SEPA
United States
Environmental Protection
Agency
Office of
Toxic Substances
Washington, DC 20460
January 1980
EPA-560/13-80-004
Toxic Substances
Materials Balance
for Chlorophenols
Level I - Preliminary
Review
Copy
-------
FINAL REPORT
LEVEL I MATERIALS BALANCE:
CHLOROPHENOLS
Prepared for:
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF PESTICIDES AND TOXIC SUBSTANCES
SURVEY AND ANALYSIS DIVISION
Task No. 5
Contract No. 68-01-5793
Michael Callahan - Project Officer
C. Richard Cothern - Task Manager
Prepared by:
JRB ASSOCIATES, INC.
8400 Westpark Drive
McLean, Virginia 22102
Project Manager: Karen Slimak
Task Leader: Robert L. Hall
Contributing Writers: Tien Nguyen
Phuoc Le
Mike Katz
Submitted: February 4, 1980
-------
THE FINAL REPORT PRESENTED HERE RESULTED FROM A LEVEL I
MATERIALS BALANCE STUDY ON CHLOROPHENOLS. THE RESULTS WERE
BASED ON AN ANALYSIS OF LITERATURE SUPPLIED BY EPA. ALTHOUGH
SUPPLEMENTARY INFORMATION UNDOUBTEDLY EXISTS, OBTAINING IT
WAS OUTSIDE THE SCOPE OF THIS TASK. THE LEVEL I REPORT IS
INTENDED TO SERVE AS A FOCUS OF DISCUSSION AND AS A BASIS
FOR FUTURE MATERIALS BALANCE STUDIES; IT IS NOT MEANT TO BE
A DEFINITIVE STUDY.
-------
LEVELS OF ENVIRONMENTAL MATERIALS BALANCES
Materials balance studies are performed at three levels or
depths of study and effort. In general the study of a chemical
proceeds sequentially through these three levels. Particular
chemicals are assigned to-be studied at one of the levels on the
basis of availability of information. The three levels are
described below:
Level I:
A LEVEL I MATERIALS BALANCE requires the lowest level of effort
and involves a survey of readily available information for construct-
ing the materials balance. Ordinarily, many assumptions must be
made in accounting for gaps in information; however, all are
substantiated to the greatest degree possible. Where possible the
uncertainties in numerical values are given, otherwise they are
estimated. Data gaps are identified and recommendations are made
for filling them. A Level I materials balance relies heavily on
the EPA's Chemical Information Division (CID) to provide readily
available information. The first draft of most Level I Materials
Balances is completed within a three to six week period; CID
literature searches are generally completed within two weeks. Thus
the total time required for preparation of the initial draft of a
Level I materials balance ranges from five to eight weeks.
Level II:
A LEVEL II MATERIALS BALANCE involves a greater level of effort,
including an in-depth search for all information relevant to the
materials balance. The search includes all literature (concentrating
on primary references), contacts with trade associations, other
agencies, and industry to try to uncover unpublished information,
and possibly site investigations. Uncertainties and further data needs
are identified in the Level II report. Recommendations for site
sampling needs for Level III are also identified.
Level III:
A LEVEL III MATERIALS BALANCE generally involves the assimilation
of new data obtained. It builds on the Level II literature searches
and reviews of industrial production data by filling in data gaps
through site visits and monitoring. The data generated for a Level III
Materials Balance are intended to be statistically valid and have known
confidence values. Level III Materials Balances are also intended to
provide a basis for regulations or legal proceedings.
-------
ABSTRACT
This report presents a Level I materials balance study on 2-chlorophenol,
4-chlorophenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol, 2,3,4, 6-tetrachloro-
phenol and pentachlorophenol. Areas of major interest were production quantities,
producers, consumption amounts and emissions to air, land, and water related to
the above sources. The estimated production quantities in 1976 of the compounds
studied were as follows: 2-chlorophenol, 9000 kkg; 4-chlorophenol, 9800
kkg; 2,4-dichlorophenol, 39,000 kkg; 2,4,5-trichlorophenol, 6300 kkg; 2,3,4,6-
tetrachlorophenol, 1,800 kkg; and pentachlorophenol, 22,000 kkg. Waterborne
emission was considered to be the main pathway of chlorophenols release to the
environment because of the physical characteristics of these chemicals. The
estimated quantities of aquatic emissions associated with the chlorophenols
studied were as follows: 2-chlorophenol, 430 kkg; 4-chlorophenol, 650 kkg;
2,4-dichlorophenol, 870 kkg; 2,4,5-trichlorophenol, 105 kkg; 2,3,4,6-tetrachloro-
phenol, 67-160 kkg; pentachlorophenol, 840-1400 kkg. Throughout this report,
estimations and assumptions were made in places where needed information was not
available. Bases for these estimations were stated and defined. Recommendations
for further studies were also made.
-------
TABLE OF CONTENTS
Abstract Page
List of Tables v
List of Figures vi
List of Abbreviations vii
Executive Summary viii
1.0 Introduction 1-1
1.1 Physical Properties of Chlorophenols 1-3
2.0 Monochlorophenols 2-1
2.1 2-Chlorophenol 2-2
2.1.1 Production of 2-Chlorophenol ' 2-5
2.1.2 Uses 2-8
2.1.3 Summary 2-11
2.2 4-Chlorophenol 2-11
2.2.1 Production 2-11
2.2.2 Uses 2-16
2.2.3 Summary 2-24
3.0 2,4-Dichlorophenol 3-1
3.1 Flow Diagram for 2,4-Dichlorophenol 3-1
3.2 Direct Production of 2,4-Dichlorophenol 3-1
3.2.1 Amounts Produced 3-1
3.2.2 Amounts Imported 3-5
3.3 Emissions Due to Production and Imports 3-5
3.3.1 Emission Due to Production 3-5
3.3.2 Emissions Due to Imports 3-11
3.3.3 Emissions Due to Other Sources of Production 3-12
3.4 Emissions Due to Consumption and Use 3-12
3.4.1 2,4-Dichlorophenoxyacetic Acid (2,4-D) Manufacture 3-12
3.4.2 Timber Processing 3-16
3.4.3 Leather Tanning and Finishing 3-17
3.4.4 Impurities in 2,4-D 3-17
-------
Page
3.4.5 Degradation of 2,4-D in the Environment 3-17
3.5 Summary 3-17
4.0 2,4,5-Trichlorophenol 4-1
4.1 Direct Production of 2,4,5-Trichlorophenol (2,4,5-TCP) 4-1
4.2 Amount Imported 4-7
4.3 Emissions Due to Production and Imports 4-8
4.3.1 Emissions Due to Production 4-8
4.3.2 Emissions Due to Imports 4-11
4.3.3 Emissions Due to Other Sources of Production 4-12
4.4 Emissions Due to Consumption and Use 4-12
4.4.1 Amounts of 2,4,5-Trichlorophenoxyacetic Acid and 4-12
Derivatives and Trichlorophenol Sodium Salt
Produced
4.4.2 Emissions to Air 4-13
4.4.3 Emissions to Water 4-13
4.4.4 Emissions Due to Disposal of Solid Residues 4-14
4.4.5 Degradation of 2,4,5-TCP in Derivatives 4-15
4.4.6 Direct Use of 2,4,5-TCP 4-16
4.5 Summary 4-17
5.0 Tetrachlorophenol 5-1
6.0 Pentachlorophenol 6-1
6.1 Environmental Flow Diagram for PCP 6-1
6.2 Production ' 6-4
6.3 Consumption and Uses 6-6
6.3.1 Wood Preservation 6-7
6.3.2 Pressed Board and Insulation Board Manufacture 6-7
6.3.3 Other PCP Uses 6-7
6.4 Emissions to the Environment 6-12
6.4.1 Production of PCP 6-12
iii
-------
6.4.2 Formulation of PCP Products g_^y
6.4.3 Distribution and Storage of PCP and PCP Derivatives 6-17
6.4.4 Releases from Uses 6-18
6.5 Summary of Pentachlorophenol Materials Balance 6-24
7.0 Major Emission Locations 7-1
8.0 Data Gaps g ,
8.1 Identification of Major Producers and the Annual 8-1
Production Quantities of Chlorophenols
8.2 Level of Chlorinated Phenols Contained in the End 8-1
Products as Contaminants
8.3 Information on Environmental Emissions 8-2
List of References
IV
-------
LIST OF TABLES
Table Page No,
1.1 Physical Properties of Commercially Important 1-4
Chlorophenols
2.1 Uses of 4-Chlorophenol (1976) 2-25
3.1 Production and Sales of 2,4-Dichlorophenol (kkg) 3-3
4.1 Producers of 2,4,5-Trichlorophenol 4-3
4.2 Production and Imports of 2,4,5-TCP and its Acid, 4-4
Acid Derivatives and Salts
4.3 Molecular Weights of 2,4,5-TCP and its Derivatives 4-5
6.1 Pentachlorophenol Producers 6-4
6.2 Estimated Supply and Demand for Pentachlorophenol 6-5
6.3 Quantities of Wood Products Treated with Pentachlorophenol, 6-9
1975
7.1 Major Emission Locations 7-2
-------
LIST OF FIGURES
Figure No. Page No,
1.1 Process Flow for Chlorination of Phenol 1-2
2.1 Producer and Production Sites for 2- and 4-Chlorophenol 2-3
2.2 Flow Diagram of 2-Chlorophenol 2-4
2.3 Materials Balance for 2-Chlorophenol (kkg) 2-12
2.4 Flow Diagram of 4-Chlorophenol 2-13
2.5 Locations of Quinizarin Production Facilities 2-18
2.6 Materials Balance for 4-Chlorophenol (kkg) 2-26
3.1 Flow Diagram for 2,4-Dichlorophenol, 1976 (kkg) 3-2
3.2 Producers and Production Sites for 2,4-D 3-13
3.3 Materials Balance for 2,4-Dichlorophenol (kkg) 3-18
4.1 Flow Diagram for 2,4,5-Trichlorophenol 4-2
4.2 Production Schematic for 2,4,5-Trichlorophenol 4-9
Production by Hydrolysis of 1,2,4,5-Tetrachlorobenzene
4.3 Materials Balance for 2,4,5-Trichlorophenol (kkg) 4-18
5.1 Materials Balance for Tetrachlorophenol (kkg) 5-2
6.1 Flow Diagram for Pentachlorophenol (kkg) 6-2
6.2 Pentachlorophenol Producers 6-3
6.3 Geographical Distribution of Wood Preserving Plants 6-8
in the U.S.
6.4 Geographical Distribution of Hardboard Manufacturing 6-10
Facilities in the U.S.
6.5 Geographical Distribution of Insulation Board 6-11
Manufacturing Facilities in the U.S.
6.6 Production Process for Pentachlorophenol 6-14
6.7 Materials Balance for Pentachlorophenol (kkg) 6-25
VI
-------
LIST OF ABBREVIATIONS
2,4-DCP
2,4-D
PCP
TCDD
2,4,5-TCP
2,4,5-T
MCP
DCB
POTW
2,4-dichlorophenol
2,4-dichlorophenoxyacetic acid
pentachlorophenol
2,3,7,8-tetrachlorodibenzo-p_-dioxin
2,4,5-trichlorophenol
2,4,S^trichlorophenoxyacetic acid
monochlorophenol
dichlorobenzene
Publicly-Owned Treatment Works
Numbers in parentheses are references; see reference list of report.
Superscript numbers are footnotes; see the end of the table or figure.
Vll
-------
EXECUTIVE SUMMARY
This Level I materials balance reports on emissions due to production
and use of several representatives of the class of chlorophenols. The compounds
specifically designated by the Task Order for study are 2-chlorophenol; 2,4-
dichlorophenol; 2,4,5-trichlorophenol; 2,3,4,6-tetrachlorophenol; and penta-
chlorophenol. We have also included 4-chlorophenol in this study.
The chlorophenols are solid compounds with slight water solubility.
They have low vapor pressures. The production and uses of the individual
compounds will be summarized below. In almost all cases, production, use and
emissions data were not readily available so that the values presented are
based on estimates and extrapolations.
The figures included with this summary present the data and emissions
estimated for each compound for the year 1976.
Monochlorophenols
2- and 4-Chlorophenol are each synthesized by two major methods:
chlorination of benzene and hydrolysis of dichlorobenzene. The total estimated
amounts of each isomer produced in 1976 were: 2-chlorophenol, 9000 kkg;
4-chlorophenol, 9800 kkg. Phenol chlorination accounted for an estimated 78%
of 2-chlorophenol and 87% of 4-chlorophenol, with the rest produced by
dichlorobenzene hydrolysis. Emissions to water were the largest category of
emissions due to production: 190 kkg/year in 1976 for 2-chlorophenol;
210 kkg/year for 4-chlorophenol.
In the absence of direct data, we estimated the major consuming process
of monochlorophenols to be further chlorination to yield higher chlorophenols.
Emissions to water from these uses were approximately the same as those due
to production: 190 kkg/year for further chlorination of 2-chlorophenol;
180 kkg/year for 4-chlorophenol in 1976.
Vlll
-------
2,4-Dichloropheno^
2,4-dichlorophenol is synthesized by two routes: chlorination of phenol
(estimated 80%; 31,200 kkg in 1976) and chlorination of chlorophenols (estimated
20%; 7,800 kkg). Emissions from these processes were almost entirely aqueous:
819 kkg/year estimated emissions to water; 39 kkg/year to air. The other major
source of estimated emissions was production of the pesticide 2,4-D from
2,4-dichlorophenol. This process released an estimated 2.1 kkg to the air and
42 kkg to water in 1976. Breakdown of 2,4-D in the soil could be a major source
of land emissions, but further data are necessary to evaluate this point.
2^4,5-Trichlorophenol
2,4,5-Trichlorophenol is synthesized by hydrolysis of 1,2,4 ,5-tetrachloro-
benzene. In the absence of direct data, production was estimated to be 6500
kkg in 1976. Diazotization of 2,4,5-trichloroaniline produced an estimated 10
kkg in L976. Emissions due to production were estimated to be 94 kkg to water,
7 kkg to air and 6 kkg to land in 1976. In several consumption processes,
total emissions were estimated to be significant but allocation to an environmental
medium was not possible. For instance, we estimated that all 433 kkg used in
1976 as fungicides may be released to air + land + water, but the distribution
could not be estimated.
2,3^4,6-Tetrachlorophenol
The tetrachlorophenol was produced in the smallest amount of the chlorophenols
studied: 1800 kkg in 1976. It is formed by chlorination of phenol in the
presence of a catalyst. Its major use (estimated 67% of production) was as a
wood preservative. Compared to the other chlorophenols, releases from
tetrachlorophenol production were relatively small. Leaching from preserved wood
poles could be significant, at 770 kkg in 1976.
IX
-------
Pentachlorophenol
Pentachlorophenol showed a 1978 production of 22,000 kkg. It is produced
by chlorination of phenol using a catalyst. An estimated 12 kkg were released
to air during this process, along with 660 kkg to water. It has many uses based
on its biocidal and preservative properties. A leading source of estimated
emissions was its use in homes and gardens (110 kkg emitted to water, 380 kkg
emitted to soil). A major source of release could be from utility poles
treated with PCP, as a result of PCP leaching and evaporation. A preliminary
estimate indicated that this source could emit up to 9600 kkg to land and water.
The locations with the greatest concentration of chlorophenol-producing
capacity were Midland, Michigan, and Sauget, Illinois.
This report contains many best-guess estimates of important figures,
such as production amounts and emission factors. This is because much of the
desired information was proprietary and therefore confidential. Access to
this information would be necessary for more detailed analysis of chlorophenols
emissions.
The materials balances of the chlorophenols are summarized in Figures ES-1
through ES-6. Each figure refers to the most recent year for which data were
available: 1976. In calculating the summary equation for each materials
balance, the terms "Amount Consumptively Used" and "Amount Non-Consumptively Used"
are the amount of compound entering the process minus the emissions due to the
process. This prevents double-accounting of emissions.
-------
liNO u,];. I
X
H-
"..7j,.rTi,r. i
—
_ 1
^hl.l... .l,l..l».«4
^,..1 l^~. 1,1.. 1
-.u.1.... i .^.T^n; i
1 l
Figure ES-1 Materials Balance for 2-Chlorophenol (kkg)
-------
x
H-
P-
Figure ES-2 Materials Balance for 4-Chlorophenol (kkg)
-------
X
H-
P-
rn^lurllM. \
11 *il
2.1 41
o lion
41.4* 6J1.I JIOO
Figure ES-3 Materials Balance for 2,4-Dichlorophenol (kkg)
-------
O (I • •
I t I I
i t r
i i i
O 0 400 tDO
I f t < 1)
Figure ES-4 Materials Balance for 2,4,5-Trichlorophenol (kkg)
-------
OlHSUKFTlVt USES
EHVIIIOKMLNTU. kttCASES
UATtfc __ SOI.ID
" "
5l*tSi 7110 tfc| 16OO
&IIKMAM OF MATERIALS BALAMCti
- Amount
0.) I
-O -0
3.0 10 I)
0.* 0 O-
444 MO*
Figure ES-5 Materials Balance for Tetrachlorophenol (kkg)
-------
cuMsuwrivi uses cmir^m HANTS
ULCASFS OF tCt
fUiur.i
0
Product tun by
Ctilut Inai lutt
of ri.euul
2 1 . UllO
(•t>ait*
uh
ttom Slo<:kpt !«•
CtilOf Inailon ol
0
h«t*tlOlla» 0(
reoi.cl.loro-
- 0
rrc«iiu>nt
0
—., ,.-«- .
Upo.c.
lU-rCF (•purity
tu-riT ,
? JOO fruducttua **JO<1 I'*°°
K-PCP "
10 rroduciloo 10 j K.Prr ,.r...,,r
/v 0
/
fr? i^uric AciJ
lu
E.fort*
1 .100
1. IOO
1 ,100
J70 ror' '»
'* 'I ( ion u
So i n«ci>rleld»
~l ' 150)1
'" " llwi
( JO 1 1
)o > | AdtiiAlv* rrt««cv.
1 'I c Ion
1 IW f 1
^^r"p""rv-
1 ( ',0 ) I
Plywood *nd Fiber
proof in* 1,100
IIOBA «nd Uarden
Application* SiO
lloiblctdo
110
^good pr«««rv«tlon
1 S , (100
• o ^-o
— -v o o.i 0,5 i.o
. «* 0 ~0 0.5 0.5
,1 T 1 9600
—0 ~0 -vO «/0
in
-0 0.5 0.5 1.0
'
""
" "° 17 * 0 11
. .0 * 0 t
loit «M. 51.. ,,.,„„.
