United States Office of Water (4303) EPA-821-R-97-018
Environmental Protection Off ice of Air and Radiation . October 1997
Agency Office of Air Quality Planning and
Standards (RTF)
vxERA, The Pulp, Paper, and Paperboard
Point Source Category
Part 430; Final Rule
-------
-------
This copy of the Pulp and Paper Industry "Cluster Rules" is
being provided as a service to the public before Federal
Register Publication. It is subject to editing and
reformatting to conform to Federal Register requirements.
The only official version of this document will be that
published in the Federal Register.
For the reasons set out in the preamble, title 40, chapter I
of the Code of Federal Regulations is amended as follows:
1. Part 430 is revised to read as follows:
PART 430-THE PULP, PAPER, AND PAPERBOARD POINT SOURCE
CATEGORY
General Provisions
Sec.
430.00 Applicability.
430.01 General definitions.
430.02 Monitoring requirements.
430.03 Best management practices (BMPs)plans for spent
pulping liquor, soap, and turpentine management, spill
prevention, and control.
Subpart A-Dissolving Kraft Subcategory
Sec.
430.10 Applicability; description of the dissolving kraft
subcategory.
430.11 Specialized definitions.
430.12 Effluent limitations representing the degree of
effluent reduction attainable by the application
'of best practicable control technology currently
available (BPT).
430.13. Effluent limitations guidelines representing the
degree of effluent reduction attainable by the
best conventional pollutant control technology
(BCT) .
430.14 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best available technology economically
achievable (BAT).
430.15 New source performance standards (NSPS).
430.16 Pretreatment standards for existing sources
(PSES).
430.17 Pretreatment standards for new sources (PSNS).
785
-------
Subpart B-Bleached Papergrade Kraft and Soda Subcategory
Sec.
430.20 Applicability; description of the bleached
papergrade kraft and soda subcategory.
430.21 Specialized definitions.
430.22 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best practicable control technology currently
available (BPT).
430.23 Effluent limitations representing the degree of
effluent reduction attainable by the best
conventional pollutant control technology (BCT).
430.24 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best available technology economically
achievable (BAT).
430.25 New source performance standards (NSPS).
430.26 Pretreatment standards for existing sources
(PSES).
430.27 Pretreatment standards for new sources (PSNS).
430.28 Best management practices (BMPs).
Subpart: C-Unbleached Kraft Subcategory
Sec.
430.30 Applicability; description of the unbleached kraft
subcategory.
430.31 Specialized definitions.
430.32 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best practicable control technology currently
available (BPT).
430.33 Effluent limitations representing the degree of
effluent reduction attainable by the best
conventional pollutant control technology (BCT).
430.34 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best available technology economically
achievable (BAT).
430.35 New source performance standards (NSPS).
430.36 Pretreatment standards for existing (PSES).
430.37 Pretreatment standards for new sources (PSNS).
Subpart D-Dissolving Sulfite Subcategory
Sec.
430.40
Applicability; description of the dissolving
sulfite subcategory.
786
-------
430.41 Specialized definitions.
430.42 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best practicable control technology currently
available (BPT).
430.43 Effluent limitations representing the degree of
effluent reduction attainable by the best
conventional pollutant control technology (BCT).
430.44 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best available technology economically
achievable (BAT).
430.45 New source performance standards (NSPS).
430.46 Pretreatment standards for existing sources
(PSES).
430.47 Pretreatment standards for new sources (PSNS).
Subpart E-Papergrade Sulfite Subcategory
Sec.
430.50 Applicability; description of the papergrade
sulfite subcategory.
430.51 Specialized definitions.
430.52 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best practicable control technology currently
available (BPT).
430.53 Effluent limitations representing the degree of
effluent reduction attainable by the best
conventional pollutant control technology (BCT).
430'. 54 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best available technology economically
achievable (BAT).
430.55 New source performance standards (NSPS).
430.56 Pretreatment standards for existing sources
(PSES).
430.57 Pretreatment standards for new sources (PSNS).
430'. 58 Best management practices (BMPs) .
Subpart P-Semi-Chemical Subcategory
Sec.
430.60 Applicability; description of the semi-chemical
subcategory.
430.61 Specialized definitions.
430.62 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best practicable control technology currently
available (BPT).
787
-------
430.63 Effluent limitations representing the degree of
effluent reduction attainable by the best
conventional pollutant control technology (BCT).
430.64 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best available technology economically
achievable (BAT) .
430.65 New source performance standards (NSPS).
430.66 Pretreatment standards for existing sources
(PSES).
430.67 Pretreatment standards for new sources (PSNS).
Subpart G-Mechanical Pulp Subcategory
Sec.
430.70 Applicability; description of the mechanical pulp
subcategory.
430.71 Specialized definitions.
430.72 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best practicable control technology currently
available (BPT).
430.73 Effluent limitations representing the degree of
effluent reduction attainable by the best
conventional pollutant control technology (BCT).
430.74 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best available technology economically
achievable (BAT).
430.75 New source performance standards (NSPS).
430.76 Pretreatment standards for existing sources
(PSES).
430.77 Pretreatment standards for new sources (PSNS).
Subpart H-Non-Wood Chemical Pulp Subcategory
Sec.
430.80 Applicability; description of the non-wood
chemical pulp subcategory.
430.81 Specialized definitions.
430.82 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best practicable control technology currently
available (BPT).
430.83 Effluent limitations representing the degree of
effluent reduction attainable by the best
conventional pollutant control technology (BCT).
430.84 Effluent limitations representing the degree of
effluent reduction attainable by the application
788
-------
of best available technology economically
achievable (BAT) .
430.85 New source performance standards (NSPS).
430.86 Pretreatment standards for existing sources
(PSES).
430.87 Pretreatment standards for new sources (PSNS).
Subpart I-Secondary Fiber Deink Subcategory
Sec.
430.90 Applicability; description of the secondary fiber
deink subcategory.
430.91 Specialized definitions.
430.92 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best practicable control technology currently
available (BPT).
430.93 Effluent limitations representing the degree of
effluent reduction attainable by the best
conventional pollutant control technology (BCT).
430.94 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best available technology economically
achievable (BAT).
430.95 ' New source performance standards (NSPS).
430.96 Pretreatment standards for existing sources
(PSES).
430.97 Pretreatment standards for new sources (PSNS).
Subpart J-Secondary Fiber Non-Deink Subcategory
Sec.
430.100 Applicability; description of the secondary fiber
non-deink subcategory.
430.101 Specialized definitions.
430.102 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best practicable control technology currently
available (BPT).
430.103 Effluent limitations representing the degree of
effluent reduction attainable by the best
conventional pollutant control technology (BCT).
430.104 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best available technology economically -
achievable (BAT) .
430.105 New source performance standards (NSPS).
430.106 Pretreatment standards for existing sources
(PSES).
789
-------
430.107 Pretreatment standard's for new sources (PSNS).
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.
430.111 Specialized definitions.
430.112 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best practicable control technology currently
available (BPT).
430.113 Effluent limitations representing the degree of
e'ffluent reduction attainable by the best
conventional pollutant control technology (BCT).
430.114 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best available technology economically
achievable (BAT).
430.115 New source performance standards (NSPS).
430.116 Pretreatment standards for existing sources
(PSES).
430.117 Pretreatment standards for new sources (PSNS).
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.
430.121 Specialized definitions.
430.122 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best practicable control technology currently
available (BPT).
430.123 Effluent limitations representing the degree of
effluent reduction attainable by the best
conventional pollutant control technology (BCT).
430.124 Effluent limitations representing the degree of
effluent reduction attainable by the application
of best available technology economically
achievable (BAT).
430.125 New source performance standards (NSPS).
430.126 Pretreatment standards for existing sources
(PSES).
430.127 Pretreatment standards for new sources (PSNS).
790
-------
APPENDIX A to Part 430 Methods 1650 and Method 1653
Authority: Sections 301, 304, 306, 307, 308, 402, and 501
of the Clean Water Act, as amended, (33 U.S.C. 1311, 1314,
1316, 1317, 1318, 1342, and 1361), and Section 112 of the
Clean Air Act, as amended (42 U.S.C. 7412).
General Provisions
§430.00 Applicability.
(a) This part applies to any pulp, paper, or
paperboard mill that discharges or may discharge process
wastewater .pollutants to the waters of the United States, or
that introduces or may introduce process wastewater
pollutants into a publicly owned treatment works.
(b) The following table presents the subcategorization
scheme codified in this Part, with references to former
subpart designations contained in the 1997 edition of 40 CFR
parts 425 through 699:
791
-------
Ill
*w
o
C
0
-H
jj
B(_l
d
w
c-
cri
H
H
s^
iH
«
-H
d
r«
-H
er Subparts Conta
425 through 699
£5
(u
o a
K
ID ?i
0) u
o 0
o "*
rl
0)
4-t
JJ
*2
^
rti
g
&
i
w
rt
o
"M
n<
ID
N
H
o
cn
0
4J
(d
o
45
3
W
1
§
§
03
H
B
a
H
P
r£j
C
PYPES OF PRODUCTS
^
o
H
EH
§;
N r-1
S H
3 i 1
§ g G
fr. « n
sd
0
R
CO
Q m
iSi
o 5
u
£
m
rH
rH
-H
JJ
4-1
rl
JJ
id
ft
i_]
ft
cn
rt
-H
rH
O
ra
-H
P
jj
4-i
id
»2
-H
rH
O
ra
ra
-rl
P
4
d
0
o
d id
rt 0
id rH
4*
SH JJ
0 id
S1 m
(d ra
ft M
0 ft
ra id
M ft
rrt
ID
O (D
o rt ^
-H ft^
rrt
TJ .
V-i >d ra
Id rt rH
O Cd rH
fi ft'g
0 rH
ft rt id
(D Ql *U
ft O
*. rn
* UJ
"*" "IB*"* ij
UT" ffl »r<
CQ "* *
x""* 01 «,
*jr| 2 nJ
*rj fcs o.
M-I rt §
rtf M
H * ft
T3 ^
43 0 rrt
U Id g
rd g rt
*" o m M
ra ^ u ra rt
rH r* ^ 43
rH S pH 'd
-H S ra
S ~ ra id -H
unbleached kraft
oducts (Aa) ; pull
mi -chemical (cros
unbleached kraft
1 cooking liquor
system (Va)
k A) id
JJ ft M -d U >,
ns 0) -H n
Ti (IJ rt g (D
r-l ID JJ -H 0) >
OJ X -H 43 rrt O
ft -H MH g U U
Id g rH O 1 0)
ft rt U -H rH
k ra g
Ti 0) JJ (U rH
rt rrt rH id ra id
id jJ id o
O H M JJ -H
ft jj a) rt g
rH -d rt ft m v
s rt ft
rH O
O rH
TO rH
ra o>
-H U
d
JJ 0)
id ra
0
ft U
I-H ra
fit
-H
> 0)
rH JJ
0 -H
ra M-I
M rH
-H rt
P w
P
ra
C ""*
H '
4n "3
ra s
g 0)
* jJ
ft "H
2 "3
ft CQ
^ 0) -^
o S1 ft
rH Jj rH
43 fi, rt
rH ft 44
(!) i) ra
S id g
S S
i i y^
-rH Q^ Ti
g 0
rt ra
0 c rt
3*0
lit tj p
S ft g
cn ^ 0
0 rj 3
ft ~^ ra
id ra
ft "d 0
0 rH
jj ra ft
id rt
in 0 O
0 M
(ti S
ft ra rt
0 U
*d rt id
rt d1 >
(fl -H
rt 0
ft 43 rl
rH U 0
rt 0 43
ft JJ &
d
0
ra
rH Id
o 43
d i >i
1-0 g jj m
0 g i ra rt rH P)
d rt g Id -rl Id rH
id -H rt 43 rt -H rt
rH 0 0 -H 1 O U ft
Cn jJ i-H ra g g 0
k-Hid0rtragraft0
04HO rt-«H ftf3j ftCO'd
ft rH Cn T) rH i-H fS
id rt id o rt rt M
ft w i S ra ft i ft i Cn
H
-H
-d
o
ra
id
k
O
0
ra
id
43
id
-H
rt
o
g
id
rt
id
-H
ra
rt
ra
rH
semi -chemical mil
jj
id
M
0
fltf
ft
^^
rt m
id '
ft 0
rH M
rt id
ft 43
rH
id
-Chemic
-H
g
0
ra
fe
-------
jj
nS
* S
0)
ns y ^
a S o
O "^ *~^
d ^ ns
d . ra
ns d JJ rH
ns r* i
o O
3 Cj ft
a 5 ra T3
X! ^> n
r\ ^ ^
fUl
i5. 2 c 3
r ns O
groundwood chemi -mechanical mills
.hrough the application of the thei
arse paper, molded pulp products,
Ntt) ; and pulp and fine paper at gr
fO tQ 0}
^ JZ| "g J^
O "H ft* -H
PJ S E
a TS ^-d
O H O
* § ft §
id Ti Ti
C3 *, fn
ft ^ ^
rH O 'S'"' O
3 5-1 S 5-1
ft Ol ^^ Ol
ft
rH
3
ft
rH
rd
CJ
H
fi
ns
XI
u
cu
S
0
non-wood chemical pulp mills
jj
nS
M
CU
ft
ns
ft
1
ns
a
3
ft
rH
ns
0
-H
x!
CJ
T)
O
i ft
En rH
O 3
S ft
a
5-1
o
^
ra
5H
(U
nS
ft
(D
3
ra
ra
-H
jj
deink mills including fine papers,
jj
rtf
M ^
(U nj
ft O
rd ^-I
a
M
"« -S
nS 5-<
a
a ra
rH S
3 C)
ft a
5H »
cu
-H
fa
i?
C3 j»fj
o c
O -H
CU CU
ra o
H
^
CU
ft
cu ft
C JJ ft 0)
S 3 rd JJ
S O ft ra
if; X{ CU nS
JJ JJ £5
, -H ra
£ S ns g
0 SO
3 cu S ^
o *
u
5-j ^
O °
x) J2
!i
3 rrt
li i VJ
m gj
integrated mills using wood fiber
lightweight papers at nonintegrati
at nonintegrated mills (Xa)
W rrl
O g ra
S S SH
10 rH
O f-H
f ^
O Ti
!H 0)
j i
Ti (C
onintegrated mills (Sa) ; filter ai
s (Y«) ; and paperboard at noninteg]
fl rH
r-l
JJ -rl
IB B
ra TS
5-1 (U
0) JJ
ft ns
m 5-i
ft Oi
0) JJ
ra -H
ra rj
-H O
S e
s
M TJ O ft
OJ C ^ rH
4J CIS M-l ^
i 1 CM
~rK T^
fa fl 5^ Ti
cu (d O m
(U O 45 ns
ra i cu u
ra a ft 5^
-H O (d 3
EH a ft ft
,q
r-
CTl
en
rH
^
rH
rH
MH
through 699, edition revised as o
in
ra
j_)
rd
ft
S
rj
_
,t
vr
CU
XI
jj
rt
H
Ti
0)
P!
H
id
JJ
a
o
u
ra
-H
jj
5-1
(d
ft
45
3
ra
to
-rH
m
-------
§430.01 General definitions.
In addition to the definitions set forth in 40 CFR part
401 and 40 CFR 403.3, the following definitions apply to
this part:
(a) Adsorbable organic halides (AOX). A bulk
parameter that measures the total mass of chlorinated
organic matter in water and wastewater.
(b) Annual average. The mean concentration, mass
loading or production-normalized mass loading of a pollutant
over a period of 365 consecutive days (or such other period
of time determined by the permitting authority to be
sufficiently long to encompass expected variability of the
concentration, mass loading, or production-normalized mass
loading at the relevant point of measurement).
(c) Bleach,plant. All process equipment used for
bleaching beginning with the first application of bleaching
agents (e.g., chlorine, chlorine dioxide, ozone, sodium or
calcium hypochlorite, or peroxide), each subsequent
extraction stage, and each subsequent stage where bleaching
agents are applied to the pulp. For mills in Subpart E of
this part producing specialty grades of pulp, the bleach
plant includes process equipment used for the hydrolysis or
extraction stages prior to the first application of (
bleaching agents. Process equipment used for oxygen
delignification prior to the application of bleaching agents
is not part of the bleach plant.
794
-------
(d) Bleach plant effluent. The total discharge of
process wastewaters from the bleach plant from each physical
bleach line operated at the mill, comprising separate acid
and alkaline filtrates or the combination thereof.
(e) Chemical oxygen demand (COD). A bulk parameter
that measures the oxygen-consuming capacity of organic and
inorganic matter present in water or wastewater. It is
expressed as the amount of oxygen consumed from a chemical
oxidant in a specific test.
(f) Elemental chlorine-free (ECF). Any process for
bleaching pulps in the absence of elemental chlorine and
hypochlorite that uses exclusively chlorine dioxide as the
only chlorine-containing bleaching agent.
(g) End of the pipe. The point at which final mill
effluent is discharged to waters of the United States or
introduced to a POTW.
(h) Fiber line. A series of operations employed to
convert wood or other fibrous raw material into pulp. If
the final product is bleached pulp, the fiber line
encompasses pulping, de-knotting, brownstock washing, pulp
screening, centrifugal cleaning, and multiple bleaching and
washing stages.
(i) Minimum level(ML). The level at which the
analytical system gives recognizable signals and an
acceptable calibration point. The following minimum levels
apply to pollutants in this part.
795
-------
Pollutant
2,3,7,8 -TCDD
2,3,7,8-TCDF
Trichlorosyringol
3,4,5 -Trichlorocatechol
3,4, 6 -Trichlorocatechol
3,4,5 -Trichloroguaiacol
3,4, 6 -Trichloroguaiacol
4,5, 6-Trichloroguaiacol
2,4,5 -Trichlorophenol
2,4, 6 -Trichlorophenol
Tetrachlorocatechol
Tetrachloroguaiacol
2,3,4, 6-Tetrachlorophenol
Pentachlorophenol
AOX
Method
1613
1613
1653
1653
1653
1653
1653
1653
1653
1653
1653
1653
1653
1653
1650
Minimum level
10 pg/La
10 pg/La
2.5 ug/Lb
5.0 ug/Lb
5.0 ug/Lb
2.5 ug/Lb
2.5 ug/Lb
2.5 ug/Lb
2.5 ug/Lb
2.5 ug/Lb
5.0 ug/Lb
5 . 0 ug/Lb
2.5 ug/Lb
5.0 ug/Lb
20 ug/Lb
" picograms per liter.
micrograms per liter.
(j) New source. (1) Notwithstanding the criteria
codified at 40 CFR 122.29(b)(1), a source subject to subpart
B or E of this part is a "new source" if it meets the
definition of "new source" at 40 CFR 122.2 and
(i) It is constructed at a site at which no other
source is located; or
(ii) It totally replaces the process or
production equipment that causes the discharge of pollutants
at an existing source, including the total replacement of a
796
-------
fiber line that causes the discharge of pollutants at an
existing source, except as provided in paragraph (j)(2) of
this section; or
(iii) Its processes are substantially independent
of an existing source at the same site. In determining
whether these processes are substantially independent, the
Director shall consider such factors as the extent to which
the new facility is integrated with the existing plant; and
the extent to which the new facility is engaged in the same
general type of activity as the existing source.
(2) The following are examples of changes made by
mills' subject to Subparts B or E of this part that alone do
not cause an existing mill to become a "new source":
(i) Upgrades of existing pulping operations;
(ii) Upgrades or replacement of pulp screening and
washing operations;
(iii) Installation of extended cooking and/or
oxygen delignification systems or other post-digester, pre-
bleaching delignification systems;
(iv) Bleach plant modifications including changes
in methods or amounts of chemical applications, new chemical
applications, installation of new bleaching towers to
facilitate replacement of sodium or calcium hypochlorite,
and installation of new pulp washing systems; or
(v) Total replacement of process or production
equipment that causes the discharge of pollutants at an
797
-------
existing source .(including a replacement fiber line) , but
only if such replacement is performed for the purpose of
achieving limitations that have been included in the
discharger's NPDES permit pursuant to § 430.24(b).
(k) Non-continuous discharger. (1) Except as
provided in paragraph (k)(2) of this section, a
non-continuous discharger is a mill which is prohibited by
the NPDES authority from discharging pollutants during
specific periods of time for reasons other than treatment
plant upset control, such periods being at least 24 hours in
duration. A mill shall not be deemed a non-continuous
discharger unless its permit, in addition to setting forth
the prohibition described above, requires compliance with
the effluent limitations established for non-continuous
dischargers and also requires compliance with maximum day
and average of 30 consecutive days effluent limitations.
Such maximum day and average of 30 consecutive days effluent
limitations for non-continuous dischargers shall be
established by the NPDES authority in the form of
concentrations which reflect wastewater treatment levels
that are representative of the application of the best
practicable control technology currently available, the best
conventional pollutant control technology, or new source
performance standards in lieu of the maximum day and average
of 30 consecutive days effluent limitations for conventional
pollutants set forth in each subpart.
798
-------
(2) A mill is a non-continuous discharger for the
purposes of determining applicable effluent limitations
under Subparts B or E of this part (other than conventional
limits for existing sources) if, for reasons other than
treatment plant upset control (e.g., protecting receiving
water quality), the mill is prohibited by the NPDES
authority from discharging pollutants during specific
periods of time or if it is required to release its
discharge on a variable flow or pollutant loading rate
basis.
(1) POTW. Publicly owned treatment works as defined
at 40 CFR 403.3(o).
(m) Process wastewater. For Subparts B and E only, '
process wastewater is any water that, during manufacturing
or processing, comes into direct contact with or results
from the production or use of any raw material, intermediate
product, finished product, byproduct, or waste product. For
purposes of Subparts B and E of this part, process
wastewater includes boiler blowdown; wastewaters from water
treatment and other utility operations; blowdowns from high
rate (e.g., greater than 98 percent) recycled non-contact
cooling water systems to the extent they are mixed and co-
treated with other process wastewaters; wastewater,
including leachates, from landfills owned by pulp and paper
mills subject to Subparts B or E of this part if the
wastewater is commingled with wastewater from the mill's
799
-------
manufacturing or processing facility; and storm waters from
the immediate process areas to the extent they are mixed and
co-treated with other process wastewaters. For purposes of
this part, contaminated groundwaters from on-site or off-
site groundwater remediation projects are not process
wastewater.
(n) Production. (1) For all limitations and
standards specified in this part except those pertaining to
AOX and chloroform: Production shall be defined as the
annual off-the-machine production (including off-the-machine
coating where applicable) divided by the number of operating
days during that year. Paper and paperboard production
shall be measured at the off-the-machine moisture content,
except for Subpart C of this part (as it pertains to pulp
and paperboard production at unbleached kraft mills
including linerboard or bag paper and other mixed products,
and to pulp and paperboard production using the unbleached
kraft neutral sulfite semi-chemical (cross recovery)
process), and Subparts F and J of this part (as they pertain
to paperboard production from wastepaper from noncorrugating
medium furnish or from corrugating medium furnish) where
paper and paperboard production shall be measured in air-
dry-tons (10% moisture content). Market pulp shall be
measured in air-dry tons (10% moisture). Production shall
be determined for each mill based upon past production
practices, present trends, or committed growth.
800
-------
(2) For AOX and chloroform limitations and
standards specified in Subparts B and E of this part:
Production shall be defined as the annual unbleached pulp
production entering the first stage of the bleach plant
divided by the number of operating days during that year.
Unbleached pulp production shall be measured in air-dried-
metric-tons (10% moisture) of brownstock pulp entering the
bleach plant at the stage during which chlorine or chlorine-
containing compounds are first applied to the pulp. In the
case of bleach plants that use totally chlorine free
bleaching processes, unbleached pulp production shall be
measured in air-dried-metric tons (10% moisture) of
brownstock pulp entering the first stage of the bleach plant
from which wastewater is discharged. Production shall be
determined for each mill based upon past production
practices, present trends, or committed growth.
(o) TCDD. 2,3,7,8-tetrachlorodibenzo-p-dioxin.
(p) TCDF. 2,3,7,8-tetrachlorodibenzo-p-furan.
(q) Totally chlorine-free (TCP) bleaching. Pulp
bleaching operations that are performed without the use of
chlorine, sodium hypochlorite, calcium hypochlorite,
chlorine dioxide, chlorine monoxide, or any other
chlorine-containing compound.
(r) Wet Bar-king. Wet barking operations shall be
defined to include hydraulic barking operations and wet drum
barking operations which are those drum barking operations
801
-------
that use substantial quantities of water in either water
sprays in the barking drums or in a partial submersion of
the drums in a "tub" of water.
§ 430.02 Monitoring requirements.
This section establishes minimum monitoring frequencies
for certain pollutants. Where no monitoring frequency is
specified in this section or where the duration of the
minimum monitoring frequency has expired under paragraphs
(b)- (e) of this section, the permit writer or pretreatment
control authority shall determine the appropriate monitoring
frequency in accordance with 40 CFR 122.44 (i) or 40 CFR Part
403, as applicable.
(a) BAT, NSPS, PSES, and PSNS-monitoring frequency for
chlorinated organic pollutants. The following monitoring
frequencies apply to discharges subject to Subpart B or
Subpart E of this part:
802
-------
CAS
number
1198556
2539175
2539266
2668248
32139723
56961207
57057837
58902
60712449
87865
88062
95954
1746016
51207319
67663
59473040
Pollutant
Tetrachlorocatechol
Tetrachloroguaiacol
Trichlorosyringol
4 , 5 , 6-trichloroguaiacol
3 , 4 , 6-trichlorocatechol
3 , 4 , 5 - tri chlorocatechol
3 , 4 , 5 - trichloroguaiacol
2,3,4,6 - tetrachlorophenol
3 ,4, 6-trichloroguaiacol
Pentachlorophenol a
2,4, 6-trichlorophenol <*
2,4; 5 - trichlorophenol
2,3,7,8-TCDD
2,3,7,8-TCDF
chloroform e
AOX f
Minimum Monitoring
Frequency
non-TCF a
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
weekly
daily
TCP b
C
c
C
c
c
c
c
c
c
c
c
c
c
c
c
none
specified
non-TCF: Pertains to any fiber line that does not use exclusively
TCF bleaching processes.
TCF: Pertains to any fiber line that uses exclusively TCF
bleaching processes, as disclosed by the discharger in its permit
application under 40 CFR 122.21(g)(3) and certified under 40 CFR
122.22 or, for indirect dischargers, as reported to the
pretreatment control authority under 40 CFR 403.12(b),(d), or (e).
This regulation does not specify a limit for this pollutant for
TCF bleaching processes.
Monitoring frequency does not apply to this compound when used as
a biocide. The permitting or pretreatment control authority must
determine the appropriate monitoring frequency for this compound,
when used as a biocide, under 40 CFR 122.44(i) or 40 CFR Part 403,
as applicable.
