United States
Environmental Protection.
Agency
Office of Pollution
Prevention and Toxics
Washington, DC 2046Q
February 1995
EPA 745-R-95-002
vVEPA
TOXICS RELEASE INVENTORY
List of Toxic Chemicals within the Water
Dissociable Nitrate Compounds Category and
Guidance for Reporting
Section 313 of the Emergency Planning and Community Right-to-Know Act of 1986
(EPGRA) requires certain facilities manufacturing, processing, or otherwise using listed toxic
chemicals to report their environmental releases of such chemicals annually. Beginning with
the 1991 reporting year, such facilities also must report pollution prevention and recycling
data for'such chemicals, pursuant to section 6607 of the Pollution Prevention Act, 42 U.S.C.
13106. When enacted, EPCRA section 313 established an initial list of toxic chemicals that
was comprised of more than 300 chemicals and 20 chemical categories. EPCRA .section
313(d) authorizes EPA to add chemicals to or delete chemicals from the list, and sets forth
criteria for these, actions.
. • • ' : CONTENTS .. . " .' -'• '
Section 1. Introduction .-"......... 2
• ' 1.1 Who Must Report ................... .,. .'. ; . . ~2
1.2 ".. Thresholds . . . . . "...,-.-. . 2
1.3 Chemicals within the Water Dissociable Nitrate Compounds
Category . . . : '. . . 3
1.4 De Minimis Concentrations . ,.".';. 3
Section 2. Guidance for Reporting Chemicals within the Water Dissociable Nitrate
Compounds Category ................ . ................... 4
2.1. Chemicals within the Water Dissociable Nitrate Compounds
Category ....... . 4
• ••• 2.2. Determining Threshhold and Release Quantities for Nitrate -
Compounds 4
2.3. Reporting Nitrate Compounds Generated from the Partial or
Complete Neutralization of Nitric Acid 5
2.3.1. Estimating Nitric Acid Releases 5
2.3.2. • Estimating Treatment Efficiencies for Nitric Acid Neutralization 7
2.3.3. Estimating Releases of Nitrate Compounds Generated from the
, ' Neutralization of Nitric Acid 9
-2.4. Generation of Nitrate Compounds from Biological Wastewater "
Treatment ...:... 10
Section 3. CAS. Number List of Some of the Individual Chemicals within the Water
-Dissociable Nitrate Compounds Category . 11
Recycled/Recyclable . Printed with Vegetable Oil Based Inks on 100% Recycled Paper (50% Postconsumer)
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Section 1. Introduction
On November 30, 1994 EPA added 286 chemicals and chemical categories, which
include 39 chemicals as part of two delineated categories, to the list of toxic chemicals
subject to reporting under section 313 of the Emergency Planning and Community
Right-to-Know Act of 1986 (EPCRA), 42 U.S.C. 1 1001. These additions are described at 59
FR 61432, and are effective January 1, 1995 for reports due July 1, 1996. Six chemical
categories (nicotine and salts, strychnine and salts, polycyclic aromatic compounds, water
dissociable nitrate compounds, diisocyanates, and polychlorinated alkanes) are included in
these additions. At the time of the addition, EPA indicated that the Agency would develop,
as appropriate, interpretations and guidance that the Agency determines are necessary to
facilitate accurate reporting for these categories. This document constitutes such guidance for
the water dissociable nitrate compounds category.
Section 1.1 Who Must Report
A plant, factory, or other facility is subject to the provisions of EPCRA section 313, if
it meets all three of the following criteria:
• It conducts manufacturing operations (is include in Standard Industrial
Classification (SIC) codes 20 through 39); and
• It has 10 or more full-time employees (or the equivalent 20,000 hours per
year); and
• It manufacturers, imports, processes, or otherwise uses any of the toxic
chemicals listed on the EPCRA section 3 13 list in amounts greater than the
"threshold" quantities specified below.
Section 1.2 Thresholds
Thresholds are specified amounts of toxic chemicals used during the calendar year that
.'•'trigger' reporting requirements^ [[[ ' [[[ [[[ ; .........
' ''
If a facility manufactures or imports any of the listed toxic chemicals, the threshold
quantity will be:
• 25,000 pounds per toxic chemical or category over the calendar year.