Dr>t,rav»il * rnttnloaa
Figure ES-6 Materials Balance for Pentachlorophenol (kkg)
-------
1.0 INTRODUCTION
This report has been prepared in response to a task order from the United
States Environmental Protection Agency (EPA) for a Level I materials balance
study on chlorophenols. A draft report was submitted September 7, 1979, and
has been revised and rewritten as this report. The specific compounds listed
in the Task Order are 2-chlorophenol; 2,4-dichlorophenol; 2,4,5-trichlorophenol;
2,3,4,6-tetrachlorophenol; and pentachlorophenol. In order to accomodate this
multiple materials balance, a separate chapter is presented on each compound.
Within each chapter are sections on emissions due to production and imports,
emissions due to consumption, and emissions due to other sources. Each
chapter will present the compound's overall materials balance, and the text
and footnotes will describe how derived values were obtained.
Chlorophenols are used as wood preservatives, fungicides, herbicides,
molluscicides, mold inhibitors, antiseptics and disinfectants. In addition,
they are also used as precursors for the synthesis of dyes, pigments and
pesticides. They form a class of synthetic organic chemicals used as pesticides
and chemical intermediates at a rate exceeding 100 million pounds per year
(EPA, 1975a).
All of the chlorophenols discussed in this report are synthesized by the
same basic process: chlorination of phenol by molecular chlorine:
The reaction proceeds readily, and the chlorophenols produced will serve as
reactants for further chlorination reactions. These reactions are carried out
industrially by the process flow shown in Figure-1.1. The respective chapters
will refer back to this figure in discussions of emissions. (A prill tower
produces aggregated (prilled) product by passing it counter-current to water
mist in a column.)
1-1
-------
FIGURE 1.1 PROCESS FLOW FOR CHLORINATION OF PHENOL
I
CAUSTIC SODA
-VENT
VENT-
WATER
PHENOL
VENT
CHLORINE
CATALYST
C6C1XOH •
BY-PRODUC.T
TARS TO
INCINERATION
EXC£SS-<-
WASTEWATER
TO TREATMENT
•PRINCIPAL PROCESSING ROUTE
FOR ALTERNATIVE PRODUCT-TYPE
OUST & PART CULATE
1. Tracor-Jitco, 1977a
-------
1.1 PHYSICAL PROPERTIES OF CHLOROPHENOLS
The physical properties of the most important chlorophenols are summarized
in Table 1.1. They are solids at room temperature and all have a pungent,
medicinal odor. They are at most slightly soluble in water. Their salts,
however, are soluble in aqueous base. The volatility of the compounds generally
decreases, and the melting and boiling point generally increase, as the number
of chlorine atoms substituted on the benzene ring increases. Vapor pressures
are relatively low.
1-3
-------
TABLE 1.1 PHYSICAL PROPERTIES OF COMMERCIALLY IMPORTANT CHLOROPHENOLS
^\^ Compound
^v.
^N.
Property ^~\^^
Melting point (°C)
Boiling point (°C)
Dissociation
constant (K ) at
25°C a
2
Solubility (g/lOOg)
Water (25°C)
Temperature at
which the vapor
pressure equals
Immllg
4-Chlorophenol
A 0-41
219
6.6xlO~10
2.71
49.8
2,4-Dichloro-
phenol
43-44 *
210-211
2.1xlO~8
parti al
53.0
2,4,6-trichloro-
plienol
68
246
3.8xlO~8
insol.
76.5
2,4,5-trichloro-
phenol
68
245-246
3.7xlO"8
partial
72.0
.
2,3,4,6-tetra-
chlorophenol
69-70
164/23mra
4.2xlO"6
0.10
100.0
pentachloro-
phenol
190
309-310
1.2xlO~5
14-19 ppm
0.0005 nun
Hg (20°C)
SOURCES: EPA (1975 a) and Weast (1977)
"When quantitative data were not available, qualitative characterizations were presented as a general guide.
-------
2.0 MONOCHLOROPHENOLS
There are several .monochlorophenols. The types of monochlorophenols
and their molecular structures are given below:
c>-chlorophenol
2-chlorophenol
m-chlorophenol
3-chlorophenol
jD-chlorophenol
4-chlorophenol
The types of monochlorophenols which are most commonly found in commercial
and industrial use are the o- and p- isomers. They are both produced from the
same chemical process and are used in the same manner. The m-chlorophenol
is rare as the conditions required for its formation are difficult to achieve.
This discussion will focus on the two common forms of monochlorophenol.
The information available on the monochlorophenols is as follows:
1. The production quantity of quinizarin in 1976 was reported at 7.79 x
1C)2 kkg (USITC). Quinizarin is a product made from the reaction
of p-chlorophenol with phthalic anhydride.
2. An estimated 9000 kkg of 2-chlorophenol were produced in 1976
(Tracor-Jitco, 1977c). The basis of this estimation was not
discussed in their report.
3. Percentages of ^-dichlorobenzene and £-dichlorobenzene used
respectively in the production of 2-chlorophenol and 4-chlorophenol
were obtained from the Stanford Research Institute estimates
(Stanford Research Institute, 1975).
Other than the above data, information on other production processes,
production quantities, consumption quantities and emissions were unavailable.
Many assumptions and estimations were made in order to describe the environmental
flow of monochlorophenols and possible emissions quantities. It should be noted
that these derived quantities were not necessarily based on actual data, but
2-1
-------
were meant to serve as illustrations of the possible flow of monochlorophenols
in the environment and potential emissions to air, land and water released by
the producing and consuming industries.
More monitoring data are needed to properly assess the source and quantity
of emissions of monochlorophenols from these industries. Information on
production processes, production quantities and consumption quantities are
also needed in further studies.
The discussion on monochlorophenols is divided as follows:
Section 2.1 - 2-chlorophenol
2.1.1 - Production of 2-chlorophenol
2.1.2 - Uses
2.1.3 - Summary
Section 2.2 - 4-chlorophenol
2.2.1 - Production of 4-chlorophenol
2.2.2 - Uses
2.2.3 - Summary
2.1 2-CHLOROPHENOL
2-chlorophenol was produced in 1976 by Dow Chemical Company in Midland,
Michigan and by Monsanto Company in Sauget, Illinois. The annual production
capacity of Dow Chemical plant was reported from 5,000 to 7,500 kkg; the
Monsanto plant had an annual production capacity of 10,000 to 12,000 kkg;
the Monsanto plant had an annual production capacity of 10,000 to 12,000 kkg
(Tracor-Jitco, 1977c). Figure 2.1 shows the locations of 2-chlorophenol and
4-chlorophenol production plants in the United States. Figure 2.2 shows a
flow diagram for 2-chlorophenol.
2-2
-------
FIGURE 2.1 PRODUCERS AND PRODUCTION SITES FOR 2 - CHLOROPHENOL AND 4 - CHLOROPHENOL
ho
I
U)
Moncanto Company
Sauget, IL
Dow Chemical
Midland. MI
-------
FIGURE 2.2 ENVIRONMENTAL FLOW DIAGRAM OF 2 - CHLOROPHENOL
to
-£>
NATURAL
SOURCES
DIRECT SOURCES
1.DIRECT CHLORINA-
TION OF PHENOL
2.HYDROLYSIS OF Qr
DICHLOROBENZENE
3.MISCELLANEOUS
PRODUCTION
METHODS
INDIRECT SOURCES
1.CHLORINATION OF
POTW
2.LAB. PREPARATION
3.STOCKPILE
A.BY-PRODUCT OF
OTHER CHEMICAL
PROCESSES
PRODUCTION OF
2-CHLOROPHENOL
PRODUCTION OF
»DICHLORO-
PHENOLS
PRODUCTION OF
TRICHLORO-
PHENOLS
RODUCTION OF
lETRACHLORO-
HENOLS
PRODUCTION OF
PHENOLIC RESINS
AS A SOLVENT IN:
-EXTRACTION OF ORGANIC
SULFUR & NITROGEN COM-
POUNDS FROM COAL
-CLEANING CARBONACEOUS
DEPOSITS FROM RUBBER
IND. VESSELS
-------
2.1.1 Product ion of 2-chlorophenol
There are several methods of preparation of 2-chlorophenol which have
been used by industry. Direct chlorination of phenols has been the most widely
used process, although hydrolysis of chlorinated benzene is also feasible.
Other exotic synthetic routes are applicable but do not contribute greatly to
the total production of 2-chlorophenol. We will discuss the direct chlorination
and the hydrolysis method of 2-chlorophenol production.
2.1.1.1 Hydrolysis of Chlorinated Benzene
2-chlorophenol (2-CP) can be produced by the hydrolysis of £-dichlorobenzene
(p_-DCB). Generally, hydrolysis is carried out in aqueous alkali solutions at
high temperatures and under pressure (PEDCo, 1979b). This process has an
average yield of 86% (PEDCo, 1979b). This estimation was based on the yield
range of 85 to 90% given by Kirk-Othmer (1969). The main reaction in this process
is:
Aq. Alkali Solution
heat, pressure
£-dichlorobenzene (o-DCB) 2-chlorophenol
Stanford Research Institute has estimated that in 1976, 12% of the total
production of o-dichlorobenzenes was consumed in the production of 2-chlorophenol
(SRI, 1975). The total production of ^-dichlorobenzene in 1976 was reported to be
2.2 x 10^ kkg (USITC). This production volume was based on the quantities
reported by the manufacturers. Therefore, the total quantity of 2-chlorophenol
produced by the hydrolysis of ^-dichlorobenzene can be calculated by multiplying
the following factors:
1) The percentage of £-dichlorobenzene used in the production
of 2-chlorophenol,
2) Total production of o-dichlorobenzene,
2-5
-------
3) The reciprocal of the molecular weight of o-dichlorobenzene,
4) The percent of theoretical yield obtained, and
5) The molecular weight of 2-chlorophenol,
That is:
(0.12) (2.2 x 104 kkg o-DCB) (1 kkmo^Le o-DCB) (0.86 kkmole 2-CP)
(146.9 kkg ^-DCB) (kkmole o-DCB) :
(128.5 kkg 2-CP) = 2.0 x 103 kkg 2-chlorophenol
(kkmole 2-CP)
The unreacted materials are usually recycled for.other uses.
2.1.1.2 Direct Chlorination of Phenol
Direct chlorination of phenol with molecular chlorine is the most widely
used production process for 2-chlorophenol. In this preparation method,
4-chlorophenol is formed as a chief product and 2-chlorophenol is produced
as a by-product. The distribution of these two products was estimated to be
45% 2-chlorophenol and 55% 4-chlorophenol. This estimation is based on the
chemistry of phenol. The -OH group of phenol is a strong ortho/para director,
and therefore, upon chlorination of phenol, the reaction proceeds to produce
2- and 4-chlorophenol. Based on similar processes such as bromination and
sulfonation of phenol, it was assumed that the yield of the para product
would be greater than the yield of the ortho product (Morrison and Boyd,
1973). A yield of 45% ortho product and 55% para product was estimated
based on the slower reactivity of chlorination compared to that of the
bromination.
The principal reaction involved in this process is:
OH
OH
phenol
Cl,
chlorine
4-chlorophenol
.55% yield
2-chlorophenol
45% yield
2-6
-------
The total production of 2-chlorophenol in 1976 was estimated to be 9,000 kkg
(Tracor-Jitco, 1977c). The basis of this figure was not reported. Assuming that
no other production methods of 2-chlorophenol, except the hydrolysis method,
contribute any significant quantity to the total production of 2-chlorophenol,
the total production of 2-chlorophenol from the direct chlorination of phenol
was estimated by subtracting the total annual production of 2-chlorophenol from
the production quantity derived from the hydrolysis method. Therefore;
(9 x 103 kkg) - (2 x 103 kkg) = 7 x 103 kkg 2-chlorophenol
2.1.1.3 Indirect Production Sources of 2-chlorophenol
The most probable inadvertent source of 2-chlorophenol production was
the chlorination of municipal water containing chlorophenol precursors such as
phenol or cresol. It was estimated that the annual production of 2-chlorophenol
from the treatment of municipal water amounted to 15 kkg in 1976 (Versar, Inc.,
1977a). There were some uncertainties in the derivation method for this
estimation and more monitoring data are needed to properly assess this indirect
production source of 2-chlorophenol.
2.1.1.4 Imports
The quantity of 2-chlorophenol imported was not reported in 1976. It was
estimated that the amount would be negligible compared to the total production
quantity.
2.1.1.5 Other Potential Production Sources
Production of 2-chlorophenol as a by-product of other chemical production
processes (except the direct chlorination of phenol) was not mentioned in the
literature. Stockpiles of 2-chlorophenol were not reported or mentioned in
the past. Laboratory preparations of 2-chlorophenol were estimated to be
minimal ( < 0.1 kkg3); these would not contribute significantly to the total
production amount.
3 JRB estimate.
2-7
-------
2.1.1.6 Emissions of 2-Chlorophenol Due> to Production
No information on the emissions of 2-chlorophenol to the environment was
readily available. We estimated that most of 2-chlorophenol emissions during
production would be released to water, and that the aquatic emission factor
would be approximately the same as for 2,4-dichlorophenol emissions. This
estimate was based on similar aqueous solubility properties and similar produc-
tion processes for the two chemicals.
The estimated emissions of 2-chlorophenol to water were estimated by
multiplying the total production quantity of 2-chlorophenol by the emission
factor obtained for 2,4-dichlorophenol (see Section 3.3.1.1.2). Therefore:
(9.0 x 103 kkg) (2.1 x 10~2 kkg/kkg) = 1.9 x 102 kkg 2-chlorophenol to water
Atmospheric emissions were estimated to be 5% of the aquatic discharge
(see Section 3.3.1.1.1), and were calculated as follows:
2
(1.9 x 10 kkg) (0.05) = 9.5 kkg 2-chlorophenol emitted to air
Emission to land was estimated to be negligible.
2.1.2 Uses
Most of the 2-dichlorophenol produced in 1976 was consumed in the production
of higher chlorinated phenols; a small amount was used in the production of
phenolic resins. 2-Chlorophenol has also been utilized as a solvent in the
extraction process of organic sulfur and nitrogen compound from coal, and as
a cleaning solvent in the removal of carbonaceous deposits from vessels and
tanks of the rubber industry (Kirk-Othmer, 1969; Tracor-Jitco, 1977c).
Information on the quantity of 2-chlorophenol consumed in the above uses
was not available. We estimated that in 1976, 99% of the total production of
2-chlorophenol was consumed in the production of higher chlorinated phenols
and the remaining 1% accounted for all minor uses (phenolic resin formulation,
solvents).
-------
2.1.2.1 Production of Higher Chlorinated Phenols
2,4-Dlchlorophenol and 2,6-dichlorophenol are produced by direct chlorination
of 2-chlorophenol. Trichlorophenols and tetrachlorophenols can also be formed
if further chlorination is carried out (Kirk-Othmer, 1969). Pentachlorophenol
is produced by chlorination of trichlorophenols and tetrachlorophenols at
higher temperature condition and in the presence of catalyst (see Section 6.1).
It was estimated that in 1976, 99% of the total production of 2-chlorophenol
was used in this production process, but this percentage was only estimated for
calculation purposes and was not based on literature sources. Additional
information is needed to confirm this estimate. The total quantity of 2-
chlorophenol used in the production of higher chlorinated phenol was then
estimated as follows:
total annual
production of
2-chlorophenol
(0.99) =
quantity of 2-chlorophenol
used in the production of
higher chlorophenols
(9.0 x 103 kkg) (0.99) = 8.9 x 103 kkg
2.1.2.1.1 Emissions of 2-Chlorophenol from the Production of Higher
Chlorinated Phenols
Again, no information on the emissions of 2-chlorophenol to the environment
was available. We assumed that most of 2-chlorophenol emissions would be
associated with the aqueous stream, based on the physical characteristics of the
_2
compound. An estimated emission factor of 2.1 x 10 kkg/kkg was appropriate
for calculation purposes by analogy to 2,4-dichlorophenol (Section 3.3.1.1.2).
The aquatic emission of 2-chlorophenol from this production process was then
estimated by multiplying the total consumption quantity by the emission factor.
Therefore,
(8.9 x 103 kkg) (2.1 x 10~2 -j—§•) = 1.9 x 102 kkg 2-chlorophenol to water
tckg
2-9
-------
o
Atmospheric emissions were estimated to be 5% of the total aquatic discharge.
Therefore, emissions to the air were estimated as follows:
(total water emission) (0.05) = (total emission to air)
(1.9 x 102 kkg) (0.05) =- 9.5 kkg 2-chlorophenol emitted to air
2-Chlorophenol in land-destined waste materials was estimated to be negligible.
It should be noted that these emission quantities are best-guess estimates,
and are subject to confirmation by monitoring data.
2.1.2.2 Minor Uses
There was no information on the use of 2r-chlorophenol in the production
process of phenolic resins. We estimated that in 1976, 0.5% of the total
production of 2-chlorophenol was used in the production of phenolic resins;
thus, the consumption of 2-chlorophenol in phenolic resin manufacturing was
estimated by multiplying the total production of 2-chlorophenol by 0.5%.
Therefore:
(9.0 x 103 kkg) (.0.005) = 45 kkg 2-chlorophenol
Little detailed information exists on the use of 2-chlorophenol as
solvents. We estimated that in 1976, 0.5% of the total production of
2-chlorophenol was used as solvents. This corresponds to 45 kkg 2-chlorophenol
(calculated as above).
2.1.2.2.1 Emissions Due to Minor Uses
There was little information on the emissions of 2-chlorophenol from minor
uses. We estimated that the amount of 2-chlorophenol discharged to the
environment by phenolic resin production facilities was 2% of the total consumption
of 2-chlorophenol for this process. This estimate was made for calculation
purposes only, and was not based on literature sources. Assuming that there was
no control on the waste discharge from this process, then the emissions of
2-chlorophenol would be estimated as follows:
aJRB estimates. See Section 3.3.3.1.1.
2-10
-------
total consumption
of 2-chlorophenol
for this process
(0.02)
emission of
2-chlorophenol
from this process
(45 kkg) (0.02) = 0.9 kkg 2-chlorophenol emitted due to phenolic resin
production
It was reasonable to assume that most of 2-chlorophenol used as a solvent
was released directly to the environment. This would amount to 45 kkg of
2-chlorophenol emitted to the environment.
It should be noted that the above estimations were not based on actual
data and should be adjusted upon confirmation by monitoring or other
experimental information.
2.1.3 Summary
Because of che lack of available information, many values were derived
based on assumptions and estimations. These estimates should be verified in
later studies to properly assess the environmental emissions of 2-chlorophenol.
Figure 2.3 shows the materials balance diagram for 2-chlorophenol.