803
-------
CAS number
1198556
2539175
2539266
2668248
32139723
56961207
57057837
58902
60712449
87865
88062
95954
1746016
51207319
67663
Pollutant
Tetrachlorocatechol
Tetrachloroguiacol
Trichlorosyringol
4,5, 6-trichloroguaiacol
3,4, 6-trichlorocatechol
3,4, 5-trichlorocatechol
3,4,5 - trichloroguaiacol
2,3,4, 6 - tetrachlorophenol
3,4, 6-trichloroguaiacol
Pentachlorophenol e
2,4, 6 - trichlorophenol e
2,4, 5 -trichlorophenol e
2,3,7,8-TCDD
2,3,7,8-TCDF
Chloroform
Minimum Monitoring
Frequency
non-ECFa
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
weekly
Advanced
ECF b'f
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
monthly
TCF c
d
d
d
d
d
d
d
d
d
d
d
d
d
d
d
non-ECF: Pertains to any fiber line that does not use exclusively
ECF or TCF bleaching processes.
Advanced ECF: Pertains to any fiber line that uses exclusively
Advanced ECF bleaching processes, or exclusively ECF and TCF
bleaching processes as disclosed by the discharger in its permit
application under 40 CFR 122.21(g)(3) and certified under 40 CFR
122.22. Advanced ECF consists of the use of extended
delignification or other technologies that achieve at least the
Tier I performance levels specified in § 430.24(b) (4) (i) .
TCF: Pertains to any fiber line that uses exclusively TCF
bleaching processes, as disclosed by the discharger in its permit
application under 40 CFR 122.21(g)(3) and certified under 40 CFR
122.22.
This regulation does not specify a limit for this pollutant for
TCF bleaching processes.
Monitoring frequency does not apply to this compound when used as
a biocide. The permitting authority must determine the
appropriate monitoring frequency for this compound, when used as a
biocide, under 40 CFR 122.44(i).
805
-------
f Monitoring requirements for these pollutants by mills certifying
as Advanced ECF in their NPDES permit application or other
communication to the permitting authority will be suspended after
one year of monitoring. The permitting authority must determine
the appropriate monitoring frequency for these pollutants beyond
that time under 40 CFR 122.44 (i).
(d) Reduced monitoring frequencies for AOX under the
Voluntary Advanced Technology Incentives Program (year one).
The following monitoring frequencies apply to direct
dischargers enrolled in the Voluntary Advanced Technology
Incentives Program established under Subpart B of this part
for a duration of one year after achievement of the
applicable BAT limitations specified in § 430.24(b) (4) (i) or
NSPS specified in § 430.25(c) (2) :
CAS
Number
59473040
Pollutant
AOX
Non-ECF, any
Tier a
daily
Advanced
ECF, any
Tier b
weekly
TCP, any
Tier c
none
specified
a non-ECF: Pertains to any fiber line that does not use exclusively
ECF or TCF bleaching processes.
b Advanced ECF: Pertains to any fiber line that uses exclusively
Advanced ECF bleaching processes or exclusively ECF and TCF
bleaching processes, as disclosed by the discharger in its permit
application under 40 CFR 122.21(g)(3) and certified under 40 CFR
122.22. Advanced ECF consists of the use of extended
delignification or other technologies that achieve at least the
Tier I performance levels specified in § 430.24(b) (4) (i) .
0 TCF: Pertains to any fiber line that uses exclusively TCF
bleaching processes, as disclosed by the discharger in its permit
application under 40 CFR 122.21(g)(3) and certified under 40 CFR
122:22.
(e) Reduced monitoring frequencies for AOX under the
Voluntary Advanced Technology Incentives Program (years two
through five). The following monitoring frequencies apply
806
-------
to mills enrolled in the Voluntary Advanced Technology
Incentives Program established under Subpart B of this part
for a duration of four years starting one year after
achievement of the applicable BAT limitations specified in §
430.24(b) (4) (i) or NSPS specified in § 430.25 (c) (2) :
807
-------
1
fa
Z
0)
u
Pi
J>
T)
d
tt)
u
crj
!>
d
0)
0
s
1
fa
u
1
a
o
Pi
JJ
JJ
rH
rH
o
ft
w
rtj
0
tl
tt)
-H
EH
pT
cd
H
H
H
1
rl
CJ tt)
fa -H
W EH
.a
M
I-H
5^
fa 0)
a -H
_Q
H
1
rl
fa tt)
0 -H
H EH
M
tt)
-rl
EH
Sw,
Pi
cd
rl
tt)
jj
^j
*
d
tt)
-rl
M-l
-H
tt) U
fi 0)
0 ft
P! to
rH
rH
cd
£j
a
m
rH
rl
tt)
rl
cd
3
K*1
rH
43
JJ
Pi
i
^,
rH
-H
cd
X
0
0
0
n
5
a\
Lfl
cn
«
-rl
45
U
(d
tt)
rH
43
fe
O
rl
O
fa
O
m
^"i
rH
0)
-H
Ol
rj
r-H
o
X
4)
(D
w
j3
Jj
0
to
tt>
O
JJ
cd
r]
| 1
0)
c
-H
i-H
^
0)
-H
M-l
£x,
pj
(d
o
4->
ta
C3
-rl
cd
4J
D
ft
fa
u
w
1
E3
O
d
01
a)
01
01
.
Ol
tt)
to
01
tt)
u
o
ft
cn
PJ
-H
r{
U
cd
tt>
rH
Q
fa
CJ
EH
T3
a
cd
fa
u
H
^t
rH
^
-H
01
0
rH
O
X
tt)
£_j
O
consists
fa
u
H
d
0)
o
a
cd
d
=1!
CM
CM
CM
CN
H
0!
fa
O
o
^j*
rl
tt)
d
Pi
d
a)
-H
M-l
-H
JJ
rl
U
d
s
CB
^.^
(y^
^^
01
*
i-H
CM
CM
CM
i-H
DJ
fa
U
o
*3*
rl
D
d
^J
Pi
o
-H
4J
cd
CJ
-H
rH
ft
ft
cd
H
in
tt)
H
EH
0
4J
4J
to
cd
D
rH
JJ
cd
tt)
J>
0)
-H
rj
U
cd
[J
cd
jj
Ol
-H
01
0
rH
U
-------
(3) Immediate Process Area: The location at the mill
where pulping, screening, knotting, pulp washing, pulping
liquor concentration, pulping liquor processing, and
chemical recovery facilities are located, generally the
battery limits of the aforementioned processes. "Immediate
process area" includes spent pulping liquor storage and
spill control tanks located at the mill, whether or not they
are located in the immediate process area.
(4) Intentional Diversion: The planned removal of
spent pulping liquor, soap, or turpentine from equipment
items in spent pulping liquor, soap, or turpentine service
by the mill for any purpose including, but not limited to,
maintenance, grade changes, or process shutdowns.
(5) Mill: The owner or operator of a direct or
indirect discharging pulp, paper, or paperboard
manufacturing facility subject to this section.
(6) Senior Technical Manager: The person designated by
the mill manager to review the BMP Plan. The senior
technical manager shall be the chief engineer at the mill,
the manager of pulping and chemical recovery operations, or
other such responsible person designated by the mill manager
who has knowledge of and responsibility for pulping and
chemical recovery operations.
(7) Soap: The product of reaction between the alkali
in kraft pulping liquor and fatty acid portions of the wood,
809
-------
turpentine that do occur. BMPs must be developed according
to best engineering practices and must be implemented in a
manner that takes into account the specific circumstances at
each mill. The BMPs are as follows:
(1) The mill must return spilled or diverted spent
pulping liquors, soap, and turpentine to the process to the
maximum extent practicable as determined by the mill,
recover such materials outside the process, or discharge
spilled or diverted material at a rate that does not disrupt
the receiving wastewater treatment system.
(2) The mill must establish a program to identify and
repair leaking equipment items. This program must include:
(i) Regular visual inspections (e.g., once per
day) of process areas with equipment items in spent pulping
liquor, soap, and turpentine service;
(ii) Immediate repairs of leaking equipment
items, when possible. Leaking equipment items that cannot
be repaired during normal operations must be identified,
temporary means for mitigating the leaks must be provided,
and the leaking equipment items repaired during the next
maintenance outage;
(iii) Identification of conditions under which
production will be curtailed or halted to repair leaking
equipment items or to prevent pulping liquor, soap, and
turpentine leaks and spills; and
(iv) A means for tracking repairs over time to
811
-------
identify those equipment items where upgrade or replacement
may be warranted based on frequency and severity of leaks,
spills, or failures.
(3) The mill must operate continuous, automatic
monitoring systems that the mill determines are necessary to
detect and control leaks, spills, and intentional diversions
of spent pulping liquor, soap, and turpentine. These
monitoring systems should be integrated with the mill
process control system and may include, e.g., high level
monitors and alarms on storage tanks; process area
conductivity (or pH) monitors and alarms; and process area
sewer, process wastewater, and wastewater treatment plant
conductivity (or pH) monitors and alarms.
(4) The mill must establish a program of initial and
refresher training of operators, maintenance personnel, and
other technical and supervisory personnel who have
responsibility for operating, maintaining, or supervising
the operation and maintenance of equipment items in spent
pulping liquor, soap, and turpentine service. The refresher
training must be conducted at least annually and the
training program must be documented.
(5) The mill must prepare a brief report that
evaluates each spill of spent pulping liquor, soap, or
turpentine that is not contained at the immediate process
area and any intentional diversion of spent pulping liquor,
soap, or turpentine that is not contained at the immediate
812
-------
containment for spent pulping liquor bulk storage tanks.
(8) The mill must install and maintain secondary
containment for turpentine bulk storage tanks.
(9) The mill must install and maintain curbing, diking
or other means of isolating soap and turpentine processing
and loading areas from the wastewater treatment facilities.
(10) The mill must conduct wastewater monitoring to
detect leaks and spills, to track the effectiveness of the
BMPs, and to detect trends in spent pulping liquor losses.
Such monitoring must be performed in accordance with
paragraph (i) of this section.
(d) Requirement to develop a BMP Plan. (1) Each mill
subject to this section must prepare and implement a BMP
Plan. The BMP Plan must be based on a detailed engineering
review as described in paragraphs (d)(2) and (3) of this
section. The BMP Plan must specify the procedures and the
practices required for each mill to meet the requirements of
paragraph (c) of this section, the construction the mill
determines is necessary to meet those requirements including
a schedule for such construction, and the monitoring program
(including the statistically derived action levels) that
will be used to meet the requirements of paragraph (i) of
this section. The BMP Plan also must specify the period of
time that the mill determines the action .levels established
under paragraph (h) of this section may be exceeded without
triggering the responses specified .in paragraph (i) of this
814
-------
section.
(2) Each mill subject to this section must conduct a
detailed engineering review of the pulping and chemical
recovery operations -- including but not limited to process
equipment, storage tanks, pipelines and pumping systems,
loading and unloading facilities, and other appurtenant
pulping and chemical recovery equipment items in spent
pulping liquor, soap, and turpentine service -- for the
purpose of determining the magnitude and routing of
potential leaks, spills, and intentional diversions of spent
pulping liquors, soap, and turpentine during the following
periods of operation:
(i) Process start-ups and shut downs;
(ii) Maintenance;
(iii) Production grade changes;
(iv) Storm or other weather events;
(v) Power failures; and
(vi) Normal operations.
(3) As part of the engineering review, the mill must
determine whether existing spent pulping liquor containment
facilities are of adequate capacity for collection and
storage of anticipated intentional liquor diversions with
sufficient contingency for collection and containment of
spills. The engineering review must also consider:
(i) The need for continuous, automatic monitoring
systems to detect and control leaks and spills of spent
815
-------
pulping liquor, soap, and turpentine;
(ii) The need .for process wastewater diversion
facilities to protect end-of-pipe wastewater treatment
facilities from adverse effects of spills and diversions of
spent pulping liquors, soap, and turpentine;
(iii) The potential for .contamination of storm water
from the immediate process areas; and
(iv) The extent to which segregation and/or collection
and treatment of contaminated storm water from the immediate
process areas is appropriate.
(e) Amendment of BMP Plan. (1) Each mill subject to
this section must amend its BMP Plan whenever there is a
change in mill design, construction, operation, or
maintenance that materially affects the potential for leaks
or spills of spent pulping liquor, turpentine, or soap from
the immediate process areas.
(2) Each mill subject to this section must complete a
review and evaluation of the BMP Plan five years after the
first BMP Plan is prepared and, except as provided in
paragraph (e)(1) of this section, once every five years
thereafter. As a result of this review and evaluation, the
mill must amend the BMP Plan within three months of the
review if'the mill determines that any new or modified
management practices and engineered controls are necessary
to reduce significantly the likelihood of spent pulping
liquor, soap, and turpentine leaks, spills, or intentional
816
-------
(ii) Records of initial and refresher training
conducted in accordance with paragraph (c)(4) of this
section;
(iii) Reports prepared in accordance with
paragraph (c)(5) of this section; and
(iv) Records of monitoring required by paragraphs
(c)(10) and (i) of this section.
(h) Establishment of wastewater treatment system
influent action levels. (1) Each mill subject to this
section must conduct a monitoring program, described in
paragraph (2) of this section, for the purpose of defining
wastewater treatment system influent characteristics (or
action levels), described in paragraph (3) of this section,
that will trigger requirements to initiate investigations on
BMP effectiveness and to take corrective action.
(2) Each mill subject to this section must employ the
following procedures in order to develop the action levels
required by paragraph (h) of this section:
(i) Monitoring parameters. The mill must collect
24-hour composite samples and analyze the samples for a
measure of organic content (e.g., Chemical Oxygen Demand
(COD) or Total Organic Carbon (TOC)). Alternatively, the
mill may use a measure related to spent pulping liquor
losses measured continuously and averaged over 24 hours
(e.g., specific conductivity or color).
(ii) Monitoring locations. For direct
818
-------
dischargers, monitoring must be conducted at the point
influent enters the wastewater treatment system. For
indirect dischargers monitoring must be conducted at the
point of discharge to the POTW. For the purposes of this
requirement, the mill may select alternate monitoring
point(s) in order to isolate possible sources of spent
pulping liquor, soap, or turpentine from other possible
sources of organic wastewaters.that are tributary to the
wastewater treatment facilities (e.g., bleach plants, paper
machines and secondary fiber operations).
(3) By the date prescribed in paragraph (j)(1)(iii) of
this section, each existing discharger subject to this
section must complete an initial six-month monitoring
program using the procedures specified in paragraph (h)(2)
of this section and must establish initial action levels
based on the results of that program. A wastewater
treatment influent action level is a statistically
determined pollutant loading determined by a statistical
analysis of six months of daily measurements. The action
levels must consist of a lower action level, which if
exceeded will trigger the investigation requirements
described in paragraph (i) of this section, and an upper
action level, which if exceeded will trigger the corrective
action requirements described in paragraph (i) of this
section.
819
-------
(4) By the date prescribed in paragraph (j)(1)(vi) of
this section, each existing discharger must complete a
second six-month monitoring program using the procedures
specified in paragraph (h) (2) of this section and must
establish revised action levels based on the results of that
program. The initial action levels shall remain in effect
until replaced by revised action levels.
(5) By the date prescribed in paragraph (j)(2) of this
section, each new source subject to this section must
complete a six-month monitoring program using the procedures
specified in paragraph (h) (2) of this section and must
develop a lowe±- action level and an upper action level based
on the results of that program.
(6) Action levels developed under this paragraph must
be revised using six months of monitoring data after any
change in mill design, construction, operation, or
maintenance that materially affects the potential for leaks
or spills of spent pulping liquor, soap, or turpentine from
the immediate process areas.
(i) Monitoring, corrective action, and reporting
requirements. (1) Each mill subject to this section must
conduct daily monitoring of the influent to the wastewater
treatment system in accordance with the procedures described
in paragraph (h)(2) of this section for the purpose of
detecting leaks and spills, tracking the effectiveness of
the BMPs, and detecting trends in spent pulping liquor
820
-------
once per year.
(j) Compliance deadlines. (1) Existing direct and
indirect dischargers. Except as provided in paragraph
(j)(2) of this section for new sources, indirect discharging
mills subject to this section must meet the deadlines set
forth below. Except as provided in paragraph (j)(2) of this
section for new sources, NPDES permits must require direct
discharging mills subject to this section to meet the
deadlines set forth below. If a deadline set forth below
has passed at the time the NPDES permit containing the BMP
requirement is issued, the NPDES permit must require
immediate compliance with such BMP requirement(s).
(i) Prepare BMP Plans and certify to the
permitting or pretreatment authority that the BMP Plan has
been prepared in accordance with this regulation not later
than [insert date 12 months after date of publication] ;
(ii) Implement all BMPs specified in paragraph
(c) of this section that do not require the construction of
containment or diversion structures or the installation of
monitoring and alarm systems not later than [insert date 12
months after date of publication].
(iii) Establish initial action levels required by
paragraph (h)(3) of this section not later than [insert date
12 months after date of publication].
(iv) Commence .operation of any new or upgraded
822
-------
after commencement of discharge, based on six months of
monitoring data obtained prior to that date in accordance
with the procedures specified in paragraph (h)(2) of this
section.
Subpart A-Dissolving Kraft Subcategory
§ 430.10 Applicability; description of the dissolving kraft
subcategory.
The provisions of this subpart apply to discharges
resulting from the production of dissolving pulp at kraft
mills.
§ 430.11 Specialized definitions.
For the purpose of this subpart, the general
definitions, abbreviations, and methods of analysis set
forth in 40 CFR part 401 and § 430.01 of this part shall
apply to this subpart.
§ 430.12 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), except that non-continuous
dischargers shall not be subject to the maximum day and
824
-------
average of 30 consecutive days limitations but shall be
subject to annual average effluent limitations:
Subpart A
Pollutant
or
pollutant
property
BODS
TSS
PH
BPT effluent limitations
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
23.6
37.3
(J)
Average of daily
values for 30
consecutive days
12.25
20.05
0)
Non-continuous
dischargers
6.88
11.02
H
the range of 5.0 to 9.0 at all times.
(b) The following limitations establish the quantity
or quality of pollutants or pollutant properties, controlled
by this section, resulting from the use of wet barking
operations, which may be discharged by a. point source
subject to the provisions of this subpart. These
limitations are in addition to the limitations set forth in
paragraph (a) of this section and shall be calculated using
the proportion- of the mill's total production due to use of
logs which are subject to such operations. 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:
825
-------
Subpart A
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
3.2
6.9
C1)
Average of daily
values for 30
consecutive days
1.7
3.75
(l)
Non-continuous
dischargers
(Annual Average)
0.95
2.0
t1)
Within the range of 5.0 to 9.0 at all times.
(c) The following limitations establish the quantity
or quality of pollutants or pollutant parameters, controlled
by this section, resulting from the use of log washing or
chip washing operations, which may be discharged by a point
source subject to the provisions of this subpart. These
limitations are in addition to the limitations set forth in
paragraph (a) of this section and shall be calculated using
the proportion of the mill's total production due to use of
logs and/or chips which are subject to such operations. Non-
continuous dischargers shall not be subject to the maximum
day and average of 30 consecutive days limitations, but
shall be subject to the annual average effluent limitations:
826
-------
Subpart A
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.35
0.70
(x)
Average of daily
values for 30
consecutive days
0.2
0.4
C1)
Non- continuous
dischargers
(Annual Average)
0.1
0.2
(l)
xWithin the range of 5.0 to 9.0 at all times.
(d) The following limitations establish the quantity
or quality of pollutants or pollutant properties, controlled
sr
by this section, resulting from the use of log flumes or log
ponds, which may be discharged by a point source subject to
the provisions of this subpart. These limitations are in
addition to the limitations set forth in paragraph (a) of
this section and shall be calculated using the proportion of
the mill's total production due to use of logs which are
subject to such operations. Non-continuous dischargers
shall not be subject to the maximum day and average of 30
consecutive days limitations but shall be subject to the
annual average effluent limitations:
827
-------
Subpart A
Pollutant
or
pollutant
property
BODS
TSS
PH
BPT effluent limitations
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.6
1.45
(x)
Average of daily
values for 30
consecutive days
0.35
0.8
(l)
Non-continuous
dischargers
(Annual Average)
0.2
0.4
H
xWithin the range of 5.0 to 9.0 at all times.
§ 430.13 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 § 430.12 of this subpart for the best practicable control
technology currently available (BPT) .
§ 430.14 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
828
-------
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 Ib) 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:
Subpart A
Pollutant or
pollutant property
Pentachlorophenpl
Trichlorophenol
BAT effluent limitations
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0025
0.016
Milligrams/liter
(0.011) (55.1)/y
(0.068) (55.1)/y
y = wastewater discharged in kgal per ton of product
§ 430.15 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
829
-------
average effluent limitations. Also, for non-continuous
dischargers, concentration limitations (mg/1) 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:
Subpart A
Pollutant or
pollutant property
BODS
TSS
pH
Pentachlorophenol
Tr i chlorophenol
NSPS
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
15.6
27.3
(l )
Average of
daily
values for
30
consecutive
days
8.4
14.3
t1 )
Non - cont inuous
Dischargers
(Annual Average)
4.4
7.5
(x )
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0025
0.016
Milligrams/liter
(0.012) (50.7)/y
(0.074) (50.7)/y
y = wastewater discharged in kgal per ton at all times
the range of 5.0 to 9.0 at all times.
830
-------
§ 430.16 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 A
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSES
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.011) (55.1)/y
(0.082) (55. l)/y
Kg/kkg (or pounds per
1,000 Ib) of product8
0.0025
0.019
y = wastewater discharged in kgal per ton of product
aThe following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
§ 430.17 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
831
-------
biocides. Permittees not using chlorophenolic-containing
biocid.es must certify to the permit-issuing authority that
they are not using these biocides:
Subpart A
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSNS
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.012) (50. 7) /y
(0.089) (50.7)/y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0025
0.019
y = wastewater discharged in kgal per ton of product
"The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
Subpart B-Bleached Papergrade Kraft and Soda Subcategory
§ 430.20 Applicability; description of the bleached
papergrade kraft and soda subcategory.
The provisions of this subpart apply to discharges
resulting from: the production of market pulp at bleached
kraft mills; the integrated production of paperboard, coarse
paper, and tissue paper at bleached kraft mills; the
integrated production of pulp and fine papers at bleached
kraft mills; and the integrated production of pulp and paper
at soda mills.
§ 430.21 Specialized definitions.
(a) The general definitions, abbreviations, and
methods of analysis set forth in 40 CFR part 401 and §
430.01 of this part apply to this subpart.
832
-------
(b) Baseline BAT limitations or NSPS means the BAT
limitations specified in §430.24(a)(1) or (2), as
applicable, and the NSPS specified in § 430.25(b)(1) or (2),
as applicable, that apply to any direct discharger that is
not "enrolled" in the "Voluntary Advanced Technology
Incentive's Program. "
(c) Enroll means to notify the permitting authority
that a mill intends to participate in the "Voluntary
Advanced Technology Incentives Program." A mill can enroll
by indicating its intention to participate in the program
either as part of its application for a National Pollutant
Discharge Elimination System (NPDES) permit, or through
separate correspondence to the permitting authority as long
as the mill signs the correspondence in accordance with 40
CPR 122.22.
(d) Existing effluent quality means the level at which
the pollutants identified in § 430.24(a)(1) are present in
the. effluent of a mill "enrolled" in the "Voluntary Advanced
Technology Incentives Program."
(e) Kappa number is a measure of the lignin content in
unbleached pulp, determined after pulping and prior to
bleaching.
(f) Voluntary Advanced Technology Incentives Program
is the program established under § 430.24(b) (for existing
direct dischargers) and § 430.25 (c) (for new direct
dischargers) whereby participating mills agree to accept
833
-------
enforceable effluent limitations and conditions in their
NPDES permits that are more stringent than the "baseline BAT
limitations or NSPS" that would otherwise apply, in exchange
for regulatory- and enforcement-related rewards and
incentives.
§ 430.22 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 B
Pollutant
or
pollutant
parameter
BODS
TSS
pH
BPT effluent limitations for
bleached kraft facilities where market pulp is produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
15.45
30.4
(*)
Average of daily
values for 30
consecutive days
8.05
16.4
t1)
Non- continuous
dischargers
(Annual Average)
4.52
9.01
(l)
^Within the range of 5.0 to 9.0 at all times.
834
-------
Subpart B
Pollutant
or
pollutant
parameter
BODS
TSS
PH
BPT effluent limitations for
bleached kraft facilities where paperboard, coarse paper,
and tissue paper are produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
13.65
24.0
(l)
Average of daily
values for 30
consecutive days
7.1
12 . 9
(*) '
Non-continuous
di s chargers
(Annual Average)
3.99
7.09
t1)
the range of 5.0 to 9.0 at all times.
Subpart B
Pollutant
or
pollutant
parameter
BOD5
TSS
pH
BPT effluent limitations for
bleached kraft facilities where pulp and fine papers are
produced
'Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
10.6
22.15
t1)
Average of daily
values for 30
consecutive days
5.5
11.9
(x)
Non-continuous
dischargers
(Annual Average)
3.09
6.54
(x)
Within the range of 5.0 to 9.0 at all times.
835
-------
Subpart B
Pollutant
or
pollutant
parameter
BODS
TSS
pH
BPT effluent limitations for
soda facilities where pulp and paper are produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any
1 day
13.7
24.5
(*)
Average of daily
values for 30
consecutive days
7.1
13.2
(x)
Non-continuous
dischargers
(Annual Average)
3.99
7.25
t1)
the range of 5.0 to 9.0 at all times.
(b) The following limitations establish the quantity
or quality of pollutants or pollutant properties, controlled
by this section, resulting from the use of wet barking
operations, which may be discharged by a point source
subject to the provisions of. this subpart. These
limitations are in addition to the limitations set forth in
paragraph (a) of this section and shall be calculated using
the proportion of the mill's total production due to use of
logs which are subject to such operations:
836
-------
Subpart B
Pollutant
or
pollutant
parameter
BODS
TSS
pH
BPT effluent limitations for
bleached kraft facilities where market pulp is produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1 day
2.3
5.3
(x)
Average of daily
values for 30
consecutive days
1.2
2.85
H
Non - cont inuous
dischargers
(Annual Average)
0.70
1 . 55
(a)
Within the range of 5.0 to 9.0 at all times.
Subpart B
Pollutant
or
pollutant
parameter
BODS
TSS
PH
BPT effluent limitations for
bleached kraft facilities where paperboard, coarse paper,
and tissue paper are produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
2.25
5.75
t1)
Average of daily
values for 30
consecutive days
1.2
3.1
t1)
Non-continuous
dischargers
(Annual Average)
0.65
1.70
(*)
xWithin the
837
-------
Subpart B
Pollutant
or
pollutant
parameter
BODS
TSS
pH
BPT effluent limitations for
bleached kraf t facilities where pulp and fine papers ' are
produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
1.95
5.3
t1)
Average of daily
values for 30
consecutive days
1.0
2.85
C1)
Non-conti nuou s
dischargers
(Annual Average)
0.55
1.55
(l)
Within the range of 5.0 to 9.0 at all times.
Subpart B
Pollutant
or
pollutant
parameter
BOD5
TSS
pH
BPT effluent limitations for
soda facilities where pulp and papers are produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
2.05
5.25
(l)
Average of daily
values for 30
consecutive days
1.1
2.8
(l)
Non- continuous
dischargers
(Annual Average)
0.60
1.55
H
aWithin the range of 5.0 to 9.0 at all times.
