EGD No.\2\ Compound (g/ sec. 9.6 With Without
mL) (percent) ascorbic ascorbic
s X acid P acid P
(%) (%)
----------------------------------------------------------------------------------------------------------------
1001............... 4-chlorophenol........ 25 64 72-144 40-236
1202............... 2,4-dichlorophenol.... 50 14 84-120 84-118
1102............... 2,4-dichlorophenol-d3. 25 54 64-160 56-170 58-135 27-143
1003............... 2,6-dichlorophenol.... 50 20 66-148 58-170
1004............... 2,4,5-trichlorophenol. 50 14 78-140 82-128
1005............... 2,4,6-trichlorophenol. 50 20 72-142 72-146
1006............... 2,3,4,6- 50 14 80-132 82-132
tetrachlorophenol.
1207............... pentachlorophenol..... 100 6 90-111 84-120
1107............... pentachlorophenol- 25 21 58-169 61-157 8-143 27-167
\13\C6.
1208............... 4-chloroguaiacol...... 25 20 88-120 88-120
1108............... 4-chloroguaiacol- 25 104 68-148 64-152 59-121 43-168
\13\C6.
1009............... 3,4-dichloroguaiaco\4\ 50 18 80-126 82-126
1010............... 4,5-dichloroguaiacol.. 50 14 82-121 80-128
1011............... 4,6-dichloroguaiacol.. 50 16 82-126 86-120
1012............... 3,4,5- 50 16 78-130 80-134
trichloroguaiacol.
1013............... 3,4,6- 50 16 64-152 74-140
trichloroguaiacol.
1214............... 4,5,6- 50 14 92-106 88-116
trichloroguaiacol.
1114............... 4,5,6- 25 48 66-146 74-140 48-131 51-139
trichloroguaiacol-
\13\C6.
1215............... tetrachloroguaiacol... 100 7 84-115 81-126
1115............... tetrachloroguaiacol- 25 22 57-173 65-161 35-120 27-161
\13\C6.
1016............... 4-chlorocatechol...... 25 48 76-140 80-124
1017............... 3,4-dichlorocatechol.. 50 24 66-154 78-134
1018............... 3,6-dichlorocatechol.. 50 16 78-136 84-126
1219............... 4,5-dichlorocatechol.. 50 8 84-118 86-122
1119............... 4,5-dichlorocatechol- 25 78 68-144 66-142 33-129 0-190
\13\C6.
1020............... 3,4,5- 100 17 60-166 72-128
trichlorocatechol.
1021............... 3,4,6- 100 17 74-138 64-149
trichlorocatechol\4\.
1222............... tetrachlorocatechol... 100 29 46-234 81-132
1122............... tetrachlorocatechol- 25 39 48-227 63-152 14-118 0-184
\13\C6.
1223............... 5-chlorovanillin...... 50 20 94-208 84-118
1123............... 5-chlorovanillin- 25 84 68-160 70-144 51-126 32-254
\13\C6.
1024............... 6-chlorovanillin...... 50 22 82-128 80-126
1025............... 5,6-dichlorovanillin.. 100 9 67-146 77-140
1026............... 2-chlorosyringaldehyde 50 28 76-130 72-156
1027............... 2,6- 100 14 82-129 60-183
dichlorosyringaldehyd
e.
1028............... trichlorosyringol..... 50 18 76-136 66-174
----------------------------------------------------------------------------------------------------------------
Sample Matrix Internal Standard
----------------------------------------------------------------------------------------------------------------
184................ 3,4,5-trichlorophenol. 100 47 62-185 68-144 56-116 24-167
----------------------------------------------------------------------------------------------------------------
\1\ Specifications derived from multi-laboratory testing of draft method.
\2\ Four-digit numbers beginning with 10 indicate a pollutant quantified by the internal standard method; four-
digit numbers beginning with 11 indicate a labeled compound quantified by the internal standard method; four-
digit numbers beginning with 12 indicate a pollutant quantified by isotope dilution.
\3\ Test concentrations are in units of g/mL.
\4\ Specification derived from isomer.