2.2 4-CHLOROPHENOL
2.2.1 Production of 4-chloropheno^L
The majority of 4-chlorophenol is produced by the direct chlorination of
phenol. Hydrolysis of chlorinated benzene contributes a small quantity to the
total production of 4-chlorophenol (Kirk-Othmer, 1969). Figure 2.4 shows the
environmental flow diagram of 4-chlorophenol.
2-11
-------
Hiti-<]ii<:,i*irrtVC
ir-iKS
[„,.,«. u.1.. • ..-. I-h
-• .•'•-•-> }~
__L_±J£ I-
L^ff
c
C"
^
HIlrLl
pliidiit-t I ixi ul
Ll,t«f
chlurl»«iaJ
phcrliul 1B|1UI I t (<:•
I |.l..:uullr 1 ^Woul Ic "•'"•
Figure 2.3 Materials Balance for 2-Chlorophenol (kkg)
-------
FIGURE 2.4 ENVIRONMENTAL FLOW DIAGRAM OF 4 - CHLOROPHENOL
AS AN ANTI-
GUMMINC AGENT FOR
GASOLINE
AS A SOLVENT IN THE
MINERAL OIL REFIN-
ING PROCESS
-------
2.2.1.1 Hydrolysis of £-Dichlorobenzene
The hydrolysis of £-dichlorobenzene (g-DCB) follows the same procedure
described in section 2.1.1.1. The only difference is the raw material used in
the production process; p-dichlorobenzene rather than o-dichlorobenzene is used
to form 4-chlorophenol (Kirk-Othmer, 1969).
Stanford Research Institute has estimated that in 1976, 10% of the total
production of £-dichlorobenzene was consumed in the production of 4-chlorophenol
(Stanford Research Institute, 1975). The total production of £-dichlorobenzene
4
was reported to be 1.7 x 10 kkg in 1976. Therefore the production of 4-chloro-
phenol (4-CP) was estimated as follows (see Section 2.1.1.1 for methods of
calculation):
(0.10)(1.7 x 104 kkg £-DCB) (1 kkmole p-DCB) (0.86 kkmole 4-CP)
(146.9 kkg £-DCB) (kkmole £-DCB) X
(128.5 kkg 4-CP) . , ,n3 , . , , ,, , , , , ,' , , .
fkkm 1—4 CP') = 1.3 x 10 kkg of 4-chlorophenol produced by hydrolysis
2.2.1.2 Direct Chlorination of Phenol
As pointed out in Section 2.1.1.2 most 4-chlorophenol was produced by
the direct chlorination of phenol. Yield of 4-chlorophenol was estimated at
55% . The quantity of 2-chlorophenol produced via the direct chlorination
3
process was estimated at 7.0 x 10 kkg in 1976. Thus, the production of 4-
chlorophenol was estimated by multiplying the quantity of 2-chlorophenol produced
from phenol by the ratio 55%/45%. Therefore;
7rf"TT\ = 8.6 x 10 kkg 4-chlorophenol produced by chlorination
The total production of 4-chlorophenol in 1976 was then estimated by
adding the production of 4-chlorophenol via, the direct chlorination process
to the quantity of 4-chlorophenol produced by the hydrolysis method:
33 3
8.6 x 10 kkg + 1.3 x. 10 kkg = 9.9 x 10 kkg 4-chlorophenol produced
a See Section 2.1.1.1
2-14
-------
2.2.1.3 Chlorination by POTW
As pointed out in section 2.1.1.3, chlorination of municipal water is a
potential indirect source of production of 2-chlorophenol and 4-chlorophenol.
The total estimated amount of 2-chlorophenol produced by this source was
15 kkg in 1976. Assuming that, the mechanism of this reaction is the same as
that occuring in the direct chlorination of phenol (see section 2.1.1.2,
2.2.1.3), it was assumed that the same product ratio is obtained in this case.
Thus the quantity of 4-chlorophenol can be calculated by multiplying the
quantity obtained for 2-chlorophenol by the ratio 55%/45%:
(15 kkg) .' ' = 18 kkg 4-chlorophenol produced indirectly
2.2.1.4 Imports
The quantity of 4-chlorophenol imported was not reported in 1976.
2.2.1.5 Other Production Sources
No information on other possible production processes such as stockpiles
or laboratory preparations was available. We estimated that the quantity
contributed by these sources would be small compared to the total production
quantity of 4-chlorophenol.
2.2.1.6 Emissions of 4-chlorophenol from Production
Little detailed information exists on the emissions of 4-chlorophenol
to the environment. Using the same reasoning previously discussed (see section
2.1.1.6), we estimated that most of 4-chlorophenol was emitted to water and
_2
the aquatic emission factor of 2.1 x 10 kkg/kkg of 4-CP produced was used.
Therefore, by using the same calculation method we estimated the total aquatic
discharge from the production of 4-chlorophenol:
(9.9 x 103 kkg) (2.1 x 10~2 kkg/kkg) = 2.1 x 102kkg 4-chlorophenol
emitted to water
2-15
-------
Accordingly, emission to the air was estimated as in section 2.1.1.6 by
multiplying the total aquatic discharge by 5%:
(2.1 x 102 kkg) (0.05) = 1.1 x 101 kkg 4-chlorophenol emitted to air
Emission to land was estimated to be negligible.
2.2.2 Uses
As shown in Figure 2.4, 4-chlorophenol was used in the production of
higher chlorinated phenols, quinizarin, indophenols and chromones. It was also
consumed in the production of germicides and miticides. Its salt finds use
as an anti-gumming agent for gasoline. It has also been used as a solvent in
the refining of mineral oil and as a denaturant of ethanol. (Kirk-Othmer, 1969).
Information on most of these production processes was not available.
2.2.2.1 Production of Higher Chlorinated Phenols
Most 4-chlorophenol produced in the United States was used for the production
of 2,4-dichlorophenol (Kirk-Othmer, 1969); 2,6-dichlorophenol was not formed
upon direct chlorination of 4-chlorophenol. Trichlorophenols and tetrachloro-
phenols were also produced by the chlorination of 4-chlorophenol.
We estimated that in 1976, 87% of the total production of 4-chlorophenol
was used in the production of higher chlorinated phenols. It should be noted
that this estimation was only used for calculation purposes and was not based
on any literature values. The amount of 4-chlorophenol used in this production
process was calculated by multiplying the total production quantity by a
factor of 0.87. Therefore:
(9.9 x 103 kkg) (0.87) = 8.6 x 10 kkg 4-chlorophenol consumed
2.2.2.1.1 Emissions Due to 4-Chlorophenol Chlorination
Information on the emissions of 4-chlorophenol to the environment was not
available. Using the assumptions and estimations discussed in section 3.1.2.1.1,
_2
we arrived at an aquatic emission factor of 2.1 x 10 kkg per kkg consumed and
2-16
-------
estimated that emissions to air were 5% of emissions to water. Emissions to land
were estimated to be negligible. The total emission of 4-chlorophenol to water
was estimated by multiplying the total consumption of 4-chlorophenol for this
process by the aquatic emission factor. In that case;
(8.6 x 103 kkg) (2.1 x 10~2 kkg/kkg) = 1.8 x 102 kkg 4-chlorophenol
emitted to water due to further
chlorination
Emissions of 4-chlorophenol to air were then estimated by multiplying the
emission quantity to water by 0.05:
2
(1.8 x 10 kkg) (0.05) = 9 kkg 4-chlorophenol emitted to air due to
further chlorination
2.2.2.2 Production of Quinizarin
In 1976, the production of quinizarin was reported at 1,717,000 Ibs. or
2
7.79 x 10 kkg (USITC). The production plants were American Cyanamid,
Tom Rivers Corp., Tennessee Eastman Corp., Harshaw Chemical Corp,, and E, I.
DuPont de Nemours Co. The plant locations are shown in figure 2.5.
4-chlorophenol was used as a raw material in the production of quinizarin.
The basic reactions in this process are:
o
O ^ DI1
phthalic anhydride 4-chlorophenol
0 OH
f?^O»
OCJ6
0 Cl
vv
Heat '
(i)
-4-chlorophenol
(2)
l-hydroxy-4-chloro-anthraqu i«one
Hydrolysis
1»4—dihydroxyanthraqulnone or
quinizarin
(3)
2-17
-------
FIGURE 2.5 LOCATIONS OF QUINIZARIN PRODUCTION FACILITIES
00
•The location of Dupont
plant la unknown.
Harshav Chemical Corp.,
Cleveland, OH
American Cyanamld
Wayne, NJ
Toms River Co.
Toms River, NJ
Tennessee Eastman Co.
Kingsport, TN
-------
We estimated that a 90% conversion rate would be achieved for each reaction
step. This estimation was based on engineering judgements on the economic
feasibility of industrial processes. The total amount of 4-chlorophenol consumed
in the production of quinizarin was calculated by multiplying the following
factors:
(1) The total production of quinizarin produced in 1976.
(2) The reciprocal of the molecular weight of quinizarin.
(3) The reciprocal percent of theoretical yield for reaction (3)
(4) The reciprocal percent of theoretical yield for reaction (2)
(5) The reciprocal percent of theoretical yield for reaction (1)
(6) The molecular weight of 4-chlorophenol.
Therefore;
(7.79 x 102) ( 1 ) ( 1 ) (_1_) ( 1 ) (128.56) 2
(240.23) (0.90) (0.90) (0.90) . ,f u , °
4-chlorophenol
(1) (2) (3) (4) (5) (6) consumed in
quinizarin synthesis
This calculated figure amounted to 5% of the total consumption of
4-chlorophenol in 1976.
2.2.2.2.1 Emissions Due to Quinizarin Synthesis
Information on emissions of 4-chlorophenol from the production of quinizarin
was not available. We estimated that the amount of 4-chlorophenol contained in
the end-product quinizarin would be minimal, but more information is needed to
confirm this assumption.
It was estimated that emissions to water were 3% of the total consumption of
4-chlorophenol in this process, based on the water solubility of the chemical,
and considering similar production processes for chemical intermediates used in
dye manufactures. Therefore, the total water emissions were estimated by
multiplying the amount of 4-chlorophenol consumed by this process by the emission
factor.
2 1
(5.7 x 10 kkg) (0.03) = 1.7 x 10 kkg 4-chlorophenol emitted to water
2-19
-------
Because of the low volatility of 4-chlorophenol, emissions to air were
estimated to be 5% of the total aquatic emission. Emissions to air were
obtained by multiplying the aquatic emission by the factor of 0.05:
(1.7 x 10 kkg) (0.05) = 8.5 x 10" kkg 4-chlorophenol emitted to air
The amount of 4-chlorophenol present in land-destined waste discharged
by the production of quinizarin was estimated to be negligible compared to
the total emission.
2.2.2.3 Production of Indophenols and Chromones
4-Chlorophenol reacts with 2-alkylacetoacetates in the presence of
phosphorus pentoxide to produce chromones. Likewise, it reacts with indene
hydrochloride and o-nitrobenzenesulfonic acids to produce indophenols. The
produced indophenols and chromones have been used in the dye industry.
(Kirk-Othmer, 1969)
Information on the production quantities and processes for these chemical
intermediates was not available. We estimated that 3% of the total production
of 4-chlorophenol was consumed in the production of these chemicals. Thus,
the total consumption of 4-chlorophenol in these production processes was
estimated by multiplying the annual production quantity by the 3% factor:
3 2
(9.9 x 10 kkg) (0.03) = 3.0 x 10 kkg 4-chlorophenol consumed
2.2.2.3.1 Emissions Due to Indophenol and Chromone Synthesis
Based on similar production processes for chemical intermediates used in
the manufacturing of dyes (see section 2.2.2.2.1) we estimated that 3% of the
4-chlorophenol consumed was lost as waterborne emission from these production
processes. The total aquatic emission was calculated by the general method
described in section 3.2.2.2.1. In this case,
2
(3.0 x 10 kkg) (0.03) = 9.0 kkg 4-chlorophenol emitted to water
2-20
-------
The atmospheric emissions associated with this process were then
estimated by multiplying the waterborne emission by a factor of 5% (see
section 3.2.2.2.1). Therefore,
(9.0 kkg) (0.05) = 4.5 x 10~ kkg 4-chlorophenol emitted to air
As mentioned in previous estimates, emissions to land were estimated to
be negligible.
Again, it should be mentioned that the above calculations and estimations
do not reflect actual emission data due to lack of information on the
production quantities, production processes, and emission factors.
2.2.2.4 Production of Germicides and Miticides
4-chlorophenol reacts with benzyl chloride to produce 0-(4-chlorophenyl)-
o-cresol, a widely used germicide. The reaction of 4-chlorophenol with
£-chloro-benzenesulfonyl chloride gives £-chlorophenyl-p-chloro-benzenesulfonate,
a miticide sold by Dow Chemical Company. (Kirk-Othmer, 1969). Other information
pertaining to the production methods and quantities was not available.
We assumed that 2% of the total 4-chlorophenol production in 1976 was
consumed in the synthesis of germicides and miticides. This assumption was
made only for calculation purposes. The total consumption of 4-chlorophenol
was then obtained by multiplying the total annual production of 4-chlorophenol
by 2%. Therefore:
3 2
(9.9 x 10 ) (0.02) = 2.0 x 10 kkg 4-chlorophenol consumed in germicide
and miticide synthesis
2.2.2.4.1 Emissions Due to Germicide and Miticide Synthesis
Little information pertaining to the production process and quantity of
germicides and miticides was available. Based on a similar pesticide synthesis
process (synthesis of PCP salt, see section 6.4.4.1), we estimated the water-
_3
borne emission factor to be 1.5 x 10 kkg per kkg of 4-chlorophenol consumed,
and the emission factor to air as 5 x 10 kkg/kkg consumed. The total emission
2-21
-------
to water was estimated by multiplying the amount of 4-chlorophenol used in the
production of germicides and miticides by the waterborne emission factor:
(2.0 x 102 kkg) (1.5 x 10~3 kkg/kkg) = 3.0 x 10-1 kkg 4-chlorophenol
emitted to water
The emission of 4-chlorophenol to air was calculated by multiplying the
annual consumption of 4-chlorophenol in this process by the airborne emission
factor:
(2.0 x 102 kkg) (5 x 10~5 kkg/kkg) = 1.0 x 10~2 kkg 4-chlorophenol
emitted to air
Emission to land was estimated to be negligible compared to the total
emission quantity.
4-Chlorophenol may be present in the finished germicide or miticide
products as a contaminant, but the amount could not be estimated and was
considered negligible compared to the bulk emissions from the production
facilities.
Again, these assumptions and estimations should be verified in further
studies.
2.2.2.5 Use of 4-Chlorophenol as a Denaturant for Ethanol
There was no information on the amount of 4-chlorophenol used as a
denaturant for ethanol (Kirk-Othmer, 1969). We estimated that in 1976, 1% of
the total consumption of 4-chlorophenol was used in the denaturation of ethanol.
This estimate was based on the following reasoning. In 1976, 4.0 x 10 kkg of
ethanol were consumed in the United States (USITC). We estimated that 80% of
the total ethanol production quantity was denatured, and the remaining 20% was
100% pure ethanol. Therefore, the estimated total denatured ethanol in 1976
was calculated by multiplying the total consumption of ethanol by a factor of
0.8;
(4.0 x 10 kkg) (0.8) = 3.2 x 10 kkg denatured ethanol produced in 1976
2-22
-------
We then assumed that the 4-chlorophenol used as a denaturant for ethyl
alcohol was present in the range of 0.01% to 0.05% (w/w) in ethanol. Therefore,
an average of 0.03 weight % of 4-chlorophenol was assumed to be contained in
the denatured ethanol. The estimated amount of 4-chlorophenol used as a
denaturant for ethanol can then be calculated by multiplying the total denatured
ethanol consumption by a factor of 0.03%:
(3.2 x 10 kkg) (0.0003) = 9.6 x 10 kkg 4-chlorophenol used for
ethanol denaturation
This figure would then amount to approximately 1% of the total consumption
3
of 4-chlorophenol (9.9 x 10 kkg).
2.2.2.5.1 Emissions Due to Use as a Denaturant for Ethanol
4-Chlorophenol is readily soluble in ethanol, Thus, we assumed that all
the 4-chlorophenol used as a denaturant of ethanol would be released to the
environment by the dispersive uses of ethyl alcohol. Therefore, the total
emissions of 4-chlorophenol from this use amounted to 9.6 x 10 kkg in 1976.
2.2.2.6 Miscellaneous Uses of 4-Chlorophenol
Besides the above uses, 4-chlorophenol has also been used as a solvent in
the refining of mineral oil, and its salts (sodium and potassium 4-chlorophenate)
have been used as antigumming agents for gasoline and wash liquids for fuel gas
purification (Kirk-Othmer, 1969). Information on these miscellaneous uses was
not available. We estimated that the remaining 2% of the total production of
4-chlorophenol was consumed by these uses. This quantity can be calculated by
multiplying the total consumption of 4-chlorophenol by a factor of 0.02:
3 • 2
(9.9 x 10 kkg) (0.02) = 2.0 x 10 kkg 4-chlorophenol for miscellaneous uses
2.2.2.6.1 Emissions Due to Miscellaneous Uses
We estimated that the emission of 4-chlorophenol to the environment
attributed to miscellaneous uses was 60% of the amount consumed ,for these uses.
This estimate was based on the following: 1) the use as a solvent would all
2-23
-------
be released to the environment; 2) a small amount was released during the
formulation of the antigumming agents. This percentage did not represent
the exact emission quantity released from these uses, but it served as a
basis for calculation purposes.
The total emissions to the environment were calculated by multiplying
the total quantity of 4-chlorophenol consumed by these miscellaneous uses
by the 60% factor:
2 2
(2.0 x 10 kkg) (0.6) = 1.2 x 10 kkg 4-chlorophenol emitted due to
miscellaneous uses
2.2.3 Summary
Table 2.1 shows a summary of the estimated breakdown of 4-chlorophenol
uses in 1976 and the quantity of 4-chlorophenol consumed by each of these
categories.
Figure 2.6 shows the materials balance diagram for 4-chlorophenol.
2-24
-------
Table 2.1 USES OF 4-CHLOROPHENOL (1976)
Type of Uses
Percentage of the
total consumption
of 4-chlorophenol
Quantity of
4-chlorophenol
consumed (kkg)
Production of
higher chlorinated
phenols
87%c
8.6 x 10"
Production of
quinizarin
5%
5.7 x 10'
Production of indo-
phenols & chromones
3%c
3.0 x 10
Production of germi-
cides and miticides
2%c
2.0 x 10
As a denaturant for
ethanol
9.6 x 10
1
Miscellaneous uses
2%'
2.0 x 10'
Total
100%
9.9 x 10"
JRB estimate
2-25
-------
>H I AM IN ANTS
I AMP VATBN
„...., .,.,.,„ h
r i
.rtri.,' I—
~ »,!„,;.,. ;, H
—
|
« _. I
uh
CMui-lti.il lull uj
[' 1
.........or.