If a facility processes any of the listed toxic chemicals, the threshold quantity will be:
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If ,a facility otherwise uses any of the listed toxic chemicals (without incorporating it
into any product or producing it at the facility), the threshold quantity is:
• 10,000 pounds per toxic chemical or category over the calendar year. < •'
EPCRA section 313 requires threshold determinations for chemical categories to be
based on the total of all chemicals in the category manufactured, processed, or otherwise
used. For example, a facility that manufactures three members of a chemical category would
count the total amount of all three chemicals manufactured towards the manufacturing ,
threshold for that category. When filing reports for chemical categories, the releases are
determined in the same manner as the thresholds. One report is filed for the category and all
releases are reported on this form.
Section 1.3 Chemicals within the Water Dissociable Nitrate Compounds Category
EPA is providing a list of CAS numbers and chemical names to aid the regulated
community in determining whether they need to report for the water dissociable nitrate
compounds category. The list includes individual chemicals within the water dissociable
nitrate compounds category. If a facility is manufacturing, processing, oV otherwise using a
chemical which is on this list, they must report this chemical. However,'this list is not
exhaustive. If a facility is manufacturing, processing, or otherwise using a water dissociable
nitrate compound, they must report the chemical, even if it does not appear on the list.
Section IA De Minimis Concentrations
The water dissociable nitrate compounds category is subject to the one percent de
minimis concentration. Thus, mixtures that contain members of this category in excess, of the
de minimis should be factored into threshold and release determinations. " - -
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Section 2. Guidance for Reporting Chemicals within the Water Dissociable Nitrate
Compounds Category
Note: for the purposes of reporting under the nitrate compounds" category, water
dissociable means that the nitrate ion dissociates from its counterion when in solution.
i •."", ;'; '.•'•' . i 'ij i
Section 2.1 Chemicals within the Water Dissociable Nitrate Compounds Category
Chemicals within the nitrate compounds category are only reportable when in aqueous
solution. All water dissociable nitrate compounds are included in the nitrate compounds
category with the exception of ammonium nitrate. Ammonium nitrate (solution) is an ,
individually listed chemical on the EPCRA section 313 list and is reported as a separate
chemical if the manufacture, process or otherwise use thresholds are exceeded. Specifically
listed section 313 chemicals, such as ammonium "nitrate (solution), are not included in
threshhold determinations for chemical categories such as the water dissociable nitrate
compounds category. Specifically listed toxic chemicals are subject to their own individual
threshold determination.
Section 2.2 Determining Threshhold and Release Quantities for Nitrate Compounds
The total nitrate compound, including both the nitrate ion portion and the counterion,
is included in the nitrate compounds category. When determining threshold amounts, the
total weight of the nitrate compound is to be included in all calculations. However, only the
nitrate ion portion is to be included when determining the amount of the chemicals within the
nitrate compounds category that is released, transferred, or otherwise managed in wastes.
Example 1: In a calendar year, a facility manufactures as by-products 20,000 pounds of
sodium nitrate (NaNO3) and 10,000 pounds of calcium nitrate (Ca(NO3)2), both in aqueous
solutions, and releases these solutions to wastewater streams. The total quantity of nitrate
compounds manufactured by the facility is the sum of the two chemicals, or 30,000
pounds, which exceeds the manufacturing threshold quantity of 25,000 pounds. The
facility therefore is required to report for the nitrate compounds category. By weight, the
nitrate ion portion is 72.96 percent of sodium nitrate and is 75.57 percent of calcium
nitrate. Of the 20,000 pounds of the sodium nitrate in solution, 72.96 percent or 14,592
pounds is nitrate ion, and similarly, of the 10,000 pounds of the calcium nitrate in
solution, 75.57 percent or 7,557 pounds is nitrate ion. The total nitrate ion in aqueous
solution released by the facility is the sum of the nitrate ion in the two solutions or 22,149
pounds (reported as 22,000 pounds). . ' '
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Section 2.3 Reporting Nitrate Compounds Generated from the Partial or Complete
Neutralization of Nitric Acid
Nitric acid is an individually listed chemical on the original EPCRA section :313-list
and is reported as a separate chemical if the manufacture, process or otherwise use thresholds
are exceeded. The partial or complete neutralization of nitric acid results in the formation of
nitrate compounds which are reported as chemicals within the nitrate compounds category if
their manufacture, process or otherwise use thresholds are exceeded,,"
Mineral acids such as nitric acid may be present in aqueous waste streams that are
sent to on-site neutralization or are discharged to a publicly owned treatment,works (POTW)
or other off-site treatment facility. As stated in_the Toxic Chemical Release Inventory
Reporting Form R and Instructions document (revised 1993 version, EPA 745-K-94-Q01),.
