Chemosphere 43 (2001) 167±182

Global hexachlorobenzene emissions

Robert E. Bailey *

Bailey Associates, 4115 Elm Court, Midland, MI 48642, USA

Received 24 November 1999; accepted 17 May 2000

Abstract

Information from a variety of sources has been assembled to give a global picture of hexachlorobenzene (HCB)
emissions in the mid 1990s. No single overwhelming source of HCB was identi®ed. The best estimates of global HCB
emissions from di€erent categories of sources are as follows: pesticides application ± 6500 kg/yr; manufacturing ± 9500
kg/yr; combustion ± 7000 kg/yr, includes 500 kg from biomass burning. This adds up to total current HCB emissions of
approximately 23,000 kg/yr with an estimated range 12,000±92,000 kg/yr. A substantial portion of HCB measured in
the atmosphere is thought to come from volatilization of ``old'' HCB on the soil from past contamination along with
unidenti®ed sources. No information on potential sources in developing countries was available. Ó 2001 Elsevier
Science Ltd. All rights reserved.

Keywords: Hexachlorobenzene (HCB); Inventory; Sources

1. Introduction the atmosphere for wide distribution is included in this

Hexachlorobenzene (HCB) has been observed all
over the world in air, water and biota (Zell and Balls-
chmiter, 1980; Muir et al., 1992; Simonich and Hites,
1995; Fellin et al., 1996; Tremolada et al., 1996; Weber
and Goerke, 1996). Its vapor pressure, water solubility
and persistence in the environment combine to facilitate
the long-range transport of HCB and its bioaccumula-
tion. Because of the bioaccumulation and persistence of
HCB as well as its potential toxicity, HCB is on many
di€erent lists for regulation and management. Successful
risk management for HCB will require knowledge of all
the current sources of HCB as well as the likely impact
of any management action.
The objective of this study was to collect the available
information on emissions of HCB to facilitate an un-
derstanding of possible responses to proposed regula-
tion. Only HCB which was applied or disposed of in a
manner where it would be available for movement into
*
Fax: +1-517-835-3410.
report. For example, HCB as a contaminant in pesti-
cides was assumed to be applied on or near the surface
of the soil where it can volatilize. HCB incinerated at
high temperature for destruction or placed in secure
underground disposal facilities was assumed to be iso-
lated from the environment with a negligible fraction
available for movement in the environment.
The values and numbers in this report each have
some uncertainty associated with them, sometimes more
than an order of magnitude. Rather than choosing the
appropriate number of signi®cant ®gures for each value
in the text and tables, the values have been carried
through with all ®gures as originally reported. The
rounding o€ and discussion of uncertainty is then
reserved for the ®nal summary.
1.1. HCB in the environment
The concentrations of HCB in the North American
and Northern European environment have dropped
substantially in the past 35 years as shown by many
studies. For example, Rapaport and Eisenreich (1988)