1
Si .».*,» Me. I
»i 1
TOTAI. **v)b kh«
SIXIKAMV (1C NA1KHIAI.S DA
-
^
,.«..»'
V
.AMI:E:
C_
"' '•!•»-»
l"t"U
1
'i ?A lit' (iiuilucL toil
VilnlLiln
1
1. 0. Ill' 1 cioducilon uf
I i ciiTuMMlEa
1 1 !
, „.,„! ,
1 — ise^ — J
._.
» .' . Ill1
«.».
,.,.!„'
Cl III
U.Ur
* *
.»*ll«lbU J l-^.i<» l«
T !±^1^ 1 ( n v%f,-i
ncHllKlbU ( l»|*urlly In
1 clirt>«f_>nca . f
"•I'liiiiU j 1
• iB^Hiri t ie« in
-^.'uS.r'
B. „»
•
ut .Lie..) u|| I
1 ••• — ' J (._ t ( 111M
1, 1. t«l Ik,
Figure 2.6 Materials Balance for 4-Chlnrophenol (kkg)
-------
3.0 2,4-DICHLOROPHENOL
This chapter presents the information available on the major dichlorophenol:
2,4-dichlorophenol (2,4-DCP). The environmental flow diagram is presented first,
followed by a discussion of how the values were obtained.
3.1 FLOW DIAGRAM FOR 2,4-DICHLOROPHENOL
Figure 3.1 shows the flow diagram for 2,4-DCP, summarizing sources, uses, and
emissions during the year 1976.
3.2 DIRECT PRODUCTION OF 2,4-DICHLOROPHENOL
3.2.1 Amounts Produced
No precise data on yearly production of 2,4-DCP were available. USITC did
not publish data because this would reveal relative market positions of the two
large and one small producers. Therefore, we had to estimate the amount of
2,4-DCP produced. Our best estimate was 39,000 kkg for the year 1976 (the year
chosen for the overall materials balance). This result was obtained by selecting
one of the three estimates obtained by different methods, as shown below and on
Table 3.1.
The first estimate was by Tracor-Jitco, Inc. (1977a). Based on USITC data for
production of other chlorophenols, they estimated 1976 production of 2,4-DCP to be
14,000 kkg. This must be a minimum estimate for two reasons: 1) Tracor-Jitco
(1977a) pointed out a result by EPA (1973) estimating the 2,4-DCP production
capacities of Dow and Monsanto as 4550-6150 kkg and 10,250-13,550 kkg,
respectively. The sum of the low ends of the ranges is 14,800 kkg — somewhat
higher than Tracor-Jitco's estimate. 2) Tracor-Jitco (1977a) stated that only
Dow and Monsanto made 2,4-DCP in 1976, whereas USITC listed Rhodia as a producer
in 1976 also. Because of these uncertainties, and the lack of documentation for
Tracor-Jitco's estimate, a second approach was sought.
3-1
-------
OJ
I
hJ
O.i
—I-
Figure 3.1 Flow Diagram for 2,4-Dichlorophenol, 1976 (kkg)
-------
TABLE 3.1 PRODUCTION AND SALES OF 2,4-DICHLOROPHENOL (kkg)~
PRODUCER"
1977
PRODUCTION SALES
1976
PRODUCTION SALES
1970
PRODUCTION SALES
Dow Chemical
Midland, MI
Monsanto
Sauget, IL
Rhod ia
Freeport, TX
Transvaal
Jacksonville, AR
4,031
39,000
14.0007
14,800 -
19.8002
1,911
36,7353 19.7626
4
5
6
7
Phone conversation with USITC revealed that production numbers were not publishable for any year because
there were only three manufacturers (Dow, Monsanto, Rhodia) and the third was so small as to permit the
others to estimate the competitor's share of the market.
This is the range of capacities presented in Tracor-Jitco (1977a) and attributed to an estimate by EPA
(1973).
Value from EPA (1975a) , estimated from the amount of 2,4-D produced. The 2,4-D production and basis for
the estimate were not stated, so the accuracy of the number cannot be evaluated.
Derived from estimation of 2,4-D production as described in Section 3.2.1.
Stanford Research Institute, 1975 and 1978.
USITC, 1960- 1978.
Tracor-Jitco, 1977a.
-------
A second way to estimate production of 2,4-DCP was to assume that the manu-
facture of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) consumed a fixed
proportion of 2,4-DCP produced each year. This method was used by EPA (1975a)
and the fraction that related annual United States production of 2,4-D with their
estimated 2,4-DCP production for the same year was 0.48-0.54, depending on the
year. The 0.54 ratio for 2,4-D / 2,4-DCP was used in low production, low-demand
years. When production and demand for 2,4-D increased in the late 1960s due to
military use, EPA (1975a) used the 0.48 ratio (apparently assuming a larger
contribution from imports). The bases for these numbers were unstated, but the
values were consistent with 2,4-D being the major use of 2,4-DCP (Tracor-Jitco,
1977a).
When the 0.54 ratio was used for 2,4-D / 2,4-DCP production, we obtained a
production estimate of 39,000 kkg 2,4-DCP produced in 1976 (justifying the use
of the low-production ratio; production in a high-demand year like 1968 was
estimated to be 78,000 kkg). This result was based on a 2,4-D production of
21,000 kkg, which was derived as follows: 1) Total production of phenoxyacetic
acid herbicides in 1976 was "approximately 60 million pounds" (USITC, 1977,
p. 264). We interpreted this to mean ± 10%. 2) Of these 27,000 kkg, approximately
6,000 kkg were due to 2,4,5-T production (see Chapter 4). 3) Therefore, 2,4-D
derivatives must account for the remainder: 21,000 kkg with an uncertainty of
t 20%. Thus, 2,4-DCP production was:
(21,000 kkg 2,4-D) 7 0.54 = 39,000 kkg 2,4-DCP in 1976
A third value for production was the sum of the capacities of the two major
producers. Tracor-Jitco (1977a) attributed to EPA (1973) an estimate that the
annual capacities of Dow and Monsanto were 4550-6150 kkg and 10,250-13,650 kkg,
respectively. The sum was 14,800-19,800 kkg/yr.
In estimating the 1976 production of 2,4-DCP, we had three independently-
derived values: 14,000 kkg; 14,800-19,800 kkg; and 39,000 kkg. We used the
estimate of 39,000 kkg 2,4-DCP produced in 1976 for the following two reasons:
1) It was based most directly on USITC reports; and 2) it gave a worst-case
estimate when used to calculate emissions.
3-4
-------
Four methods of synthesizing 2,4-DCP are available to industry. These are:
1) chlorination of phenol with Cl_; 2) chlorination of monochlorophenols with Cl~;
3) chlorination of phenol with N,N - dichlorourea; and 4) chlorination of phenols
with SCLC1-. According to EPA (1976a), the predominant process for synthesis of
chlorophenols was the direct chlorination of phenol or chlorophenol with Cl_. To
derive an estimate of the amounts of 2,4-DCP produced by chlorination of the
respective feedstocks, it was assumed that chlorophenol would have more economic
value as a product than as a feedstock. Therefore, it was estimated that overall
80% of the feedstock would be phenol and 20% would be chlorophenol. This proportion
was then used to calculate our estimates of the amounts produced by each process:
(0.80) (39,000 kkg) = 31,200 kkg by direct chlorination of phenol
(0.20 (39,000 kkg) = 7,800 kkg by direct chlorination of chlorophenol
(Since the same emission factors were applied to the two processes in calculations
of releases to the environment, altering the proportions of the two processes would
only change the distribution of emissions between the processes and not the total
emissions.)
3.2.2 Amounts Imported
The amount of 2,4-DCP imported was not regularly reported by the USITC. Tracor-
Jitco (1977a) cited a personal communication with USITC as the source of an import
value for 1975: 30.5 kkg. In the absence of other data, we assumed that 30.5 kkg
of 2,4-DCP were imported in 1976.
3.3 EMISSIONS DUE TO PRODUCTION AND IMPORTS
3.3.1 Emissions Due to Production
Direct data on emissions to air, land, or water during the production of 2,4-DCP
were not in the readily available literature. Similarly, emission factors and
monitoring data from which to calculate them were unavailable. We were able to
estimate emissions based on our best judgement estimates of emission factors for
each production process. Emissions were then calculated by the operation:
(production in kkg) x (emission factor in kkg released / kkg produced).
3-5
-------
The estimates of the emission factors for air, land, and water during 2,4-DCP
production were based on the process flow diagram in Figure 1.1 (Tracor-Jitco,
1977a). We assumed that the diagram applied to both the Dow and Monsanto
processes (the two major producers), although it was probably based on published
descriptions of the Dow facility in Midland, Michigan (Sittig, 1974).
3.3.1.1 Chlorination of Phenol
3.3.1.1.1 Emissions to Air
2,4-DCP may be released to the air at the following points during its manufacture
by the phenol chlorination process (see Figure 1.1): the reactor vent, the prill
tower vent, the dryer vent, and the incineration of sludge (discussed later). We
estimated that 31 kkg/year of 2,4-DCP were released to the air during this process
in 1976. In the absence of data on emission factors to the air during chlorination
of phenol, our estimate was derived from an estimated emission factor of 1 x 10 kkg/
kkg product, within an order of magnitude. This value was based on the following:
1) Each vent is preceded by a scrubber (estimated efficiency, 95%). 2) 2,4-DCP has
a relatively low vapor pressure (Chapter 1). 3) Leaks and breakdowns make a
negligible contribution over the course of a year. Emissions were.then calculated as
follows:
(31,200 kkg) x (1 x 10~3 kkg/kkg) = 31 kkg released to air
3.3.1.1.2 Emissions to Water
2,4-DCP may be released to the water at the following points during its
manufacture by the phenol chlorination process: scrubber water, separator. We
estimated that 665 kkg/year of 2,4-DCP were released to the water during this
process in 1976. In the absence of monitoring data on 2,4-DCP production waste
_2
streams, our estimate was derived from an estimated emission factor of 2.1 x 10 kkg/
kkg product. This value was based on the following: 1) 2,4-DCP comes in contact
with a large liquid volume during its synthesis. 2) It is sparingly soluble in
water (Chapter 1). 3) It is very difficult to remove all phenols from aqueous
waste streams. 4) Data on the Dow plant were relevant to the other producer,
Monsanto. 5) The efficiency of the water treatment process used by Dow (trickling
filter plus activated sludge treatment) was 86%, as reported for pilot plant
3-6
-------
studies on this sequence (Tracor-Jitco, 1977a). 6) 85% of the synthesized 2,4-DCP
was isolated; the rest entered the waste water stream. 7) 86% of this 2,4-DCP was
removed by water treatment before release from the plant. The overall emission
factor, then, was:
(0.15) (0.14) = 2.1 x 10"2 kkg/kkg product, or 2.1% release.
The uncertainty of this factor was estimated to be +10%, -30%.
Emissions were then calculated as follows:
(31,200 kkg) x (2.1 x 10~2 kkg/kkg) = 655 kkg/year 2,4-DCP released
to water
This emission was a near-maximum estimate because 1) the production value,
31,200 kkg/yr, was a maximum value; and 2) the emission factor was more likely to
be too high (if efficiencies and recoveries were better than estimated) than too
low. The uncertainty in the emissions to water was estimated to be +10%, -70%
3.3.1.1.3 Emissions to Air Due to Incineration of Solid Residues
Solid residues containing 2,4-DCP can be formed at the following points in the
phenol chlorination process: still residues, sludge from wastewater treatment,
ash from incinerator. We estimated that 0.2 kkg of 2,4-DCP was released to the air
due to treatment of this solid residue in 1976. Releases to water and land were
estimated to be zero. In the absence of monitoring data on incinerator plumes,
our estimate was derived from an emission factor of 2.5 x 10 kkg/kkg product for
reactor tars and 3.2 x 10 kkg/kkg product for biological treatment sludge.
Disposal of incineration ash was estimated to produce no emissions of 2,4-DCP.
The emission factor for disposal of reactor tars was estimated based on the
following: 1) Reactor tars were estimated to contain 1 x 10 kkg 2,4-DCP/kkg
product, because it would be economically advantageous to extract the 2,4-DCP from
the tar if it amounted to as much as 1-5% of the product yield. 2) Incineration
of this tar (1000°C) (Sittig, 1974) was 95% efficient. 3) Capture of released
2,4-DCP by the incinerator scrubber (Sittig, 1974) was 95% efficient. The emission
factor for tar incineration was calculated as:
(0.05) x (0.05) x (1 x 10~3) = 2.5 x 10~6 kkg 2,4-DCP released/kkg product
3-7
-------
The releases to air due to incineration of reactor tars were then calculated by
the process:
(31,200 kkg) x (2.5 x 10 kkg./kkg product) = 0.1 kkg/year 2,4-DCP emitted
to the atmosphere due to
reactor tar incineration
We estimated the uncertainty of this value as +100%, -50%.
The emission factor for disposal of biological treatment sludge was estimated
based on the following: 1) 15% of 2,4-DCP synthesized entered the water waste
stream. 2) Of this, 86% was removed by the trickling filt.er/activated .sludge
sequence (Tracor-Jitco, 1977a). 3) Since 2,4-DCP is degradable by acclimated
sludge (EPA, 1975a), we estimated that only 1% of aqueous 2,4-DCP was carried over
unchanged into the sludge. 4) Incineration of this sludge (1000°C) (Sittig, 1974)
was 95% efficient. 5) Capture of released 2,4-DCP by the incineration scrubber
(Sittig, 1974) was 95% efficient. The emission factor for sludge incineration was
calculated as:
(0.15) x (0.86) x (0.01) x (0.05) x (0.05) = 3.2 x 10"6 kkg/kkg product
The releases to air due to disposal of biological treatment sludge were then
calculated to be:
(31,200 kkg) x (3.2 x 10~ kkg/kkg product) = 0.1 kkg/year 2,4-DCP
emitted to the atmosphere
due to disposal of biological
treatment sludge
We estimated the uncertainty of this number as -1-500%, -95% (mostly due to the
estimate of the amount of 2,4-DCP carried unchanged into the sludge).
The sum of air emissions due to solid residue disposal was then estimated to
be 0.1 kkg +0.1 kkg = 0.2 kkg/year.
3.3.1.1.4 Emissions to Land
It was estimated that disposal of incinerator ash produced zero emissions of
2,4-DCP. There was no mention in the literature (Sittig, 1974) of direct application
of 2,4-DCP - containing wastes to land.
3-8
-------
3.3.1.2 Chlorination of Monochlorophenols
3.3.1.2.1 Emissions to Air
2,4-DCP may be released to the air at the following points during its manufacture
by the chlorophenol chlorination process (see Figure 1.1): the reactor vent,
the prill tower vent, the dryer vent, and the incineration of sludge (discussed
later). We estimated that 8 kkg of 2,4-DCP were released to the air during this
process ••'.n 1976. In the absence of data on emission factors to the air during
chlorination of chlorophenol, our estimate was derived from an estimated emission
factor of 1 x 10 kkg/kkg product, within an order of magnitude. This value was
based on the following: 1) Each vent was preceded by a scrubber (estimated
efficiency, 95%). 2) 2,4-DCP has a relatively low vapor pressure (Chapter 1).
3) Leaks and breakdowns made a negligible contribution over the course of a year.
Emissions were then calculated as follows:
(73800 kkg) x (1 x 10~3 kkg/kkg) = 8 kkg released to air
3.3.1.2.2 Emissions to Water
2,4-DCP may be released to the water at the following points during its
manufacture by the chlorophenol chlorination process (see Figure 1.1): scrubber
water, separator. We estimated that 164 kkg of 2,4-DCP were released to the
water during this process in 1976. In the absence of monitoring data on 2,4-DCP
production waste streams, our estimate was derived from an estimated emission
_2
factor of 2.1 x 10 kkg/kkg product. This value was based on the following:
1) 2,4-DCP came in contact with a large liquid volume during its synthesis,
2) It is sparingly soluble in water (Chapter 1). 3) It was very difficult to
remove all phenols from aqueous waste streams. 4) Data on the Dow plant were
relevant to the other producer, Monsanto. 5) The efficiency of the water
treatment process used by Dow (trickling filter plus activated sludge treatment)
was 86%, as reported for pilot plant studies on this sequence (Tracor-Jitco, 1977a).
6) 85% of the synthesized 2,4-DCP was isolated; the rest entered the waste water
stream. 7) 86% of this 2,4-DCP was removed by water treatment before release from
the plant. The overall emission factor, then is:
(0.15) (0.14) = 2.1 x 102 kkg/kkg product, or 2.1% release
3-9
-------
Emissions were then calculated as follows:
_o
(7,800 kkg) x (2.1 x 10 kkg/kkg) = 164 kkg/year 2,4-DCP released to water
This emission was a near-maximum estimate because 1) the 1976 production
value, 7,800 kkg, was a maximum value; and 2) the emission factor was more likely
to be too high (if efficiencies and recoveries were better than estimated) than too
low. The uncertainty in the emissions to water was estimated to be +10%, -70%.
3.3.1.2.3 Emissions to Air Due to Incineration of Solid Residues
Solid residues containing 2,4-DCP can be formed at the following points in
the chlorophenol chlorination process (see Figure 1.1): still residues, sludge
from wastewater treatment, ash from incinerator. We estimated that 0.0 kkg of
2,4-DCP was released to the air due to treatment of this solid residue in 1976.
Releases to waste water and land were estimated to be zero. In the absence of
monitoring data on incinerator plumes, our estimate was derived from an emission
-6 -6
factor of 2.5 x 10 kkg/kkg product for reactor tars and-3.2 x 10 kkg/kkg
product for biological treatment sludge. Disposal of incinerator ash was estimated
to produce no emissions of 2,4-DCP.
The emission factor for disposal of reactor tars was estimated based on the
following: 1) Reactor tars were estimated to contain 1 x 10 kkg 2,4-DCP/kkg
product, because it would be economically advantageous to extract the 2,4-DCP from
the tar if it amounted to as much as 1-5% of the product yield. 2) Incineration
of this tar (1000°C) (Sittig, 1974) was 95% efficient. 3) Capture of released
2,4-DCP by the incinerator scrubber (Sittig, 1974) was 95% efficient. The
emission factor for tar incineration was calculated as:
(0.05) x (0.05) x (1 x 10~3) = 2.5 x 10~6 kkg 2,4-DCP released/kkg product
The releases to air due to incineration of reactor tars were then calculated by
the process:
(7,800 kkg) x (2.5 x 10~6 kkg/kkg product) = 0.02 kkg/year 2,4-DCP
emitted to the atmosphere due
to reactor tar incineration
We estimated the uncertainty of this value as +100%, -50%.