BILLING CODE 6560-50-P

[[Page 18747]]

[GRAPHIC] [TIFF OMITTED] TR15AP98.035

[[Page 18748]]

[GRAPHIC] [TIFF OMITTED] TR15AP98.036

[[Page 18749]]

[GRAPHIC] [TIFF OMITTED] TR15AP98.037

[[Page 18750]]

[GRAPHIC] [TIFF OMITTED] TR15AP98.038

BILLING CODE 6560-50-C

[[Page 18751]]

20.0 Glossary of Definitions and Purposes

These definitions and purposes are specific to this method but
have been conformed to common usage as much as possible.
20.1 Units of weight and measure and their abbreviations
20.1.1 Symbols.

deg.C degrees Celsius
L microliter
< less than
> greater than
% percent

20.1.2 Alphabetical characters.

cm centimeter
g gram
h hour
ID inside diameter
in. inch
L liter
M Molecular ion
m meter
mg milligram
min minute
mL milliliter
mm millimeter
m/z mass-to-charge ratio
N normal; gram molecular weight of solute divided by hydrogen
equivalent of solute, per liter of solution
OD outside diameter
pg picogram
ppb part-per-billion
ppm part-per-million
ppt part-per-trillion
psig pounds-per-square inch gauge
v/v volume per unit volume
w/v weight per unit volume
20.2 Definitions and acronyms (in alphabetical order).
Analyte: A chlorophenolic tested for by this method.
The analytes are listed in Table 1.
Calibration standard (CAL): A solution prepared from a secondary
standard and/or stock solutions and used to calibrate the response
of the instrument with respect to analyte concentration.
Calibration verification standard (VER): The mid-point
calibration standard (CS3) that is used to verify calibration. See
Table 4.
Chlorophenolics: collectively, the analytes listed in Table 1.
CS1, CS2, CS3, CS4, CS5: See Calibration standards and Table 4.
Field blank: An aliquot of reagent water or other reference
matrix that is placed in a sample container in the laboratory or the
field, and treated as a sample in all respects, including exposure
to sampling site conditions, storage, preservation, and all
analytical procedures. The purpose of the field blank is to
determine if the field or sample transporting procedures and
environments have contaminated the sample.
GC: Gas chromatograph or gas chromatography.
HRGC: High resolution GC.
IPR: Initial precision and recovery; four aliquots of the
diluted PAR standard analyzed to establish the ability to generate
acceptable precision and accuracy. An IPR is performed prior to the
first time this method is used and any time the method or
instrumentation is modified.
K-D: Kuderna-Danish concentrator; a device used to concentrate
the analytes in a solvent.
Laboratory blank: See Method blank.
Laboratory control sample (LCS): See Ongoing precision and
recovery standard (OPR).
Laboratory reagent blank: See Method blank.
May: This action, activity, or procedural step is neither
required nor prohibited.
May not: This action, activity, or procedural step is
prohibited.
Method blank: An aliquot of reagent water that is treated
exactly as a sample including exposure to all glassware, equipment,
solvents, reagents, internal standards, and surrogates that are used
with samples. The method blank is used to determine if analytes or
interferences are present in the laboratory environment, the
reagents, or the apparatus.
Minimum level (ML): The level at which the entire analytical
system must give a recognizable signal and acceptable calibration
point for the analyte. It is equivalent to the concentration of the
lowest calibration standard, assuming that all method-specified
sample weights, volumes, and cleanup procedures have been employed.
MS: Mass spectrometer or mass spectrometry.
Must: This action, activity, or procedural step is required.
OPR: Ongoing precision and recovery standard (OPR); a laboratory
blank spiked with known quantities of analytes. The OPR is analyzed
exactly like a sample. Its purpose is to assure that the results
produced by the laboratory remain within the limits specified in
this method for precision and recovery.
PAR: Precision and recovery standard; secondary standard that is
diluted and spiked to form the IPR and OPR.
Preparation blank: See Method blank.
Primary dilution standard: A solution containing the specified
analytes that is purchased or prepared from stock solutions and
diluted as needed to prepare calibration solutions and other
solutions.
Quality control check sample (QCS): A sample containing all or a
subset of the analytes at known concentrations. The QCS is obtained
from a source external to the laboratory or is prepared from a
source of standards different from the source of calibration
standards. It is used to check laboratory performance with test
materials prepared external to the normal preparation process.
Reagent water: Water demonstrated to be free from the analytes
of interest and potentially interfering substances at the method
detection limit for the analyte.
Relative standard deviation (RSD): The standard deviation times
100 divided by the mean.
RF: Response factor. See Section 10.5.1.
RR: Relative response. See Section 10.4.4.
RSD: See Relative standard deviation.
Should: This action, activity, or procedural step is suggested
but not required.
Stock solution: A solution containing an analyte that is
prepared using a reference material traceable to EPA, the National
Institute of Science and Technology (NIST), or a source that will
attest to the purity and authenticity of the reference material.
VER: See Calibration verification standard.

[FR Doc. 98-9613 Filed 4-14-98; 8:45 am]
BILLING CODE 6560-50-P}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}}

Notices For
2009
2008
2007
2006
2005
2004
2003
2002
2001
2000
1999
1998
1997
1996
1995
1994

[[pp. 18703-18751]] National Emission Standards for Hazardous Air Pollutants for

Local Navigation