(c) The following limitations establish the quantity
or quality of pollutants or pollutant parameters, controlled
by this section, resulting from the use of log washing or
chip washing operations, which may be discharged by a point
source subject to the provisions of this subpart. These
limitations are in addition to the limitations set forth in
paragraph (a) of this section and shall be calculated using
838
-------
the proportion of the mill's total production due to use of
logs and/or chips which are subject to such operations:
Subpart B
Pollutant
or
pollutant
parameter
BODS
TSS
pH
BPT effluent limitations for
bleached kraft facilities where market pulp is produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.2
0.6
H
Average of daily
values for 30
consecutive days
0.1
0.3
H
Non - cont inuous
dischargers
(Annual Average)
0.1
0.15
H
^Within the range of 5.0 to 9.0 at all times.
Subpart B
Pollutant
or
pollutant
parameter
BODS
TSS
pH
BPT effluent limitations for
bleached kraft facilities where paperboard, coarse paper,
and tissue paper are produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.25
0.65
H
Average of daily
values for 30
consecutive days
0.15
0.35- -
n
Non-continuous
dischargers
(Annual Average)
0.05
0.20
(x)
"Within the range, of 5.0 to 9.0 at all times.
839
-------
Subpart B
Pollutant
or
pollutant
parameter
BODS
TSS
PH
BPT effluent limitations for
bleached kraft facilities where pulp and fine papers are
produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.2
0.55
t1)
Average of daily
values for 30
consecutive days
0.1
0.3
(:) '.
Non - c ont i nuou s
dischargers
(Annual Average)
0.05
0.15
C1)
Within the range of 5.0 to 9.0 at all times.
Subpart B
Pollutant
or
pollutant
parameter
BODS
TSS
pH
BPT effluent limitations for
soda facilities where pulp and papers are produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.15
0.5
(a)
Average of daily
values for 30
consecutive days
0.1
0.25
(*)
Non- continuous
dischargers
(Annual Average)
0.05
0.15
H
xWithin the range of 5.0 to 9.0 at all times.
(d) The following limitations establish the quantity
or quality of pollutants or pollutant properties, controlled
by this section, resulting from the use of log flumes or log
ponds, which may be discharged by a point source subject to
the provisions of this subpart. These limitations are in
addition to the limitations set forth in paragraph (a) of
840
-------
this section and-shall be calculated using the proportion of
the mill's total production due to use of logs which are
subject to such operations:
Subpart B
Pollutant
or
pollutant
parameter
BODS
TSS
PH
BPT effluent limitations for
bleached kraft facilities where market pulp is produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.4
1.15
H
Average of daily
values for 30
consecutive days
0.2
0.6
(x)
Non- continuous
dischargers
(Annual Average)
0.15
0.35
(*)
Within the range of 5.0 to 9.0 at all times.
Subpart B
Pollutant
or
pollutant
parameter
BODS
TSS
PH
BPT effluent limitations for
bleached kraft facilities where paperboard, coarse paper,
and tissue paper are produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.45
1.25
(l)
Average of daily
values for 30
consecutive days
0.25
0.7
C1)
Non- continuous
di s chargers
(Annual Average)
0.10
0.35
t1')
1Wxthin the range of 5.0 to 9.0 at all times.
841
-------
Subpart B
Pollutant
or
pollutant
parameter
BODS
TSS
PH
BPT effluent limitations for
bleached kraft facilities where pulp and fine papers are
produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.35
1.15
n
Average of daily
values for 30
consecutive days
0.2
0.6
(l)
Non-continuous
dischargers
(Annual Average)
0.10
0.30
(a)
Within the range of 5.0 to 9.0 at all times.
Subpart B
Pollutant
or
pollutant
parameter
BODS
TSS
PH
BPT effluent limitations for
soda facilities where pulp and papers are produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.3
1.1
H
Average of daily
values for 30
consecutive days
0.2
0.55
(J)
Non- continuous
dischargers
(Annual Average)
0.10
0.35
H
xWithin the range of 5.0 to 9.0 at all times.
§ 430.23 Effluent limitations 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 must achieve
842
-------
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 in § 430.22
of this subpart for the best practicable control technology
currently available (BPT).
§ 430.24 Effluent limitations representing the degree of
effluent reduction attainable by the application of 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 must achieve
the following effluent limitations representing the degree
of effluent reduction attainable by the application of the
best available technology economically achievable (BAT).
(a) Except as provided in paragraph (b) of this
section--(1) the following effluent limitations apply with
respect to each fiber line that does not use an exclusively
TCP bleaching process, as disclosed by the discharger in its
NPDES permit application under 40 CFR 122.21(g)(3) and
certified under 40 CFR 122.22:
843
-------
Subpart B
Pollutant-
or
pollutant property
TCDD
TCDF
Chloroform
Trichlorosyringol
3,4,5-
trichlorocatechol
3,4,6-
trichlorocatechol
3,4,5-
trichloroguaiacol
3,4,6-
trichloroguaiacol
4,5,6-
trichloroguaiacol
2,4, 5-trichlorophenol
2,4, 6-trichlorophenol
Tetrachlorocatechol
Tetrachloroguaiacol
2,3,4,6-
tetrachlorophenol
Pentachlorophenol
AOX
COD
BAT effluent limitations
Maximum for any
1 day
-------
This regulation does not specify this type of limitation for this
pollutant; however, permitting authorities may do so as
appropriate.
picograms per liter.
grams per 1,000 kilograms (g/kkg).
[Reserved].
(2) The following effluent limitations apply with
respect to each fiber line that uses exclusively TCF
bleaching processes, as disclosed by the discharger in its
NPDES permit application under 40 CFR 122.21(g)(3) and
certified under 40 CFR 122.22:
Subpart B
Pollutant or
pollutant
property
AOX
COD
BAT effluent limitations (TCF)
Continuous dischargers
Maximum for
any 1 day
Monthly
average
Non-continuous
dischargers
Maximum for
any 1 day
Annual
Average
kg/kkg(or pounds per 1,000 Ib) of product
-------
quality or the discharger's current effluent limitations
established under CWA section 301(b)(2), whichever are more
stringent, for the pollutants identified in paragraph (a)(1)
of this section (with the exception of COD). For AOX, the
permitting authority must determine existing effluent
quality for each fiber line enrolled in the Voluntary
Advanced Technology Incentives Program at the end of the
pipe based on loadings attributable to that fiber line. For
the remaining pollutants, with the exception of COD, the
permitting authority must determine existing effluent
quality for each fiber line enrolled in the Voluntary
Advanced Technology Incentives Program at the point where
the wastewater containing those pollutants leaves the bleach
plant. These limitations must be recalculated each time the
NPDES permit of a discharger enrolled in the Voluntary
Advanced Technology Incentives Program is reissued, up to:
(i) [insert date 6 years from date of
publication] for all pollutants in paragraph (a)(1) of this
section except AOX; and
(ii) The date specified in paragraph
(b) (4) (ii) of this section for achieving the applicable AOX
limitation specified in paragraph (b) (4) (i) .
(2) Best Professional Judgment Milestones:
Narrative or numeric limitations and/or special permit
conditions, as appropriate, established by the permitting
846
-------
authority on the basis of his or her best professional
judgment that reflect reasonable interim milestones toward
achievement of the effluent limitations specified in
paragraphs (b)(3) and (b)(4) of this section, as applicable.
(3) Six-year Milestones: By [insert date six
years from the date of publication], all dischargers
enrolled in the Voluntary Advanced Technology Incentives
Program must achieve the following:
(i) The effluent limitations specified in
paragraph (a)(1) of this section, except that, with respect
to AOX, dischargers subject to Tier I effluent limitations
specified in paragraph (b)(4)(i) of this section must
achieve the AOX limitation specified in that paragraph; or
(ii) For dischargers that use exclusively TCF
bleaching processes as of [insert date six years from the
date of publication], the effluent limitations specified in
paragraph (a)(2) of this section.
847
-------
to
§
-H
4J
R
«
4J
CO
m
c
o
H
oi
S >i
§ S S?
E a! a!
rl TJ
X rl
0! O rH
£ *M
it
1 >
a Si
s >i
-rl TJ
X rl
n) O H
E MI
Total pulping area
condensate, evaporator
condensate, and bleach
plant wastewater flow
(Annual Average)
o> H1
rl U
s I
nit
«
4)
-H
£-<
TJ
U
r- 1
S
V
vo
o
oo
m
o
eH
A
trj tj
o 2 05
§ ffl § m
0 * -rl n ,g -H
3 "3 £ 5
H
t.
tt)
-H
EH
o
u
S
v
o
rH
O
ro
o
10 cubic meters/kkg
A
~-~.
H
H
k
fit
tL>
"yj
a
u
2
v
o
o
rH
rH
O
5 cubic meters/kkg
a
S3
H
H
j ]
j_l
tt)
-rl
EH
to
M -H
tt)
CO SH
tn tt)
fl) O £>
0 JJ E
0 3
rl M fi
ft O
-H ai
fl1 ft ft
-H ai
A T) M
O tt)
a! JJ a)
tt) nS k
rH SH tt)
* s-s
fa tt)
K -H
>i tt) O
rH JJ ft
tt) ai
!> SH tt)
M rH JJ
3 -H
rH IW O
U JJ
ne that does not use ex
recovery system of all
ludes all filtrates up
-H rH U
rH OS S
0 -rl
tt) E M
ft tt) -H
M-l U JJ
S tt) -
c! X! H
OS JJ
O O 0)
4J JJ -H
EH
a 1? rl
-rl -H tt)
ftf rH T!
JJ U C
tt) U
P< 0)
0) fi
fa JJ -H
O tt) XJ
H rH U
1 ft OS
S S tt)
O O rH
e u xi
Rl -Q
01
a
-H
JJ JJ
as -H
JJ E
rH 0)
rH ft
ft -
M (D
aS >
rH fl)
O O
"rH pC]
jj
a! JJ~
ft{2
d) jj
JJ rH
rH
rl O
O ft
CO
^~. -rl
i-H
O
O
n
O
an -H
JJ
H a!
-H JJ
-rl
^cf S
tt) -rl
4-i
-H M-l
U O
0)
ft 0)
rH JJ
d)
> M
tt) -H 0)
JJ
-------
(ii) Deadlines. (A) A discharger enrolled
in Tier I of the Voluntary Advanced Technology Incentives
Program must achieve the Tier I limitations in paragraph
(b) (4) (i) of this section by [insert date six years from the
date of publication].
(B) A discharger enrolled in Tier II of
the Voluntary Advanced Technology Incentives Program must
achieve the Tier II limitations in paragraph (b)(4)(i) of
this section by [insert date eleven years from the date of
publication].
(C) A discharger enrolled in Tier III
of the Voluntary Advanced Technology Incentives Program must
achieve the Tier III limitations in paragraph (b) (4) (i) of
this section by [insert date sixteen years from the date of
publication].
(c) [RESERVED].
(d) The following additional effluent limitations
apply to all dischargers subject to this section in
accordance with the previous subcategorization scheme unless
the discharger certifies to the permitting authority that it
is not using these compounds as biocides. Also, for non-
continuous dischargers, concentration limitations (mg/1)
shall apply. Concentration limitations will only apply to
non-continuous dischargers:
849
-------
Subpart B
Pollutant or pollutant
property
Pentachlorophenol
Trichlorophenol
Supplemental BAT effluent limitations for
bleached kraft facilities where market pulp is
produced
Maximum for any 1 day
kg/kkg
(or pounds per 1,000
Ib) of product
0.0019
0.012
Milligrams /liter
(0.011) (41. 6) /y
(0.068) (41. 6) /y
y = wastewater discharged in kgal per ton of product
Subpart B
Pollutant or pollutant
property
Pentachlorophenol
Trichlorophenol
Supplemental BAT effluent limitations for
bleached kraft facilities where paperboard,
coarse paper, and tissue paper are produced
Maximum for any 1 day
kg/kkg
(or pounds per 1,000
Ib) of product
0.0016
0.010
Milligrams /liter
(0.011) (35.4)/y
(0.068) (35.4)/y
y = wastewater discharged in kgal per ton of product
850
-------
Subpart B
Pollutant or pollutant
property
Pentachlorophenol
Trichlorophenol
Supplemental BAT effluent limitations for
bleached kraft facilities where pulp and fine
papers are produced and soda facilities where
pulp and paper are produced
Maximum for any 1 day
kg/kkg
(or pounds per 1,000
Ib) of product
0.0014 .
0.0088
Milligrams/liter
(0.011) (30.9)/y
(0.068) (30.9)/y
y = wastewater discharged in kgal per ton of product
(e) Pursuant to 40 CFR 122.44(1) and 122.45(h), a
discharger must demonstrate compliance with the effluent
limitations in paragraph (a)(1) or (b)(3) of this section,
as applicable, by monitoring for all pollutants (except for
AOX and COD) at the point where the wastewater containing
those pollutants leaves the bleach plant. The permitting
authority may impose effluent limitations and/or monitoring
requirements on internal wastestreams for any other
pollutants covered in this section as appropriate under 40
CFR 122.44 (i) and 122.45.(h). In addition, a discharger
subject to a limitation on total pulping area condensate,
evaporator condensate, and bleach plant wastewater flow
under paragraph (b)(4)(i) of this section, for Tier II and
Tier III, must demonstrate compliance with that limitation
by establishing and maintaining flow measurement equipment
to monitor these flows at the point or points where they
leave the pulping area, evaporator area, and bleach plant.
851
-------
§ 430.25 New source performance standards (NSPS).
New sources subject to this subpart must achieve the
following new source performance standards (NSPS), as
applicable.
(a) The following standards apply to each new source
that commenced discharge after [insert date 10 years before
the date 60 days from the date of publication} and before
[insert date 60 days from the date of publication} , provided
that the new source was constructed to meet these standards:
Subpart B
Pollutant
or
pollutant
property
BODS
TSS
PH
1982 New Source Performance Standards for
bleached kraft facilities where market pulp is produced
Continuous dischargers
Maximum for any 1
day
Average of daily
values for 30
consecutive days
Non- continuous
dischargers
Annual average
kg/kkg (or pounds per 1,000 Ib)
of product
10.3
18.2
(x)
5.5
9.5
t1)
2.88
5.00
t1)
(*) Within the range of 5.0 to 9.0 at all times.
852
-------
Subpart B
Pollutant
or
pollutant
property
BODS
TSS
pH
1982 New Source Performance Standards for
bleached kraft facilities where paperboard, coarse paper,
and tissue paper are produced
Continuous dischargers
Maximum for any 1
day
Average of daily
values for 30
consecutive days
Non - c ont inuous
di s chargers
Annual average
kg/kkg (or pounds per 1,000 Ib)
of product
8.5
14.6
(*)
4.6
7.6
H
2.41
4.00
(l)
Within the range of 5.0 to 9.0 at all times.
Subpart B
Pollutant
or
pollutant
property
BOD5
TSS
pH
1982 Hew Source Performance Standards for
bleached kraft facilities where pulp and fine papers are
produced and soda facilities where pulp and paper are
produced
Continuous dischargers
Maximum for any 1
day
Average of daily
values for 30
consecutive days
Non- continuous
dischargers
Annual average
kg/kkg (or pounds per 1,000 Ib)
of product
5.7
9.1
(x)
3 .1
4.8
f1)
1.62
2.53
H
Within the range of 5.0 to 9.0 at all times.
(b) Except as provided in paragraph (c) of this
section--(1) The following standards apply with respect to
853
-------
each new source fiber line that does not use an exclusively
TCP bleaching process, as disclosed by the discharger in its
NPDES permit application under 40 CFR 122.21(g)(3) and
certified under 40 CFR 122.22, and that commences discharge
after [insert date 60 days from publication] :
854
-------
Subpart B
Pollutant
or
pollutant property
TCDD
TCDF
Chloroform
Trichlorosyringol
3,4,5-
trichlorocatechol
3,4,6-
trichlorocatechol
3,4,5- ,
trichloroguaiacbl
3,4,6-
trichloroguaiacol
4,5,6-
trichloroguaiacol
2 , 4 , 5-trichlorophenol
2,4, 6-trichlorophenol
Tetrachlorocatechol
Tetrachloroguaiacol
2,3,4,6-
tetrachlorophenol
Pentachlorophenol
i
AOX
BODS
TSS
pH
NSPS
Maximum for any
1 day
-------
COD
C1)
"
-------
pollutant; however, permitting authorities may do so as
appropriate.
c [Reserved].
d Kilograms per 1,000 kilograms (kg/kkg).
C1) Within the range of 5.0 to 9.0 at all times.
(c) With'respect to each new source fiber line that is
enrolled in the Voluntary Advanced Technology Incentives
Program, dischargers subject to this section must achieve:
(1) The standards specified in paragraph (b)(1)
of this section (except for AOX) or paragraph (b)(2) of this
section, as applicable; and
857
-------
8
G
CQ
(U
U
4J
tQ
8
CO
CN
CQ
CQ
53
£
cl
M
fU
CO
a)
-H
4J
(D
R
M
H
CTI
O
rH
O
JS
o
.dvanced Te
<:
OJ
r-<
rH
O
(D
4J
(C
e
H
rH
{D
"5i
X! ^
vJ ^^^
"" tn
.«
0
*»J
fe
e^
fi
o
(3
rH ^
I 2
H co
g >
cd
1 1"*-
-H T3
X !-l
cd O H
g '1 1
_j ^
* f?
s 2
§ fi
td
g >i
g td td
-H -d
cd O H
g m
k A3 -,
DOS
cd JJ td H
co td to Hi
k k rH ^ 0)
cd o A3 *o M H
(3 [> (3 '{d to
^ ^ ^ co ^
3 !
CQ
t>1
S-l
(D
^
o
U
0
J_l
iH
td
U
-H
g
to
r]
CJ
CO
JJ
0
JJ
Dn
a
H
i-l
O
U
CO
CO
JJ
CO
Oi
£
0
o
tn
S
-H
XI
CJ
cd
CO
A3
£-|
cd
rH
j3
U
H
JJ
^j
cd
ft
to
f{
jj
Sn
O
it-l
. s
-H
* -
H
O
O
CO
r^i
K7)
a
-H
T!
CO
-H
t-l
-H
O
CO
ft
CO
rH
CO
^
(U
rH
£
£3
g
-H
S3
-H
g
fl)
A3
jj
pj
cd
A3
jj
CQ
CQ
to
rH
CQ
a
cd
CO
g
S
h3
S
V
=
in
a
-H
JJ
JJ
-H
g
rH
CO
ft
«.
M
a;
^
-------
(d) These additional standards apply to all new
sources, regardless of when they commenced discharge, in
accordance with the previous subcategorization scheme unless
the discharger certifies to the permitting authority that it
is not using -these compounds as biocides. Also, for non-
continuous dischargers, concentration limitations (mg/1)
shall apply. Concentration limitations will only apply to
non-continuous dischargers:
Subpart B
Pollutant or pollutant
property
Pentachlorophenol
Trichlorophenol
Supplemental NSPS for
bleached kraft facilities where market pulp is
produced
Maximum for any 1 day
kg/kkg
(or pounds per 1,000
Ib) of product
0.0019
0.012
Milligrams /liter
(0.013) (36. 6) /y
(0.077) (36.6)/y
y = wastewater discharged in kgal' per ton of product
Subpart B
Pollutant or pollutant
property
Pentachlorophenol
Trichlorophenol
Supplemental NSPS for
bleached kraft facilities where paperboard,
coarse paper, and tissue paper are produced
Maximum for any 1 day
kg/kkg
(or pounds per 1,000
lb)of product
0.0016
0.010
Milligrams /liter
(0.012) (31.7)/y
(0.076) (31.7)/y
y = wastewater discharged in kgal per ton of product
859
-------
Subpart B
Pollutant or pollutant
property
Pentachlorophenol
Trichlorophenol
Supplemental NSPS for
bleached kraft facilities where pulp and fine
papers are produced and soda facilities where
pulp and paper are produced
Maximum for any 1 day
kg/kkg
(or pounds per 1,000
Ib) of product
0.0014
0.0088
Milligrams/liter '
(0.014) (25.1)/y
(0.084) (25.1)/y
y = wastewater discharged in kgal per ton of product
(e) Pursuant to 40 CFR 122.44(1) and 122.45(h), a
discharger must demonstrate compliance with the limitations
in paragraph (b)(1) or (c)(1) of this section, as
applicable, by monitoring for all pollutants (except for
AOX, COD, BOD5, TSS, and pH) at the point where the
wastewater containing those pollutants leaves the bleach
plant. The permitting authority may impose effluent
limitations and/or monitoring requirements on internal
wastestreams for any other pollutants covered in this
section as appropriate under 40 CFR 122.44 (i) and 122.45(h).
In addition, a discharger subject to a limitation on total
pulping area condensate, evaporator condensate, and bleach
plant wastewater flow under paragraph (c)(2) of this section
must demonstrate compliance with that limitation by
establishing and maintaining flow measurement equipment
monitoring these flows at the point or points where they
leave the pulping area, evaporator area, and the bleach
860
-------
plant.
§ 430.26 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).
(a) (1) The following pretreatment standards apply
with respect to each fiber line operated by an indirect
discharger subject to this section, unless the indirect
discharger discloses to the pretreatment control authority
in a report submitted under 40 CFR 403.12(b) that it uses
exclusively TCF bleaching processes at that fiber line.
These pretreatment standards must be attained on or before
[insert date 3 years from publication date] :
861
-------
Subpart B
Pollutant
or
pollutant property
TCDD
TCDF
Chloroform
Trichlorosyringol
3,4,5-
trichlorocatechol
3,4,6-
trichlorocatechol
3,4,5-
trichloroguaiacol
3,4,6-
trichloroguaiacol
4,5,6-
trichloroguaiacol
2,4, 5-trichlorophenol
2, 4, 6-trichlorophenol
Tetrachlorocatechol
Tetrachloroguaiacol
2,3,4,6-
tetrachlorophenol
Pentachlorophenol
AOX
PSES
Maximum for any
1 day
-------
with respect to each fiber line operated by an indirect
discharger subject to this section if the indirect
discharger discloses to the pretreatment control authority
in a report submitted under 40 CFR 403.12(b) that it uses
exclusively TCP bleaching processes at that fiber line.
These pretreatment standards must be attained on or before
[insert date 3 years from publication date] :
Subpart B
Pollutant or
pollutant
parameter
AOX
PSES (TCP)
Maximum for any 1 day
-------
Subpart B
Pollutant or pollutant
property
Pentachlorophenol
Trichlorophenol
Supplemental PSES for
bleached kraft facilities where market pulp is
produced
Maximum for any 1 day
kg/kkg
(or pounds per 1,000
lb)of product
0.0019
0.014
Milligrams /liter
(0.011) (41.6)/y
(0.082) (41.6)/y
y = wastewater discharged in kgal per ton of product
Subpart B
Pollutant or pollutant
property
Pentachlorophenol
Trichlorophenol
Supplemental PSES for
bleached kraft facilities where paperboard,
coarse paper, and tissue paper are produced
Maximum for any 1 day
kg/kkg
(or pounds per 1,000
Ib) of product
0.0016
0.012
Milligrams /liter
(0.011) (35.4)/y
(0.082) (35.4)/y
y = wastewater discharged in kgal per ton of product
Subpart B
Pollutant or pollutant
property
Pentachlorophenol
Trichlorophenol
Supplemental PSES for
bleached kraft facilities where pulp and fine
papers are produced and soda facilities where
pulp and paper are produced
Maximum for any 1 day
kg/kkg
(or pounds per 1,000
Ib) of product
0.0014
0.011
Milligrams /liter
(0.011) (30.9)/y
(0.082) (30.9)/y
y = wastewater discharged in kgal per ton of product
(c) An indirect discharger must demonstrate compliance
864
-------
with the pretreatment standards in paragraph (a)(1) of this
section by monitoring at the point where the wastewater
containing those pollutants leaves the bleach plant.
§ 430.27 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).
(a) (1) The following pretreatment standards apply
!
with respect to each fiber line that is a new source, unless
the indirect discharger discloses to the pretreatment
control authority in a report submitted under 40 CFR 403.12
that it uses exclusively TCF bleaching processes at that
fiber line:
865
-------
Subpart B
Pollutant
or
pollutant property
TCDD
TCDF
Chloroform
Trichlorosyringol
3,4,5-
trichlorocatechol
3,4,6-
trichlorocatechol
3,4,5-
trichloroguaiacol
3,4,6-
trichloroguaiacol
4,5,6-
trichloroguaiacol
2,4, 5-trichlorophenol
2, 4, 6-trichlorophenol
Tetrachlorocatechol
Tetrachloroguaiacol
2,3,4,6-
tetrachlorophenol
Pentachlorophenol
AOX
PSNS
Maximum for any
1 day
-------
indirect discharger subject to this section if the indirect
discharger discloses to the pretreatment control authority
in a report submitted under 40 CFR 403.12(b) that it uses
exclusively TCP bleaching processes at that fiber line:
Subpart B
Pollutant or
pollutant
parameter
AOX
PSNS (TCP)
Maximum for any 1 day
-------
Subpart B
Pollutant or pollutant
property
Pentachlorophenol
Trichlorophenol
Supplemental PSNS for
bleached kraft facilities where market pulp is
produced
Maximum for any 1 day
kg/kkg
(or pounds per 1,000
lb)of product
0.0019
0.014
Milligrams /liter
(0.013) (36. 6) /y
(0.093) (36.6) /y
y = wastewater discharged in kgal per ton of product
Subpart B
Pollutant or pollutant
property
Pentachlorophenol
Trichlorophenol
Supplemental PSNS for
bleached kraft facilities where paperboard,
coarse paper, and tissue paper are produced
Maximum for any 1 day
kg/kkg
(or pounds per 1,000
Ib) of product
0.0016
0.012
Milligrams /liter
(0.012) (31.7)/y
(0.092) (31.7)/y
y = wastewater discharged in kgal per ton of product
Subpart B
Pollutant or pollutant
parameter
Pentachlorophenol
Trichlorophenol
Supplemental PSNS for
bleached kraft facilities where pulp and fine
papers are produced and soda facilities where
pulp and paper are produced
Maximum for any 1 day
kg/kkg
(or pounds per 1,000
Ib) of product
0.0014
0.011
Milligrams /liter
(0.014) (25.1)/y
(0.101) (25. I) /y
y = wastewater discharged in kgal per ton of product
(c) An indirect discharger must demonstrate compliance
with the pretreatment standards in paragraph (a)(1) and of
868
-------
this section by monitoring at the point where the wastewater
containing those pollutants leaves the bleach plant.
§430.28 Best management practices (BMPs).
The definitions and requirements set forth in 40 CFR
430.03 apply to facilities in this subpart.
Subpart C--Unbleached Kraft Subcategory
§430.30 Applicability; description of the unbleached kraft
subcategory.
The provisions of this subpart are applicable to
discharges resulting from: the production of pulp and paper
at unbleached kraft mills; the production of pulp and paper
at unbleached kraft-neutral sulfite semi-chemical (cross
recovery) mills; and the production of pulp and paper at
combined unbleached kraft and semi-chemical mills, wherein
the spent semi-chemical cooking liquor is burned within the
unbleached kraft chemical recovery system.