3-10
-------
The emission factor for disposal of biological treatment sludge was estimated
based on the following: 1) 15% of 2,4-DCP synthesized entered the water waste
stream. 2) Of this, 86% was removed by the trickling filter/activated sludge
sequence (Tracor-Jitco, 1977a). 3) Since 2,4-DCP is degradable by acclimated
sludge (EPA, 1975), we estimated that only 1% of aqueous 2,4-DCP was carried over
unchanged into the sludge. 4) Incineration of this sludge (1000 C) (Sittig, 1974)
was 95% efficient. 5) Capture of released 2,4-DCP by the incineration scrubber
(Sittig, 1974) was 95% efficient. The emission factor for sludge incineration
was calculated as:
(0.15) x (0.86) x (0.01) x (0.05) x (0.05) = 3.2 x 10~6 kkg/kkg product
The releases to air due to disposal of biological treatment sludge were then
calculated to be:
(7,800 kkg) x (3.2 x 10~ kkg/kkg product) = 0.02 kkg/year 2,4-DCP emitted
to the atmosphere due to disposal
of biological treatment sludge
We estimated the uncertainty of this number as +500%, -95% (mostly due to the
estimate of the amount of 2,4-DCP carried unchanged into the sludge).
The sum of air emissions due to solid residue disposal was then estimated to
be 0.02 kkg + 0.02 kkg = 0.04 kkg/year.
3.3.1.2.4 Emissions to Land
It was estimated that disposal of incinerator ash produced zero emissions
of 2,4-DCP. There was no mention in the literature (Sittig, 1974) of direct
application of 2,4-DCP containing wastes to land.
3.3.2 Emission Due to Imports
We estimate that the transport and storage of imported 2,4-DCP would make a
negligible contribution to total air, land, and water emissions. This was based on
the following: 1) Imports of 2,4-DCP (Section 3.2.2) were only 31 kkg in 1976 --
a very small fraction of production (0.08%); 2) The emission factor for a process
analogous to the storage of 2,4-DCP — the storage of aniline — is about 4 x 10
kkg/kkg stored (Hydroscience, Inc., 1979). The calculated emission to air would
be 0.001 kkg/year due to storage.
3-11
-------
3.3.3 Emissions Due to Other Sources of Production
3.3.3.1 Emissions Due Co Chlorination of Phenol-Containing Water
Phenol is easily chlorinated by dissolved Cl,., and chlorophenols are formed
by chlorinating phenol-containing waste waters or drinking water supplied (Tracor-Jitco,
1977a; EPA., 1977). We estimated the amount of 2,4-DCP produced in drinking water
by chlorination of phenol to be 8.2 kkg in 1976. This estimate was based on the
following: 1) The National Organics Monitoring Survey (EPA, 1977) reported that
the average 2,4-DCP concentration in 56 drinking water samples containing the
compound was 0.18 ppb; 2) The daily usage of water in the U.S. was 148 gal/day/
person (Metcalf and Eddy, 1972); 3) In order to give a maximum estimate, we
assumed that the entire water supply contained 0.2 ppb 2,4-DCP. Actually only 56
out of 117 samples contained 2,4-DCP. The amount of 2,4-DCP present was estimated
to be;
Q -5
(148 gal/day/person) x (2 x 10 people) x (3.791 kg/gal) x (10 kkg/kg) x
_Q
(365 day/year) x (0.2 x 10 ) = 8.2 kkg 2,4-DCP present per.year
This was a maximum estimate because: 1) There were phenol-free water supplies in
the U.S.; 2) An unknown amount of the 2,4-DCP was already present in the intake
water.
3.4 EMISSIONS DUE TO CONSUMPTION AND USE
3.4.1 2,4-Dichlorophenoxyacetic AcjLd (2j_4-D) Manufacture
According to Tracor-Jitco (1977a), and EPA (1975a) the major use of 2,4-DCP
in 1976 was the synthesis of the herbicide 2,4-D.
3.4.1.1 Producers of 2,4-D
Figure 3.2 shows the names and locations of the firms listed as 1976 producers
of 2,4-D by USITC (1977). Producers of 2,4-D are to be distinguished from
formulators of commercial products containing 2,4-D, who purchase starting materials
and do not synthesize them. There were approximately 240 formulators listed by
PEDCo Environmental (1979), and the number of formulations produced for sale was
in the hundreds.
3-12
-------
FIGURE 3.2 PRODUCERS AND PRODUCTION SITES FOR 2,4-D
Rhodla, Inc.
Chlpraan Div.
Portland, OR
-------
3.4.1.2 Amounts of 2,4-D Produced
No comprehensive data were available on 2,4-D production, and production
figures for individual companies were proprietary. Therefore, we made an
estimate of 2,4-D production by using other data from USITC (1977). It was
estimated that 21,000 kkg of 2,4-D were produced in 1976. The selection of this
value was based on the following: USITC (1977) data show a production of 2,4~D
isooctyl ester and dimethylamine salt totaling 10,900 kkg. Other derivatives were
not included in this total, so it was a minimum. We estimated 2,4-D production
by another method (described in section 3.2.1) and obtained 21,000 kkg as the 1976
production of 2,4-D. We have used this latter value in further calculations for
the following reasons: 1) We know that the actual production was greater than
just the sum of two derivatives; and 2) less uncertainty was involved in calculating
the 21,000 kkg value (section 3.2.1).
Of the producers of 2,4-D listed in Figure 3.2, Dow was credited with 90% of
the market with Rhodia holding the other 10% (EPA, 1976b). It appeared that
Transvaal stopped making 2,4-D between 1973 and 1976. Transvaal was a producer
before 1973, according to Ottinger et_ al. (1973), but neither USITC (1977) nor
EPA (1976a) listed Transvaal as a producer in 1976. Consequently, it is absent
from Figure 3.3.
By applying the market percentages given above to the total 2,4-D production,
the 1976 production attributable to the two producers would be: Dow, 18,900 kkg;
Rhodia, 2,100 kkg.
3.4.1.3 Emissions Due to 2,4-D Synthesis
3.4.1.3.1 Emissions to the Air
2,4-DCP can be released to the air by venting during 2,4-D synthesis. We
estimated that 2.1 kkg of 2,4-DCP were emitted to the air during this process in
1976. In the absence of direct data on emissions or emission factors to the air,
-4
we estimated an emission factor of 1 x 10 kkg 2,4-DCP emitted/kkg 2,4-D produced.
The basis for this estimate was as follows: 1) We assumed that the production
processes for 2,4-D synthesis are generally similar to those of 2,4-DCP synthesis.
3-14
-------
2) We noted that Dow Chemical, the major producer, synthesized 2,4-D at its
Midland, MI, plant; therefore, the emission control characteristics considered
for 2,4-DCP synthesis also applied to 2,4-D synthesis. 3) In section 3.1.1.1 we
estimated the emission factor for release of 2,4-DCP to air during 2,4-DCP production
_3
to be 1 x 10 kkg/kkg product. 4) The emission factor should have been about one
order of magnitude smaller for 2,4-D synthesis, because (a) most of the 2,4-DCP
was consumed in the first step of the process, and (b) unreacted 2,4-DCP was
-4
captured and recycled. We therefore estimated that an emission factor of 1 x 10
kkg/kkg 2,4-D produced was appropriate within an order of magnitude. Application
of this emission factor to the synthesis of 2,4-D yielded:
(21,000 kkg 2,4-D) x (1 x 10~A kkg/kkg 2,4-D) = 2.1 kkg 2,4-DCP released
to the air due to 2,4-D
synthesis in 1976
3.4.1.3.2 Emissions to Water
No direct information was available on amounts of 2,4-DCP released to water
during 2,4-D synthesis. However, published emission factors for waste streams from
anonymous plants producing 2,4-D permitted calculation of 2,4-DCP releases to water.
The amount released to water was estimated to be 42 kkg/year. This emission was
based on an emission factor of 2.01 x 10 kkg/kkg product, which was estimated as
follows: 1) EPA published monitoring data for two anonymous plants producing
2,4-D, and presented the results as emission factors for phenols (assumed; total
phenols) in the waste streams. The values were: 1.61 kg phenols/kkg 2,4-D product
(a daily average); 2.75 kg/kkg (a daily composite) and 1.67 kg/kkg (a plant-supplied
estimate). 2) We had no reason a priori to discard any of the values. 3) Therefore,
we used the average of these values. 4) In using this average, we were assuming
that all "phenol" was 2,4-DCP. The emission factor was therefore a maximum value.
The emission factor for release of 2,4-DCP to water during 2,4-D synthesis was
_3
2.01 x 10 kkg/kkg product. Emissions were obtained by the operation:
(21,000 kkg produced) x (2.01 x 10~3 kkg/kkg) = 42 kkg 2,4-DCP released to
water due to 2,4-D synthesis
in 1976
3-15
-------
The uncertainty of the emission factor was estimated to be +5%, -90% (since
it was a maximum). The production value for 2,4r-D was a maximum value also.
Therefore, the amount of emissions (42 kkg/year) was a maximum, and had an estimated
uncertainty of +5%, -95%.
3.4.1.3.3 Emissions Due to Disposal of Solid Residues
Direct data were not available on emissions due to disposal of solid residues
from 2,4-D production. These residues would be formed as reactor tars, and as
biological waste water treatment sludge. We estimated the total release to air
due to incineration of solids containing 2,4-DCP to be 0.1 kkg 2,4-DCP in 1976.
This estimate was based on the following: 1) We assumed the efficiencies estimated
in section 3.3.1.1.3 for disposal of solid residues during 2,4-DCP production were
valid for 2,4-D production in the same or a similar plant. 2) The only modification
was that there would be less 2,4-DCP in the sludge because 2,4-DCP was consumed in
the first step of the process. 3) The overall emission factor for reactor tar would
be the same as for 2,4-DCP synthesis: 2.5 x 10 kkg/kkg product. 4) The emission
factor for biological treatment sludge would be 5-fold lower: (3.2 x 10 kkg/kkg
product) x (0.2) = 6.4 x 10 kkg/kkg product. Applying these emission factors
to 2,4-D synthesis yielded the emission amounts:
(2.5 x 10~ kkg/kkg product) x (21,000 kkg) = 0.05 kkg from tars
(6.4 x 10~? kkg/kkg) x (21,000 kkg) = 0.01 kkg from sludge
The sum was 0.06 kkg of 2,4-DCP released to air due to disposal of solid residues.
This is entered on Figures 3.1 and 3.3 as 0.1 kkg.
3.4.2 Timber Processing
Versar (1977b) reported a value for total emissions of 2,4-DCP to water by
the timber processing industry in 1976. The estimate was 4 kkg (gross annual
discharge). We had no way to evaluate the accuracy of this estimate.
3-16
-------
3.4.3 Leather Tanning and Finishing
Versar (1977b) reported a value for total emissions of 2,4-DCP to water by the
leather tanning and finishing industry. The estimate was 0.1 kkg (gross annual
discharge). We had no way to evaluate the accuracy of this estimate.
3.4.4 Impurities in 2,4-D
The content of 2,4-DCP in commerical preparations of 2,4-D was confidential
information and could not be obtained by JRB. In order to get this information,
Mrs. Willa Garner (Registration Division, OPP, 755-1397) would be contacted and
given the registration number of the pesticide of interest. Mr. Jesse Mayes in
Central Files (755-9315) supplied upon request the registration number of one of
the hundreds of 2,4-D formulations: 464-1 is a Dow product containing 2,4-D.
In addition, Ms. Alice Morgan of Dow Chemical cited a Dr. Phil Kearney at U.S.D.A.
(location not known) as an authority on impurities in pesticides.
3.4.5 Degradation of 2,4-D in the Environment
2,4-D is relatively labile in the environment and can yield 2,4-DCP by either
metabolic or photochemical breakdown (Kirk-Othmer, 1969). The "persistence" of
2,4-D in soils is one month (Kirk-Othmer, 1969). We have estimated the release
of 2,4-DCP to soil to be 2,100 kkg in 1976, based on the following: 1) We assumed
all 2,4-D produced in 1976 was used agriculturally. 2) We assumed all 2,4-D used
was broken down in the soil via 2,4-DCP. 3) However, 2,4-DCP is readily degraded
(Kirk-Othmer, 1969; EPA, (1975a) so that the steady-state level of 2,4-DCP was
assumed to be only 10% of the 2,4-D level. The amount of 2,4-DCP present in the
soil on the average at any time during the year was: (21,000 kkg 2,4-D) x (0.10)
2100 kkg. This value has a large uncertainty, but is included in the materials
balance as an estimate of the possible contribution by this source. A materials
balance on 2,4-D has probably been performed by Office of Pesticide Programs,
3.5 SUMMARY
Figure-3.3 is the materials balance diagram for 2,4-DCP. It summarizes the
contributions of each process discussed to air, land, and water emissions. Emissions
to water during production processes are the major source of emissions.
3-17
-------
Sill.tU WAiti
IHI.im.NAf IUM
|-MVIUII4ra:NlAt. llHI tAiHi
AIM UAim I.AMIi
U)
I
00
O.I I
0 2100
iUM;
iillMMAKY III'
an.i 1100 *
Figure 3.3 Materials Balance for 2,4-Dichlorophenol (kkg)
-------
4.0 2,4,5-TRICHLOROPHENOL
4.1 DIRECT PRODUCTION OF 2,4,5-TRICHLOROPHENOL (2,4,5-TCP)
Figure 4.1 shows the environmental flow diagram for this chlorophenol.
4.1.1 Amounts Produced
2,4,5-Trichlorophenol was sold in commercial quantities by a number of
producers in 1976, among them Dow Chemical Company, Hooker Chemical Company,
Northeastern Pharmaceutical and Chemical Company and Transvaal Company (EPA,
1975a). These companies synthesized 2,4,5-TCP by the hydrolysis of 1,2,4,5-
tetrachlorobenzene (EPA 1975a). Table 4.1 identifies the location of each
plant.
Production quantities for trichlorophenols were company confidential informa-
tion and have not been reported since 1970. Table 4.2 lists U. S. production
and import quantities between 1960 and 1970. 2,4,5-Trichlorophenoxyacetic acid
(2,4,5-T) and its derivatives are synthesized from trichlorophenol.
Since there were no data available after 1970, we estimated that the quantities
shown on Table 4.2 for 1970 were representative of the past nine years. This
estimate was based on analysis of the 2,4,5-T production in Table 4.2. The data
appeared to show a pattern in which 2,4,5-T production (and therefore 2,4,5-TCP
production) was returning to pre-military-use levels. The demand for 2,4,5-T
probably leveled in the 1970-1976 period. Post-1976, demand and production were
undoubtedly declining due to environmental regulations. In the absence of data,
however, we estimated that 1976 production of 2,4,5-TCP and its derivatives was
similar to the 1960 value.
The actual production of 2,4,5-TCP was extracted from Table 4.2 by making
estimates about the relative amount of 2,4,5-T produced compared to its several
derivatives. MRI (1972) suggested that "little" of the 2,4,5-T produced remains
4-1
-------
*. i ft
.L_L.5
l..'.4,l 1L1MAI IIIIIWJ- I " *
bt K2KUK j
. _ **>'"' 1
n o o
J. 1. 1.
U ti ()
! •• I « I-
T T t
-*
4 CM)
L^T'^llllJ
t "LIL j
"[ r... i
t t t
|, i. L
'"" Js^'5"lCu '" -
-^
L*r±l ,
i
rul-4_-^Jr
t
LnJ ...........
"r
j
13
I
Hl»..l.l.l (!•!.(» j
Figure A.I Flow Diagram of 2,4,5-Trlchlorophenol (kkg)
-------
TABLE 4.1 PRODUCERS OF 2,4,5-TRICHLOROPHENOL
Company
Dow Chemical Company
Hooker Chemical Company
Northeastern Pharmceutical and
Chemical Company
Transvaal Company
Plant Location
Midland, Michigan
Niagara Falls, New York
Verona, Missouri
Jacksonville, Arkansas
-------
TABLE 4.2 PRODUCTION AND IMPORTS OF 2,4,5-TCP AND ITS ACID,
ACID DERIVATIVES AND SALTS (EPA, 1975a, AND ENTOMA, 1975)
(kkg)
1960
1961
1962
1963
1964
1965
1966
1967
1968
1969
1970
-
U. S. Production
U. S. Imports
U. S. Production
U. S. Imports
U. S. Production
U. S. Imports
U. S. Production
U. S. Iniports
U. S. Production
U. S. Imports
U. S. Production
U. S. Imports
U. S. Production
U. S. Imports
U. S. Production
U. S. Imports
U. S. Production
U. S. Imports
U. S. Production
U. S. Imports
U. S. Production
U . S . Impo rts
PHENOL AND
SALTS
4,550
N/A
4,990
N/A
5,440
N/A
5,440
N/A
6,350
N/A
5,900
N/A
8,160
N/A
11,340
N/A
12,700
N/A
N/A
N/A
N/A
N/A
2,4,5-T and
DERIVATIVES
6,350
N/A
6,800
N/A
8,620
N/A
8,620
N/A
10,880
N/A
11,340
N/A
14,990
0
19,050
44.1
— - • - — i
27,220
179.4
8,160
20.6
6,350
0
-------
TABLE 4.3 MOLECULAR WEIGHTS OF 2,4,5-TCP AND ITS DERIVATIVES
COMPOUND
2,4, 5-Trichlorophenol
2,4,5-TCP Sodium Salt
2,4,5-T (Acid)
2,4,5-T Isooctylester
MOLECULAR WEIGHT
197
219
255
367
4-5
-------
as an acid for sale. We estimated that the quantity of 2,4,5-T sold was
approximately 20 percent of the total 2,4,5-T and Derivatives (6350 kkg -
Table 4.2). The remaining 80 percent was assumed to be of the same
molecular weight as 2,4,5-T isooctylester (see Table 4.3 for compound
molecular weights used). The selection of 2,4,5-T isooctylester was made
because 1100-1800 kkg of the derivative were synthesized by Thompson-Hayward
Chemical Company (MRI, 1972). This represented about a third of the total
1960 sales of 2,4,5-T derivatives (80 percent of 6350 kkg). The quantity
of 2,4,5-TCP contained in 2,4,5-T and Derivatives was estimated as follows:
2,4,5-T 0.2 x 6350 kkg x 197 * 255 = 981 kkg
2,4,5-T derivatives 0.8 x 6350 kkg x 197 ^ 367 = 2727 kkg
Subtotal 2,4,5-TCP 3708 kkg
This subtotal was the quantity of 2,4,5-TCP contained in the 2,4,5-T and
Derivatives column of Table 4.2 in 1960.
To determine the remaining quantity of 2,4,5-TCP produced, the amount of
2,4,5-TCP contained in the Phenol and Salts column (Table 4.2) less the amount
sold for use in 2,4,5-T and Derivatives were calculated.