0045-6535/01/$ - see front matter Ó 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 0 0 ) 0 0 1 8 6 - 7
168 R.E. Bailey / Chemosphere 43 (2001) 167±182
reported on the historical atmospheric deposition rates
of HCB by analysis of cores from ombrotrophic peat
bogs in eastern North America. They observed generally
low deposition rates up to the 1940s with an increase to
a maximum in the 1960s and some decline by 1980.
More localized contamination by HCB and other chlo-
rinated chemicals, in particular chlorobenzenes, is de-
scribed by Oliver and Nicol (1992) and Durham and
Oliver (1983) based on analysis of sediment cores from
Lake Ontario. The peak concentration of HCB corre-
sponds to 1960 with much lower concentrations
throughout the 1970s and early 1980s. The recent report
on the ®rst few years of operation of the Integrated
Atmospheric Deposition Network (Cortes et al., 1998;
Cortes, 1999) shows a continuing 5±10% per year de-
crease in the atmospheric concentration of HCB at dif-
ferent sites around the Great Lakes. An approximately
10% per year decrease in HCB concentrations has also
been reported in Lake Ontario lake trout (Huestis et al.,
1996) and in Great Lakes gull eggs (Bishop et al., 1992;
Petit et al., 1994; Pekarik et al., 1999). Similar declines in
HCB concentrations have also been reported in Europe.
An example is the publication by Bignert et al. (1998).
Laboratory studies on the volatilization of HCB
from soil indicate the rate to be a function of organic
content, temperature and exposure to the atmosphere as
expected (Beall, 1976; Nash and Gish, 1989; Wang and
Jones, 1994). In general, the laboratory experiments
suggest substantial HCB volatilization over the course
of a year from its application in agriculture. There is no
information on soil concentrations of HCB, which could
be used to estimate a global HCB budget. Ho€ et al.
(1996) calculated that dissolved HCB in the upper Great
Lakes was in approximate equilibrium with the atmo-
sphere. This suggests that negligible waterborne HCB
from industrial e‚uent is entering the Great Lakes at
present (Mackay and Bentzen, 1997). McConnell et al.
(1996) studied the air±water±gas exchange of HCB in
Lake Baikal, Russia. They found HCB concentrations in
both air and water to be similar to those reported in the
Great Lakes by Ho€ et al. (1996). Wu et al. (1997) report
extensive contamination of Lake Ya-Er sediments and
surrounding soil with HCB, HCH, and other chlori-
nated compounds from a major chemical production
plant between the years 1960 and 1987. Their reported
concentrations of HCB range up to 57 ppm in sediments
and 38 ppm in soil. This area clearly could be contrib-
uting to the atmospheric burden of HCB by volatiliza-
tion.
1.2. Emissions summaries
The proceedings of the Hexachlorobenzene Sympo-
sium in Lyon, FR, in 1985 constitute the most complete
source of information on the presence and behavior of
HCB to date (Morris and Cabral, 1986). In particular,
chapters by Tobin (1986), Rippen and Frank (1986), and
Jaco€ et al. (1986) have useful information on the state
of knowledge about HCB emissions at that time. Rippen
and Frank estimated worldwide HCB emissions of 10±
100 tons/yr. Axenfeld et al. (1992) estimated HCB
emissions for Europe as from 1982 to 1985 (including
the European portion of the USSR) to be 51,132 kg/yr.
The majority of this, 33,964 kg, was attributed to the use
of contaminated pesticides, without specifying the
method of estimation. A European HCB emissions in-
ventory has been prepared by TNO (Netherlands Or-
ganization for Applied Scienti®c Research), drawing on
various national inventories with total European annual
emissions of 8040 kg (Berdowski and Bloos, 1997).
Franke et al. (1996) quotes the German BUA (Berater-
gremium f ur umweltrelevante Altsto€e) report on HCB
for total industrial and anthropogenic environmental
emissions of HCB in Germany to be 200 kg/yr along
with 10,000±50,000 kg/year remobilized from soil.
Carpenter et al. (1986) provided one of the most
complete assessments of potential sources of HCB in the
US to date, drawing on several other EPA reports on
di€erent aspects of HCB in the environment, with esti-
mated total HCB emissions in the US of 17,798±29,163
kg/yr. HCB releases are included in the toxic chemical
release inventory (TRI), compiled by the USEPA each
year based on reports from each of the large sites
covered by Section 313 of the Emergency Planning and
Community Right-To-Know Act of 1986. The 1990±
1997 average of direct releases of HCB to air and water
in the US, which were reported in the TRI (USEPA,
1998c), was 399 kg/yr with a total of 186 kg reported for
1997. (The TRI database includes two apparent
reporting errors, which were excluded from this calcu-
lation.) The 1990 US emissions inventory of HCB and
other Section 112(c)(6) pollutants (USEPA, 1998b)
reports national HCB emissions of 2.30 tons (2100 kg)/
yr.
A summary of HCB emissions in the US and Canada
by Cohen et al. (1995) focuses on transport to the Great
Lakes with modeling of atmospheric emissions from all
parts of the US and Canada. One conclusion of this
large project was that estimated current North American
HCB emissions could only account for a fraction, ap-
proximately 10%, of the observed atmospheric HCB
concentrations around the Great Lakes. An interpreta-
tion of these results is that the HCB is transported across
the oceans to the Great Lakes region. Cohen et al.
(1995) estimated total HCB emissions in the US and
Canada to be within a range of 4600±40,000 kg/yr with a
``midpoint'' of 10,400 kg/yr. The recent Canadian ``Di-
oxins and Furans and Hexachlorobenzene Inventory of
Releases'' reports 57 kg/yr from combustion sources,
treated wood, and chlorinated chemical production
(Government of Canada, 1999). Benazon (1999) has
prepared a draft inventory of HCB emissions in Ontario
 R.E. Bailey / Chemosphere 43 (2001) 167±182 169

and reports 1998 HCB emissions of about 20 kg in Waste materials contaminated with HCB were often
Ontario. casually handled prior to the 1970s. A red silicate slag
from copper production in Germany prior to 1945,
1.3. Uses of HCB ``Kieselrot'', contains 10±20 ppm HCB and reportedly
was used as aggregate for park paths and playgrounds
HCB has been used in the past for a variety of (Theisen et al., 1993). HCB-containing still bottoms
applications from which it could potentially enter the were spread in a municipal land®ll in Louisiana in 1972
environment: (Quinlivan et al., 1977).