on-site-acid neutralization and its efficiency must be reported in Part II, section 7A of Form R
(waste treatment methods and efficiency section). For purposes of reporting on Form R, EPA
considers a waste mineral acid at a pH 6 or higher to be 100 percent neutralized (water
discharges to receiving streams or POTWs are reported as zero). The nitrate compounds
produced from the complete neutralization (pH 6.0 or above) of nitric acid are reportable
under the nitrate compounds category arid should be included in" all threshold and release
calculations. Two Form R reports would be required if the manufacture, process or otherwise
use thresholds are exceeded for nitric acid and for the .nitrate compounds category. ; •
If the nitric acid treatment efficiency is not equal to 100 percent (pH is less than 6),
the amount of the acid remaining in the waste stream which.is released to the environment -.
on-site or off-site must be reported in Part-II of Form R. The nitrate compounds produced
from the partial neutralization of nitric acid are reportable under the nitrate compounds
category and should be included in all threshold and release calculations. Two reports would
again be,required if the manufacture, process or otherwise use thresholds are exceeded for
nitric acid and for the nitrate compounds category. • -
Section 2.3.1 Estimating Nitric Acid Releases
The pH of the Waste stream can be used to calculate the amount of nitric, acid in the
stream and the efficiency of neutralization. The pH is a measure of the acidity or alkalinity
of a waste stream and can be obtained readily using a pH meter or pH sensitive paper. The
pH scale itself varies from 0 to 14.
The total nitric acid concentration (ionized and un-ionized) in pounds/gallon can be
calculated by using the pH value of the solution, the molecular weight and ionization constant
of the acid, and appropriate conversion factors. The total acid concentration for nitric acid for
different pH values is listed in Table 1. The calculation of mineral acid concentrations and
the derivation of Table 1 are discussed in a separate directive, Estimating Releases for
Mineral Acid Discharges Using pH Measurements, and in an addendum to this directive.
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The procedure outlined in this guidance document for calculating the quantity of
nitrate compounds formed from the complete or partial neutralization of nitric acid can be
used if nitric acid is the only mineral acid in a solution. In addition, the calculation of nitric .
acid releases using only pH measurements is a rough estimate. The subsequent calculation of
nitrate compound releases is therefore also only a rough estimate. The estimates can be made
for a waste stream with a steady pH below 6 or for one whose pH temporarily drops to below
pH 6. Facilities should use their best engineering judgement and knowledge of the solution to
evaluate how reasonable the estimates are.
Table 1. Nitric Acid Concentration Versus pH
PH
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8 %
Nitric Acid Concentration
(Ibs/gallon)
0.5200000
0.3300000
0.2100000 ^
0.1300000
0.0830000
0.0520000
0.0330000
0.0210000
0.0130000
0.0083000
0.0052000
0.0033000
0.0021000
0.0013000
0.0008300
PH
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
5.2
5.4
5.6
5.8
6.0
Nitric Acid Concentration
(Ibs/gallon);
0.0005200
0.0003300
0.0002100
0.0001300
0.0000830
0.0000520
0.0000330
0.0000210
0.0000130
0.0000083
0.0000052
0.0000033
0.0000021
0.0000013
0.0000008
0.0000005
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Example 2: In a calendar year, a facility transfers 1.0 million gallons of a solution
containing nitric acid (HNO3), at pH 4, to a POTW. Using Table 1, a pH of 4
corresponds to a concentration of 0.0000520 Ibs HNO3/gallon of solution. The weight of
HNO3 transferred can be estimated using the equation:
Transfer of HNO3 = (concentration of HNO3) x (effluent flow rate)
Substituting the example values into the above equation yields: ,
Transfer of HNO3 = 0.0000520 Ibs/gal HNO3 x 1,000,000 gal solution/yr
= 521bs/yr ."•... ; / _ - - , .-'•'. ' ...