Production quantities of 2,4,5-T for Dow and of 2,4,5-T isooctylester for
Thompson-Hayward were given by MRI (1972). Using these production figures,
it was estimated that approximately 45 percent of the 2,4,5-TCP contained in
2,4,5-T and Derivatives was purchased from other manufacturers. The remaining
quantity of 2,4,5-TCP and Salts was:
4-6
-------
(Phenol and Salts (Table 4.2)) - (0.45 x Subtotal of TCP for 2,4,5-T
and Derivatives)
= 2881 kkg
If the remainder was 100% 2,4,5-TCP, then the total 2,4,5-TCP was 2881 kkg +
3708 kkg = 6589 kkg. At the other extreme, if the remainder was 100% salt, then
the total 2,4,5-TCP was (2881 kkg x molecular weight of phenol * molecular weight
of salt) + 3708 kkg = 6300 kkg. This value will be used for further preparation
of the materials balance. The error range of this value was estimated to be +5%
(since the 100% 2,4,5-TCP assumption represents an upper bound) and -40% (in the
case of less-than-capacity production by the two companies with available pro-
duction data (MRI, 1972)).
Another method of producing 2,4,5-TCP was by the diazotization of 2,4,5-
trichloroaniline. There were no sources that suggested that this method was
used. Therefore, we estimated that no more than 0.2 percent of the total U. S.
production was formulated in this manner.
4.2 AMOUNT IMPORTED
The amount of 2,4,5-TCP imported is not regularly reported by the USITC.
ENTOMA (1975) cited the quantities through 1970. The quantity of 2,4,5-TCP
imported was never greater than 0.5 percent of total production (Table 4.2).
Excess U. S. production capacity due to the Viet Nam War would suggest that
there were no imports of 2,4,5-TCP in 1976. In the absence of other data,
we assumed that this value has been applicable for the past eight years.
. 4-7
-------
4.3 EMISSIONS DUE TO PRODUCTION AND IMPORTS
4.3.1 Emissions Due to Production
Data on emissions to air, land and water during production of 2,4,5-TCP
were not available in the literature. The basic approach to evaluating emissions
during production of 2,4,5-TCP was to use the operation: (production in kkg) x
(emission factor in kkg released/kkg produced). The ultimate sources of an
emission factor are waste stream monitoring data, but in the absence of these
data a best guess judgement was made based on engineering and economic principles.
An estimate of emission factors for air, water and land releases during 2,4,5-
TCP production was based on the process flow diagram in Figure 4.2 (EPA 1975a).
We assumed the diagram applied to all manufacturers although it was probably
based on published descriptions of the Dow facility in Midland, Michigan (EPA,
1975a).
4.3.1.1 Emissions to Air
We estimated the air emission factor to be 1 x 10 kkg/kkg product, within
an order of magnitude. This was based on air emission analysis in Section 3.3.1.1.1
(2,4-dichlorophenols). Application of this emission factor to total 2,4,5-TCP
production yielded:
(6510 kkg) (1 x 10~3 kkg/kkg produced) = 7 kkg 2,4,5-TCP emitted to air
in 1975 due to production
4.3.1.2 Emissions to Water
The water emission factor was estimated to be higher than that for air due to
the large volumes of water used in the 2,4,5-TCP process, the product's sparing
4-8
-------
FIGURE 4.2 PRODUCTION SCHEMATIC FOR 2,4,5-TRICHLOROPHENOL PRODUCTION
BY HYDROLYSIS OF 1,2,4,5-TETRACHLOROBENZENE (EPA 1975a)
.SOLVENT
HC1
1 ,2,4,5-TETRACHLOROBENZENE
METHANOL
SODIUM HYDROXIDE
COIL REACTOR
ACIDIFIER
2,4,5-TRICIILOROAflISOLE
o
1/1 _J
>-. O
O O
2,4,5-TRICHLORO-
—*• PHENOL
-------
solubility in water (Section 1), and the impossibility of removing all phenols
in the waste streams. Data on the Dow plant were assumed to be representative
of all manufacturers. .Biological treatment, including trickling filter plus
activated sludge, at the Dow plant was calculated to be from 90 - 100 percent
efficient (Versar, 1975). Assuming that 85 percent of the 2,4,5-TCP produced
was isolated, the remaining quantity entered the waste water (Section 3.3.1.1.2)
The overall emission factor was:
_
(0.1 fraction not removed) x (0.15 fraction in waste water) = 1.5 x 10 kkg/
kkg product or
1.5 percent
release
This factor was applied to total production to obtain water emissions:
(6510 kkg) (1.5 x 10~2 kkg/kkg produced) = 98 kkg 2,4,5-TCP emitted to water
due to production in 1976
This represented a near-maximum estimate if the extraction efficiency was higher
than stated. The uncertainty of the water treatment emissions was proposed to
be + 50 percent.
4.3.1.3 Emissions Due to Solid Wastes
Solid residues containing phenols would be produced as heavy ends waste,
sludge from wastewater treatment and ash waste from incineration.
Reactor tars were estimated to contain approximately 1 x 10" kkg/kkg product
(Section 3.3.1.1.3).
The emission factor from sludge would be the product of efficiency of the
waste treatment times the wastes lost to the water or:
4-10
-------
(0.15 fraction in wastewater) (0.9 fraction removed) = 0.135 kkg 2,4,5-TCP
in sludge/kkg product
However, since (by analogy to 2,4-DCP) 2,4,5-TCP is probably degradable by
acclimated sludge, we estimated that the sludge contains between 1 and 10 percent of
the original amount. The sludge emission factor is thus 0.00135-0.0135 kkg/kkg
product.
This sludge was then incinerated and the waste gases scrubbed (MRI, 1972).
Incineration efficiency varied from 95 percent (Section 3.3.1.1.3) to 99 percent
(Versar, 1975) and scrubber efficiency was approximately 95 percent (Section
3.3.1.1.3). The emission factor to air for sludge treatment was:
(0.00135 to 0.0135) (.01 to .05) (.05) = 6.8 x 10~7 to 3.4 x 10~5 kkg/
kkg product
This factor was applied to total 2,4,5-TCP production and the result was
added to the air emissions estimated in Section 4.2.1:
(6510 kkg) (6.8 - 340 x 10~7 kkg/kkg product) = 4.4 - 220 x 10~3 kkg
2,4,5-TCP emitted to air
due to solid waste incin-
eration in 1976
4.3.2 Emissions Due to Imports
We estimated that the transport and storage of imports made a negligible
contribution to total air, land and water emissions. Also, since we proposed
\
that there are no imports at present, the losses would similarly be zero.
4-11
-------
4.3.3 Emissions Due to Indirect Sources of Production
4.3.3.1 Emissions Due to Chlorination of Phenol-Containing Water
An upper limit on the quantity of 2,4,5-TCP produced in this process was
calculated using the follox^ing: 1) The National Organics Monitoring Survey
(NOMS) (EPA, 1977) reported that 2,4,5-TCP was detected although not quantifi-
able in U. S. drinking water samples. 2) The annual usage of water in the
U. S. is 4.169 x 1013 liters per year (Metcalf and Eddy, 1972, and Section
3.3.3.1). 3) In order to give a maximum estimate, we assumed that the minimum
level quantified by NOMS (0.01 mg/liter) was contained in the entire U. S.
water supply.
The maximum quantity present was estimated to be:
(4.169 x 1013 liters/year) ( 0.01 mg/liter) (10~9 kkg/mg) = 400 kkg per year
4.4 EMISSIONS DUE TO CONSUMPTION AND USE
4.4.1 Amounts of 2,4,5-Trichlorophenoxyacetic Acid and Derivatives and
Trichlorophenol Sodium Salt Produced
Data on production of 2,4,5-T and derivatives and 2,4,5-TCP sodium salt
are shown in Table 4.2 Figure 4.1 identifies those quantities of 2,4,5-TCP
used to synthesize each compound. These quantities were previously calculated
in Section 4.1. Data were not available on the amount of 2,4,5-TCP and all
derivatives made by individual companies.
4-12
-------
4.4.2 Emissions to the Air
2,4,5-TCP can be vented to the air during the synthesis of its derivatives.
We estimated that nearly 0.5 kkg annually was emitted during these processes.
In the absence of direct data on emissions or emission factors to the air, we
estimated an emission factor of 1 x 10" kkg/kkg 2,4,5-TCP used during synthesis
of derivatives. The basis for this estimate was as'follows: 1) We assumed
that the production processes for 2,4,5-T, its derivatives and 2,4,5-TCP sodium
salt are generally similar to those of 2,4,5-TCP synthesis. 2) We noted that
Dow Chemical, a major 2,4,5-TCP producer, synthesized 2,4,5-T and other deriva-
tives at its Midland, MI, plant; therefore, the emission control characteristics
considered for 2,4,5-TCP synthesis also applied to 2,4,5-T synthesis. 3) In
Section 4.2, we estimated the emission factor for release of 2,4,5-TCP to air
during 2,4,5-TCP production to be 1 x 10~3 kkg/kkg product. 4) The release
factor during consumption should be about one order of magnitude smaller,
because (a) most of the 2,4,5-TCP was consumed in the first step of each process,
and (b) unreacted 2,4,5-TCP would be captured and recycled. We therefore estimated
1 -4
that an emission factor of 1 x 10 kkg/kkg 2,4,5-TCP used during synthesis of its
derivatives was appropriate within an order of magnitude. Application of this
emission factor to the synthesis of 2,4,5-TCP derivatives yielded:
(5010 kkg) (1 x 10~4 kkg/kkg) =0.5 kkg to the air annually
4.4.3 Emissions to Water
Again, no direct information was available on releases to water during
2,4,5-TCP derivative synthesis. However, published emission factors for waste
4-13
-------
streams from anonymous plants producing 2,4,5-T have permitted an extrapolation
of 2,4,5-TCP releases to water. The amount released to water during synthesis
of 2,4,5-TCP derivatives was estimated to be 11 kkg per year. This emission
was based on an emission factor of 2.18 x 10" kkg/kkg product, which was
estimated as follows: 1) EPA (1976a) published monitoring data for an anony-
mous plant producing 2,4,5-T and presented the results as emission factors for
phenols (assumed: total phenols) in the waste streams. The values were:
1.61 kg phenols/kkg 2,4,5-T product (a daily average) and 2,75 kg/kkg (a daily
composite). 2) We had no reason a priori to discard either of the values.
3) Therefore, we used the average of these values. 4) In using this average,
we were assuming that all "phenol" is 2,4,5-TCP. The emission factor was there-
fore a maximum value. The emission factor for release of 2,4,5-TCP to water
_2
during derivative synthesis was 2.18 x 10 kkg/kkg product. Emissions were
obtained by the operation:
(5010 kkg produced) x (2.18 x 10~3 kkg/kkg) = 10.9 kkg 2,4,5-TCP released
to water in 1976 due to con-
sumptive uses
The uncertainty of the emission factor was estimated to be + 5 percent,
- 90 percent (since it was a maximum). The production value for 2,4,5-TCP was
a maximum value also. Therefore, the amount of emissions (10.9 kkg/year) was
a maximum, and had an estimated uncertainty of + 5 percent, - 95 percent.
4.4.4 Emissions Due to Disposal of Solid Residues
Direct data were not available on emissions due to disposal of solid residues
from 2,4,5-TCP derivative production. These residues would be formed as reactor
4-14
-------
tars, and as biological waste water treatment sludge. We estimated a total
release to air due to incineration of solids containing 2,4,5-TCP to be negligible
("xO.5 kkg). This estimate was based on the following: 1) We assumed the
efficiencies estimated in Section 4.3.1.3 for disposal of solid residues during
2,4,5-TCP production were valid for 2,4,5-TCP derivatives production in the same
or a similar plant. 2) The only modification was that there would be less
2,4,5-TCP in the sludge because 2,4,5-TCP was consumed in the first step of the
process. 3) The overall emission factor for reactor tar would be the same as
for 2,4,5-TCP synthesis: 3.b x 10~5 kkg/kkg product. 4) The emission factor
for biological treatment sludge would be 5-fold lower:
(3.4 x 10~5 kkg/kkg product) x (0.2) = 6.8 x 10~6 kkg/kkg product
Applying these emission factors to 2,4,5-TCP derivative synthesis yielded the
emission amounts:
(3.4 x 10~5 kkg/kkg) x (5010 kkg) = 0.17 kkg from tars
(6.8 x 10~6 kkg/kkg) x (5010 kkg) = 0.034 kkg from sludge
The sum was 0.2 kkg of 2,4,5-TCP released to air due to disposal of solid
residues. This is entered on Figures 4.1 and 4.3 as~0 kkg.
4.4.5 Degradation of 2,4,5-TCP in Derivatives
2,4,5-TCP derivatives are relatively labile in the environment and can
yield 2,4,5-TCP by either metabolic or photochemical breakdown (Kirk-Othmer,
1969). For example, the "persistence" of 2,4,5-T in soils is five months
4-15
-------
(Kirk-Othmer, 1969). We have estimated the release of 2,4,5-TCP to soil to
be 100 kkg in 1976, based on the following: 1) We assumed all 2,4,5-T and
other derivatives produced in 1976 were used agriculturally. 2) We assumed
all 2,4,5-TCP derivatives used were broken down in the soil via 2,4,5-TCP.
3) However, 2,4,5-TCP is readily degraded (Kirk-Othmer, 1969; EPA, 1975a)
so that the steady-state level of 2,4,5-TCP was assumed to be only 2 percent
of the level of 2,4,5-TCP derivatives. The amount of 2,4,5-TCP present in the
soil on the average at any time during the year was:
(5010 kkg 2,4,5-TCP derivatives) (0.02) = 100 kkg
This value had a large uncertainty, but was included as an estimate of the
possible contribution by this source. A materials balance on 2,4,5-T is
probably on file at the Office of Pesticide Programs. This materials balance
would improve the estimate of the quantity of 2,4,5-TCP in the environment due
to degradation.
4.4.6 Direct Use of 2,4,5-TCP
2,4,5-TCP was used directly as a fungicide, preservative and antimildew
treatment. Information on the distribution and method of application was not
readily available. As an upper limit, we estimated 1300 kkg (the total quantity
of 2,4,5-TCP not converted to other products) would be released. This would take
place either by direct application (fungicide) or by the disposal or products
treated with 2,4,5-TCP (preservative or antimildew). Without further data, it
was impossible to quantify the specific releases to air, land or water for the
phenol.
4-16
-------
4.5 SUMMARY
Figure 4.3 is the materials balance diagram for 2,4,5-TCP. It summarizes
the contributions of each process discussed to air, land, and water emissions.
4-17
-------
00
.y_
r l"7^7!
H '•«•'•"•- —^- »- "-
I duel Ion
iir»b; t.-,io khN
^Ut»tAHT UK HATtHIAlS BAlAMCKt
h-ra-i
00*6
' * 90 III
00*10
0 4lM» 400
f 1 < 13
° o _J_
Figure 4.3 Materials Balance for 2,4,5-Trichlorophenol (kkg)
-------
5.0 TETRACHLOROPHENOL
Tetrachlorophenol was not produced as a separate chemical in 1976. Rather,
it was a by-product, mostly as the 2,3,4,6-isomer in commercial pentachloro-
phenol (PCP) (Federal Register, 1978). Its concentration in PCP has been
reported to range from 4 to 10 percent by weight. Its physical properties
are not drastically different from those of pentachlorophenol (see Chapter 1).
For the above reasons, the materials balance for tetrachlorophenol was estimated
using the same assumptions and information which are discussed in Chapter 6,
the chapter on pentachlorophenol.
Figure 5.1 presents the summary of the materials balance for tetrachlorophenol.
The emission factors to air, water and land were assumed to be the same as those
used in the PCP chapter for each process and end use.
The annual production of tetrachlorophenol was .estimated at 8 percent of PCP
production, or 1800 kkg in 1976. The major indirect source was the. release to
land from stockpiles, i.e., leaching from preserved wood utility poles. Those
releases were estimated at 770 kkg in 1976 based on the PCP discussion in
Chapter 6.
Uses of PCP contaminated with tetrachlorophenol as a fungicide, herbicide
and in home and garden applications also accounted for significant releases of
tetrachlorophenol. Those include 6.3 kkg to air, 13 kkg to water, and 41 kkg
to land. Next in order of importance were the releases from the production of
PCP, which amounted to 1.8 kkg to air and 53 kkg to water in 1976. JRB estimated
that total releases of tetrachlorophenol to air were between 8.7 and 98 kkg,
those to water were 67 to 160 kkg, and those to land from 44 to 130 kkg in 1976.
5-1
-------
OMSUMI-TIVE USES
AMP ETHHT8
OBIT AM I HANTS
HUH-OlHSIIKTllVh
uses
CNVIIUWtUtTAl.
UKTttt _
Ul
I
O.J 0
0.12 -0
0.1
< I.I
3.0 10
0.4 o
o.i ..*•'
0.*
Jl*
SIMSt J4IO h
_ 65.J) Ut 1 8*0 fcfcg
Figure 5.1 Materials Balance for Tetrachlorophenol (kkg)
-------
6.0 PENTACHLOROPHENOL (PCP)
This chapter discusses the materials balance, production statistics,
consumption and uses information for pentachlorophenol (which include the
production of pentachlorophenol salts, and the lauric acid ester of PCP),
and presents estimates of releases to land, air and water.
6.1 ENVIRONMENTAL FLOW DIAGRAM FOR PCP
Figure «-3 shows the flow diagram for PCP based on the 1978 estimate of
22,000 kkg of PCP produced in the U. S. (Versar, 1979) and the 1978 export
figure of 1100 kkg (Bureau of Census, 1978). No information on imports was
reported in the available literature.
Natural sources contributed insignificant emissions. The major indirect
sources of emissions included releases to land from stockpiles, which-consisted
mostly of leaching from preserved wood poles. Those releases were estimated
to be 9,600 kkg per year. Uses of PCP as a fungicide, herbicide, and home and
garden applications also accounted for significant annual emissions. Those
included 80 kkg to air, 506 kkg to land, and 154 kkg to water. Next in order
of importance were the emissions from the direct production of PCP, which
amounted to 12 kkg per year to air and 660 kkg per year to water.
JRB estimated that the environmental releases of PCP from direct sources to
air totaled 120-720 kkg, those to water were 800-1400 kkg, and those to land
were 500-1100 kkg. The basis for those estimates is presented in the sections
below.
6-1
-------
TSCA Status Report for existing Chemicals
f
(Toxic Integration Information Series),
In-house
P,0,: Doreen Sterling
OPII PID TIB
-------
JL_
•>
12
:hlorli,uil.>ii of ,,l.cnol
i
Li.i.n
j '
. 0
1 u
, .
pill
(2
O
Z.