§ 430.31 Specialized definitions.
For the purpose of this subpart, the general
definitions, abbreviations, and methods of analysis set
forth in 40 CFR part 401 and § 430.01 of this part shall
.apply to this subpart.
§ 430.32 Effluent limitations representing the degree of
effluent reduction attainable by the application of the best
practicable control technology currently available (BPT).
869
-------
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 C
Pollutant
or
pollutant
property
BODS
TSS
PH
BPT effluent limitations for
unbleached kraft facilities
Kg/kkg (or pounds per 1,000 Ib) of product
Maximum for any 1
day
5.6
12.0
(l)
Average of daily values for 30
consecutive days
2.8
6.0
(x)
Subpart C
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
unbleached kraft facilities producing pulp and paper using
the unbleached kraft-neutral sulfite semi-chemical (cross
recovery) process
Kg/kkg (or pounds per 1,000 lb) of product
Maximum for any 1
day
8.0
12.5
C1)
Average of daily values for
consecutive days
30
4.0
6.25
(x)
lWithin the range of 6.0 to 9.0 at all times.
870
-------
Subpart C
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
unbleached kraft facilities where pulp and paper are
produced using a combined unbleached kraft and semi-
chemical, process, wherein the spent semi-chemical cooking
liquor is burned within the unbleached kraft chemical
recovery system
Kg/kkg (or pounds per 1,000 Ib) of product
Maximum for any 1
day
a
a
a
Average of daily values for 30
consecutive days
a
a
a
a[Reserved].
§ 430.33 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), except
that ndn-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:
871
-------
Subpart C
Pollutant
or
pollutant
property
BODS
TSS
PH
BCT effluent limitations for
unbleached kraft facilities
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
5.6
12.0
H
Average of daily
values for 30
consecutive days
2.8
6.0
C1)
Non- continuous
dischargers
(Annual Average)
1.9
3.6
(l)
^Within the range of 6.0 to 9.0 at all times .
Subpart C
Pollutant
or
pollutant
property
BODS
TSS
pH
BCT effluent limitations for unbleached kraft-neutral
sulfite semi-chemical (cross recovery) process and/or a
combined unbleached kraft and semi-chemical process,
wherein the spent semi -chemical cooking liquor is burned
within the unbleached kraft chemical recovery system
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
8.0
12.5
t1)
Average of daily
values for 3 0
consecutive days
4.0
6.25
'(*)
Non-continuous
dischargers
(Annual Average)
2.9
3.57
t1)
^Within the range of 6.0 to 9.0 at all times.
§ 430.34 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
872
-------
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 Ib), 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:
Subpart C
Pollutant or
pollutant, property
Pentachlorophenol
Trichlorophenol
BAT effluent limitations for
unbleached kraft facilities
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.00058
0.00053
Milligrams/ liter
(0.011) (12. 6) /y
(0.010) (12.6)/y
y = wastewater discharged in kgal per ton of product
873
-------
Subpart C
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
BAT effluent limitations for
unbleached kraft facilities where pulp and paper
are produced using the unbleached kraft-neutral
sulfite semi-chemical (cross recovery) process
and/or a combined unbleached kraft and semi-
chemical process, wherein the spent semi-chemical
cooking liquor is burned within the unbleached
kraft chemical recovery system
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.00064
0.00059
Milligrams/ liter
(0.011) (14.0)/y
(0.010) (14.0)/y
y - wastewater discharged in kgal per ton of product
§ 430.35 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/1) 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:
874
-------
Subpart C
Pollutant or
pollutant property
BODS
TSS
PH
Pentachlorophenol
Trichlorophenol
NSPS for
unbleached kraft facilities where
linerboard is produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
3.4
5.8
C1 )
Average of
daily
values for
30
consecutive
days
1.8
3.0
(x )
Maximum for any 1
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.00058
0.00053
Non-continuous
Dischargers
(Annual Average)
0.94
1.6
(M
day
Milligrams/
liter
(0.015) (9.4)/y
(0.013) (9.4)/y
y = wastewater discharged in kgal per ton at all times
875
-------
Subpart C
Pollutant or
pollutant property
BODS
TSS
PH
Pentachlorophenol
Trichlorophenol
NSPS for
unbleached kraft facilities where
bag paper and other mixed products are produced)
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
5.0
9.1
(x )
Average of daily
values for 30
consecutive days
2.7
4.8
(1 )
Non-
continuous
Dischargers
(Annual
Average)
1.4
2.5
t1 )
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.00058
0.00053
Milligrams/
liter
(0.012) (11.4)/y
(0.011) (11.4)/y
y = wastewater discharged in kgal per ton at all times
the range of 5.0 to 9.0 at all times.
876
-------
Subpart C
Pollutant or
pollutant property
BODS
TSS
pH
Pentachlorophenol
Trichlorophenol
NSPS for
unbleached kraft facilities where pulp and paper
are produced using the unbleached kraft-neutral
sulfite semi -chemical (cross recovery) process
and/ or a combined unbleached kraft and semi-
chemical process, wherein the spent semi-chemical
cooking liquor is burned within the unbleached
kraft chemical recovery system
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
3.9
7.3
t1 )
Average of
daily
values for
,30
consecutive
days
2.1
3.8
(1 )
Non- continuous
Dischargers
(Annual Average)
1.1
1.9
t1 )
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.00064
0.00059
Milligrams/
liter
(0.013) (11.5)/y
(0.012) (11.5)/y
y = wastewater discharged in kgal per ton at all times
xWithin the range of 5.0 to 9.0 at all times.
§ 430.36 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
877
-------
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 those
biocides. PSES must be attained on or before July 1, 1984:
Subpart C
Pollutant or'
pollutant property
Pentachlorophenol
Tri chlorophenol
PSES for
unbleached kraft facilities
Maximum for any 1 day
Milligrams/ liter
(0.011) (12. 6) /y
(0.010) (12.6)/y
Kg/kkg (or pounds per 1,000
Ib) of product3
0.00058
0.00053
y = wastewater discharged in kgal per ton of product
"The following equivalent mass limitations are provided as guidance in
cases where POTWs find it necessary to impose mass effluent limitations.
Subpart C
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSES for
unbleached kraft facilities where pulp and paper
are produced using the unbleached kraft -neutral
sulfite semi-chemical (cross recovery) process
and/or a combined unbleached kraft and semi-
chemical process, wherein the spent semi-chemical
cooking liquor is burned within the unbleached
kraft chemical recovery system
Maximum for any 1 day
Milligrams/liter
(0.011) (14.0)/y
(0.010) (14.0)/y
Kg/kkg (or pounds per 1,000
Ib) of product3
0.00064
0.00059
y = wastewater discharged in kgal per ton of product
"The following equivalent mass limitations are provided as guidance in
cases where POTWs find it necessary to impose mass effluent limitations.
878
-------
§ 430.37 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 C
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSNS for
unbleached kraft facilities where linerboard
produced
is
Maximum for any 1 day
. Milligrams/liter
(0.015) (9.4)/y
(0.013) (9.4) /Y
Kg/kkg (or pounds per 1,000
Ib) of product3
0.00058
0.00053
y = wastewater discharged in kgal per ton of product
aThe following equivalent mass limitations are provided as guidance in
cases where POTWs find it necessary to impose mass effluent limitations.
879
-------
Subpart C
Pollutant or
pollutant property
Pent achl oropheno 1
Trichlorophenol
PSNS for
unbleached kraft facilities where bag paper
other mixed products are produced
and
Maximum for any 1 day
Milligrams/liter
(0.012) (11.4)/y
(0.011) (11. 4) /y
Kg/kkg (or pounds per 1,
Ib) of product3
000
0.00058
0.00053
y = wastewater discharged in kgal per ton of product
"The following equivalent mass limitations are provided as guidance in
cases where POTWs find it necessary to impose mass effluent limitations.
Subpart C
Pollutant or
pollutant property
Pentachlorophenol
Tri chlorophenol
PSNS for
unbleached kraft facilities where pulp and paper
are produced using the unbleached kraft-neutral
sulfite semi-chemical (cross recovery) process
and/or a combined unbleached kraft and semi-
chemical process, wherein the spent semi-chemical
cooking liquor is burned within the unbleached
kraft chemical recovery system
. Maximum for any 1 day
Milligrams /liter
(0.013) (11.5)/y
(0.012) (11.5)/y
Kg/kkg (or pounds per 1,000
Ib) of product3
0.00064
0.00059
y = wastewater discharged in kgal per ton of product
"The following equivalent mass limitations are provided as guidance in
cases where POTWs find it necessary to impose mass effluent limitations.
Subpart D--Dissolving Sulfite Pulp Subcategory
§ 430.40 Applicability; description of the dissolving
sulfite pulp subcategory.
The provisions of this subpart are applicable to
discharges resulting from the production of pulp at
880
-------
dissolving sulfite mills.
§ 430.41 Specialized definitions.
For the purpose of this subpart, the general
definitions, abbreviations, and methods of analysis set
forth in 40 CFR part 401 and § 430.01 of this part shall
apply to this subpart.
§ 430.42 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), 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:
881
-------
Subpart D,
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
dissolving sulfite pulp facilities where nitration grade
pulp is produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
41.4
70.65
-------
S.ubpart D
Pollutant
or
pollutant
property
BODS
TSS
PH
BPT effluent limitations for
dissolving sulfite pulp facilities where cellophane grade
pulp is produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
48.05
70.65
(^
Average of daily
values for 30
consecutive days
24.95
38.05
(l)
Non - cont inuous
dischargers
(Annual Average)
14.0
20.9
(l)
^within the range of 5.0 to 9.0 at all times.
Subpart D
Pollutant
or
pollutant
property
BODS
TS'S
pH
BPT effluent limitations for
dissolving sulfite pulp facilities where acetate grade
pulp is produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
50.80 0)
70.65
(2)
Average of daily
values for 30
consecutive days
26.40 C1}
38.05
(2)
Non-continuous
dischargers
(Annual Average)
14.83 (x)
20.9
(2)
BODS effluent limitations were remanded (Weyerhaeuser Company, et al v.
Costle, 590 F. 2nd 1011; D.C. Circuit 1978).
2Within the range of 5.0 to 9.0 at all times
(b) The following limitations establish the quantity
or quality of pollutants or pollutant properties, controlled
by this section, resulting from the use of wet barking
\
operations, which may be discharged by a point source
subject to the provisions of this subpart. These
883
-------
limitations are in addition to the limitations set forth in
paragraph (a) of this section and shall be calculated using
the proportion of the mill's total production due to use of
logs which are subject to such operations. 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 D
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day,
0.7
0.15
(x)
Average of daily
values for 30
consecutive days
0.35
0.1
C1)
Non - cont inuous
dischargers
(Annual Average)
0.2
0.05
H
xWithin the range of 5.0 to 9.0 at all times.
(c) The following limitations establish the quantity
or quality of pollutants or pollutant parameters, controlled
by this section, resulting from the use of log washing or
chip washing operations, which may be discharged by a point
source subject to the provisions of this subpart. These
limitations are in addition to the limitations set forth in
paragraph (a) of this section and shall be calculated using
the proportion of the mill's total production due to use of
logs and/or chips which are subject to such operations. Non-
continuous dischargers shall not be subject to the maximum
884
-------
day and average of 30 consecutive days limitations, but
shall be subject to the annual average effluent limitations
Subpart D
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.15
0.15
(x)
Average of daily
values for 30
consecutive days
0.1
0.1
-(l)
Non-continuous
dischargers
(Annual Average)
0.05
0.05
H
'Within the range of 5.0 to 9.0 at all times.
(d) The following limitations establish the quantity
or quality of pollutants or pollutant properties, controlled
by this section, resulting from the use of log flumes or log
ponds, which may be discharged by a point source subject to
the provisions of this subpart. These limitations are in
addition to the limitations set forth in paragraph (a) of
this section and shall be calculated using the proportion of
'the mill's total production due to use of logs which are
subject to such operations. Non-continuous dischargers
shall not be subject to the maximum day and average of 30
consecutive days limitations but shall be subject to the
annual average effluent limitations:
885
-------
Subpart D
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.15
0.15
C1)
Average of daily
values for 30
consecutive days
0.1
0.1
t1)
Non-continuous
dischargers
(Annual Average)
0.05
0.05
(x)
aWithin the range of 5.0 to 9.0 at all times.
§ 430.43 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 § 430.42 of this subpart for the best practicable control
technology currently available (BPT).
§ 430.44 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
886
-------
existing point source subject to this subpart where
chlorqphenolic-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 Ib) 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:
Subpart D
Pollutant or
pollutant property
Pentachlorophenol
Tri chlorophenol
BAT effluent limitations for
dissolving sulfite pulp facilities where
nitration, viscose, or cellophane pulps are
produced
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0030
0.019
Milligrams/liter
(0.011) (66.0)/y
(0.058) (66.0)/y
y = wastewater discharged in kgal per ton of product
887
-------
Subpart D
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
BAT effluent limitations for
dissolving sulfite pulp facilities where acetate
grade pulp is produced
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0033
0.021
Milligrams/liter
(0.011) (72.7)/y
(0. 068) (72 .7) /y
y = wastewater discharged in kgal per ton of product
§ 430.15 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 BODS and TSS, but shall be subject to annual
average effluent limitations. Also, for non-continuous
dischargers, concentration limitations (mg/1) 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 bfocides must
certify to the permit-issuing authority that they are not
using these biocides:
888
-------
Subpart D
Pollutant or
pollutant property
BODS
TSS
pH
Pentachlorophenol
Trichlprophenol
NSPS for
dissolving sulfite pulp facilities where
nitration grade pulp is produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
.Maximum for any 1
day
26.9
40.8
C1 )
Average of
daily
values for
30
consecutive
days
14.5
21.3
(l )
Non - cont inuous
Dischargers
(Annual Average)
7.59
11.2
(l )
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0030
0.019
Milligrams /liter
(0.012) (59.0)/y
(0.012) (59.0)/y
y = wastewater discharged in kgal per ton at all times
'Within the range of 5.0 to 9.0 at all times.
889
-------
Subpart D
Pollutant or
pollutant property
BODS
TSS
PH
Pentachlorophenol
Trichlorophenol
NSPS for
dissolving sulfite pulp facilities where viscose
grade pulp is produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
28.7
40.8
t1 )
Average of
daily
values for
30
consecutive
days
15.5
21.3
(x )
Non- continuous
Dischargers
(Annual Average )
8.12
11.2
(M
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0030
0.019
Milligrams/liter
(0.012) (59.0) /y
(0.012) (59.0)/y
y = wastewater discharged in kgal per ton at all times
Within the range of 5.0 to 9.0 at all times.
890
-------
Subpart D
Pollutant or
pollutant property
BOD 5
TSS
PH
Pentachlorophenol
Trichlorophenol
NSPS for
dissolving sulfite pulp facilities where
cellophane grade pulp is produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
31.2
40.8
f1 )
Average of
daily
values for
30
consecutive
days
16.8
21.3
(l )
Non-continuous
Dischargers
(Annual Average)
8.80
11.2
' ' (* )
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0030
0.019
Milligrams /liter
(0.012) (59.0) /y
(0.076) (59.0)/y
y = wastewater discharged in kgal per ton at all times
'Within the range of 5.0 to 9.0 at all times.
891
-------
Subpart D
Pollutant or
pollutant property
BODS
TSS
PH
Pentachlorophenol
Trichlorophenol
NSPS for
dissolving sulfite pulp facilities where acetate
grade pulp is produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
39.6
41.1
(l )
Average of
daily
values for
30
consecutive
days
21.4
21.5
t1 )
Non- continuous
Dischargers
(Annual Average)
11.2
11.3
(l )
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0033
0.021
Milligrams /liter
(0.012) (65.7) /y
(0.075) (65.7)/y
y = wastewater discharged in kgal per ton at all times
Within the range of 5.0 to 9.0 at all times.
§ 430.46 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
892
-------
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 D
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSES for
dissolving sulfite pulp facilities where
nitration, viscose, or cellophane grade pulps are
produced
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.011) (66.0) /y
(0.082) (66. 0) /y
Kg/kkg (or pounds per
1,000 Ib) of product a
0.0030
0.023
y = wastewater discharged in kgal per ton of product
aThe following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
Subpart D
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSES for
dissolving sulfite pulp facilities where acetate
grade pulp is produced
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.011) (.72 .7) /y
(0.082) (72.7)/y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0033
0.025
y = wastewater discharged in kgal per ton of product
aThe following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
§ 430.47 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
893
-------
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 D
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSNS for
dissolving sulfite pulp facilities where
nitration, viscose, or cellophane grade pulps are
produced
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.012) (59.0) /y
(0.092) (S9.0)/y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0030
0.023
y = wastewater discharged in kgal per ton of product
"The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
Subpart D
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSNS for
dissolving sulfite pulp facilities where acetate
grade pulp is produced
Maximum for any 1 day
Milligrams /liter (mg/1)
(0.012) (65.7) /y
(0.091) (65.7) /y
Kg/kkg (or pounds per
1,000' Ib) of product3
0.0033
0.025
y = wastewater discharged in kgal per ton of product
"The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
894
-------
Subpart E-Papergrade Sulfite Subcategory
§ 430.50 Applicability; description of the papergrade
sulfite subcategory.
The provisions of this subpart apply to discharges
resulting from the: integrated production of pulp and paper
at papergrade sulfite mills, where blow pit pulp washing
techniques are used; and the integrated production of pulp
and paper at papergrade sulfite mills where vacuum or
pressure drums are used to wash pulp.
§ 430.51 Specialized definitions
(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
§ 430.01 of this part apply to this subpart.
(b) Sulfite cooking liquor is defined as bisulfite
cooking liquor when the pH of the liquor is between 3.0 and
6.0 and as acid sulfite cooking liquor when the pH is less
than 3.0.
(c) For this subpart, the segments for the papergrade
sulfite subcategory are defined as follows:
(1) The calcium-, magnesium-, or sodium-based
sulfite pulp segment consists of papergrade sulfite mills
where pulp and paper are produced using an acidic cooking
liquor of calcium, magnesium, or sodium sulfite, unless
those mills are specialty grade sulfite mills;
895
-------
(2) The ammonium-based sulfite pulp segment
consists of papergrade sulfite mills where pulp and paper
are produced using an acidic cooking liquor of ammonium
sulfite, unless those mills are specialty grade sulfite
mills; .
(3) The specialty grade sulfite pulp segment
consists of those papergrade sulfite mills where a
significant portion of production is characterized by pulp
with a high percentage of alpha cellulose and high
brightness sufficent to produce end products such as plastic
molding compounds, saturating and laminating products, and
photographic papers. The specialty grade segment also
includes those mills where a major portion of production is
91 ISO brightness and above.
§ 430.52 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):
896
-------
Subpart E
[Bisulfite liquor/surface condensers]
Pollutant
or
pollutant
property
BODS
TSS
pH.
BPT effluent limitations for
papergrade sulf ite facilities where blow pit washing
techniques are used
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
31.8
43.95
(x)
Average of daily
values for 30
consecutive days
16.55
23.65
H
Non- continuous
dischargers
(Annual Average)
9.30
12.99
(l.)
Within the .range of 5 . 0 to 9.0 at all times.
Subpart E
[bisulfite liquor/barometric condensers]
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent .limitations for
papergrade sulfite facilities where blow pit washing
techniques are used
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
. 34.7
52.2
H
Average of daily
values for 30
consecutive days
18.05
28.1
(J)
Non - cont inuous
dischargers
(Annual Average)
10.14
15.44
(l)
"Within the range of 5 . 0 to 9.0 at all times .
897
-------
Subpart E
[Acid sulfite liquor/surface condensers]
Pollutant
or
pollutant
property
BODS
TSS
PH
BPT effluent limitations for
papergrade sulfite facilities where blow pit washing
techniques are used
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
32.3
43.95
(l)
Average of daily
values for 30
consecutive days
16.8
23.65
t1)
Non- continuous
dischargers
(Annual Average)
9.44
12.99
(a)
*Within the range of 5.0 to 9.0 at all times.
Subpart E
[Acid sulfite liquor/barometric condensers]
Pollutant
or
pollutant
property
BODS
TSS
PH
BPT effluent limitations for
papergrade sulfite facilities where blow pit washing
techniques are used
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
. 35.55
52.2
(')
Average of daily
values for 30
consecutive days
18.5
28.1
H
Non-continuous
dischargers
(Annual Average)
10.39
15.44
(l)
lWithin the range of 5.0 to 9.0 at all times.
898
-------
Subpart E
[Bisulfite liquor/surface condensers]
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
papergrade sulfite facilities where vacuum or pressure
drums are used to wash pulp
Kg/kkg (or pounds per 1, 000 Ib) of product
Continuous dischargers
Maximum for any 1
day
26.7
43.95
(x)
Average of daily
values for 30
consecutive days
13.9
23.65
C1)
Non-continuous
dischargers
(Annual Average)
7.81
12.99
(x)
^Within the range of 5.0 to 9.0 at all times.
Note: Limitations above do not apply to mills using continuous
digesters.
Subpart E
[bisulfite liquor/barometric condensers]
Pollutant
or
pollutant
property
BODS
.TSS
pH
BPT effluent limitations for
papergrade sulfite facilities where vacuum or pressure
drums are used to wash pulp
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
29.4
52.2
H
Average of daily
values for 30
consecutive days
15.3
28.1
t1)
Non- continuous
dischargers
(Annual Average)
8.60
15.44
t1)
the range of 5.0 to 9.0 at all times.
Note: Limitations above do not apply to mills using continuous
digesters.
899
-------
Subpart E
[Acid sulfite liquor/surface condensers]
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
papergrade sulfite facilities where vacuum or pressure
drums are used to wash, pulp
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
29.75
43.95
(l)
Average of daily
values for 30
consecutive days
15.5
23.65
(l)
Non- continuous
dischargers
(Annual Average)
8.71
12.99
P)
Within the range of 5.0 to 9.0 at all times.
Note: Limitations above do not apply to mills using continuous
digesters.
Subpart E
[Acid sulfite liquor/barometric condensers]
Pollutant
or
pollutant
property
BODS
TSS
PH
BPT effluent limitations for
papergrade sulfite facilities where vacuum, or pressure
drums are used to wash pulp
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
32.5
52.2
(l)
Average of daily
values for 30
consecutive days
16.9
28.1
(l)
Non- continuous
dischargers
(Annual Average)
9.49
15 .44
P)
Within the range of 5.0 to 9.0 at all times.
Note: Limitations above do not apply to mills using continuous
digesters.
900
-------
Subpart E
[Continuous digesters]
Pollutant
or
pollutant
property
BODS
TSS
PH
BPT effluent limitations for papergrade sulfite facilities
where vacuum, or pressure drums are used to wash pulp
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
38.15
53.75
(x)
Average of daily
values for 30
consecutive days
19.85
28.95
t1)
Non- continuous
dischargers
(Annual Average)
11.15
15.91
(*)
Within,the range of 5.0 to 9.0 at all times.
(b) The following limitations establish the quantity
or quality of pollutants or pollutant properties, controlled
by this section, resulting from the use of wet barking
operations, which may be discharged by a point source
subject to the provisions of this subpart. These
limitations are in addition to the limitations set forth in
paragraph (a) of this section and shall be calculated using
the proportion of the mill's total production due to use of
logs which are subject to such operations:
901
-------
Subpart E
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
papergrade sulf ite facilities where blow pit washing
techniques are used
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
2.7
7.5
(l)
Average of daily
values for 30
consecutive days
1.45
3.95
n
Non - cont inuous
dischargers
(Annual Average)
0.80
2.19
(i)
JWithin the range of 5.0 to 9.0 at all times.
Subpart E
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
papergrade sulfite facilities where vacuum or pressure
drums are used to wash pulp
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
3.05
7.5
(l)
Average of daily
values for 30
consecutive days
1.6
3.95
H
Non -cont inuous
dischargers
(Annual Average)
0.90
2.19
(x)
Within the range of 5.0 to 9.0 at all times.
(c) The following limitations establish the quantity
or quality of pollutants or pollutant parameters, controlled
by this section, resulting from the use of log washing or
chip washing operations, which may be discharged by a point
source subject to the provisions of this subpart. These
limitations are in addition to the limitations set forth in
902
-------
paragraph (a) of this section and shall be calculated using
the proportion of the mill's total production, due to use of
logs and/or chips which are subject to such operations:
Subpart E
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
papergrade sulfite facilities where blow pit washing
techniques are used
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.15
2.55
C1)
Average of daily
values for 30
consecutive days
0.1
1.35
(a)
Non- continuous
dischargers
(Annual Average)
0.05
0.75
, (x)
^Within the range of 5.0 to 9.0 at all times.
Subpart E
Pollutant
or
pollutant
property
BODS
TSS
PH
BPT effluent limitations for
papergrade sulfite facilities where vacuum or pressure
drums are used to wash pulp
Kg/kkg (or pounds per 1,000 >lb) of product
Continuous dischargers
Maximum for any 1
day
0.35
2.55
t1)
Average of daily
values for 30
consecutive days
0.2
' 1.35
(a)
xwithin the range of 5.0 to 9.0 at all times .
Non- continuous
dischargers
(Annual Average)
O.l
0 .75
(l)'
(d) The following limitations establish the quantity
or quality of pollutants or pollutant properties, controlled
by this section, resulting from the use of log'flumes or log
903
-------
ponds, which may be discharged by a point source subject to
the provisions of this subpart. These limitations are in
addition to the limitations set forth in paragraph (a) of
this section and shall be calculated using the proportion of
the mill's total production due to use of logs which are
subject to such operations:
Subpart E
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
papergrade sulfite facilities where blow pit washing
techniques are used
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.35
1.7
(x)
Average of daily
values for 30
consecutive days
0.2
0.9
(l)
Non- continuous
dischargers
(Annual Average)
0.1
0.5
t1)
lWithin the range of 5.0 to 9.0 at all times.
Subpart E
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
papergrade sulfite facilities where vacuum or pressure
drums are used to wash pulp
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.7
1.70
-------
§ 430.53 Effluent limitations 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 must 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 in § 430.52 of this subpart for the
best practicable control technology currently available
(BPT).
§ 430.54 Effluent limitations representing the degree of
effluent reduction attainable by the application of 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 must achieve
the following effluent limitations representing the degree
of effluent reduction attainable by the application of the
best available technology economically achievable (BAT).
(a) (1) The following effluent limitations apply to
all dischargers in the calcium-, magnesium-, or sodium-based
sulfite pulp segment:
905
-------
Subpart E
Production of Calcium-, Magnesium-, or Sodium-based Sulfite
Pulps
Pollutant
or
pollutant
property
AOX
COD
BAT effluent limitations
Continuous dischargers
Maximum for
any 1 day
Monthly
Average
Non- continuous dischargers
Maximum for
any 1 day
Annual
average
kg/kkg (or pounds per 1,000 Ib) of product
-------
Subpart E- -Production of Ammonium-based Sulfite Pulps
Pollutant
or
pollutant property
TCDDa
TCDFa
Chloroform8
Trichlorosyringol3
3 , 4 , 5 - trichlorocatechol3
3,4, 6-trichlorocatechola
3,4, 5-trichloroguaiacola
3,4,6- trichloroguaiacol3
4,5, 6- trichloroguaiacola
2,4, 5-trichlorophenola
2,4, 6-trichlorophenola
Tetrachlorocatechol3
Tetrachloroguaiacol3
2,3,4, 6-tetrachlorophenola
Pentachlorophenola
AOX
COD
BAT effluent limitations
Maximum for any
1 day
-------
the particular "pollutant.