Example 3: A facility had an episodic release of nitric acid (HNO3) in which the waste -
stream was temporarily below pH 6. During the episode, the waste water (pH 2.0) was
discharged to a river for 20 minutes at a rate of 100 gallons per minute. Using Table i, a
pH of .2.0 for,HNO3 represents a concentration of 0.0052000 Ibs HNO3/gallon of solution:
The amount of the HNQ3 released can be estimated using the following equation-
Release of HNO3 = (concentration of HNO3) x (effluent flowrate).
Substituting the example values in the above equation: r -
Release of HNO3 = 0.0052000 Ibs/gal x 100 gal/min x 20 min
. . =10 ibs •••--'. .-.'. . .'. ..;
Section 2.3.2 Estimating Treatment Efficiencies for Nitric Acid Neutralization
• • t -. '."'-.•'
Nitric acid solutions that are neutralized to a pH of 6 or above have a treatment
efficiency of 100 percent. If nitric, acid is neutralized to a pH less than 6, then the importable
treatment efficiency is somewhere between 0 and 100 percent. It is possible to estimate the
neutralization treatment efficiency using nitric acid concentration values directly from Table 1
in the equation given below. The concentrations correspond to the pH values before arid after
.treatment. ''•._.". , • .
Treatment Efficiency = (I-E)/I x 100 . v
where I = acid concentration before treatment and
E = acid concentration after treatment
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Example 4: A nitric acid (HNO3) waste-stream of pH 2.4 is neutralized to pH 4.6. Using
Table 1, the initial nitric acid concentration is 0.0021000 mol/liter and the final
concentration is 0.0000130 mol/liter. Substituting these values into the equation for
treatment efficiency:
Treatment Efficiency = (0.0021000 - 0.0000130)70.0021000 x 100
= 99.4 percent. ' '
For strong acids only (including nitric acid), the net difference in pH before and after
treatment can be used to estimate the treatment efficiency since pH is directly proportional to
the acid concentration. For example, a pH change of one unit results in a treatment efficiency
of 90 percent, whether the pH change is from pH 1 to pH 2 or from pH 4 to pH 5. Table 2
summarizes treatment efficiencies for various pH changes (the pH change is the difference
between the initial pH and the pH after neutralization). In the table, some pH changes result
in the same treatment efficiency values due to rounding to one decimal place.
Table 2. Nitric Acid Treatment Efficiencies for Various pH Changes
pH Change
1.0
1.1
1.2
1.3
1.4
. 1.5
1.6
1.7
1.8
1.9
Treatment Efficiency (%)
90.0
92.1
93.7
95.0
96.0
96.8
97.5
98.0
98.4
98.7
pH Change
2.0
2.1
2.2
2.3
2.4
2.5 .
2.6
2.7
2.8
2.9 -
3.0
Treatment Efficiency (%)
99.0
99.2
99.4
99.5
99.6
99.7
99.8
99.8
99.8
99.9
99.9
Example 5: If a nitric acid (HNO3) waste stream of pH 2 is treated to pH 4, the pH
change is 2 units. Using Table 2 above, the treatment efficiency is given as 99.0 percent.
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Section 2.3*3 Estimating Releases of Nitrate Compounds Generated from the
Neutralization of Nitric Acid
The nitrate compounds produced from the complete neutralization (pH 6.0 or above)
or partial neutralization (pH less than 6) of nitric acid are reportahle under the nitrate
compounds category if the appropriate threshold is met and should be included in all
threshold and release calculations. In order to determine the quantity of a nitrate compound
generated and released, the quantity of nitric; acid released must be known (or calculated from
the equations used in Examples 2 and 3 above) as well, as the nitric acid .treatment efficiency
(calculated from the equations used in Examples, 4 and 5 above). , J '
The neutralization of nitric acid will most likely result in the generation of monovalent
nitrate compounds (such as sodium nitrate and potassium nitrate). The quantity of these
compounds formed in kilomoles will be equal to the quantity of the nitric acid neutralized in
kilomoles. If divalent nitrate'compounds are formed (such as calcium nitrate), the quantity of
these compounds formed in kilomoles will be equal to one-half the quantity of the nitric acid
neutralized in kilomoles. Similarly, if trivalent nitrate compounds are formed (such as iron
(III) nitrate), the quantity formed of these compounds in kilomoles will be equal to one-third
the quantity of the nitric acid neutralized in kilomoles. Note: to calculate the releases of
nitrate compounds generated froni the neutralization of nitric, acid, the molecular weight of
the nitrate compound formed must be used. Molecular weights of some of the individual
chemicals within the water dissociable nitrate compounds category are given in Table 3.