I oi). or it.
not
JO 0
-; ^._
1 . 1 00
of H:P,
. J) 0.046
0
0
np
i.
n
u
20.000
1
.100
70
r~
L
KOI .„-
1 a 1 1 ui
— |-
' 1
i.nij/i
'.'J'io
10
10
A
A
-
1
A
A
A
1-lyw.m.J and Klb«.b«.rd
1 . 1 (10
j h(l 1 _
SSO
iluit.lt Idc (.>L>il-i:iu|i
on doiowui »_iop)
J „ 1 }« ^
IS.fMm
|o LL-i — -:
Convera tun to N«-PCP
(2,300) *
4h
jo L_L_W
Convrrnlan lo K-HCP
(10) «0.2
| L^ -v
Co,,.Ur«lo.. to L-orlc
(10) «0.2
-'
J
J
i
U i
0
2.3(Ml
46
0
10
0
I.
(701))
U
It
A
(7UO)
K
A
(50}
I
I
A
1
A
(50)
1
KunKl,:ld, tur a^
(700)
I/.
t | ClfiO) t,
1 05) 1 .
| 0.7
F'luiglcldtx In cooling
(700)
14
J « 1.' !*f£
,„,.,„ ,,.,,,„
(50)
1
i i y
| 0 U, .
|o Lfl — .
AJIiesl vu Hictierval Ion
(MM
, o LQ^'_._
Ltialliut oftnerviil ion
(50)
1
~ L
U
. 1.
U
^_
• I
" (25)
0-5- i.
"n^
" (25)
" (25)
0.5 L
Figure 6.1 Flow Diagram for Pentachlorophenol (kkg)
-------
Rfifchold (Tacoma, WA)
a\
I
OJ
Vulcan
(Wichita;
KS.)
Figure 6.2 Pentachlorophenol Producers
-------
6.2 PRODUCTION
PCP has been marketed since 1930 in the U. S. Table 6.1 shows the pro-
ducers of PCP, their locations and capacities in 1978. Monsanto discontinued
their PCP production in 1978, and thus is not shown. Monsanto*s capacity
prior to 1978 was 12,000 kkg per year. Figure 6.2 shows the geographic dis-
tribution of the PCP producers (Tracor-Jitco, 1976b). The estimated supply
and demand for PCP are shown in Table 6-2 (Versar, 1979). During the 1960s,
production of PCP grew at a rate of 2 percent per year — from about 17,700
kkg to about 21,300 kkg. In the 1970s, the production of PCP has remained
relatively unchanged, except in 1974 and 1975.
The data on plant capacity were compatible with a 1977 memorandum prepared
by the American Wood Preservers Institute, and hence appear valid. The pro-
duction statistics through 1977 were compatible with those published by the
U. S. International Trade Commission. The demand estimates appeared reasonable
because they are usually equal to, or slighly greater than the production
statistics for any single year, and also because the production in the follow-
ing year was shown to have increased in order to meet the demand level for the
previous year.
Table 6.1 Pentachlorophenol Producers
Capacity in 1978
Producer Location kkg
Dow
Reichold
Vulcan
Midland, MI
Tacoma, WA
Wichita, KS
11,000
9,100
7,300
-------
Table .6.2
ESTIMATED SUPPLY AND DEMAND FOR PENTACHLOROPHENOL
(iN KKlu)
1960 1965 1970 1973 1.974 1975 1976 1977 1978 1979 1981
Capacity 25,400 35,400 31,300 33,100 33,100 33,100 27,700 27,700
Production 17,800 19,800 21,400 21,100 23,700 17,900 19,900 20,400 21,300
Demand 17,800 19,800 21,400 21,100 23,700 17,900 20,000 21,300 21,300 21,300 23,100
cr-
I
SOURCE: Versar, 1979
-------
Approximately 60 formulators were registered with EPA for products con-
taining PCP. Their names and addresses were listed in the Federal Register
(1978). As for indirect sources, pentachlorobenzene has been shown to be
metabolized in rats to give PCP (EPA, 1975a). No quantitative estimate of
this process was found in the available literature, but it was assumed to be
insignificant compared to industrial production. Chlorination of water con-
taining phenol does not result in PCP (EPA, 1975b).
6.3 CONSUMPTION AND USES
The flow pattern for PCP use is included in Figure 6.1 which also summarizes
the environmental releases for PCP. The end use pattern was based on informa-
tion gathered from EPA (1975a), Tracor-Jitco (1977b), and Versar (1979). No
major discrepancy among those references was found.
As shown, PCP was used mostly in the preservation of wood and the production
of sodium pentachlorophenate. Pentachlorophenol used in wood preserving accounted
for 78 percent of total PCP production. Twelve percent of the PCP produced was
used for sodium pentachlorophenate (Na-PCP) production. The USITC listed Dow
as the only producer of Na-PCP in 1976. Sodium pentachlorophenate was used
mainly as a fungicide and bactericide. Since no information was available
as to the uses for potassium pentachlorophenate, we have assumed that it
was used similarly to the sodium salt because of chemical similarity between
the two. No uses were reported in the available literature for the lauric acid
ester, although it was a registered pesticide product. We have assumed that
production of these compounds was limited, amounting to 10 kkg annually for
each compound. This was compatible with the information from Federal Register
(1978), which showed that 0.6 percent of registered PCP products contain
6-6
-------
potassium pentachlorophenate, and 0.8 percent contain PCP lauric acid ester.
The remaining 10 percent of the PCP was used in miscellaneous applications,
including several minor ones and three major ones which were: (a) to water-
proof fiberboard and plywood, (b) in home and garden applications, and (c) as
an herbicide. The following sections discuss those end uses for which informa-
tion was available.
6.3.1 Wood Preservation
Figure 6.3 shows the location of wood preservation plants (Environmental
Science and Engineering, 1978). Table 6.3 lists the quantity of wood products
treated with PCP in 1975 (AWPI, 1977). From the table, it is seen that most
of PCP was used for the treatment of poles and lumber. The AWPI report showed
that the total amount of wood treated with PCP was 61 MM cubic feet in 1975.
JRB estimated that 15,000 kkg of PCP were used by the industry (see Figure 6.1).
6.3.2 Pressed Board and Insulation Board Manufacture
Figures 6.4 and 6.5 are maps showing the geographic locations of the plants
producing pressed board and insulation board (Environmental Science and Engi-
neering, 1978). Based on Versar's 1979 draft on pentachlorophenol, close to
one third of the sodium pentachlorophenates was consumed by this industry, i.e.,
700 kkg of PCP went to the sodium salt which was used by the pressed board and
insulation board industry.
6.3.3 Other PCP Uses
After accounting for the three principal uses of the PCP salts, which were
reported (Versar, 1979) as: (a) treatment of sap stain which occurred on un-
seasoned logs, (b) pressed board and insulation board manufacture, and (c)
6-7
-------
FIGURE 6.3
GEOGRAPHICAL DISTRIBUTION OF WOOD PRESERVING
PLANTS IN THE UNITED STATES
I
Co
LEGEND
Pressure
Non-Pressure
Pressure and Non-Pressure
-------
Table 6.3 Quantities of Wood Products
Treated with Pentachlorophenol,
1975
QUANTITY TREATED
PROPORTION TREATED
Total With Penta
WITH PENTA
Railway ties
Poles
Piling
Lumber*
Fence posts
Other
Hi
101
49
9
62
15
6
244
1 1 ion
.1
.1
.4
.9
.3
.3
.1
cu f
0
32
0
17
10
0
60
t
.4
.2
.4
. 1
.0
.8
.9
%_
0
65
4
27
65
13
24
.4
.0
.0
.0
. 0
.0
.y
* Includes timbers and crossarrns
[NOTE: Components nay not add to totals due to rounding
SOURCE: AWPI, 1977
6-9
-------
FIGURE 6.4
GEOGRAPHICAL DISTRIBUTION OF HARDBOARD
MANUFACTURING FACILITIES IN THE UNITED STATES
I
I-1
o
LEGEND
© Wet-Wet Process
Ijjj Wet-Dry Process
f£) Wol-Dry/lnBulallon
-------
FIGURE 6.5
GEOGRAPHICAL DISTRIBUTION OF INSULATION BOARD
MANUFACTURING FACILITIES IN THE UNITED STATES
LEGEND
O Mechanical Pulping
Q Thermo-mechanlcal Pulping
A Thormo-mochanlcal Pulping
and/or Hardboard
-------
prevention of slime and mold^in cooling towers, it was estimated by JRB that
only 200 kkg of PCP were consumed as sodium salt in minor uses as bactericides,
and for the preservation of textiles, adhesive, and leather. As no information
was reported in the available literature regarding the amount going to each
end use, and since those account for a minor portion of the PCP salt, JRB
estimated that each of those minor uses accounted for 50 kkg of PCP per year.
For the PCP that was not converted to salts, based on the percentage going
to each end use as reported by Versar (1979), JRB estimated that 1100 kkg were
used in plywood and fiberboard waterproofing, 570 kkg were used in home and
garden applications (control of termites, preservative'in paints for porch
and lawn furniture, trailers and boats, and bird repellant which was applied
to trees), and 190 kkg were used as an herbicide (mostly in non-crop areas and
dormant crop areas).
6.4 EMISSIONS TO THE ENVIRONMENT
6.A.I Production of PCP
This section discusses the production process and presents estimates of
environmental releases. Pentachlorophenol is produced by the chlorination
of phenol. The reaction chemistry is shown below:
OH
Is
catalyst,
elevated
temp.
Cl
6-12
-------
In PGP production, the chlorination reaction is performed at atmospheric
pressure. The temperature of the phenol in the primary reactor at the
beginning of the reaction is in the range of 65-130° C. Then a metallic chloride
catalyst, such as ferric chloride or aluminum chloride, is added and the temper-
ature is progressively increased to maintain a temperature of about 10° C over
the product's melting point. The product is a mixture of tri-, tetra- and
pentachlorophenols, with the proportion of PCP increasing with time at the
expense of the other two chlorophenols. The reaction is completed in 5 to 15
hours. The off-gas for the chlorination reactor (mainly HC1) is sent to a
scrubber reactor containing phenol. It is held at a temperature such that the
chlorine is essentially depleted by reacting with phenol and forming a mixture
of lower chlorinated phenols. This material is normally recycled to the PCP
reactor. The residual gas is pure HC1. The production process is illustrated
in Figure 6.6.
6.4.1.1 Air Emissions
PCP has a relatively low vapor pressure. At the highest temperature that
can be expected in the reactor (200° C), its vapor pressure was calculated to
be only 26.3 mm Hg based on a correlation shown in the CRC Handbook of Chemistry
and Physics. Thus, the quantity of PCP in vapor form which was emitted to air
would be small. For PCP particulates, an upper bound was given in EPA (1978),
at 5.5 x 10" kkg pollutant/kkg product. This was considered an upper bound
because that emission factor also included particulates from fuel combustion.
No rationale was given in that report as to how the number was derived, but the
author cited two references which he used. Thus, particulate emissions were
estimated as:
6-13
-------
Phenol
I
M
J>-
HCI
Recycle to.
Chlorine
Planf
SOURCK: AWI'I, 1977
Figure 6.6 Production Process for PenCachlorophenol
-------
(22,000 kkg PCP) (5.5 x 10~4 ) = 12 kkg of PCP particulate per year
Since this was an upper bound estimate, the uncertainty was + 50 percent,
- 90 percent.
Because the biodegradation rate for PCP was slower than that of dichloro-
phenol (EPA, 1975a), an emission factor into the sludge was estimated at
_2
2 x 10 kkg/kkg of PCP product, as compared to an estimated factor of
1.3 x 10" 3 kkg/kkg for 2,4-DCP (see Chapter 3). Assuming a 95 percent in-
cineration efficiency for this sludge, followed by scrubbing at 95 percent
efficiency, the amount of PCP released to the air from sludge treatment was
estimated as follows:
(22,000 kkg) (2 x 10~3 kkg/kkg) (0.05 fraction not incinerated) x
(0.05 fraction not scrubbed) = 0.11 kkg of PCP released to air due to
production
The amount returned to the plant in the scrubber water was assumed to be
sent to the wastewater treatment unit.
6.4.1.2 Water Emissions
Based on a plant study with respect to 2,4-D production at Dow, dikes have
been used around production/storage areas to prevent spills. Dow also has a
holding pond which is automatically switched in during emergencies (MRI, 1972)
Therefore, in the absence of better information, it was assumed that risk of
releases from spillage was negligible for PCP plants. PCP has been shown to
6-15
-------
degrade in activated soil more slowly than 2,4-DCP (EPA, 1975a), there-
fore the water emission was estimated to be higher than that of 2,4-DCP,
(estimated in Chapter 3) or approximately 0.03 kkg emitted per kkg product,
with an uncertainty of +50%, -90%, or:
(22,000 kkg PCP) (0.03 kkg PCP release) = 660 kkg PCP to water in 1978
kkg PCP produced
6.4.1.3 Solid Waste Disposal
In a Midwest Research Institute survey, Dow reported that they had on-site
quality control laboratory facilities, and frequently monitored the raw
materials and reaction intermediates as well as the final product (MRI, 1972).
MRI hypothetized that production runs that were so far "off-specification"
that they needed to be discarded would be extremely rare. Therefore, JRB
assumed that this source of release was 0.1 percent of production rate.
Reactor tars would contribute another 0.1 percent at the maximum. This
estimate by JRB was based on economics because a relatively high PCP content
in tars would suggest that some sort of tar reclaiming would be carried out
and thus would result in a low PCP content in tars. PCP in solid waste was
estimated as:
(22,000 kkg PCP) (0.002 kkg/kkg) = 44 kkg PCP emitted in solid wastes
due to production
Assuming 90 percent was incinerated, the amount going to landfill was:
(44 kkg) (0.1) = 4.4 kkg PCP-containing residues to landfill
6-16
-------
The PCP emitted to air from the incineration process was:
(0.05 fraction surviving incineration) (0.05 fraction not scrubbed) x
(39.6 kkg) = 0.10 kkg PCP emitted to air due to disposal of solid wastes
This was negligible compared to the particulate emission from processing as
discussed in the section on air emissions.
6.4.2 Formulations of PCP Product
PCP in the solid form produced by manufacturers was formulated into solutions
or briquettes. Some of the formulations were reported in the Federal Register
(1978). Since pesticides and herbicides also exist as dusts, PCP could also
conceivably be formulated into dust form. Lacking adequate information in this
Level I study, JKB assumed that the environmental releases at formulating plants
were similar to those from production plants. JRB assumed that major users pur-
chase the PCP in bulk as a solid, whereas the PCP used in home and garden applica-
tions, and as an herbicide is forumlated. The emissions thus calculated are shown
in Figure 6.1.
6.4.3 Distribution and Storage of PCP and PCP Derivatives
The movement of PCP from the three manufacturers to the end-users involved
transportation, warehousing, redistribution and storage or shelving at the point
of purchase. Losses during distribution have been estimated by MRI (1972) to be
between 0.01 and 0.1 percent for pesticides. PCP is shipped by producers as a
prilled solid in bags, a pelleted solid- in bags and in bulk, and in one-half
and one-ton blocks with a metal hook cast in the center. Bags and solid blocks
are shipped in trucks and freight cars, bulk shipments are by hopper trucks
6-17
-------
and railroad cars (AWPI, 1977). JRB assumed an average emission factor
of 0.05 percent:
(20,000 kkg PCP) (0.0005 kkg/kkg) = 10 kkg PCP emitted due to distribution
in 1978
JRB also estimated that 95 percent of the shipments were by truck and
rail, and 5 percent by water transport. Therefore, 9.5 kkg were released to
land and 0.5 kkg was released to water.
6.A.4 Environmental Releases from Uses
The following sections discuss the releases from various uses of PCP.
6.4.4.1 Production of PCP Salts and Laurie Acid Ester
No information was available as to the production and formulation of PCP
derivatives. Assuming 98 percent yield in the production of PCP derivatives,
the PCP present as a contaminant would be an order of magnitude less than in
the production of PCP itself. Therefore, in this case, the emission factors
for PCP would be an order of magnitude smaller than those estimated in Section
6.4.1. .
Thus, air emissions of PCP were estimated at 5 x 10 kkg' per kkg of PCP
derivative produced, resulting in negligible emissions for the production of
the relatively small amounts of Na-PCP, K-PCP and lauric acid ester. Similarly,
_T
water emissions were estimated at 1.5 x 10 kkg per kkg PCP derivative.. Pro-
duction of Na-PCP resulted in the following estimated release to water:
6-18
-------
(2300 kkg PCP) (1.15 kkg Na-PCP) (1.5 x 10~3 kkg PGP lost) =3.97 kkg PGP
kkg PCP kkg Na-PCP produced emitted to water
due to derivative
synthesis
The release from the K-PCP and lauric acid ester production was negligible
because the quantity of Na-PCP produced was much larger than the other two.
Assuming incineration of solid waste, land release would be negligible.
6.4.4.2 Herbicide and Home and Garden Applications
When PCP was used as a herbicide, essentially all of that PCP was released
to the environment. Versar (1979) assumed that 10 percent goes to air, 20
percent to water, and 70 percent to land. The authors did not explain how
they came up with the estimate. Nevertheless, it appeared a reasonable first
cut attempt at quantifying the releases to the three media. Thus, for the 180
kkg of PCP that were used as an herbicide, 20 kkg went to air, 38 kkg went to
water and 120 kkg were released to land.
For home and garden uses, Versar assumed the same distribution to air,
land and water as above. This resulted in an estimate of 60 kkg to air, 390
kkg to land, and 120 kkg to water on an annual basis. The validity of the
estimate could not be checked in this Level I study because there was not
enough information in the available literature. The assumption of total
release may have been too conservative, because PCP used with paint on porch
and lawn furniture, for example, would appear to remain attached to the surface
of the wood for some length of time.
6.4.4.3 Wood Preservation
Versar (1979) estimated that 1 kkg of PCP was released to water and 4 kkg
discharged to publicly-owned treatment works. Environmental Sciences and
6-19
-------
Engineering reported in a 1978 study that the treated effluents from wood
preserving plants contained an average of 0.082 Ib PCP per 1000 cubic feet,
and untreated discharges contain 0.383 Ib PCP per 1000 cubic feet. From the
data reported in the ES & E study, JRB calculated that an average of 1.14
gallons of waste water per day was generated per cubic foot of preserved wood.