This regulation does not specify this type of limitation for this
pollutant;'however, permitting authorities may do so as
appropriate.
[Reserved].
(ii) The following effluent limitations
apply to all dischargers in the ammonium-based sulfite pulp
segment with respect to each fiber line that uses
exclusively TCP bleaching processes, as disclosed by the
discharger in its NPDES permit application under 40 CFR
122.21(g)(3) and certified under 40 CFR 122.22:
Subpart E - Production of Ammonium-based Sulfite Pulps
Pollutant or
pollutant
property
AOX
COD
BAT effluent limitations (TCP)
Continuous dischargers
Maximum for
any 1 day
Monthly
average
Non-continuous
dischargers
Maximum for
any 1 day
Annual
Average
kg/kkg (or pounds per 1000 Ib) of product
-------
Subpart E--Production of Specialty Grade Sulfite Pulps
Pollutant
or
pollutant property
TCDDa
TCDFa
Chloroform3
Trichlorosyringol3
3,4,5 -,trichlorocatechola
3,4, 6-trichlorocatechola
3,4,5 - trichloroguaiacola
3,4, 6-trichloroguaiacola
4,5, 6-trichloroguaiacola
2 , 4 , 5 - trichlorophenol3
2,4, 6 - trichlorophenola
Tetrachlorocatechol3
Tetrachloroguaiacol3
2,3,4, 6 - tetrachlorophenola
Pent achl or opheno la
f
AOX
COD
BAT effluent limitations
Maximum for any
1 day
-------
b "
-------
using these compounds as biocides. Also, for non-continuous
dischargers, concentration limitations (mg/1) shall apply.
Concentration limitations will only apply to non-continuous
dischargers::
Subpart E
Pollutant or
pollutant
property
Pentachlorophenol
Trichlorophenol
Supplemental BAT effluent limitations
Maximum for any 1 day
kg/kkg
(or pounds per
1,000 Ib) of
product
0.00058exp(0. 017x)
0.0036exp(0.017x)
Milligrams /liter
( (0.011) (12.67)exp(0.017x) ) /y
( (0.068) (12.67)exp(.0.017x) ) /y
x = percent sulfite pulp in final product
y = wastewater discharged in kgal per ton of product
(c) Pursuant to 40 GFR 122.44(i) and 122.45(h), a
discharger must demonstrate compliance with the limitations
in paragraphs (a)(2) or (a)(3) of this section, as
applicable, by monitoring for all pollutants (except for AOX
and COD) at the point where the wastewater containing those
pollutants leaves the bleach plant. The permitting
authority may impose effluent limitations and/or monitoring
requirements on internal wastestreams for any other
pollutants covered in this section as appropriate under 40
CFR 122.44 (i) and 122.45(h).
§ 430.55 New source performance standards (NSPS).
New sources subject'to this subpart must achieve the
following new source performance standards (NSPS), as
911
-------
applicable.
(a) The following standards apply to each new source
regardless of when it commenced discharge:
Subpart E
Pollutant
or
pollutant
property
BODS
TSS
PH
1982 NSPS
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
4.38exp(0.017x)
5.81exp(0.017x)
(l) .
Average of daily
values for 30
consecutive days
2.36exp(0.017x)
1 3.03exp(0.017x)
(l)
Non- continuous
dischargers
(Annual Average )
Average of daily
values for 30
consecutive days
divided by 1.91
Average of daily
values for 30
consecutive days
divided by 1.90
f1)
x = percent sulfite pulp in final product
Within the range of 5.0 to 9.0 at all times.
(b) The following standards apply with respect to each
new source fiber line that commences discharge after [insert
date 60 days from publication] .
(1) The following standards apply to all new
sources in the calcium-, magnesium-, or sodium-based sulfite
pulp segment:
912
-------
Subpart E
Production of Calcium-, Magnesium-, or Sodium-based Sulfite
Pulps
Pollutant
or
pollutant
property
AOX
COD
NSPS
Continuous dischargers
Maximum for
any 1 day
Monthly
Average
Non-continuous dischargers
Maximum for
any 1 day
Annual
average
kg/kkg (or pounds per 1,000 Ib) of product
-------
Subpart E--Production of Ammonium-based Sulfite Pulps
Pollutant
or
pollutant property
TCDDa
TCDF"
Chloroform*
Trichlorosyringol"
3,4, 5-trichlorocatechola
3,4, 6-trichlorocatechola
3,4,5 -trichloroguaiacol3
3,4, 6-trichloroguaiacola
4,5, 6-trichloroguaiacola
2,4, 5-trichlorophenola
2,4, 6-trichlorophenola
Tetrachlorocatechol3
Tetrachloroguaiacol*
2,3,4, 6-tetrachlorophenola
Pentachlorophenol3
AOX
COD
NSPS
Maximum for any
1 day
-------
40 CFR 122.22.
b "
-------
Subpart E--Production of Specialty Grade Sulfite Pulps
Pollutant
.or
pollutant property
TCDDa
TCDF"
Chloroform3
Trichlorosyringol3
3,4, 5 - trichlorocatechol3
3,4, 6-trichlorocatechola
3,4,5 - trichloroguaiacola
3,4, 6- trichloroguaiacol3
4,5, 6 -trichloroguaiacol1
2,4, 5-trichlorophenola
2,4, 6-trichlorophenola
Tetrachlorocatechol3
Tetrachloroguaiacol
2,3,4, 6- tetrachlorophenol3
Pentachlorophenol3
AOX
COD
NSPS
Maximum for any
1 day
-------
b "
-------
dischargers, concentration limitations (mg/1) shall apply.
Concentration limitations will only apply to non-continuous
dischargers:
Subpart E
Pollutant or
pollutant
property
Pentachlorophenol
Tr i chlorophenol
Supplemental NSPS
Maximum for any 1 day
kg/kkg =
(or pounds per
1,000 Ib) of
product
0.00058exp(0.017x)
0.0036exp(0.017x)
Milligrams/liter
( (0.015) (9.12)exp
( (0.094) (9.12)exp
(0.017x) )/y
(0.017x) )/y
x = percent sulfite pulp in final product
y =s wastewater discharged in kgal per ton of product
(d) Pursuant to 40 CFR 122.44(i) and 122.45(h), a
discharger must demonstrate compliance with the standards in
paragraphs (b)(2) or (b)(3) of this section, as applicable,
by monitoring for all pollutants (except for AOX, COD, BOD5/
TSS, and pH) at the point where the wastewater containing
those pollutants leaves the bleach plant. The permitting
authority may impose effluent limitations and/or monitoring
requirements on internal wastestreams for any other
pollutants covered in this section as appropriate under 40
CFR 122.44 (i) and 122.45(h).
§ 430.56 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:
918
-------
comply with 40 CFR part 403; and achieve the following
pretreatment standards for existing sources (PSES).
(a) The following pretreatment standards must be
attained on or before [insert date 3 years from publication
date] .
(1) The following pretreatment standards apply to
all indirect dischargers in the calcium-,, magnesium-, or
sodium-based sulfite pulp segment:
919
-------
Subpart E
Production of Calcium-, Magnesium-, or Sodium-based Sulfite
Pulps
Pollutant
or
pollutant
property
AOX
PSES
Maximum for any 1 day
Monthly Average
kg/kkg (or pounds per 1,000 Ib) of product
-------
Subpart E--Production of Ammonium-based Sulfite Pulps
Pollutant
or
pollutant property
TCDDa
TCDFa
Trichlorosyringola
3,4, 5 -trichlorocatechola
3,4, 6-trichlorocatechola
3,4, 5 - trichloroguaiacola
3,4, 6-trichloroguaiacola
4,5, 6-trichloroguaiacola
2,4, 5-trichlorophenola
2,4, 6-trichlorophenola
Tetrachlorocatechola
Tetrachloroguaiacola
2,3,4, 6-tetrachlorophenola
Pentachlorophenol3
PSES
Maximum for any
1 day
-------
40 CFR 403.12 (b) that it uses exclusively TCP bleaching
processes at that fiber line:
Subpart E - Production of Ammonium-based Sulfite Pulps
Pollutant or
pollutant
parameter
AOX'
PSNS (TCP)
Maximum for any 1 day
-------
(3)(i) The following pretreatment standards apply
to all indirect dischargers in the specialty grade sulfite
pulp segment:
Subpart E--Production of Specialty Grade Sulfite Pulps
Pollutant
or
pollutant property
TCDDa
TCDFa
Trichlorosyringol3
3,4, 5 - trichlorocatechol3
3 , 4 , 6-trichlorocatechola
3,4, 5-trichloroguaiacola
3,4, 6-trichloroguaiacola
4,5, 6-trichloroguaiacola
2,4, 5-trichlorophenola
2, 4, 6-trichlorophenola
Tetrachlorocatechola
Tetrachloroguaiacol3
2,3,4, 6-tetrachlorophenola
Pent achl oropheno la
PSES
Maximum for any
1 day
-------
apply with respect to each fiber line operated by an
indirect discharger producing specialty grade sulfite pulps
if the indirect discharger discloses to the pretreatment
control authority in a report submitted under 40 CFR
403.12(b) that it uses exclusively TCP bleaching processes
at that fiber line. These pretreatment standards must be
attained on or before [insert date 3 years from publication
date]:
Subpart E
Pollutant or
pollutant
parameter
AOX
PSES (TCP)
Maximum for any 1 day
-------
Subpart E
Pollutant or
pollutant
property
Pentachlorophenol
Trichlorophenol
Supplemental PSES
Maximum for any . 1 day
kg/kkg
(or pounds per
1,000 -Ib) of
product
0.00058exp(0.017x)
0.0043exp(0.017x)
Milligrams /liter
( (0.011) (12.67)
( (0.082) (12.67)
exp (0. 017x) ) /y
exp(0.017x) ) /y
x = percent sulfite pulp in final product
y = wastewater discharged in kgal per ton of product
(c) An indirect discharger must demonstrate compliance
with the pretreatment standards in paragraphs (a)(2) or
(a)(3) of this section, as applicable, by monitoring for all
pollutants at the point where the wastewater containing
those pollutants leaves the bleach plant.
925
-------
§ 430.57 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).
(a) (1) The following pretreatment standards apply to
each indirect discharger in the calcium-, magnesium-, or
sodium-based sulfite pulp segment that is a new source:
Subpart E
Production of Calcium-, Magnesium-, or Sodium-based Sulfite
Pulps
Pollutant
or
pollutant
property
AOX
PSNS
Maximum for any 1 day
Monthly Average
kg/kkg (or pounds per 1,000 Ib) of product
-------
Subpart E--Production of Ammonium-based Sulfite Pulps
Pollutant
or
pollutant property
TCDDa
TCDFa
Trichlorosyringol3
3,4, 5-trichlorocatechola
3 , 4 , 6 - trichlorocatechol3
3 , 4 , 5 - trichloroguaiacola
3,4, 6-trichloroguaiacola
4,5,6 - trichloroguaiacol3
2,4, 5-trichlorophenola
2,4, 6-trichlorophenola
Tetrachlorocatechol3
Tetrachloroguaiacol3
2,3,4, 6-tetrachlorophenola
Pentachlorophenol3
PSNS
Maximum for any
1 day
-------
pretreatment control authority in a report submitted under
40 CFR 403.12(b) that it uses exclusively TCP bleaching
processes at that fiber line:
Subpart E - Production of Ammonium-based Sulfite Pulps
Pollutant or
pollutant
parameter
AOX
PSNS (TCP)
Maximum for any 1 day
-------
Subpart E--Production of Specialty Grade Sulfite Pulps
Pollutant
or
pollutant property
TCDDa
TCDFa
Trichlorosyringol3
3,4,5- trichlorocatechol3
3,4,6 -trichlorocatechola
3,4, 5-trichloroguaiacola
3,4, 6-trichloroguaiacola
4, 5, 6-trichloroguaiacola
2 , 4 , 5-trichlorophenola
2,4, 6-trichlorophenola
Tetrachlorocatechola
Tetrachloroguaiacol3
2,3,4, 6-tetrachlorophenola
Pentachlorophenol3
PSNS
Maximum for any
.1 day
-------
pulps if the indirect discharger discloses to the
pretreatment control authority in a report submitted under
40 CFR 403.12(b) that it uses exclusively TCP bleaching
processes at that fiber line:
Subpart E - Production of Specialty Grade Sulfite Pulps
Pollutant or
pollutant
parameter
AOX
PSNS (TCF)
Maximum for any 1 day
-------
Subpart E
Pollutant or
pollutant
property
Pentachlorophenol
Trichlorophenol
Supplemental PSNS
Maximum for any 1 day
kg/kkg
(or pounds per
1,000 lb) of
product
0.00058exp(0.017x)
0.0043exp(0.017x)
Milligrams /liter
( (0.015) (9.12)exp
( (0.114) (9.12)exp
(0.017x) )/y
(0.017x) )/y
x = percent sulf ite pulp in final product
y = wastewater discharged in kgal per ton of product
(c) An indirect discharger must demonstrate compliance
with the pretreatment standards in paragraphs (a)(2) or
(a)(3) of this section, as applicable, by monitoring for all
pollutants at the point where the wastewater containing
those pollutants leaves the bleach plant.
§ 430.58 Best management practices (BMPs).
The definitions and requirements set forth in 40 CFR
430.03 apply to facilities in this subpart.
Subpart F--Semi-Chemical Subcategory
§ 430.60 Applicability; description of the semi-chemical
subcategory.
The provisions of this subpart are applicable to
discharges resulting from the integrated production of pulp
and paper at semi-chemical mills.
931
-------
§ 430.61 Specialized definitions.
For the purpose of this subpart, the general
definitions, abbreviations, and methods of analysis set
forth in 40 CFR part 401 and § 430.01 of this part shall
apply to this subpart.
§ 430.62 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) :
Subpart F
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations
ammonia base mills
Kg/kkg (or pounds per 1,000 Ib)
Maximum for any 1 day
8.0
10.0
H
for
of product
Average of daily values for
30 consecutive days
4.0
5.0
(*)
aWithin the range of 6.0 to 9.0 at all times.
932
-------
Subpart F
Pollutant
or
pollutant
property
BODS
TSS
PH .
BPT effluent limitations
sodium base mills
Kg/kkg (or pounds per 1,000 Ib)
Maximum for any 1 day
8.7
11.0
n
for
of product
Average of daily values for
30 consecutive days
4.35
5.5
(l)
tne range or 6.0 to 9.0 at all times.
§ 430.63 Effluent limitations guidelines representing the
degree of effluent reduction attainable by the application
k
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 § 430.62 of this subpart for 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
determined by dividing the-average-of-30-consecutive-days
limitations for BODS by 1.36 and TSS by 1.36.
933
-------
§ 430.64 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 Ib), but shall be
subject to concentration limitations. Concentration
limitations are only applicable to non-continuous
dischargers. Permittees not using chlorophenolic-contairiing
biocides must certify to the permit-issuing authority that
they are not using these biocides:
Subpart F
Pollutant or
pollutant property
Pentachlorophenol
Tr i chl orophenol
BAT effluent limitations
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0012
0.00043
Milligrams /liter
(0.029) (10.3) /y
(0.010) (10.3) /y
y = wastewater discharged, in kgal per ton of product
§ 430.65 New source performance standards (NSPS) .
Any new source subject to this subpart must achieve the
934
-------
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 BODS and TSS, but shall be subject to annual
average effluent limitations. Also, for non-continuous
dischargers, concentration limitations (mg/1) 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:
935
-------
Subpart F
Pollutant or
pollutant property
BOD5
TSS
PH
Pentachlorophenol
Trichlorophenol
NSPS
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
3.0
5.8
(i )
Average of
daily
values for
30
consecutive
days
1.6
3.0
(1 )
Non- continuous
Dischargers
(Annual Average)
0.84
1.6
(l )
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0012
0.00043
Milligrams/liter
(0.041) (7.3)/y
(0.014) (7.3)/y
y = wastewater discharged in kgal per ton at all times
lWithin the range of 5.0 to 9.0 at all times.
§ 430.66 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
936
-------
permit-issuing authority that they are not using these
biocides. PSES must be attained on or before July 1, 1984:
Subpart F
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSES
Maximum for any 1 day
Milligrams/ liter
(0.032) (10.3)/y
(0.010) (10.3)/y
Kg/kkg (or pounds per
1,000 Ib) of product3
0 . 0014
0.00043
y = wastewater discharged in kgal per ton of product
aThe following equivalent mass limitations are provided as guidance-in
cases when POTWs find it necessary to impose mass equivalent
limitations.
§430.67 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:
937
-------
Subpart F
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSNS
Maximum for any 1 day
Milligrams/ liter
(0.045) (7. 3)/y
(0.014) (7.3)/y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0014
0.00043 .
y = wastewater discharged in kgal per ton of product
The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass equivalent |
limitations.
Subpart G-Mechanical Pulp Subcategory
§ 430.70 Applicability; description of the mechanical pulp
subcategory.
The provisions of this subpart are applicable to
discharges resulting from: the production of pulp and paper
at groundwood chemi-mechanical mills; the production of pulp
and paper at groundwood mills through the application of the
thermo-mechanical process; the integrated production of pulp
and coarse paper, molded pulp products, and newsprint at
groundwood mills; and the integrated production of pulp and
fine paper at groundwood mills.
§ 430.71 Specialized definitions.
For the purpose of this subpart, the general
definitions, abbreviations, and methods of analysis set
forth in 40 CFR part 401 and §430.01 of this part shall
938
-------
apply to this subpart.
§ 430.72 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), 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 G
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
mechanical pulp facilities where pulp and paper at
groundwood chemi -mechanical mills are produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
13.5
19.75
C1)
Average of daily
values for 30
consecutive days
7.05
10.65
H
Non-continuous
dischargers
(Annual Average)
3.96
5.85
(x)
'Withxn the range of 5.0 to 9.0 at all times.
939
-------
Subpart G
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
mechanical pulp facilities where pulp and paper at
groundwood mills are produced through the application of
the thermo-mechanical process
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
10.6
15.55
P)
Average of daily
values for 30
consecutive days
5.55
8.35
(M
Non- continuous
dischargers
(Annual Average)
3.12
4.59
(*)
Within the range of 5.0 to 9.0 at all times.
Subpart G
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
mechanical pulp facilities where the integrated production
of pulp and coarse paper, molded pulp products, and
newsprint at groundwood mills occurs
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
7.45
12.75
t1)
Average of daily
values for 30
consecutive days
3.9
6.85
(l)
Non- continuous
dischargers
(Annual Average)
2.19
3.76
(*)
Within the range of 5.0 to 9.0 at all times.
940
-------
Subpart G
Pollutant
or
pollutant
property
BODS
TSS
PH
BPT effluent limitations for
mechanical pulp facilities where the integrated production
of pulp and fine paper at groundwood mills occurs
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
6.85
11.75
t1) .
Average of daily
values for 30
consecutive days
3.6
S.3
(M
Non- continuous
dischargers
(Annual Average)
2.0
3.5
t1)
(b) The following limitations establish the quantity
or quality of pollutants or pollutant properties, controlled
by this section, resulting from the use of wet barking
operations, which may be discharged by a point source
subject to the provisions of this subpart. These
i
limitations are in addition to the limitations set forth in
paragraph (a) of this section and shall be calculated using
the proportion of the mill's total production due to use of
logs which are subject to such operations. 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:
941
-------
Subpart G
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
mechanical pulp facilities where pulp and paper at
groundwood chemi -mechanical mills are produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.9
2'. 6
(l)
Average of daily
values for 30
consecutive days
0.45
1.45
(l)
Non-continuo\is
dischargers
(Annual Average)
0.25
0 .80
H
xWithin the range of 5.0 to 9.0 at all times.
Subpart G
Pollutant
or
pollutant
property
BODS
TSS
PH
BPT effluent limitations for
mechanical pulp facilities where pulp and paper at
groundwood mills are produced through the application of
the thermo -mechanical process
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.9
2.7
(a)
Average of daily
values for 30
consecutive days
0.45
1.45
(*)
Non- continuous
dischargers
(Annual Average)
0.3
0 .75
H
xWithin the range of 5.0 to 9.0 at all times.
942
-------
Subpart G
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
mechanical pulp facilities where the integrated production
of pulp and coarse paper, molded pulp products, and
newsprint at groundwood mills occurs
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
1.15
2.0
C1)
Average of daily
values for 30
consecutive days
0.55
1.1
H
Non- continuous
dischargers
(Annual Average)
0.30
0.60
C1)
'Within the range of 5.0 to 9.0 at all times,
Subpart G
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for '
mechanical pulp facilities where the integrated production
of pulp and fine paper at groundwood mills occurs
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
1.1
1.95
H
Average of daily
values for 30
consecutive days
0.55
1.1
n
Non - cont inuous
dischargers
(Annual Average)
0.35
0. 60
t1)
^Within the range of 5.0 to 9.0 at all times.
(c) The following limitations establish the quantity
or quality of pollutants or pollutant parameters, controlled
by this section, resulting from the use of log washing or
chip washing operations, which may be discharged by a point
943
-------
source subject to the provisions of this subpart. These
limitations are in addition to the limitations set forth in
paragraph (a) of this section and shall be calculated using
the proportion of the mill's total production due to use of
logs and/or chips which are subject to such operations. Non-
continuous dischargers shall not be subject to the maximum
day and average of 30 consecutive days limitations, but
shall be subject to the annual average effluent limitations:
Subpart G
Pollutant
or
pollutant
property
BODS
TSS
PH
BPT effluent limitations for
mechanical pulp facilities where pulp and paper at
groundwood chemi -mechanical mills are produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.05
0.25
(*)
Average of daily
values for 30
consecutive days
0.05
0.15
H
Non- continuous
dischargers
(Annual Average)
0.05
0.10
(l>
^Within the range of 5.0 to 9.0 at all times.
944
-------
Subpart G
Pollutant
or
pollutant
property
BODS
TSS
PH
BPT effluent limitations for
mechanical pulp facilities where pulp and paper at
groundwood mills are produced through the application of
the thermo -mechanical process
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.05
0.30
H
Average of daily
values for 30
consecutive days
. 0.05
- 0 . 15
P)
Non-continuous
dischargers
(Annual Average)
0.05
0.05
t1)
the range of 5.0 to 9.0 at all times.
Subpart G
Pollutant
or
pollutant
property
BODS
TSS
PH
BPT effluent limitations for
mechanical pulp facilities where the integrated production
of pulp and coarse paper, molded' pulp products, and
newsprint at groundwood mills occurs
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.15
0.20
t1)
Average of daily
values for 30
consecutive days
0.05
0 .15
C1)
Non- continuous
dischargers
(Annual Average)
0.05
0.10
H
the range of 5.0 to 9.0 at all times.
945
-------
Subpart G
Pollutant
or
pollutant
property
BODS
TSS
PH
BPT effluent limitations for
mechanical pulp facilities where the integrated production
of pulp and fine paper at groundwood mills occurs
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.15
0.2
C1)
Average of daily
values for 30
consecutive days
0.05
0.15
H
Non- continuous
dischargers
(Annual Average )
0.05
0.10
(l)
JWithin the range of 5.0 to 9.0 at all times.
(d) The following limitations establish the quantity
or quality of pollutants or pollutant properties, controlled
by this section, resulting from the use of log flumes or log
ponds, which may be discharged by a point source subject to
the provisions of this subpart. These limitations are in
addition to the limitations set forth in paragraph (a) of
this section and shall be calculated using the proportion of
the mill's total production due to use of logs which are
subject to such operations. Non-continuous dischargers
shall not be subject to the maximum day and average of 30
consecutive days limitations but shall be subject to the
annual average effluent limitations:
946
-------
Subpart G
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
mechanical pulp facilities where pulp and paper at
groundwood chemi -mechanical mills are produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.15
0.55
C1)
Average of daily
values for 30
consecutive days
0.05
0.3
(*)
Non- continuous
dischargers
(Annual Average)
0. 05
0.15
t1)
^Within the range of 5.0 to 9.0 at all times.
Subpart G
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
mechanical pulp facilities where pulp and paper at
groundwood mills are produced through the application of
the thermo-mechanical process
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.15
0 .60
H
Average of daily
values for 30
consecutive days
0.15
0.35
P)
Non- continuous
dischargers
(Annual Average)
0.05
0.15
P)
^within the range of 5.0 to 9.0 at all times.
947
-------
Subpart G
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
mechanical pulp facilities where the integrated production
of pulp and coarse paper, molded pulp' products, and
newsprint at groundwood mills occurs ',
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.25
0.45
(l)
Average of daily
values for 30
consecutive days
0.1
0.25
t1)
Non- continuous
dischargers
(Annual Average)
0 .05
0.15
(*)
xWithin the range of 5.0 to 9.0 at all times.
Subpart G
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
mechanical pulp facilities where the integrated production
of pulp and fine paper at groundwood mills occurs
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0 .2
0.4
(l)
Average of daily
values for 30
consecutive days
0.05 '
0.25
(l)
Non- continuous
dischargers
(Annual Average)
0.05
0.15
(l)
xWithin the range of 5.0 to 9.0 at all times.
(e) For those mills using zinc hydrosulfite as a
bleaching agent in the manufacturing process, the following
effluent limitations are to be added to the base limitations
set forth in paragraph (a) of this section. Permittees not
948
-------
using zinc hydrosulfite as a bleaching agent must certify to
the permit issuing authority that they are not using this
bleaching compound. Non-continuous dischargers shall not be
subject to the maximum day and average of 30 consecutive
days effluent limitations, but shall be subject to annual
average effluent limitations:
Subpart G
Pollutant
or
pollutant
property
Zinc
BPT effluent limitations for
mechanical pulp facilities where pulp and paper at
groundwood chemi -mechanical mills -are produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.34
Average of daily
values for 30
consecutive days
0.17
Non- continuous
dischargers
(Annual Average)
0.11
Subpart G
Pollutant
or
pollutant
property
Zinc
BPT effluent limitations for
mechanical pulp facilities where pulp and paper at
groundwood mills are produced through the application of
the thermo -mechanical process
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.26
Average of daily
values for 30
consecutive days
0.13
Non- continuous
dischargers
(Annual Average)
0.09
949
-------
Subpart G
Pollutant
or
pollutant
property
Zinc
BPT effluent limitations for
mechanical pulp facilities where the integrated production
of pulp and coarse paper, molded pulp products, and
newsprint at groundwood mills occurs
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.30
Average of daily
values for 30
consecutive days
0.15
Non- continuous
dischargers
(Annual Average)
0.10
Subpart G
Pollutant
or
pollutant
property
Zinc
BPT effluent limitations for
mechanical pulp facilities where the integrated production
of pulp and fine paper at groundwood mills occurs
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
0.275
Average of daily
values for 3 0
consecutive days
0.135
Non- continuous
dischargers
(Annual Average)
0.090
950
-------
§ 430.73 Effluent limitations guidelines representing the
degree of effluent reduction attainable by the application
of the best conventional pollutant control technology (BCT).