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Example 6: In a calendar year, a facility transfers 50,000 pounds of nitric acid (HNO3) to
an on-site treatment facility. The nitric acid treatment efficiency is 95 percent, and the
nitrate compound formed as a result of the treatment is sodium nitrate (NaNO3). The
quantity of nitric acid transferred that is neutralized (generating sodium nitrate) is 95
percent of 50,000 pounds or 47,500 pounds. The molecular weight of nitric acid is 63.01
kg/kmol, and the molecular weight of sodium nitrate is 84.99 kg/kmol. The quantity of
nitric acid neutralized is converted first to kilograms then to kilomoles using the following
equations:
Kilograms HNO3 neutralized = (Ibs HNO3 neutralized) x (0.4536 kg/lb)
Kilomoles HNO3 neutralized = (kg HNO3) -f (MW of HNO3 in kg/kmol).
Substituting the example values into the above equation yields:
Kilograms HNO3 neutralized = 47,500 Ibs x 0.4536 kg/lb
= 21,546 kg
Kilomoles HNO3 neutralized = 21,546 kg 4-63.01 kg/kmol
= 341.9 kmol.
The quantity of sodium nitrate generated in kilomoles is equal to the quantity of nitric
acid neutralized (341.9 kmol). The quantity of sodium nitrate generated in kilomoles is
converted first to kilograms then to pounds using the following equations:
Kilograms NaNO3 generated = (kmol NaNO3) x (MW of NaNO3 in, kg/kmol)
Pounds NaNO3 generated = (kg NaNO3) x (2.205 Ibs/kg).
Substituting the values into the above equation yields:
Kilograms NaNO3 generated = 341.9 kmol x 84.99 kg/kmol
= 29,058 kg
Pounds NaNO3 generated = 29,058 kg x 2.205 Ibs/kg
= 64,073 pounds (reported as 64,000 pounds).
The 64,000 pounds of sodium nitrate generated is the quantity used to determine whether
thresholds have been met or exceeded. The quantity of nitrate ion released is calculated
as in Example 1 above.
Section 2.4 Generation of Nitrate Compounds from Biological Wastewater Treatment
If a facility treats wastewater on-site biologically, using the activated sludge process,
for example, the facility may be generating nitrate compounds as by-products of this
biological process. The nitrate ion generated from this process will be associated with
various counterions (e.g. sodium ion, potassium ion). In the absence of information on the
identity of the counterion, a facility should assume for the purposes of EPCRA section 313
threshold determinations that the counterion is sodium ion.
10
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Section 3. CAS Number List of Some of the Individual Chemicals within the Water
Dissociable Nitrate Compounds Category
EPA is providing the following list of CAS numbers and chemical names to aid the
.regulated community in determining whether they need to report for the water dissociable
nitrate compounds category. If a facility is manufacturing, processing, or otherwise using a
chemical which is listed below, they must report this chemical. However, this list is not
exhaustive. .If a facility is manufacturing, processing, or otherwise using a water dissociable
nitrate compound, they must report this chemical, even if it does not appear on the following
list. , < .
Table 3. Listing by CAS Number of Some of the Individual Chemicals within the Water, Dissociable
Nitrate Compounds Category
Chemical Name " :.,
Aluminum nitrate, nonahydrate
Cerium (HI) ammonium nitrate, tetraliydrate
Cerium (IV) ammonium nitrate •
Barium nitrate -
Beryllium nitrate, trihydrate
Cadmium nitrate :
Cadmium nitrate, tetrahydrate
. Calcium nitrate
Calcium nitrate, tetrahydrate
Cerium (HI) nitrate, hexahydrate
Cesium nitrate
Chromium (IE) nitrate, nonahydrate
Cobalt (II) nitrate, hexahydrate
Copper (IE) nitrate, trihydrate
Copper (n) nitrate, hexahydrate
Dysprosium (III) nitrate, pentahydrate
Erbium (III) nitrate, pentahydrate
Gadolinium (III) nitrate, hexahydrate
Gallium nitrate, hydrate
Molecular Weight*
213.00 :
486.22
548.23 .