· fungicide,
1.4. Formation of HCB
· military pyrotechnic smokes,
· carbon anode treatment,
HCB is formed by the vigorous chlorination of
· aluminum ¯uxing and degassing,
benzene or a lower chlorinated benzene at elevated
· synthetic rubber peptizing agent,
temperature with a catalyst (Beck, 1986). However,
· wood preservation (HCB as active material),
HCB is formed in trace amounts in a variety of reac-
· intermediate in organic syntheses.
tions, where it persists because of its thermodynamic
stability. Thus traces of HCB are formed during the
None of these applications of HCB are believed to be
chlorination step in the manufacture of several chlorine-
currently practiced in North America or Western Eu-
containing pesticides discussed below. HCB is also
rope. However, there is believed to be some use of HCB
formed during energetic reactions involving chlorine and
as a chemical intermediate in China (Wu et al., 1997)
graphite like materials such as soot. In these reactions,
and Russia (Federov, 1993). There are several patents on
often catalyzed in part by metals, chlorine apparently
the use of HCB in military pyrotechnics, tracer bullets
reacts with the aromatic rings breaking them loose from
and infrared opaque smoke. Russia was reported to use
the structure as chlorobenzenes. Thus many combustion
HCB in their tracer bullets (Rampy, 1998) and the US
processes produce traces of HCB in a heterogeneous
military has said that they do not use HCB (Rampy,
reaction similar to the formation of poly-
1998). However, no information on the amount of HCB
chlorodibenzodioxins and furans. Similar reactions to
used at present by the military in Russia or other
yield HCB have also been reported from magnesium
countries was found. Schae€er et al. (1988) reported the
production, where coke and chlorine react with mag-
production of HCB as a minor byproduct from US army
nesium oxide to produce magnesium chloride. Electro-
HC smoke pots.
lytic production of chlorine using graphite anodes has
Carpenter et al. (1986) quoted the annual US pro-
also been reported to yield small amounts of HCB. HCB
duction of HCB as a fungicide in 1958 as 760,000 lbs
may also be formed by the trimerization of chloroacet-
(345,000 kg). The last registrations for fungicidal use of
ylenes in the combustion processes. Some of these for-
HCB in the US were canceled in 1985. HCB was
mation processes may take place in the processes
reported to have been used in substantial amounts in
described below.
Tunisia up to 1986 (IPCS, 1997) and in Mexican ag-
riculture up to 1991 (Santos-Burgoa and Downs, 1998).
It is clear that even with other potential sources of
HCB such as chemical waste, metal production and 2. HCB emissions as contaminant in pesticides
various combustion processes discussed later in this
report, agricultural use of HCB probably dominated HCB has been reported to be a trace contaminant in
HCB emissions in the 1950s and 1960s. Localized in- several pesticides which contain chlorine. This author
dustrial emissions of HCB in the 1960s were certainly has used the HCB concentration from the recent US
greater than now, as shown by the occurrence of HCB inventory (USEPA, 1998b) when additional information
contaminated sites in that era. For example, Boeckman was not available. The concentration of HCB used in
et al. (1981) and Knutzen and Oehme (1989) reported these estimations of emissions are: atrazine, 1 mg/kg;
discharges of HCB and other halo-organics from simazine, 1 mg/kg; picloram, 50 mg/kg; pentachloroni-
magnesium production had decreased by 90% since trobenzene (PCNB), 500 mg/kg (North America) and
1975 with a corresponding decrease in their concen- 1000 mg/kg (outside NA); chlorothalonil, 40 mg/kg
tration in mussels and ®sh downstream from the (North America) and 100 mg/kg (outside NA, Sasam-
magnesium plant at Porsgrunn, Norway. Vogelsang oto, 1997); dimethyl tetrachloroterephthalate (DCPA),
(1986) reported contamination of the Neckar River 1000 mg/kg; lindane, 50 mg/kg; technical hexachloro-
(Germany) with HCB and other halo-organics from cyclohexane (HCH), 100 mg/kg; pentachlorophenol, 50
aluminum and other metals processed with chlorinated mg/kg (North America) and 100 mg/kg for that used in
materials. China as a molluscicide. The production of DCPA in the
170 R.E. Bailey / Chemosphere 43 (2001) 167±182
US is reported to have ceased in the 1990s (Pearson,
1999).
The average concentration, at least for all the North
American producers, is less than the listed value.
Information reporting HCB contamination levels in
pesticides manufactured and used in developing coun-
tries such as India and China was not found. In the past,
India and China have used large volumes of chlorinated
pesticides and HCB may have been an impurity.
Extensive HCB contamination of a pesticide manufac-
turing site in central China which produced lindane and
pentachlorophenol among other products, has been
reported by Wu et al. (1997).
This author has assumed that all of the HCB con-