(a) (1) The following applies to: mechanical pulp
facilities where the integrated production of pulp and
coarse paper, molded pulp products, and newsprint at
groundwood mills occurs; and mechanical pulp facilities
where the integrated production of pulp and fine paper at
groundwood mills occurs:
(2) 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 § 430.72 of this subpart for the best
practicable control technology currently available (BPT).
(b) The following applies to mechanical pulp
facilities where pulp and paper at groundwood chemi-
mechanical mills are produced'and mechanical pulp facilities
where pulp and paper at groundwood mills are produced
through the application of the thermo-mechanical process:
[Reserved]
§ 430.74 Effluent limitations representing the degree of
951
-------
effluent reduction attainable by the application of the best j^t
9
available technology economically achievable (BAT).
(a) The following applies to mechanical pulp
facilities where pulp and paper at groundwood mills are
produced through the application of the thermo-mechanical
process; mechanical pulp facilities where the integrated
production of pulp and coarse paper, molded pulp products.,
and newsprint at groundwood mills occurs; and mechanical
pulp facilities where the integrated production of pulp and
fine paper, at groundwood mills occurs: (1) 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 Jttfe,
V
reduction attainable by the application of the best :
available technology economically achievable (BAT), except
that non-continuous dischargers shall not be subject to the
maximum day mass limitations in kg/kkg (lb/1000 Ib), but ;
shall be subject to concentration limitations.
Concentration limitations are only applicable to non-
continuous dischargers. Pentachlorophenol and
trichlorophenol limitations are only applicable at '
facilities where chlorophenolic-containing biocides are
used. Permittees not using chlorophenolic-containing
biocides must certify to the permit-issuing authority that
952
-------
they are not using these biocides. Zinc limitations are
only applicable at facilities where zinc hydrosulfite is
used as a bleaching agent. Permittees1 not using zinc
hydrosulfite as a bleaching agent must certify to the permit
issuing authority that they are not using this bleaching
compound:
Subpart G
Pollutant or
pollutant property
Pentachlorophenol
Tri chl or opheno 1
Zinc
BAT effluent limitations for
mechanical pulp facilities where pulp and paper
at groundwood mills are produced through the
application of the thermo -mechanical process
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.00097
0. 00088
0 .26
Milligrams /liter
(0.011) (21.1)/y
(0.010) (21.1)/y
(3.0) (21.1)/y
y = wastewater discharged in kgal per ton of product
953
-------
Subpart G
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
Zinc
BAT effluent limitations for
mechanical pulp facilities where the integrated
production of pulp and coarse paper, molded pulp
products, and newsprint at groundwood mills
occurs
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0011
0.00099
0.30
Milligrams /liter
(0.011) (23.8) /y
(0.010) (23 . 8) /y
(3.0) .(23. 8) /y
y ~ wastewater discharged in kgal per ton of product
Subpart G
Pollutant or
pollutant property
Pent achl oropheno 1
Trichlorophenol
Zinc
BAT effluent limitations for
mechanical pulp facilities where the integrated
production of pulp and fine paper at groundwood
mills occurs
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0010
0.00092
0.27
Milligrams /liter
(0.011) (21.9)/y
(0.010) (21.9)/y
(3.0) (21.9)/y :
y = wastewater discharged in kgal per ton of product
(b) The following applies to mechanical pulp
facilities where pulp and paper at groundwood chemi-
mechanical mills are produced:
[Reserved]
§ 430.75 New source performance standards (NSPS).
954
-------
(a) The following applies to mechanical pulp
facilities where pulp and paper at groundwood mills are
produced through the application of the thermo-mechanical
process; mechanical pulp facilities where the integrated
production of pulp and coarse paper, molded pulp products,
and newsprint at groundwood mills occurs; and mechanical
pulp facilities where the integrated production of pulp and
fine paper at groundwood mills occurs: (1) 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/1) shall apply, where
provided. Concentration limitations will only apply to non-
continuous dischargers. Pentachlorophenol and
trichlorophenol limitations are only applicable at
facilities where chlorophenolic-containing biocides are
used. Permittees not using chlorophenolic-containing
biocides must certify to the permit-issuing authority that
they are not using these biocides. Zinc limitations are
only applicable at facilities where zinc hydrosulfite is
used as a bleaching agent. Permittees not using zinc
hydrosulfite as a bleaching agent must certify to the permit
issuing authority that they are not using this bleaching
955
-------
compound:
Subpart G
Pollutant or
pollutant property
BODS
TSS
pH
Pentachlorophenol
Trichlorophenol
Zinc
NSPS for
mechanical pulp facilities where pulp and paper
at groundwood mills are produced through the
application of the thermo-mechanical process
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
4.6
8.7
0 )
Average of
daily
values for
30
consecutive
days
2 .5
4.6
t1 )
Non- continuous
Dischargers
(Annual Average)
1.3
2.4
(1 )
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.00097
0.00088
0.17
Milligrams/liter
(0.017) (13. 8) /y
(0.015) (13.8)/y
(3.0) (13. 8) /y
y = wastewater discharged in kgal per ton at all times
xWithin the range of 5.0 to 9.0 at all times.
956
-------
Subpart G
Pollutant or
pollutant property
BODS
TSS
pH
'
Pentachlorophenol
Trichlorophenol
Zinc
NSPS for
mechanical pulp facilities where the integrated
production of pulp and coarse paper, molded pulp
products, and newsprint at groundwood mills
occurs
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
-. 4.6
7.3
(a )
Average of
daily
values for
30
consecutive
days
2.5
3.8
(* )
Non-continuous
Dischargers
(Annual Average)
1.3
2.0
(l ) '
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0011
0.00099
0.21
Milligrams/liter
(0.016) (16.8)/y
(0. 014) (16.8) /y
(3.0) (16.8)/y
y = wastewater discharged in kgal per ton at all times
the range of 5.0 to 9.0 at all times.
957
-------
Subpart
Pollutant or
pollutant property
BODS
TSS
PH
Pentachlorophenol
Trichlorophenol
Zinc
NSPS for
mechanical pulp facilities where the integrated
production of pulp and fine paper at groundwood
mills occurs
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
3.5
5.8
(l )
Average of
daily
values for
30
consecutive
days
1.9
3.0
r )
Non- continuous
Dischargers
(Annual Average)
0.99
1.58
(x )
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0010
0.00092
0.19
Milligrams/ liter
(0.016) (15.4)/y
(0.014) (15.4)/y
(3.0) (15.4)/y
y = wastewater discharged in kgal per ton at all times
*Within the range of 5.0 to 9.0 at all times.
(b) The following applies to mechanical pulp
facilities where pulp and paper at groundwood chemi-
mechanical mills are produced: ;
[Reserved]
§ 430.76 Pretreatment standards for existing sources
(PSES).
(a) The following applies to mechanical pulp
958
-------
facilities where pulp and paper at groundwood mills are
produced through the application of the thermo-mechanical
process; mechanical pulp facilities where the integrated
production of pulp and coarse paper, molded pulp products,
and newsprint at groundwood mills occurs; and mechanical
pulp facilities where the integrated production of pulp and
fine paper at groundwood mills occurs: (1) 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). Pentachlorophenol and
trichlorophenol limitations are only applicable at
facilities where chlorophenolic-containing biocides are
used. Permittees not using chlorophenolic-containing
biocides must certify to the permit-issuing authority that
they are not using these biocides. Zinc limitations are
only applicable at facilities where zinc hydrosulfite is
used as a bleaching agent. Permittees not using zinc
hydrosulfite as a bleaching agent must certify to the
permit-issuing authority that they are not using this
bleaching compound. PSES must be attained on or before July
1, 1984:
959
-------
Subpart G
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
Zinc
PSES for
mechanical pulp facilities where pulp and paper
at groundwood mills are produced through the
application of the thermo -mechanical process
Maximum for any 1 day
Milligrams/ liter
(mg/1)
(0.011) (21.1)/y
(0.010) (21.1)/y
(3.0) (21.1)/y
Kg/kkg (or pounds per 1,000
Ib) of product3
0.00097
0.00088
0.26
y = wastewater discharged in kgal per ton of product
'The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
Subpart G
Pollutant or
pollutant property
Pentachlorophenol
Tri chlorophenol
Zinc
PSES for
mechanical pulp facilities where the integrated
production of pulp and coarse paper, molded piilp
products, and newsprint at groundwood mills
occurs
Maximum for any 1 day
Milligrams/liter
(mg/1)
(0.011) (23. 8) /y
(0.010) (23.8)/y
(3.0) (23. 8) /y
Kg/kkg (or pounds per 1,000
Ib) of product"
0.0011
0.00099
0.30
y = wastewater discharged in kgal per ton of product
"The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
960
-------
Subpart G
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
Zinc
PSES for
mechanical pulp facilities where the
production of pulp and fine paper at
mills occurs
integrated
groundwood
Maximum for any 1 day
Milligrams/liter
(mg/1)
(0.011) (21.9)/y
(0.010) (21.9)/y
(3.0) (21. 9) /y
Kg/kkg (or pounds per 1,000
Ib) of product3
0.0010
0.00092
0.27
y = wastewater discharged in kgal per ton of product
roiiowing equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
(b) The following applies to mechanical pulp
facilities where pulp and paper at groundwood chemi-
mechanical mills are produced:
[Reserved]
§ 430.77 Pretreatment standards for new sources (PSNS).
(a) The following applies to mechanical pulp
facilities where pulp and paper at groundwood mills are
produced through the application of the thermo-mechanical
process; mechanical pulp facilities where the integrated
production of pulp and coarse paper, molded pulp products,
and newsprint at groundwood mills occurs; and mechanical
pulp facilities where the integrated production of pulp and
fine paper at groundwood mills occurs: (1) Except as
provided in 40 CFR 403.7, any new sourcessubject to this
961
-------
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).
Pentachlorophenol and trichlorophenol limitations are only
applicable at facilities where chlorophenolic-containing
biocides are used. Permittees not using
chlorophenolic-containing biocides must certify to the
permit-issuing authority that they are not using these
biocides. Zinc limitations are only applicable at
facilities where zinc hydrosulfite is used as a bleaching
agent. Permittees not using zinc hydrosulfite as a bleaching
agent must certify to the permit issuing authority that they
are not using this bleaching compound:
Subpart G
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
Zinc
PSNS for
mechanical pulp facilities where pulp and papesr
at groundwood mills are produced through the
application of the thermo-mechanical process
Maximum for any 1 day
Milligrams/liter
(mg/1)
(0.017) (13. 8) /y
(0.015) (13.8)/y
(3.0) (13. 8) /y
Kg/kkg (or pounds per 1,000
Ib) of product3
0.00097
0.00088
0.17
y = wastewater discharged in kgal per ton of product
"The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
962
-------
Subpart G
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
Zinc
PSNS for
mechanical pulp facilities where the integrated
production of pulp and coarse paper, molded pulp
products, and newsprint at groundwood mills
occurs
Maximum for any 1 day
Milligrams/liter
(mg/1)
(0.016) (16.8)/y
(0.014) (16. 8) /y
(3.0) (16.8)/y
Kg/kkg (or pounds per 1,000
Ib) of product3
, 0.0011
0.00099
0.21
y = wastewater discharged in kgal per ton of product
aThe following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
Subpart G
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
Zinc
PSNS for
mechanical pulp facilities where the
production of pulp and fine paper at
mills occurs
integrated
groundwood
Maximum for any 1 day
Milligrams /liter
(mg/1)
(0.016) (15.4)/y
(0.014) (15.4) /y
(3.0) (15.4)/y
Kg/kkg. (or pounds per 1,000
Ib) of product3
0.0010
0.00092
0 . 19
y = wastewater discharged in kgal per ton of product
aThe following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
(b) The following applies to mechanical pulp
facilities where pulp and paper at groundwood chemi-
mechanical mills are produced:
963
-------
[Reserved]
Subpart H-Non-Wood Chemical Pulp
§ 430.80 Applicability; description of the non-wood
chemical pulp subcategory.
The provisions of this subpart are applicable to
discharges resulting from the production of pulp and paper
at non-wood chemical pulp mills. This subcategory includes,
but is not limited to, mills producing non-wood pulps from
chemical pulping processes such as kraft, sulfite, or socla.
§ 430.81 Specialized definitions.
The general definitions, abbreviations, and methods of
analysis set forth in 40 CFR 401 and § 430.01 of this part
shall apply to this subpart.
§ 430.82 Effluent limitations representing the degree of
effluent reduction attainable by the application of best
practicable control technology currently available (BPT).
[Reserved]
§ 430.83 Effluent limitations representing the degree of
effluent reduction attainable by the application of best
conventional pollutant control technology (BCT). ;
[Reserved]
§ 430.84 Effluent limitations representing the degree of
effluent reduction attainable by the application of best
964
-------
available technology economically achievable (BAT).
[Reserved]
§ 430.85 New source performance standards (NSPS)
[Reserved]
§ 430.86 Pretreatment standards for existing sources (PSES)
[Reserved]
§ 430.8-7 Pretreatment Standards for new sources (PSNS) .
[Reserved]
Subpart I-Secondary Fiber Deink
§ 430.90 Applicability; description of the
deink-subcategory.
The provisions of this subpart are applicable to
discharges resulting from the integrated production of pulp
and paper at deink mills.
§ 430.91 Specialized definitions.
For the purpose of this subpart, the general
definitions, abbreviations, and methods of analysis set
forth in 40 CFR part 401 and § 430.01 of this part shall
apply to this subpart.
§ 430.92 Effluent limitations representing the degree of
effluent reduction attainable by the application of the best
practicable control technology currently available (BPT).
965
-------
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 I
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations -
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
18.1
24.05
(l)
Average of daily
values for 30
consecutive days
9.4
12.95
(l)
Non-continuous
dischargers
(Annual Average)
5.3
7 .12
n
Within the range of 5.0 to 9.0 at all times.
§ 430.93 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:
966
-------
limitations shall be the same as those specified for
conventional pollutants (which are defined in 40 CFR 401.16)
in § 430.92 of this subpart for the best practicable control
technology currently available (BPT).
§ 430.94 Effluent limitations representing the degree of
f
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 Ib) 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:
967
-------
Subpart I
(Facilities where fine or tissue paper is produced)
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
BAT effluent limitations
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0030
0.0069
Milligrams/liter
(0.029) (24.4)/y
(0.068) (24.4)/y
y = wastewater discharged in kgal per ton of product
Subpart I
(Facilities where newsprint is produced)
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
BAT effluent limitations
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0030
0.0010
Milligrams/liter
(0.029) (24.4)/y
(0. 010) (24.4) /y
y = wastewater discharged in kgal per ton of product
§ 430.95 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/1) shall apply,
968
-------
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:
Subpart I
(Facilities where fine paper is produced)
Pollutant or
pollutant property
BODS
TSS
pH
Pentachlorophenol
Trichlorophenol
NSPS
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum . for any 1
day
5.7
8.7
(* )
Average of
daily
values for
30
consecutive
days
3.1
4.6
P )
Non -continuous
Dischargers
(Annual Average)
1.6
2.4
(1 )
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0030
0.0069
Milligrams /liter
(0.045) (15. 9) /y
(0.104) (15. 9) /y
y = wastewater discharged in kgal per ton at all times
1Wj.thin the range of 5.0 to 9.0 at all times.
969
-------
Subpart I
(Facilities where tissue paper is produced)
Pollutant or
pollutant property
BODS
TSS
pH
Pentachlorophenol
Trichlorophenol
NSPS
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
9.6
13.1
(x )
Average of
daily
values for
30
consecutive
days
5.2
6.8
0 )
Non- continuous
Dischargers
(Annual Average)
2.72
3.58
(1 )
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0030
0.0069
Milligrams /liter
(0.036) (19.5)/y
(0. 085) (19.5) /y
y « wastewater discharged in kgal per ton at all times
Within the range of 5.0 to 9.0 at all times.
970
-------
Subpart I
(Facilities where newsprint is produced)
Pollutant or,
pollutant property
BODS
TSS
PH
Pentachlorophenol
Trichlorophenol
. NSPS
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
' 6.0
12 .0
C1 )
Average of
daily
values for
30
consecutive
days
3.2
6.3
(: )
Non- continuous
Dischargers
(Annual Average)
1.7
3.3
C1 ).
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0030
0.0010
Milligrams/ liter
(0.044) (16.2)/y
(0.015) (16.2)/y
y = wastewater discharged in kgal per ton at all times
the range of 5.0 to 9.0 at all times.
§ 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
971
-------
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)
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSES
Maximum for any 1 day
Milligrams/liter
mg/1)
(0.032) (24.4)/y
(0.082) (24.4)/y
Kg/kkg ( or pounds per
1,000 Ib) of product3
0.
0.
0033
0084
y = wastewater discharged in kgal per ton of product
* 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)
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSES
Maximum for any 1 day
Milligrams /liter
mg/1)
(0.032) (24.4)/y
(0.010) (24.4) /y
, Kg/kkg ( or pounds per
1,000 Ib) of product3
0.
0.
0033
0010
y = wastewater discharged in kgal per ton of product
The following equivalent mas limitations are provided as guidance in
cases when POTWs find it necessary to impose mass equivalent.
limitations.
§ 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
972
-------
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)
Pollutant or
pollutant property
Pent achloropheno 1
Trichlorophenol
PSNS
, Maximum for any 1 day
Milligrams /liter
rag/1)
(0.049) (15.9)/y
(0.126) {15. 9) /y
Kg/kkg ( or pounds per
1,000 Ib) of product3
0.
0.
0033
0084
y = wastewater discharged in kgal per ton of product
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)
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSNS
Maximum for any 1 day
Milligrams/ liter
mg/1)
(0.040) (19.5)/y
(0.103) (19.5)/y
Kg/kkg ( or pounds per
1,000 Ib) of product3
0.
0.
0033
0084
y = wastewater discharged in kgal per ton of product
Tne following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass equivalent
limitations.
973
-------
Subpart I
(Facilities where newsprint is produced)
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSNS
Maximum for any 1 day
Milligrams/liter
mg/1)
(0.048) (16.2)/y
(0.015) (16.2)/y
Kg/kkg ( or pounds per
1,000 Ib) of product3
0 .
0.
0033
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
§ 430.100 Applicability; description of the secondary fiber
non-deink sttbcategory.
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.
§ 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 § 430.01 of this part shall apply to this
subpart.
(b) Noncorrugating medium furnish subdivision mills
974
-------
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.
§ 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
Pollutant
or
pollutant
property
BODS
TSS
PH
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 Ib) of product
Maximum for any 1 day
3.0
5.0
H
Average of daily values for
30 consecutive days
1.5
2.5
(l)
975
-------
Subpart J
Pollutant
or
pollutant
property
BODS
TSS
PH
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 Ib) of product .
Maximum for any 1 day
5.7
9.2
(x) ;
Average of daily values for
30 consecutive days
2.8
4.6
Within the range of 6.0 to 9.0 at all times.
Subpart J
Pollutant
or
pollutant
property
BODS
TSS
pH
Setteable
Solids
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 Ib)
Maximum for any 1 day
5.0
5.0
t1)
(2)
of product
Average of daily values
30 consecutive days
for
3.0
3.0
t1)
(2)
Within the range of 6.0 to 9.0 at all times.
2Not to exceed 0.2 ml/1.
(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
976
-------
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 J
Pollutant
or
pollutant
property
BOD5
TSS
pH
BPT effluent limitations for
secondary fiber non-deink facilities where tissue from
wastepaper is produced without deinking
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
1 13.7
17.05
n
Average of daily
values for 30
consecutive days
7.1
9.2
-------
[ (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 §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
BODS 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 BODS and TSS by 1.90 and
1.90.
§ 430.104 Effluent limitations representing the degree of
978
-------
.Subpart J
Pollutant or
pollutant property
Pent achl orophenol
Trichlorophenol
BAT effluent limitations for
secondary fiber non-deink facilities where
paperboard from wastepaper is produced
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.00087
0.00030
Milligrams/liter
(0.029) (7.2)/y
(0.010) (7.2)/y
y = wastewater discharged in kgal per ton of product
Subpart J
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
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 pounds
per 1,000 Ib) of
product
0.0017
0.00060
Milligrams/liter
(0.029) (14.4) /y
(0.010) (14.4) /y
y = wastewater discharged in kgal per ton of product
980
-------
Subpart J
Pollutant or
pollutant property
Pentachlorophenol
Tr i chlorophenol
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 pounds
per 1,000 Ib) of
product
0.0030
0.0011
Milligrams/liter
(0.029) (25.2)/y
(0.010) (25.2)/y
y = wastewater discharged in kgal per ton of product
Subpart J
\ Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
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 pounds
per 1,000 Ib) of
product
0.0026
0.00088
Milligrams /liter
(0.029) (21.1) /y
(0 . 010) (21.1) /y
y = wastewater discharged in kgal per ton of product
§ 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/1) shall apply,
981
-------
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:
Subpart J
Pollutant or
pollutant property
BODS
TSS
pH
Pentachlorophenol
Trichlorophenol
NSPS for
secondary fiber non-deink facilities where
paperboard from wastepaper is produced- -
noncorrugating medium furnish subdivision
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
2.6
3.5
(l )
Average of
daily
values for
30
consecutive
days
1-4
1.8
(x )
Maximum for any 1
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.00087
0.00030
Non -continuous
Dischargers
(Annual Average)
0.73
0.95
C1 )
day
Milligrams/liter
(0.065) (3.2)/y
(0.023) (3.2)/y
y = wastewater discharged in legal per ton at all times
"Within the range of 5.0 to 9.0 at all times.
982
-------
Subpart J
Pollutant or
pollutant property
BODS
TSS
PH
Pentachlorophenol
Trichlorophenol
NSPS for
secondary fiber non-deink facilities where
paperboard from wastepaper is produced- -
corrugating medium finish subdivision)
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
3.9
4.4
(l )
Average of
daily
values for
30
consecutive
days
2.1
2.3
t1 )
Non- continuous
Dischargers
(Annual Average)
1.1
1.2
(l )
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.00087
0.00030
Milligrams/ liter
(0.065) (3.2/y
(0.023) (3.2)/y
y = wastewater discharged in kgal per ton at all times
xWithin the range of 5.0 to 9.0 at all times.
983
-------
Subpart J
Pollutant or
pollutant property
BODS
TSS
PH
Pentachlorophenol
Trichlorophenol
NSPS for
secondary fiber non-deink facilities where
builders ' paper and roofing felt from wastepaper
are produced
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
1.7
2.7
C1 )
Average of
daily
values for
30
conse.cutive
days
0.94
1.40
P )
Maximum for any 1
Kg/kkg (or pounds
per 1,.000 Ib) of
- product
0.0017
0. OOOSO
Non-continuous
Dischargers
(Annual Average)
0.49
0.74
: c1 )
day
Milligrams/ liter
(0.155) (2.7)/y
(0.053) (2.7) /y
y = wastewater discharged in kgal per ton at all times
'witnin tne range of 5.0 to 9.0 at all times.
984
-------
Subpart J
Pollutant or
pollutant property
BODS
TSS
PH
Pentachlorophenol
Tr i chlorophenol
NSPS for
secondary fiber non-deink facilities where tissue
from wastepaper is produced without deinking
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
4.6
10.2
(l )
Average of
daily
values for
30
consecutive
days
2.5
5.3
(x )
Non - cont inuous
Dischargers
(Annual Average)
1.3
2.8
(l )
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0030
0.0011
Milligrams/liter
(0.045) (16.3)/y
(0.015) (16.3)/y
y = wastewater discharged in kgal per ton at all times
xWithin the range of 5.0 to 9.0 at all times.
985
-------
Subpart J
Pollutant or
pollutant property
BODS
TSS
PH
Pentach.loroph.enol
Tr i chlorophenol
NSPS for
secondary fiber non-deink facilities where molded
products from wastepaper are produced without
de inking
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
2.1
4.4
(l )
Average of
daily
values for
30
consecutive
days
1.1
2.3
(1 )
Non-continuous
Dischargers
(Annual Average)
0.58
1.21
(1 )
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0 .0025
0.00088
Milligrams /liter
(0.107) (5.7)/y
(0.037) (5.7)/y
y = wastewater discharged in kgal per ton at all times
the range of 5.0 to 9.0 at all times.
§ 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
986
-------
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
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSES for
secondary fiber non-deink facilities where
paperboard from wastepaper is produced
Maximum for any 1 day :
Milligrams/liter (mg/1)
(0.032) (7.2)/y
(0.010) (7.2)/y
Kg/kkg (or pounds per
1,000 Ib) of product.3
0.00096
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
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSES for
secondary fiber non-deink facilities where
builders ' paper and roofing felt from wastepaper
are produced
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.032) (14.4)y
(0.010) (14.4)y
Kg/kkg (or pounds per
1,000 Ib) of product*
0.0019
0. 00060
y - wastewater discharged in kgal per ton of product
The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
987
-------
Subpart J
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSES for
secondary fiber non-deink facilities where tissue
from wastepaper is produced without deinking
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.032) (25.2)y
(0.010) (25.2/y
Kg/kkg (or pounds per
1,000 Ib) of product a
0.0034
0.0011
y = wastewater discharged in kgal per ton of product
The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
Subpart J
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSES for
secondary fiber non-deink facilities where molded
products from wastepaper are produced without
deinking
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.032) (21.1)y
(0.010) (21.1)y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0028
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.
§ 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
988
-------
biocides must certify to the permit-issuing authority that
they are not using these biocides:
Subpart J
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSNS for :
secondary fiber non-deink facilities where
paperboard from wastepaper is produced
Maximum for any 1 day
Milligrams /liter (mg/1)
(0.072) (3. 2)/y
(0.023) (3. 2)/y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.00095
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
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSNS for
secondary fiber non-deink facilities where
builders ' paper and roofing felt from wastepaper
are produced
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.171) (2.7)/y
(0.053) (2. 7)/y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0019
0.00060
y = wastewater discharged in kgal per ton of product
The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
989
-------
Subpart J
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSNS for
secondary fiber non-deink facilities where tissue
from wastepaper is produced without deinking
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.049) (16.3)/y
(0.015) (16. 3)/y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0034
0.0011
y = wastewater discharged in kgal per ton of product
The following equivalent mass limitations are provided'as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
Subpart J
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSNS for
secondary fiber non-deink facilities where molded
prodiicts from wastepaper are produced without
deinking
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.118) (5.7)/y
(0.037) (5.7)/y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0028
0.00088
y = wastewater discharged in kgal per ton of product
The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
Subpart K-Pine and Lightweight Papers from Purchased Pulp
§ 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
990
-------
mills.
§ 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
§ 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. . :
§ 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
991 :
-------
effluent limitations:
Subpart K
Pollutant
or
pollutant
property
BODS
TSS
pH
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 Ib) of product
Continuous dischargers
'Maximum for any 1
day
8.2
11.0
H
Average of daily
values for 30
consecutive days
4.25
5.9
(-1)
Non- continuous
dischargers
(Annual Average)
2.4
3.2
(x)
lWitnin the range of 5.0 to 9.0 at all times.