261.34
133.02
236.42
236.42' • :'
.164.09
164.09 • . . •' ""
326.13 ,
194.91
238.01
182.94
187.56
187.56 - ... .
348.51 "
353.27
343.26
255.73 . . •
CAS Number
7784-27-2
13083-04-0
10139-51-2
10022-31-8
7787-55-5-
10325-94-7 ,.
10022-68-1
10124-37-5-
13477-34-4
10294-41-4
7789-18-6
7789=02-8
10026-22-9
10031-43-3
13478-38-1 '
10031-49-9
10031-51-3.
19598-90-4
69365-72-6
'* For hydrated compounds, e.g. aluminum nitrate, nonahydrate, the molecular weight excludes the weight of the hydrate
portion. For example, the same molecular weight is provided for aluminum nitrate, nonahydrate and aluminum nitrate.
11
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Table 3. Listing by CAS Number of Some of the Individual Chemicals within the Water Dissociable
Nitrate Compounds Category
Chemical Name
Iron (HI) nitrate, hexahydrate .
Iron (DDL) nitrate, nonahydrate
Lanthanum (HI) nitrate, hexahydrate
Lead (II) nitrate
Lithium nitrate
Lithium nitrate, trihydrate
Magnesium nitrate, dihydrate
Magnesium nitrate, hexahydrate
Manganese (II) nitrate, tetrahydrate
Neodymium (HI) nitrate, hexahydrate
Nickel (H) nitrate, hexahydrate
Potassium nitrate
Rhodium (HI) nitrate, dihydrate
Rubidium nitrate
Samarium (HI) nitrate, hexahydrate
Scandium (DDT) nitrate
Scandium (HI) nitrate, tetrahydrate
Silver nitrate
Sodium nitrate
Strontium nitrate • ,
Strontium nitrate, tetrahydrate
Terbium (III) nitrate, hexahydrate
Thorium (TV) nitrate
Thorium (TV) nitrate, tetrahydrate
Yttrium (TEE) nitrate, hexahydrate
Yttrium (HI) nitrate, tetrahydrate
Molecular Weight*
241.86
241.86
324.92
331.21
68.95
68.95 ,
148.31
148.31.
178.95
330.25
182-70.
101.10
288.92
147:47
336.37
230.97
230.97 '
169.87
84.99
211.63
211.63
344.94
480.06
480.06
274.92
274.92
CAS Number
13476-08-9
77.82-61-8 , -
10277-43-7
10099-74-8
7790-69-4
13453-76-4
15750-45-5
13446-18-9
20694-39-7
16454-60-7
13478-00-7
7757-79-1
13465-43-5
13126-12-0
13759-83-6
13465-60-6
16999-44-3
7761-88-8
7631-99-4
10042-76-9
13470-05-8
13451-19-9
13823-29-5
13470-07-0
13494-98-9
13773-69-8
' For hydrated compounds, e.g. aluminum nitrate, nonahydrate, the molecular weight excludes the weight of the hydrate
portion. For example, the same molecular weight is provided for aluminum nitrate, nonahydrate and aluminum nitrate.
12
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-. Table 3. Listing by CAS Number of Some of the Individual Chemicals within the'Water Dissociable
/' .. Nitrate Compounds Category • >
Chemical Name
Zinc nitrate, trihydrate , , /-
Zinc nitrate, hexahydrate
Zirconium (IV) nitrate, pentahydrate
Molecular Weight*
. 189.39 : - ,
189.39 •
339.24
CAS Number
131446-84-9
10196-18-6 :
13986-27-1
* For hydrated compounds, e,g. aluminum nitrate, nonahydrate, the molecular weight excludes the weight of the hydrate.
portion. For example, the same molecular weight is provided -for aluminum nitrate, nonahydrate and aluminum nitrate.
13
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