The total annual PCP discharge from wood preserving plants was:
a) lower bound (assuming all plants discharge treated effluents)
( Q.082 Ib PCP ) (!_._!4 gallon water) (0.13368 ft3 water) (61 x 106 ft3 wood)
(1000 ft-* water) ( 1 ft3 wood ) ( gallon water ) ( year )
( 1 kkg ) = 0.35 kkg/year
(2200 Ib PCP)
b) upper bound (assuming all plants discharge untreated effluents)
( 0.383 Ib PCP ) (1.14 gallon water) (0.13368 ft3 water) (61 x 106 ft3 wood)
(1000 ft3 water) (1 ft3 wood) ( gallon water ) ( year )
( 1 kkg ) = 1.6 kkg/year
(2200 Ib PCP)
JRB's estimates using the results of the ES & E report are compatible with the
estimates made by Versar. No information was given for air and land releases,
and hence JRB assumed that the emission factors were similar to those at pro-
ducing plants.
Release to air:
x
(5.5 x 10-* kkg/kkg)
8"3
6-20
-------
Solid Wastes:
15.000 kkg = 30 kkg PGP
year ' year
The PCP discharge to land from wood preserving plants was estimated at less
than 1 kkg per year by Versar (1979). The sum of PCP releases from the wood
preserving industry as estimated by Versar was 6 kkg per year. This was within
an order of magnitude of the 1.6 kkg estimate by JRB.
In addition to plant releases, the PCP released to land as a leachate from
utility poles was estimated at 960 kkg per year by Versar (1979), based on an
average loss rate of 0.05 Ibs of PCP per cubic foot for 42.3 x 10 cubic feet
of poles treated in 1974. Table 6.2 shows that 61 x 10^ ft of wood were
treated in 1975. The average quantity of PCP per cubic foot of wood was derived
by JRB as follows:
( 15,000 kkg ) (2200 Ibs) = 0.55 Ibs PCP
(60 x 106 ft3) ( kkg ) ft-5 wood
The loss ratio was:
100 = 9.1 percent per year
(0.55)
This low ratio indicated that most of the PCP was released to the environment
at the end of 12 years or so. JRB feels that it represents a rather high loss
rate, but does not have sufficient information for verifying this assertion.
6-21
-------
6.4.4.4 Leather Tanning
Versar (1979) estimated that 1 kkg per year was discharged to water, and
3 kkg per year were discharged to publicly-owned treatment works (POTW). The
estimate was based on a reported average PCP concentration. However, the
number of plants sampled was not reported in the Versar report, and hence no
validity could be attributed to that estimate. This release was 8 percent of
the JRB estimate of 50 kkg of PCP consumed by the textile industry in the form
of sodium salt. In this context, it appeared reasonable.
JRB has assumed that the level of PCP as in impurity in sodium pentachloro-
phenate was 2 percent. As an upperbound estimate, if half of this PCP salt
(25 kkg) was released to land and half to water, the PCP present as an impurity
would amount to:
(25.0 kkg PCP as salt) (0.02 kkg PCP impurity)_ 0.50 kkg PCP impurity to land
(year) (kkg PCP as salt) year
Similarly, 0.50 kkg was estimated to be released to water. The air release
was assumed to be negligible because even if it was assumed to be equal to 0.50
kkg of PCP impurity per year, it is still a small number relative to other
sources of PCP air release (e.g., herbicides).
6.4.4.5 Preservation of Adhesive and Textile and Use as a Bactericide
The available literature did not provide adequate information. As an upper
bound estimate, half of the PCP salt was assumed to be dispersed to land, and
half to water. Then, as in the previous section, 0.50 kkg PCP (as impurity)
6-22
-------
was released to land and 0.50 kkg was released to water for each of the
three end uses. Those are still small numbers relative to herbicide
emissions.
6.4.4.6 Fungicide for Treatment of Sap Stain
The PCP sodium salt was used for this purpose on freshly sawed logs and
unseasoned timber, and therefore JRB assumed that the application of the
fungicide to the surface area of the wood resulted in near total releases
within one year to land and water in equal proportions, or 300 kkg of
PCP as the sodium salt to each medium. Since the PCP itself was present
as a 2 percent impurity, 6 kkg of PCP as an impurity in the PCP salt was
released to land and another 6 kkg was released to water on an annual basis.
6.4.4.7 Fungicide in Cooling Towers
JRB estimated that 5 percent of the sodium pentachlorophenate was released
into the air. The quantity of PCP salt released to air was:
(700 kkg) (0.05) = 35 kkg PCP salt emitted due to use as a cooling
tower fungicide
The quantity of PCP impurity released to air was:
(35 kkg) (0.02) = 0.70 kkg PCP impurity emitted due to use as a
cooling tower fungicide
Assuming an 80 percent effluent treatment efficiency, the quantity of PCP
salt released to water was estimated to be:
6-23
-------
(700 -kkg) (0.20) = 140 kkg PCP salt emitted to water due to use as
a cooling tower fungicide
The PCP impurity is:
(140 kkg) (0.02) = 2.8 kkg PCP impurity emitted to water due to use
as a cooling tower fungicide
6.4.4.8 Plywood and Fiberboard Waterproofing
For the waterproofing of plywood and fiberboard, there was no information
in the available literature for JRB to estimate releases to the environment.
The total amount released should be at the maximum about half of the amount
consumed, or less than 600 kkg per y-ear. The estimate was arrived at after
considering factors such as leaching from the boards and solid waste disposal
in landfills.
6.5 Summary of Pentachlorophenol Materials Balance
The overall summary materials balance is presented in Figure 6.7.
6-24
-------
CUNSUMfflVS
(-0
en
tiH^IBUIUOtflTAL ftCt.P^SP.S OF PCp
All MATEK Sill. 10
"* UAS1E/
I.AMt)
! 0 - I t> Hj,
11. MM) It 4 > llt.lAO k*4
i 1.1 oi) ^»x
Figure 6.7 Materials Balance for Pentachlorophenol (kkg)
-------
7.0 MAJOR EMISSION LOCATIONS
This chapter will identify geographic sites with a large point source or
multiple sources. In order to permit combining data for all chlorophenols
into an overall picture, the results are presented in a summary table
(Table 7.1).
According to Table 7.1, the most likely point source of multiple chloro-
phenols was located in Midland, Michigan. Other possible sources of chloro-
phenol emissions are listed below in decreasing order of possibility.
0 Midland, Michigan
o Sauget, Illinois
o Jacksonville, Arkansas; Wichita, Kansas; and Tacoma, Washington
e Portland, Oregon; Niagra Falls, New York; and Verona, Missouri
7-1
-------
TABLE 7.1 MAJOR EMISSION LOCATIONS
CHEMICAL COMPOUNDS
I
K>
LOCATION
Midland. MI
Saugec. IL
Portland. OR
Jacksonville, AR
Niagara Falls. NY
Wichita. KS
Verona, MO
Tacoma, WA
2-chloro- 4-chloro- 2.4-dlchloro- 2.4,5-trlchloro- 2,3,4,6-tetra Pentachloro-
phenol phenol phenol phenol • chlorophenol phenol
XX X X X X
XX X X(?)
X
X X
X
X X
X
X X
-------
8.0 DATA GAPS
During the preparation of this report, a series of significant data gaps
were identified. These are discussed in this chapter and possible methods
of obtaining the needed information are suggested.
8.1 IDENTIFICATION OF MAJOR PRODUCERS AND THE ANNUAL PRODUCTION QUANTITIES
OF CHLOROPHENOLS
Information on the total production quantities of chlorinated phenols is
considered proprietary and is therefore not available. The production quantity
is the basis for most of the calculations involved in a materials balance.
Without this basis, major assumptions and estimations cannot be verified, and
an important uncertainty is introduced into the materials balance study. The
most direct way to obtain confidential data on production of chlorophenols
would appear to be the TSCA Inventory. This will yield a range of values that
would help to confirm estimates made in this report.
8.2 LEVEL OF CHLORINATED PHENOLS CONTAINED IN THE END PRODUCTS AS CONTAMINANTS
No information was available on the amount of a reactant carried over into
an end-product. An important example is the possibility of 2,4-DCP contamina-
tion in its major end-product, 2,4-D. It is rare for industrial processes to
be 100 percent effective in separating products from reactants. If contamina-
tion does occur at a considerable level, it could represent a major emission
source to the environment.
In order to obtain information on chlorophenol impurities in products, two
approaches would need to be used: 1) Information on carry-over of chlorophenols
5-1
-------
into non-pesticide products would be sought through communications with
producers and consumers, and through a search of the primary analytical
chemistry literature (probably via a Chemical Abstracts search). 2) Con-
fidential information on pesticide compositions would be requested from
Office of Pesticide Programs through appropriate administrative channels.
As described in Section 3.4.4, the procedure would be to obtain the regis-
tration numbers of pesticide products derived from chlorophenols, then
request confidential information (if available) on chemical analysis of
the products. In addition, Dr. Phil Kearney of U. S. D. A. should be
located and interviewed. Dr. Kearney was identified by a spokeswoman at
Dow Chemical as an authority on impurities in pesticides.
8.3 INFORMATION ON ENVIRONMENTAL EMISSIONS
Little information was available on emission of chlorinated phenols to
air, land, and water. Due to the lack of information it was difficult to
properly assess emissions of chlorophenols during the various processes.
Many best-guess estimates of emissions based on assumptions unverified by
data were required in this report. In order to solve this problem, monitor-
ing data on chlorophenol releases to air and water could be obtained and
made available. This would not be inordinately difficult because of the
small number of plants involved. In fact, it is possible that raw data on
emissions at Midland, MI, and Sauget, IL (the two major synthesis sites)
already exist but have not been calculated and analyzed. Likely sources for
water emissions would be the repositories of NPDES monitoring data in state
offices of approved programs or EPA regional offices for non-approved states;
3-2
-------
and Effluent Guidelines Division monitoring data on toxic wastes. Since
chlorophenols would be expected to be stable in water, samples taken and
stored could be re-analyzed. If no monitoring data are presently available,
it is recommended that effluent water samples (post-treatment) and downwind
air samples be collected at production sites in the order: 1) Midland, MI;
2) Sauget, II; 3) Jacksonville, AR; 4) Wichita, KS; 5) Tacoma, WA; 6)
Portland, OR; 7) Niagra Falls, NY; 8) Verona, MO.
Analytical data on the chlorophenol content of production plant solid
wastes would help to test the assumption that land-destined waste from
chlorophenol production contains negligible chlorophenols. These analytical
data might be obtained from individual plant operators. If not, chemical
analysis of sludge samples from each plant would be necessary. Samples
should be taken from process solid residues, biological wastewater treatment
sludges, and incinerator ash.
3-3
-------
LIST OF REFERENCES
American Wood Preservers Institute, Environmental Programs Task Group,
Subcommittee No. 6. 1977. Pentachlorophenol, A Wood Preservative.
Memorandum for the Office of Pesticide Programs, U.S. Environmental
Protection Agency, Washington, D. C.
ENTOMA (The Entomological Society of America). 1975. Pesticide Handbook -
Entoma.
Environmental Science and Engineering, Inc. 1978. Revised Technical Review
of the Best Available Technology, Best Demonstrated Technology, and
Pretreatment Technology for the Timber Products Processing Point Source
Category, Draft. U.S. Environmental Protection Agency, Washington, D. C.
Federal Register, 1978. Notice of Rebuttable Presumption Against Registration
and Continued Registration of Pesticide Products Containing Pentachlorophenol.
Vol. 43, No. 202, Wednesday, October 18, 1978.
Hydroscience, Inc. 1979. Emissions Control Options for the Synthetic
Organic Chemicals Manufacturing Industry: Aniline Trip Report for E. I.
DuPont de Nemours, Beaumont, TX, Sept. 7-8, 1977. U.S. Environmental
Protection Agency, Research Triangle Park, NC.
Kirk-Othmer. 1969. Encyclopedia of Chemical Technology, 2nd ed., Vol. 18.
Metcalf and Eddy, Inc. 1972. Wastewater Engineering: Collection, Treatment,
Disposal. McGraw-Hill.
Midwest Research Institute (MRI). 1972. The Pollution Potential in
Pesticide Manufacturing. PB-213-782, U.S. Environmental Protection Agency,
Washington, D. C.
Morrison, R.T., and Boyd, R.N. 1973. Organic Chemistry, 3rd ed., Allyn
and Bacon. Boston, MA.
Ottinger, R.S., Blumenthal, J.C., Dal Porto, D.F., Gruber, G.L., Santy, M.J.,
and Shih, C.C. 1973. Recommended Methods of Reduction, Neutralization,
Recovery or Disposal of Hazardous Waste, Vol. V, National Disposal Site
Candidate Waste Stream Constituent Profile Reports — Pesticides and Cyanide
Compounds. U.S. Environmental Protection Agency, Washington, D. C.
PEDCo Environmental. 1979a. Draft Report on Dioxins in the U.S.: A Technical
and Legislative Review, with an Assessment of Potential Exposure Problems,
Appendix D, Commercial Products Potentially Contaminated with Dioxins.
U.S. Environmental Protection Agency, Washington, D. C.
-------
LIST OF REFERENCES (Continued)
PEDCo Environmental, Inc. 1979b. Dioxins: Sources, Transport, Exposure, and
Control, Preliminary Draft. Contract No. 68-03-2577, U.S. Environmental
Protection Agency, Washington, D. C.
Sittig, M. 1974. Pollution Control in the Organic Chemical Industry. Noyes
Data Corp.
Stanford Research Institute. 1975 and 1978. Directory of Chemical Producers,
U.S.A.
Tracor-Jitco, Inc. 1977a. Production and Use, 2,4-Dichlorophenol, Chapter V.
MDSD Priority Pollutant File, U.S. Environmental Protection Agency.
Washington, D. C.
Tracor-Jitco, Inc. 1977b. Production and Use, Pentachlorophenol, Chapter V.
MDSD Priority Pollutant File, U.S. Environmental Protection Agency,
Washington, D. C.
Tracor-Jitco, Inc. 1977c. Production and Use, Chlorophenols, Chapter V.
MDSD Priority Pollutant File, U.S. Environmental Protection Agency,
Washington, D. C.
U.S. Bureau of Census, 1978. Export, Scientific Industrial Chemicals (SIC),
Base, 1978. Washington, D. C.
U.S. Environmental Protection Agency. 1973. Preliminary Environmental
Assessment of Chlorinated Naphthalenes, Silicones, Fluorocarbons, Benzene
Polycarboxylates, and Chlorophenols. PB-23S-263. Syracuse University
Research Corp., Syracuse, NY. • ,
U.S. Environmental Protection Agency. 1975a. Environmental Hazard Assessment
Series: Chlorophenols, EPA 560/8-75-003.
U.S. Environmental Protection Agency. 1975b. Identification of Organic
Compounds in Effluents from Industrial Sources. EPA 560/3-75-002.
Washington, D. C.
U.S. Environmental Protection Agency. 1976a. Development Document for Interim
Final Effluent Limitations Guidelines for the Pesticide Chemicals Manufacturing
Point Source Category. EPA 440/l-75/060d, Group II. Washington, D. C.
U.S. Environmental Protection Agency. 1976b. Economic Analysis of Interim
Final Effluent Guidelines for the Pesticides and Agricultural Chemicals
Industry — Group II. EPA 230/l-76-065f. Washington-, D. C.
U.S. Environmental Protection Agency. 1977. Organic Chemicals in Drinking
Water, Summary of the National Organics Monitoring Survey. Washington, D. C.
-------
LIST OF REFERENCES (Continued)
U.S. International Trade Commission. 1960-1978. Synthetic Organic Chemicals,
U.S. Production and Sales.
Versar, Inc. 1975. Gross Annual Discharge (GAD) to Waters in 1974: 2,4,6-
Trichlorophenol. Contract No. 68-01-3852, U.S. Environmental Protection
Agency, Washington, D. C.
Versar, Inc. 1977a. Gross Annual Discharge (GAD) to Waters in 1976:
2-Chlorophenol. Contract No. 68-01-3852, U.S. Environmental Protection
Agency, Washington, D. C.
Versar, Inc. 1977b. Gross Annual Discharge (GAD) to the Waters in 1976:
2,4-Dichlorophenol. Contract No. 68-01-3852, U.S. Environmental Protection
Agency, Washington, D.C.
Versar, Inc. 1979. Production, Consumption, Environmental Distribution, and
Related Impacts of Selected Toxic Pollutants — Pentachlorophenol, Draft.
U.S. Environmental Protection Agency, Washington, D. C.
Weast, R.C. (ed). 1977. CRC Handbook of Chemistry and Physics, 58th ed.
CRC Press, Inc., Cleveland, OH.
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-560/13-80-004
3. RECIPIENTS ACCESSION-NO.
4. TITLE AND SUBTITLE
5. REPORT DATE
February 4, 1980
Level I Materials Balance: Chlorophenols
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Robert L. Hall, Phuoc Le, Tien Nguyen, Michael Katz,
Karen Slimak
8. PERFORMING ORGANIZATION REPORT NO.
2-800-03-379-14
9. PERFORMING ORGANIZATION NAME AND ADDRESS
10. PROGRAM ELEMENT NO.
JRB Associates, Inc.
8400 Westpark Drive
McLean, VA 22102
11. CONTRACT/GRANT NO.
68-01-5793
12. SPONSORING AGENCY NAME AND ADDRESS
Survey and Analysis Division (TS-793)
Office of Pesticides and Toxic Substances
U.S. Environmental Protection Agency
Washington, D.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
Final Report
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
Project Officer - Michael Callahan
16. ABSTRACT
This report presents a Level I materials balance study on 2-chlorophenol, 4-chloro-
phenol, 2,4-dichlorophenol, 2,4,5-trichlorophenol, 2,3,4,6-tetrachlorophenol and
pentachlorophenol. Areas of major interest were production quantities, producers,
consumption amounts and emissions to air, land, and water related to the above
sources. The estimated production quantities in 1976 of the compounds studied were
as follows: 2-chlorophenol, 9000 kkg; 4-chlorophenol, 9800 kkg; 2,4-dichlorophenol,
39,000 kkg; 2,4,-5-trichlorophenol, 6300 kkg; 2,3,4,6-tetrachlorophenol, 1,800 kkg;
and pentachlorophenol, 22,000 kkg. Waterborne emission was considered to be the
main pathway of chlorophenols release to the environment because of the physical
characteristics of these chemicals. The estimated quantities of aquatic emissions
associated with the chlorophenols studied were as follows: 2-chlorophenol, 430 kkg;
4-chlorophenol, 650 kkg; 2,4-dichlorophencl, 870 kkg; 2,4,5-trichlorophenol, 105 kkg;
2 ,3 ,4 , 6-tetrachlorophenol, 67-160 kkg; pentachlorophenol, 840-1400 kkg. Throughout
this report, estimations and assumptions were made in places where needed information
was not available. Bases for these estimations were stated and defined. Recommen-
dations for further studies were also made.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group
13. DISTRIBUTION STATEMENT
Release unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
117
20. SECURITY CLASS (This pagej
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
------- |