Subpart K
Pollutant
or
pollutant
property
BODS
TSS
pH
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 Ib) of product
Continuous dischargers
Maximum for any 1
day
17.4
24.3
H
Average of daily
values for 30
consecutive days
9.1
13 .1
t1)
Non- continuous
dischargers
(Annual Average)
5.1
7.2
P)
the range of 5.0 to 9.0 at all times.
992
-------
Subpart K
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for non- integrated mills
where lightweight papers are produced from purchased pulp
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
24.1
21.6
C1)
Average of daily
values for 30
consecutive days
13.2
10.6
(l)
Non - cont inuous
dischargers
(Annual Average)
7.37
6.6
(l)
xWithin the range of 5.0 to 9.0 at all times.
Subpart K
Pollutant
or
pollutant
property
BODS
TSS
pH
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 Ib) of product
Continuous dischargers
Maximum for any 1
day
38.0
34.2
(l)
Average of daily
values for 30
consecutive days
20.9
16.7
(x)
Non -cont inuous
dischargers
(Annual Averacfe)
11.7
9.5
(x)
xWithin the range of 5.0 to 9.0 at all times.
§ 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
993
-------
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 § 430.102 of this subpart for the best practicable
control technology currently available (BPT).
§ 430.114 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 Ib) 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:
994
-------
Subpart K
Pollutant or
pollutant property
Pentachlorophenol
Tri chlorophenol
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 pounds
per 1,000 Ib) of
product
D.001'8
0.00064
Milligrams/liter
(0.029) (15.2)/y
(0.010) (15.2)/y
y « wastewater discharged in kgal per ton of product
Subpart K
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
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 pounds
per 1,000 Ib) of
product
0.0051
0.0018
Milligrams/liter
(0.029) (42.3)/y
(0.010) (42.3)/y
y « wastewater discharged in kgal per ton of product
995
-------
Subpart K
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
BAT effluent limitations for non- integrated mills
where lightweight papers are produced from
purchased pulp
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0059
0.0020
Milligrams/ liter
(0.029) (48.7)/y
(0,010). (48. 7) /y
y = wastewater discharged in kgal per ton of product
Subpart K
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
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 pounds
per 1,000 Ib) of
product
0.0093
0.0032
Milligrams /liter
(0.029) (76.9)/y
(0.010) (76.9)/y
y = wastewater discharged in kgal per ton of product
§ 430.115 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/1) shall apply,
996
-------
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:
997
-------
Subpart K
Pollutant or
pollutant property
BODS
TSS
PH
Pentachlorophenol
Tri chlorophenol
NSPS for non- integrated mills
. where fine paper is produced from purchased
pulp- -wood fiber furnish subdivision
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
3.5
4.4
t1 )
Average of
daily
values for
30
consecutive
days
1.9
2.3
(1 )
Non-continuous
Dischargers
(Annual Average)
1.0
1.2
(l )
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0018
0.00064
Milligrams /liter
(0.047) (9.4)/y
(0.016) (9.4)/y
y = wastewater discharged in kgal per ton at all times
Within the range of 5.0 to 9.0 at all times .
998
-------
Subpart K
Pollutant or
pollutant property
BODS
TSS
pH
Pentachlorophenol
Trichlorophenol
NSPS for non- integrated mills
where fine paper is produced from purchased
pulp cotton fiber furnish subdivision
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
7.8
9.5
(x )
Average of
daily
values for
30
consecutive
days
4.2
4.9
t1 )
Non- continuous
Dischargers
(Annual Average)
2 ,. 2
2.6
(z )
Maximum for any 1 day
Kg/kkg (or pounds
per 1, 000 Ib) of
product
0.0051
0.0018
Milligrams/liter
(0.039) (31.1)/y
(0.014) (31.1)/y
y - wastewater discharged in kgal per ton at all times [
*Within the range of 5.0 to 9.0 at all times.
999
-------
Subpart K
Pollutant or
pollutant property
BODS
TSS
PH
Pentachlorophenol
Trichlorophenol
NSPS for non- integrated mills
where lightweight papers are produced from
purchased pulp
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
13.7
12 .0
(1 )
Average of
daily
values for
30
consecutive
days
6.7
5.2
c1 )
Maximum for any 1
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0059
0.0020
Non-continuous
Dischargers
(Annual Average)
4.5
3.2
(M
day
Milligrams/liter
(0.037) (38.2) /y
(0. 013) (38.2) /y
y = wastewater discharged in kgal per ton at all times
tne range or 5.0 to 9.0 at all times.
1000
-------
Subpart K
Pollutant or
pollutant property
BODS
TSS
PH
Pentachlorophenol
Trichlorophenol
NSPS for non- integrated mills where lightweight
papers are produced from purchased pulp--
electrical grade papers subdivision
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
24.1
21.1
(x ).
Average of
daily
values for
30
consecutive
days
11.7
9.2
0 )
Non- continuous
Dischargers
(Annual Average)
7.9
5.. 6
(1 )
Maximum for any 1 day
Kg/kkg (or pounds
per 1, 000 Ib) of
product
0.0093
0.0032.
Milligrams/ liter
(0.033) (66.8) /y
(0.012) (66.8) /y
y = wastewater discharged in kgal per ton at all times
Htfithin the range of 5.0 to 9.0 at all times.
§ 430.116 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
1001
-------
permit-issuing authority that they are not using these
biocides. PSES must be attained on or before July 1, 1984:
Subpart K
Pollutant or
pollutant property
Pent achl oropheno 1
Tri chl orophenol
PSES for non- integrated mills
where fine paper is produced from purchased
pulp- -wood fiber furnish subdivision
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.032) (15.2)/y
(0.010) (15.2)/y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0020
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
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSES for non- integrated mills
where fine paper is produced -from purchased
pulp- -cotton fiber furnish subdivision
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.032) (42.3)/y
(0.010) (42.3)/y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0056
0.0018
y = wastewater discharged in kgal per ton of product
The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
1002
-------
Subpart K
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSES for non- integrated mills
where lightweight papers are produced from
purchased pulp
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.032) (48.7)/y
(0.010) (48.7)/y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0065
0.0032
y ~ wastewater discharged in kgal per ton of product
* The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
Subpart K
Pollutant or
pollutant property
t
Pentachlorophenol
Trichlorophenol
PSES for non- integrated mills where lightweight
papers are produced from purchased pulp--
electrical grade papers subdivision
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.032) (76. 9) /y
(0.010) (76.9)/y
Kg/kkg (or pounds per
1,000 Ib) of product2
0.010
0.0032
y = wastewater discharged in kgal per ton of product
"The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
§ 430.117 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
1003
-------
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 K
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSNS for non- integrated mills
where fine paper is produced from purchased
pulp- -wood fiber furnish subdivision
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.052) (9.4)/y
(0.016) (9. 4)/y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0020
0.00064
y = wastewater discharged in kgal per ton of product
aThe following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
Subpart K
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSNS for non- integrated mills
where fine paper is produced from purchased
pulp- -cotton fiber furnish subdivision
Maximum for any 1 day
Milligrams/liter (mg/1)
(0:044) (31.1)/y
(0.014) (31.1)/y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0056
0.0018
y = wastewater discharged in kgal per ton of product
aThe following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
1004
-------
Subpart K
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSNS for non- integrated mills
where lightweight papers are produced ' from
purchased pulp
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.041) (38.2) /y
(0.013) (38.2)/y
Kg/kkg (or pounds per
1,000 Ib) of prpduct3
0.0065 .
0.0020
y = wastewater discharged in kgal per ton of product
* The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
Subpart K
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSNS for non- integrated mills where lightweight
papers are produced from purchased pulp--
electrical grade papers subdivision
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.037) (66.8) /y
(0.012) (66. 8) /y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.010 ;
0.0032 ;
y = wastewater discharged in kgal per ton of product
The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
1005
-------
Subpart L-Tissue, Filter, Non-woven, and Paperboard from
Purchased Pulp
§ 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 nonintegrated mills; filter and non-woven papers at
nonintegrated mills; and paperboard at nonintegrated mills.
The production of electrical grades of board and matrix
board is not included in this subpart.
§ 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 § 430.01 of this part shall
apply to this subpart.
§ 430.122 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 -
1006
-------
subject to the maximum day and average of 30 consecutive
days limitations but shall be subject to annual average
effluent limitations:
Subpart L
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for
non- integrated mills where tissue papers are produced from
purchased pulp
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
11.4
10.25
C1)
Average of daily
values for 30
consecutive days
6.25
5.0
(l)
Non -continuous
dischargers
(Annual Average)
3 .49
2.84
C1)
^Within the range of 5.0 to 9.0 at all times.
i
i
Subpart L
Pollutant
or
pollutant
property
BODS
TSS
pH
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 Ib) of product
Continuous dischargers
Maximum for any 1
day
29.6
26.6
(*)
Average of daily
values for 30
consecutive days
16.3
13.0
(^
Non- continuous
dischargers
(Annual Average)
9.1
7.4
t1)
Within the range of 5.0 to 9.0 at all times.
1007
-------
Subpart L
Pollutant
or
pollutant
property
BODS
TSS
pH
BPT effluent limitations for non-integrated mills where
paperboard is produced from purchased pulp
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous dischargers
Maximum for any 1
day
6.5
,5.8
C1)
Average of daily
values for 30
consecutive days
3.6
2.8
H
Non-continuous
dischargers
(Annual Average)
2.0
1.6
C1)
cne range or 5.0 to 9.0 at all times.
§ 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 §430.122 of this subpart for the best practicable control
technology currently available (BPT).
§ 430.124 Effluent limitations representing the degree of
effluent reduction attainable by the application of the best
available technology economically achievable (BAT).
1008
-------
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 Ib) but shall' be
subject to concentration limitations. Concentration
limitations are only applicable to non-continuous
dischargers. Permittees not iUsing chlorophenolic-containing
biocides must certify to the permit-issuing authority that
they are not using these biocides:
Subpart L
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
BAT effluent limitations for
non- integrated mills where tissue papers are
produced, from purchased pulp
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product ;
0.0028
0.00096
Milligrams/liter
(0.029) (22. 9) /y.
(0.010) (22 .9) /y
y * wastewater discharged in kgal per ton of product
1009
-------
Subpart L
Pollutant or
pollutant property
Pentachlorophenol
Tri chlorophenol
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 pounds
per 1;000 Ib) of
product
0.0072
0.0025
Milligrams /liter
(0.029) (59. 9) /y
(0.010) (59.9)/y
y = wastewater discharged in kgal per ton of product
Subpart L
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
BAT effluent limitations for
non- integrated mills where paperboard is produced
from purchased pulp
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.001S
0.00054
Milligrams/ liter
(0.029) (12.9)/y
(0.010) (12. 9) /y
y = wastewater discharged in kgal per ton of product
§ 430.125 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
1010
-------
dischargers, concentration limitations (mg/1) 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:
UOll
-------
Subpart L
Pollutant or
pollutant property
BODS
TSS
pH
Pentach.loroph.enol
Trichlorophenol
NSPS for non- integrated mills where tissue papers
are produced from purchased pulp
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
7.0
6.0
(* )
Average of
daily
values for
30
consecutive
days
3.4
2.6
(l )
Non- continuous
Dischargers
(Annual Average)
2.3
1.6
(l )
Maximum for any 1 day.
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0028
0.00096
Milligrams/ liter
(0,035). (19. l)/y
(0.012) (19.1) /y
y = wastewater discharged in kgal per ton at all times
tne range of 5.0 to 9.0 at all times.
1012
-------
Subpart L
Pollutant or
pollutant property
BODS
TSS
pH
Pentachlorophenol
Trichlorophenol
,. NSPS for
non- integrated mills where filter and non-woven
papers are produced from purchased pulp
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
17.1
15.0
C1 )
Average of
daily
values for
30
consecutive
days
8.3
6.6
(l )
Non- continuous
Dischargers
(Annual Average)
5.6
4.0.
(l )
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.0072 .
0.0025
Milligrams /liter
(0.037) (47. 5) /y
(0.013) (47.5)/y
y = wastewater discharged in kgal - per ton at all times
Within the range of 5.0 to 9.0 at all times.
1013
-------
Subpart L
Pollutant or
pollutant property
BODS
TSS
pH
Pentachlorophenol
Trichlorophenol
NSPS for non- integrated mills where paperboard is,
produced from purchased pulp
Kg/kkg (or pounds per 1,000 Ib) of product
Continuous Dischargers
Maximum for any 1
day
4.0
3.5
P )
Average of
daily
values for
30
consecutive
days
1.9
1.5
(l )
Non-continuous
Dischargers
(Annual Average)
1.3
0.9
(x )
Maximum for any 1 day
Kg/kkg (or pounds
per 1,000 Ib) of
product
0.001S
0.00054
Milligrams/ liter
(0.033) (11.2)/y
(0.012) (ll.2)/y
y = wastewater discharged in kgal per ton at all times
xWithin the range of 5.0 to 9.0 at all times.
§ 430.126 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
1014
-------
permit-issuing authority that they are not using these
biocides. PSES must be.attained on or before July 1, 1984:
Subpart L
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSES for
non- integrated mills where tissue papers are
produced from purchased pulp
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.032) (22.9) /y
(0.010) (22. 9) /y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0031
0.00096
y =» wastewater discharged in kgal per ton of product
0 The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
Subpart L
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSES for '
non- integrated mills where filter and non-woven
papers are produced from purchased pulp
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.032) (59. 9) /y
(0.010) (59. 9} /y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0080
0.0025
y = wastewater discharged in kgal per ton of product
* The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations
1015
-------
Subpart L
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSES for non-integrated mills where paperboard is
produced from purchased pulp
Maximum for any 1 day
Milligrams/liter (mg/1)
(0.032) (12. 9) /y
(0.010) (12. 9) /y -
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0017
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.
§ 430.127 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:
1016
-------
Subpart L
Pollutant or
pollutant property
Pentachlorophenol
Tr i chl oropheno 1
PSNS for non- integrated mills where tissue papers
are produced from purchased pulp
Maximum for any 1 day
Milligrams/ liter (mg/1)
(0.038) (19.1)/y
(0.012) (19.1)/y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0031
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
Pollutant or
pollutant property
Pentachlorophenol
Trichlorophenol
PSNS for non -integrated mills where filter and
non-woven papers are produced from purchased pulp
Maximum for any 1 day >
Milligrams/liter (mg/1)
(0.040) (47.5) /y
(0.013) (47.5)/y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0080
0.0025
y = wastewater discharged in kgal per ton of product
The following equivalent mass limitations are provided as guidance in
cases when POTWs find it necessary to impose mass effluent limitations.
1017
-------
Subpart L
Pollutant or
pollutant property
Pent achloropheno 1
Trichlorophenol
PSNS for
non- integrated mills where paperboard is produced
from purchased pulp
Maximum for any 1 day
"Milligrams/liter (mg/1)
(0.037) (11.2)/y
(0.012) (11.2)/y
Kg/kkg (or pounds per
1,000 Ib) of product3
0.0017
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
1018
-------
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 /ig/L, and a minimum level (ML; Section 18) of 20 /zg/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°C
unt i1 analys i s.
2.2 Sample analysis: Organic halide in water is determined
by adsorption onto granular activated carbon (GAG), washing
1019
-------
the adsorbed sample and GAG to remove inorganic halide,
combustion of the sample and GAG 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
(cr) .
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
1020
-------
4.1 Solvents, reagents, glassware, and other sample
processing hardware may yield elevated readings from the
tnicro-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°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 used in the analysis results in contamination.
1021 :
-------
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.
1022
-------
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
1023
-------
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°C for at least one hour
before use.
6.1.2 PTFE liner: Cleaned as above and baked at 100 to
200°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 (GAG): 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.
1024
-------
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
1025
-------
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 (GAG).
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 (GAG). 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.
1026
-------
6.5.1.1 Combustion tube: Quartz, capable of being heated to
800 to 1000°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°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-control led 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;
4 0 mL/min O2.
B. Sequence start.
C. Hold boat in hatch for five seconds to allow
integration for baseline subtraction.
1027
-------
D. Advance boat into vaporization zone.
E. Hold boat in vaporization zone for 110 seconds.
F. Establish gas flow rates for combustion: 200 tnL/min
O2; 0 mL/min CO2; advance boat into pyrolysis' zone
(800°C).
G. Hold bpat 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 prevent backflush of electrolyte
is highly recommended.
6.5.2 Micro-coulometer system: Capable of detecting the
equivalent of 0.2 j*g of Cl" at a signal-to-noise ratio of 2;
capable of detecting the equivalent of 1 /zg of Cl" with a
relative standard deviation less than 10%, and capable of
accumulating a minimum of the equivalent of 500 (j.g of Cl"
before a change of electrolyte is required.
6.5.2.1 Micro-coulometer cell: The three cell designs
1028
-------
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.
t
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-/iL 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-/zL.
6.8 Balances. i
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
1029
-------
7.1 Granular activated carbon (GAG) : 75 to 150 /j.m (100 to
200 mesh); (Dohrmann, Mitsubishi, Carbon Plus, or
*
equivalent) , with chlorine content less than 1 /ig Cl" per
scoop (< 25 /zg Cl" per gram) , adsorption capacity greater
than 1000 /zg Cl" (as 2,4,6-trichlorophenol) per scoop
(>25,000 /zg/g) , inorganic halide retention of less than 1 izg
Cl" per scoop in the presence of 10 mg of inorganic halide
(< 20 /ig 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 /zg/mL of Cl") :
Dissolve 0.165 g NaCl in 1000 mL reagent water. This
solution is used for cell testing and for the inorganic
halide rejection test.
7.5 Ammonium chloride (NH4C1) solution (100 /zg/mL of Cl") :
1030
-------
Dissolve 0.1509 g NH4C1 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 17 g 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
1031
-------
chloride is delivered to the coulometric cell regardless of
the volume of the calibration and PAR solutions.
7.12.1 Methanol: HPLG 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 ./zg Cl" per 100
mL of solution (20, 50, 100, 300, and 800 /zg/L) .
7.12.3.3 Some instruments may have a calibration range that
does not extend to 800 /zg/L (80 ,tzg 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 /zg/L of Cl") : Partially fill a 100-mL
volumetric flask,, add 10 itL 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
1032
-------
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.1 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
1033
-------
adsorption.
8.1.3 Refrigeration: Maintain samples at a temperature of 0
to 4°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
1034
-------
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 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.
1035
-------
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 of 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 /zg/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. -
1036
-------
them to determine the concentration after spiking.
9.3.2.1 Compute the percent recovery of each analyte in
each aliquot:
, 100 (Found - Background}
% Recovery = -
T
where:
T is the true value of the spike
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 MSB 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 aliguots 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.
1038
-------
preparation (Section 11.1). If using the micro-column
procedure, adsorb the method blank using two columns, as
described in Section 11. Combust the GAG 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 GAG blanks: Analyzed daily to
demonstrate that the GAG is free from contamination.
9.4.2.1 Nitrate-washed GAG blank for the batch procedure:
Analyze a batch nitrate-washed GAG blank by adding a scoop
*
of dry GAG to the assembled filter apparatus containing the
polycarbonate membrane and washing the GAG with the nitrate
wash solution (Section 7.10) using the procedure in Section
11.2.6.
9.4.2.2 Nitrate-washed GAG blank for the column procedure:
Analyze a column nitrate-washed GAG 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 GAG in each column
separately. The results of the second analysis must be
within ±0.2 /zg Cl" of the first. A difference greater than
0 .2 /zg Cl" indicates a lack of homogeneity in the GAG that
could introduce unacceptable variability. If the difference
1040
-------
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
I
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 /zg (25 /zg 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
s
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 /-tg
level is exceeded. '
9.6 Samples that are being used for regulatory compliance
purposes shall be analyzed in duplicate.
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
1041
-------
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 Depending1 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
1042
-------
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 /ig/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 fig Cl" (20 />ig/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 nbt within the acceptable range
1043
-------
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
1044
-------
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 /iL of the sodium
chloride solution (10 /xg Cl~; Section 7.4) directly into the
titration cell electrolyte. Adjust the instrument to
produce a reading of 10 /ig Clr. . ".
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 (NH4C1) solution only.
10.3.2 Inject 100 juL of the NH4C1 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 /zg 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
1045 !
-------
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 /zg 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"
1046
-------
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 /zg/L. If not, the water or carbon shall be
i
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
1047
-------
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 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
1048
-------
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:
1
Paper or pulp mill stream
i
Evaporator condensate
Process water
Pulp mill effluent
Paper mill effluent
-ombined mill effluent
Combined bleach effluent ;
2- stage filtrate ;
E-stage filtrate
Sample
volume
(mL) *
100
100
30
10
5
1
0.5
0.5
Adsorp-
tion
volume
(mL)
100
100
50
25
25
25
25
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.
1049
-------
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.
1050
-------
11.2.1 Place the appropriate volume of sample (diluted if
necessary), preserved as described in Section 8, into an
Erlenmeyer flask.
11J2.2 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 I 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 splution in several portions.
After the level of the final;wash reaches the top of the
GAG, filter by suction until,the cake is barely dry. i The
time required for drying should be minimized to prevent
exposure of the GAG 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,
1051
-------
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
1052
-------
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 GAG 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 piL/min over the duration of the
time required to adsorb the volume. If this flow rate is
1053
-------
exceeded, adjust gas pressure, prepare another blank, and
repeat the adsorption.
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.
1054
-------
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 Jand GAG from batch adsorption.
11.4.1.1 Place the folded polycarbonate filter containing
the GAG in a quartz combustion boat, close the airlock, and
proceed with the automated sequence. dttk
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.
t
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
1055
-------
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
1056
-------
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 GAG
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: '
AOX (jig/L) = (C ~vB}
where:
C = \ig Cl' from micro-coulometer for the sample
B = [ig 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:
1057
-------
[(C.+C_) -(£+£,)]
AOX (jig/L) = l- 2-1 2
where:
C, = lig CI~ from micro-coulometer for first column from the sample
C2 = p.g Cl' from micro-coulometer for second column from the sample
#1 = V-g from micro-coulometer for first column from the reagent -water blank (Section 9.4.1)
B2 - fig Cl' 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:
(C, - 5-H100)
% Breakthrough -
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:
1058
-------
RPD =
\fAOX l + AOXJ]
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. '
1059 ^^
-------
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 /ug/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.
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
1060
-------
required. ' ;
15.2 Samples preserved with HC1 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, B.C. 20036'.
1061
-------
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
1062
-------
15th St. NW, Washington, DC 2|0005 (1989) .
16.7 "Canadian Standard Method for the Determination of
Adsorbable Organic Halides (AOX) in Waters and Wastewaters,"
l
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 IN. Lee St., Alexandria, VA
22314 (703-519-1140) .
17.0 Figures
1063
-------
a.
b. Dohrmann
c. Euroglas
Silver
Sensor
Electrode
Silver/Silver
Chloride
Reference
Electrode
Gases
In
Platinum
Electrode
Silver
Generator
Electrode
Gases
Out '
Silver/Silver
Acetate
Reference
Electrode
Stirrer
Gases
Silver
Sensor
Electrode
Gases
In
Silver
Generator
Electrode
Platinum
Electrode
Silver
Generator
Electrode
Gases Infcd
Platinum
Electrode
No Stirrer
Silver
Sensor
Electrode
Silver/Silver
Chloride
Reference
Electrode
Figure 1. Microcoulometric Titration Cells (from Reference 7)
1064
-------
Funnel
Clamp
Stain tess-
S-feeI Support
PTFE Gasket
Base
No. 5
Stopper.
Figure 2. Filter Apparatus
1065
-------
Sample
Reservoir
(1of4)
GAG Column 1
<3AC Column 2
I
Nit rate Wash
Reservoir
Figures. Schematic of the Column Adsorption System
1066
-------
1235
11
1.
2.
3.
4.
5.
6.
7.
10.
11.
1 2.
Stripping Devfce
Sample inlet for AOX
AOX Sample
Furnace
Combustion Tube :
Absorber-fifed with HjSO^ |
Tltratfoncell
S. Working electrodes
9. Measuring electrodes
St'ner
Tftraction mfc ro -processor
Gas flow and tern pe ratu le contio I device
Figure 4. Schematic of an AOX Apparatus
1067
-------
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.
°C degrees Celsius
/u<3 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,
1068
-------
per liter of solution
OD outside diameter
i
ppb part-per-billion
ppm part-per-million
ppt part-per-trillion
psig pounds-per-square inch gauge
v/v volume per iunit 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 (CSS) 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
1069
-------
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.
1070
-------
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
t
containing the specified analytes that is
purchased or prepared from stock solutions and
diluted as needed;to prepare calibration '
solutions and other solutions.
1071
-------
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.
1072
-------
VER: See Calibration verification
standard.
1073
-------
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 Envirpnmental 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
1074
-------
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
I '
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
I - -
(GC). The compounds are separated by GC and detected by a
mass spectrometer (MS) . The' labeled compounds and internal
standard serve to correct this variability of the analytical
1075
-------
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.
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).
1076
-------
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
t
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°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
1077
-------
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°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
1078
-------
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
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.
l
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°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°C for a minimum of 1 hour prior to use.
1079
-------
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°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
1080
-------
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 1
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.
I
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°C for a minimum of
one hour. ;
6.6.6 Nitrogen evaporation apparatus: Equipped with a water
bath controlled at 35 to 40°C (N-Evap, Organomation
Associates, Inc., South Berlin, MA, or equivalent),
* I
installed in a fume hood. This device may be used in place
1081
-------
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°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°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
1082
-------
shall be interfaced to the GC such.that the end of the
capillary column terminates within I 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 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.
i
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
1083
-------
data system shall be used to record and maintain list's 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.
1084
-------
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°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
i
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°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.
1085
-------
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
1086
-------
matrix internal standard (SMIS) , in methanol . The labeled
compounds and SMIS are each at a concentration of 12 . 5
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 /ig/mL; the tri chlorinated
catechols, tetrachlorinated guaiacol and catechol,
pent achl orophenol , 5 , 6 - di chl or ovani 1 1 in , and
2 , 6-dichlorosyringaldehyde are included at a. concentration.
of 100 /ig/mL; and the remaining compounds are included at a
concentration of 50 /zg/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
jj.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.
!l 087
-------
7.13.1 Into five 1000-mL aliquots of reagent water, spike
50, 100, 200, 500 and 1000 |UL 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 /zg/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 /zg/mL standard may also be used as a
1088
-------
calibration verification standard (see Section 9.6).
i
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 /iL 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
i
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
l
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 method or an alternative EPA
' 1089
-------
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°C from time of collection until extraction, and maintain
extracts at a temperature of 0 to 4°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
1090
-------
9.1 Each laboratory that uses this method is required to
i,
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.
i
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
1091
-------
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 /iL 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
\
1092
-------
determine the MDL per the procedure in 40 CFR 136, Appendix .^^
w
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.
i '
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),i 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 icompounds 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
1093 ^^
-------
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
1094
-------
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 5 //g/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
!
1095
-------
which analyses are performed, analytical system performance
is verified for all compounds. Analysis of DFTPP (Section
9.2) and the nominal 50 //g/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 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 /Kj/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..
1096
-------
9.6.1.3 Multiple peaks: Each compound injected shall give a
I
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
f , , H
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 dfe
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
i,
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
I *
compounds meet these criteria, GCMS performance/stability is
1097
-------
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
1098
-------
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 chloropheholics
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
i
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
1099
-------
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 /ig/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)
1100
-------
interferences do not preclude its use, and (3) the
guantitation 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, trie 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.
i
Also shown are the ±10% error limits (dotted lines) .
i
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.
R = the isotope ratio measured for the labeled compound.
R'm = the isotope ratio of an analytical mixture of pollutant
and labeled compounds.
1101
-------
The m/z's are selected such that Rx > Ry. if R^ 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,
area
, at the retention time of the pollutant (RT.).
1
1
L 7'2"
R = . at the retention time of the labeled compound (RT,).
\area mjz\ 1
\area at mjz (at RTj]
= -f : -4, as measured in the mixture of the pollutant and
\area at m2/z (at RTJl
labeled compounds (Figure 2), and RR = R .
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
1102
-------
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:
(* r RJ(R + 1)
RR =
+
Where: \
Rx is measured as shown in figure 3A,
R is measured as shown in figure 3B,
R is measured as shown in figure 3C.
For example, Rx = 46100/4780 = 9.644; Ry = 2650/43600 =
0.0608; R,,, = 49200/48300 = 1.1019; thus, RR = 1.114.
10.4.5 To calibrate the analytical system by isotope
dilution, analyze a 1-juL 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.1
10.5 Calibration by internal standard: The method contains
two types of internal standards, the sample matrix internal
1103
-------
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 ' -dif luorobiphenyl instrument
internal standard (IIS) is used for determination of the
labeled compounds and the SMIS. The results are used for
s
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:
RF - -
w,, *
Where:
As = the area of the chracteristic mass for the compound in the daily standard.
Ajs = the area of the characteristic mass for the internal standard.
Cjs '- the concentration of the internal standard (\iglmL).
Cs = is the concentration of the compound in the calibration standard
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
1104
-------
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 /zg/mL.
The amount of SMIS added to each solution is the same (25
£tg/mL) so that Cis remains constant. Likewise, the
concentration of IIS is constant in each solution. The area
i
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.
'
1105
-------
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
K
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
1106
-------
dilute to a final volume of 1000-mL (±50 mL) with reagent jflb,
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.
s
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
I
other as the ongoing precision and recovery (OPR) aliquot.
i
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
-------
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 /zL of the labeled compound spiking
solution (Section 7.8) into the sample and QC aliquots.
11.1.8 Spike 500 /iL of the nominal 50 /ng/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 derivatizatipn 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.
1108
-------
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
j
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, I PR
aliquots, OPR aliquots, blanks, and the associated field
samples. >
11.3.1 Stir-bar extraction of final effluents.
1109
-------
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.
1113.1.3 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
1110
-------
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
i
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
I
the funnel for two to three minutes with periodic venting.
i
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
i
flask. It may be necessary to pour the organic layer
1111
-------
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.
1112
-------
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.
i
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
I
least 10 minutes. Remove the, Snyder column and rinse the
flask and its lower j oint into the concentrator tube with 1
to 2 mL of hexane. A 5-mL syringe is recommended for this
operation.
1113
-------
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 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
1114
-------
PTFE-lined lid, and mark the level on the vial. Label with Jttfe
the sample number and store in the dark at -20 to -10°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°C
Injector temperature: | 300°C
Initial temperature: , 5DOC
Temperature program: \ 8°C/min to 270QC
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-yiL volume of the standard solution or
extract using on-column or splitless injection. For 0.5 mL
extracts, this l-/iL injection volume will contain 50 ng of
the DFB internal standard. If an injection volume other
I
than 1 {JJL is used, that volume must contain 50 ng of DFB.
1115
-------
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 /zg/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
. s
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
1116
-------
the respective areas in the OPR or VER standard, and the DFB
internal standard area is less than one-half of its
I
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
l
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
i
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
**v
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 compoundjis confirmed when the following
l
criteria are met:
1117
-------
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
1118
-------
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 /ig/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:
Cex(iig/mL) = (An x C,) / (Al x RR)
Where:
C = concentration of the pollutant in the extract.
An= area of the characteristic mlz for the
pollutant.
C{ = concentration of the labeled compound in the extract.
A, = area of the characteristic mlz 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) a;nd 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:
-------
Cex(vglmL) = (As x Cjs) I (Ais x RF)
Where:
C ex = concentration of the pollutant in the extract.
AS= area of the characteristic mlz for the pollutant.
Cjs = concentration of the internal standard in the extract
(see note below).
Ajs = area of the characteristic mlz 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 (Als) 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:
1120
-------
V
o
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.
Pritnaryl4.6 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:
_ Concentration found ,
Percent recovery - x 100
Concentration spiked
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
1121
-------
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 jug/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 /zg/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
1122
-------
14.7) and the labeled compound recovery is within the normal
range for the method (Section 13.3).
15.0 Method Performance i
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
f
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
i
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. \
1123
-------
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, B.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).
1124
-------
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) . '
1125
-------
19.0 Tables and Figures
Table 1. Chlorophenolic Compounds Determined by GCMS using
Isotope Dilution and Internal Standard Techniques
Compound
4-chlorophenol .
2 , 4 -dichlorophenol
2 , 6 -dichlorophenol
2,4, 5 - trichlorophenol
2,4, 6-trichlorophenol
2,3,4, 6-tetrachloroph-
2nol
pentachlorophenol
4-chloroguaiacol
3 , 4-dichloroguaiacol
4 , 5 -dichloroguaiacol
4 , 6 -dichloroguaiacol
3 , 4, 5-trichloroguaia-
30l
3,4, 6-trichloroguaia-
=01
4,5, 6-trichloroguaia-
30l
tetrachloroguaiacol
4 - chlorocatechol
3 , 4 -dichlorocatechol
3 , 6 -dichlorocatechol
4 , 5 -dichlorocatechol
3,4, 5-trichlorocatec-
iol
3,4, 6-trichlorocatec-
101
tetrachlorocatechol
5-chlorovanillin
5 - chl orovani 1 1 in
5, 6-dichlorovanillin
Pollutant
CAS Registry
106-48-9
120-83-2
87-65-0
95-95-4
88-06-2
58-90-2
87-86-5
16766-30-6
77102-94-4
2460-49-3
16766-31-7
57057-83-7
60712-44-9
2668-24-8
2539-17-5
2138-22-9
3978-67-4
3938-16-7
3428-24-8
56961-20-7
32139-72-3
1198-55-6
19463-48-0
18268-76-3
18268-69-4
EPA-EGD
1001
1002
1003
1004
1005
1006
1007
1008
1009
1010
1011
1012
1013
1014
1015
1016
1017
1018
1019
1020
1021
1022
1023
1024
1025
Labeled Compound
Analog
d3
»C6
»c6
13C6
»C6
13c6
13c6
13c6
CAS Registry
93951-74-7
85380-74-1
136955-39-0
136955-40-3
136955-41-4
136955-42-5
136955-43-6
136955-44-7
EPA-
EGD
1102
1107
1108
1114
1115
1119
1122
1123
1126
-------
2-chlorosyringaldehyde 76341-69-0
2,6-
iichlorosyringaldehyde
trichlorosyringol
76330-06-8 r
2539-26-6
1026
1027
1028
Sample matrix internal standard (SMIS)
3,4,5-trichlorophenol
609-19-8
184
Instrument internal standard (IIS)
2,2'-di£luorobipheny1
388-82-9
164
1127
-------
CO.
o
-H
rH
O
a
M
_[_1 ^ ^_,
(U -H
Pi H
Compound
Q»
_
W|3
^i
rH
rH
rH
in
CM
rH
H
CO
vo
o
1
rH
in
vo
o
n
00
^H
rH
CTl
4-chlorophenol
rH
O
O
rH
CTl
PI
rH
in
CM
CTl
r-
r~
o
l
p*
in
c--
o
co
rH
VD
CTl
r-
6 - di chl oropherio 1
CM
PI
o
o
rH
00
CTl
CTl
O
1
\o
CO
CTl
0
,t
VD
rH
CO
rH
CO
-dichlorophenol -d
*
CM
CM
O
rH
rH
m
H
o
in
CM
VD
o
o
rH
1
r-
CTl
CTl
o
CM
O
rH
rH
CTl
H
CO
4 -dichlorophenol
CM
CM
0
CM
rH
O
O
H
VD
T~H
in
CM
CO
i-i
-dif luorobipheny
(I.S.)
CM
CM
*
VO
rH
P)
O
rH
H
1
r-
f-
o
rH
VD
rH-
O
O
CTl
hloroguaiacol-13C(
0
*
CO
0
rH
rH
CTl
O
O
in
rH
CM
O
O
rH
I
CO
CTl
CTl
O
CO
0
rH
rH
O
O
CTl
-chloroguaiacol
*
co
0
CM
rH
rH
E-
O
m
CM
in
CTl
CO
o
i
CTl
c*.
CO
o
CO
rH
o
CM
CTl
rH
6-trichloropheno
«*
CM
in
o
0
rH
F-
m
o
in
CM
CM
tn
CTl
o
1
vo
PI
CTl
O
CO
CTl
CTl
i-H
5-trichloropheno
*
CM
*.
O
0
rH
CTl
m
o
in
CM
rH
in
r-
CTl
O
1
H
VD
CTl
O
CO
o
0
-chlorocatechol
*
vo
rH
O
rH
in
*
O
in
CM
H
CT\
CTl
O
1
CTl
t*.
cn
O
co
rH
CM
0
-dichloroguaiaco]
VD
^<
rH
rH
O
rH
CM
in
o
in
CM
CO
CTl
CTl
o
1
VD
00
CTl
o
co
CTl
CM
O
-dichloroguaiaco]
*
PI
CTl
O
O
rH
CM
r-
CM
rH
1
CM
^
CM
H
vo
p-
p)
o
! 1
5-trichloropheno
(I.S.)
<*
pT
^
CO
rH
CM
in
0
in
CM
o
a1
0
rH
1
VD
CM
O
rH
CO
rH
r-
o
-dichloroguaiaco]
in
^p
o
rH
O
rH
p~
in
0
in
CM
PI
in
0
rH
1
r-
Pl
o
rH
CO
CO
o
-dichlorocatecho]
VO
PI
CO
rH
o
rH
CO
PI
O
in
CM
CO
f-
0
rH
1
0
in
o
rH
CO
rH
PI
0
rH
,3,4, 6-tetrach-
lorophenol
CM
VD
0
o
rH
r-
vo
PI
rH
1
r-
CM
P)
rH
VO
'H
rH
rH
H
I 1
hlorovanillin-13C(
u
m
PI
CM
rH
rH
rH
O
rH
in
CM
rH
O
O
rH
1
00
CTl
CTl
O
P)
CM
rH
rH
rH
rH
rH
rH
-chlorovanillin
m
PI
CM
CM
rH
vo
<*
o
in
CM
O
CTl
O
rH
1
VD
VO
O
rH
00
rH
CO
rH
rH
rH
rH
O
l-trichloroguaiac'
VJJ
"^
P)
P)
rH
0
rH
*<
CTl
O
in
CM
*
CTl
O
rH
1
0
r-
o
rH
co
rH
CM
CM
rH
rH
-chlorovanillin
VD
*
CM
0
rH
O
VO
o
in
CM
in
o
rH
rH
1
P)
CO
O
rH
CO
rH
P)
rH
rH
-dichlorocatecho]
t
PI
r-
rH
0
rH
«
CM
H
1
00
PI
rH
VO
rH
CO
in
rH
rH
c?
ichlorocatechol-1
7
in
*
CTl
rH
rH
rH
oo
-------
tfl ^3
I~J ^"S^
Q cn
III
s
's
EH 0
D4 ^
p4 ^
H
S
o
Q "
o ra ..
H 2
<-*
-4<
CN
0
in
rH
O
O
,_J
1
00
o\
"I
o
o\
rH
rH
rH
CO
in
H
-dichlorocatechol
in
^
cn
rH
rH
cn
^j4
O
in
CN
o
vo
H
rH
1
O
CN
H
rH
CO
H
r-
D-
rH
rH
-trichloroguaiacol
in
"*1
M
CN
rH
O
rH
^
CO
*
H
1
cji
^*
^
rH
VO
rH
CO
0
H
-trichloroguaiacol-
"C6
VO
in
M^"
^
rH
H
rH
in
CN
O
in
CN
o
o
rH
1
00
cn
cn
o
<*
rH
rH
H
CO
O
CN
rH
trichloroguaiacol
t
VD
in
^
rH
CN
rH
^
*
O
O
to
in
CO
rH
rH
1
m
in
rH
rH
^
oo
rH
ro
rH
CN
rH
- trichlorocatechol
VD
^
ro
rH
CN
O
rH
O
00
o
o
in
CN
CN
CN
rH
1
CN
CO
rH
rH
^
co
rH
VD
CN
rH
-dichlorovanillin
VD
m
m
CN
o
rH
^
CO
o
in
CN
o
n
CN
rH
1
O
cn
rH
rH
^}l
00
rH
in
in
CN
rH
Lorosyringaldehyde
X!
r_)
1
OJ
VO
CN
O
H
rH
VO
in
H
1
rH
rH
in
rH
^i
VO
rH
t~
VO
CN
rH
achlorophenol - 13C6
4J
d
ft
C-
0
rH
t-H
00
CN
O
O
in
CN
o
o
rH
1
00
cn
cn
o
E^
O
rH
rH
CO
VO
CN
rH
ntachlorophenol
0)
ft
r-
o
CN
rH
ro
in
O
O
in
CO
ro
CN
rH
1
CO
O
CN
rH
^J1
CO
rH
CO
VO
CN
rH
-trichlorocatechol
in
^
ro
o
CN
o
rH
r-
00
in
H
1
ro
in
rH
^
VO
rH
cn
co
CN
rH
chloroguaiacol -13C6
ns
SH
4J
4J
in
rH
rH
rH
ro
CN
O
O
m
CN
o
o
H
1
00
cn
cn
o
in
rH
rH
rH
O
cn
CN
rH
rachloroguaiacol
tt)
4J
in
rH
CN
rH
<*
VD
p
in
CN
o
r-
CN
rH
1
O
^3*
CN
rH
^J1
CO
r-l
rH
O
ro
rH
ichlorosyringol |
SH
4J
co
CN
o
H
o
cn
vo
rH
1
O
ro
vo
H
vo
r-l
in
vo
ro
H
chlorocatechol-13C6
n!
SH
4J
tt)
CN
CN
H
H
VO
r>
o
o
in
CN
o
o
H
1
CO
cn
cn
o
CN
CN
rH
H
in
VO
ro
rH
rachlorocatechol |
4J
a)
4J
CN
CN
CN
rH
CO
rH
H
O
in
cn
m
rH
l
cn
o
ro
rH
co
H
co
r>
co
rH
, 6-dichlorosy-
ringaldehyde
CN
p-
CN
O
rH
ed by the internal standard
-H
MH
-H
4J
ft
a
3
CT1
4J
0
nj
3
rH
rH
O
ft
flS
0)
4J
n!
O
-rH
T!
ft
H
0
rH
f~\
4J
-H
^
cn
d
-H
r*
-H
Cn
0)
n
cn
j_j
0
CD
-rH
J>,
ft
laboratory (reference 12) ,
tt)
i-H
Cn
d
H
.in
ns
g
O
M-J
nj
4J
ni
TS
d
0
d
0)
m
(t!
0)
SH'
d
g
rH
O
O
m
-iH
x!
4J
d
CO
tt)
g
-H
4-1
d
O
-H
4-1
d
a;
4->
0)
SH
tt)
[H
H
rH
d
o
-H
4J
U
tt)
w
pj
-rH
to
ft
O
-H
4J
-rH
TS
d
o
u
u
CD
0)
X!
4J
cn
d
-rH
IS)
-H
rH
-H
4J
3
in
CN
VD
H
TJ
O
X!
4J
0)
s
*3*
Pi
w
g
0
SH
MH
TS
4J
ni
g
-H
4J
W
tt)
tt)
SH
(S
CO
^
O
TS
d
-H
0)
g.
-H
4-)
d
o
H
4->
d
tt)
4J
tt)
SH
4)
-H
4-)
ns
r-H
tt)
DJ
-------
-H
01
4->
02
j3
g
g
(U
02
l><
to
rH
cd
u
-H
W
rH
cd
a
cd
tt)
-rH
d
0)
0)
A
43
0
-H
43
4J
cd
rH
tt)
^
tt)
l-l
0)
43
TO
cd
*rj
-H
d
Cf*
CD
02
-H
4J
tt)
4J
^
rH
cd
td
tt)
(-*
4->
^_]
o
^1H
4J
P3
-H
O
ft
fi
o
-H
4J
cd
o
-H
i |
cd
o
0)
rH
Q
cd
4J
ft
0)
O
o
cd
13
cd
r-H
cd
rt
-rl
02
0)
rH
3
N
-H
f3
01
0
0
tt)
rl
0)
i-H
ft
g
cd
02
r^f
(U
-r)
4-1
-H
U
0)
ft
02
1
T)
O
4->
0)
g
i-H
rH
cd
cd
^
Jj
Oi
C3
-rl
g
W
02
cd
,.
r&
5-1
cd
Ti
a
cd
02
a
o
-H
4J
cd
rl
-H
i-H
cd
u
JJ
02
0)
^
O
rH
tt)
43
4-1
o
c
o
-r)
4J
cd
£_j
4J
a
42
fl)
^
td
02
tt)
r)
§
tt)
U
o
ft
ft
c
cd
tt)
i-H
0
t3
C
cd
..
02
tt)
g
1 I
o
^
02
4->
Dl
-H
tt)
IN
tt)
U
a
(U
rl
0)
M-l
tt)
rl
g
O
k
M-l
^
PQ
j*^
H
TJ
a
tt>
ft
a
^
VD
ro
H,
4J
rl
cd
P^
PH
fo
u
o
^
o
ro
-------
f
Table 3. DFTPP Mass Intensity Specifications1
1 Reference 7
Mass
51
68
69
70
127
197
198
199
275
441
442
443
Intensity Required
8 to 82% of m/z 198
less than 2% of m/z 69
11 to 91% of m/z 198
less than 2% of m/z 69
32 to 59% of m/z 198
less than 1% of m/z 198
basfe peak, 100% abundance
4 to 9% of m/z 198
11 to 30% of m/z 198
44 to 110% of m/z 443
30 to 86% of m/z 198
14 to 24% of m/z 442
1131
-------
Table 4. Characteristic m/z's of.Chlorophenolic Compounds
Compound
4 -chlorophenol
2 , 4 -dichlorophenol
2 , 4 - di chl orophenol - d3
2 , 6-dichloropheno'l
2,4, 5 - trichlorophenol
2,4, 6 -trichlorophenol
2,3,4, 6-tetrachlorophenol
pentacJU-oropftenol
pentachlorophenol"13C6
4 -chloroguaiacol
4-chloroguaiacol-13C6
3 , 4 -dichloroguaiacol
4 , 5 -dichloroguaiacol
4 , 6 -dichloroguaiacol
3,4, 5-trichloroguaiacol
3,4, 6-trichloroguaiacol
4 , 5 , 6-trichloroguaiacol
4,5, 6-trichloroguaiacol-13C6
tetrachloroguaiacol
tetrachloroguaiacol-13C6
4 -chlorocatechol
3 , 4-dichlorocatechol
3 , 6 -di chlorocatechol
4, 5 -di chlorocatechol
4 , 5-dichlorocatechol-13C6.
3,4, 5 - trichlorocatechol
3,4, 6 -trichlorocatechol
tetrachlorocatechol
tetrachlorocatechol -13C6
5-chlorovanillin
5-chlorovanillirr13C6
6-chlorovanillin
5, 6-dichlorovanillin
2 -chlorosyringaldehyde
2 , 6-dichlorosyringaldehyde
trichlorosyringol
Primary m/z
128
162
167
162
196
196
232
266
272
158
164
192
192
192
226
226
226
234
262
268
144
178
178
178
184
212
212
248
254
186
192
186
220
216
250
256
Sample Matrix Internal Standard (SMiS)
3,4, 5 -trichlorophenol
196
Instrument Internal Standard (IIS)
2,2' -dif luorobiphenyl
190
1132
-------
«-*
CQ
4J
CQ
0)
EH
0)
D
to
c
^
O
0)
o
U-J
nS
-H
Q)
4J
H
(-4
u
0)
o
at
Accepte
in
T:
H E
a r
H
. u
H "H
S »Q
y M
» o
U
"d M
* nS
O
-H
fi ft
4J k
-H O
£ U
to
a
tn ft
S g
8, &
21 u
rS IT
<* §
. 0
0 m
(U X
CQ £<
X
tn
« ^
O *~
o ?n
u 2-
1
o
&
s
Q <*.
O n
H "3
vo
1
o
^
H
1
VO
in
)henol
4-chloroj
rH
O
O
H
CO
H
^*
CO
o
H
1
co
H
O
in
rophenol
2,4-dichloi
CM
O
CM
rH
n
H
1
CM
in
n
rH
1
CO
in
o
r-
i
VD
in
0
vo
H
VD
in
in
CM
d1
i
rH
§
JS
ft
, 4-dichloro
CM
CM
O
rH
rH
O
1
CO
in
CO
H
1
o
CM
o
in
rophenol
2, 6-dichloi
o
o
H
CO
CM
1
CM
CO
0
rH
1
CO
C-
rH
O
in
orophenol
, 4,5-trichl
CM
O
O
rH
VD
1
CM
f^
CM
H
1
CM
r-
o
CM
O
in
orophenol
,4, 6-trichl
CM
in
o
o
rH
CM
1
CM
CO
CM
M
H
1
O
CO
H
O
in
rachloro-
>1
r-J W
U fi
<1) (U
J-) XI
1 ft
VD
n
CM
vo
o
o
rH
i
j
:
O
CM
1
CO
rH
rH
rH
t
O
a\
vo
Q
o
rH
ophenol
pentachlor
o
C>1
t~-
VD
rH
1
r-
CM
rH
1
CO
r-
in
i
rH
VO
en
vo
rH
1
CO
in
rH
CM
in
CM
ID
u
1
r-H
8
0)
antachlorop
ft
O
rH
rH
0
CM
1
CO
CO
o
CM
H
1
CO
CO
O
CM
in
CM
laiacol
4-chlorogi
CO
o
CM
rH
CO
VO
rH
1
ro
rH
CM
rH
1
CT)
in
CM
in
i
vo
CO
rH
1
CO
VO
0
rH
tn
CM
ID
o
ro
rH
1
rH
0
O
ns
._!
: -chlorogua:
^
CO
o
vo
CM
1
CM
CO
VD
CM
H
1
0
CO
CO
rH
O
in
iguaiacol4
, 4-dichloro
n
CPl
o
o
H
CO
CM
1
O
CO
H
CM
H
1
CM
CO
rH
O
in
iguaiacol
, 5-dichlorc
*
o
H
O
H
O
CM
1
VO
CO
vo
CM
rH
1
CM
CO
VO
rH
O
in
jguaiacol
, 6-dichlorc
*
rH
rH
O
H
*
m
l
o
CO
0
m
H
1
co
r--
vo
rH
o
in
Loroguai-
L
XI O
u u
-H nS
k
.p
i
in
r«1
CM
H
0
rH
O
1
r>
CM
in
H
1
VD
VD
rH
O
in
.
Loroguai-
L
XI O
u u
-rH OS
k
4J
i
VD
m
n
H
0
H
VO
H
1
CO
CO
VD
O
rH
1
CM
rH
O
in
Loroguai-
L-
XI O
u u
-H nS
i
VD
in
*
rH
CM
rH
-------
CTl
ro
j_J
1
H
in
H
ro
H
1
CO
*
o
*3*
tH
1
^P
p-
VO
<3*
H
1
VD
VD
00
in
CN
4,5, 6-trichloroguai-
acol-13C6
^
.
VO
CN
H
1
tH
CO
in
H
H
1
^
00
p-
o
o
H
1 tetrachloroguaiacol
in
U
IH
0)
JJ
q
fl
^
«
0)
M
D.
s
CO
r-
VD
tH
CN
VD
rH
rH
VD
in
^3*
H
1
CO
VD
in
CO
iH
1
CXI
VO
r-
o
o
tH
3 , 4 , 5-trichloropheno3
^
CO
H
Ti
O
JJ
-------
d
re
a a>
G 43
re jj
jj
ta >,
45
re -d
ga)
H
0) M-l
JJ -H
G 4J
H G
re
m ;5
jj
d
45 §
0
*d ft
(U E
H O
4-1 U
H
JJ -d
G 0
re rH
& 45
re
JJ rH
G
re re
jj
3 -i ta
tt) -H
jj
G >*
H 45
4
I.TI
c
**s^
Ol
a.
*M
O
ra
G -H
0 to
-H (U
JJ T3
nl
M G
JJ O
§ jj
u re
G u
O -H
U 4-1
H
JJ O
to 0)
-------
10 -
1.0 -
0.1 -
J L
J L
T
2
T 1 1 1 J
10 20 50 100 200
Concentration (ng/mL)
The dotted lines enclose a ±10% error window.
Figure 1. Relative Response Calibration Curve for Phenol
1136
Figure 3. Extracted Ion-Current Profiles for (3A) Unlabeled Compound, (3B) Labeled
Compound, and (3C) Equal Mixture of Unlabeled and Labeled Compounds
1138
1140
-------
Area at
VER:. See Calibration verification .standard.
1145
-------
Area at
Area at
M/Z
Area at
Figure 2. Extracted Ion-Current Profiles for Chromatographically
Resolved Labeled (Mg/Z) and Unlabeld (M-,/Z) Pairs
1137
-------
10 -
1.0 -
0.1 -
J; 1 1 L
T
10
r-
20
i
50
i r
100 200
Concentration (ng/mL)
The dotted lines enclose a ±10% enor window.
Figure 1. Relative Response Calibration Curve for Phenol
1136
-------
Area= 46100
Area= 47SO
(3BJ
Area= 2650
Area= 43600
(3CJ
Area = 49200
Aiea= 4S300
Figure 3. Extracted Ion-Current Profiles for (3A) Unlabeled Compound, (3B) Labeled
Compound, and (3C) Equal Mixture of Unlabeled and Labeled Compounds
1138
-------
J0:12
13:24 1648 20:00
Retention lime (Minutes)
I
23:12
Figure 4. Chromatograim of Chlorophenolbs
1139
-------
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.
°C degrees Celsius
AtL 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
1140
-------
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 chlorophenol'ic tested for by this method.
The analytes are listed in Table 1.
Calibration standard (CAti) : 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 (CSS) that is used to verify
calibration. See Table 4. ' . ' "
< i
Chlorophenolics: collectively, the analytes listed in
Table 1. i
CS1, CS2, CSS, CS4,, CS5:' See Calibration standards and
Table 4. '
11141 ^^
-------
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.
1142
-------
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 inthe laboratory environment, the
reagents, or the apparatus. ;
Minimum level (ML): The level at which the entire
analytical system must give a recognizable signal and
n
acceptable calibration pointjfor 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.
1143
-------
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.
1144
-------
VER: See Calibration verification standard.
1145
-------
-------
------- |