tained in pesticides is available in the environment, with
the exception of HCB contained in pentachlorophenol
used in wood treatment. While not all of the HCB is
expected to be volatilized from soil in the ®rst year after
application, continued use would build up a steady-
state concentration of HCB and annual volatilization
equal to the amount applied. However, modeling
studies have shown that only a total of 6% of the HCB
contained in pentachlorophenol used in wood treatment
is volatilized over the 35 year service life of treated
wood (Estreicher, 1999). It was assumed that treated
wood is removed from the environment at the end of its
service life. Tables 1±3 summarize the information on
potential HCB emissions in the US, Canada and
globally, respectively, as a result of pesticide use. Gia-
nessi and Anderson (1995) at the National Center for
Food and Agricultural Policy compiled the identities
and quantities of pesticides used in agricultural pro-
duction in the US. Gilding (1996) compiled use infor-
mation from the US producers in a letter to the EPA.
Information on US, Canadian and international use of
pesticides in agriculture was purchased from Landell
Mills Market Research (1996) in the UK. For the US
the quantities of Gianessi and Anderson, Landell Mills
and Gilding have been averaged in Table 1. The in-
formation from Landell Mills for Canada is inconsis-
tent with that compiled for Ontario (OMAFRA, 1994)
so that the higher of the two values is listed, recog-
nizing that additional pesticide may have been used. Li
et al. (1996) reported the global usage of both lindane
and technical HCH for 1980 and 1990. Estreicher
(1999) provided estimates of pentachlorophenol-treated
wood use in North America.
Table 3 lists total potential HCB emissions of 6463
kg/yr due to HCB as a microcontaminant in pesticides.
As most of the concentrations of HCB used are maxima,
at least for North America and Europe, the listed
amount is likely to be higher than the actual amount in
these regions. On the other hand, use of pesticides is
only reported in these tables when information was
available. Thus, there may be additional use, which was
not included. Pesticides manufactured and used in na-
tions with less stringent health and environmental reg-
ulations may have higher HCB contamination levels.
3. Other products containing HCB
A small amount of HCB is formed during the pro-
duction of perchloroethylene (perc), trichloroethylene
(TCE) and other chlorinated solvents which are puri®ed
by distillation. Emissions from their production are
discussed in the next section. HCB was not detected in
perc with a detection limit of 2 ppb and found at less
than 2 ppb in TCE (IPCS, 1997). Global emissions of
perc, TCE and methylene chloride have been summa-
rized by McCulloch and Midgley (1996) and are shown
in Tables 1±3 along with the corresponding HCB emis-
sion potential, based on the assumption that the HCB
content is one half of the method-detection limit. No
information was found which suggested that any other
common products contained HCB.
4. Manufacturing emissions
4.1. Chemical
In the production of chlorinated chemicals, inter-
mediates such as 1,2-dichloroethane and carbon tetra-
chloride, solvents such as perchloroethylene and
trichloroethylene, and pesticides, process waste-con-
taining HCB is separated and incinerated or placed in
secure underground disposal facilities, e.g., a deep well,
with a high degree of eciency in North America and
Western Europe. However, small amounts of HCB es-
cape to the air as fugitive emissions or stack emissions,
or in wastewater. The average TRI reported air and
water releases noted previously have been used in Table
1 as the best current estimate of releases in the US in the
1990s (USEPA, 1998c). Water emissions included in
TRI may, in part, represent a legacy from past con-
tamination. The TRI 1990±1997 average reported yearly
totals (399 kg) were used because values reported from
di€erent sites vary quite a lot from year to year with the
total for 1997 being the lowest at 186 kg. The emissions
for Canada, Table 2, were taken from the Canadian
inventory (Government of Canada, 1999). Canadian
HCB emissions have dropped markedly during the
1990s due to the cleanup or shutdown of many sources.
HCB emissions from the production of solvents and
other chlorinated chemicals outside North America,
Table 3, were estimated using solvent emissions as a
surrogate for all chlorinated chemical production, as
follows: it was assumed that the mix of non-North
American solvent and chlorinated chemical production
is similar to the North American mix of solvent and
chlorinated chemical production and the HCB emission
Table 1
US hexachlorobenzene emissions summary, mid 1990s, all quantities in kg/year
HCB concentration Average annual US use (kg/yr) HCB emissions (kg/yr)
Products containing HCB

Pesticides
DCPA (dacthal) 1000 ppm 677,791 677.8
Atrazine 1 ppm 32,233,523 32.2
Simazine 1 ppm 1,825,391 1.8
Picloram 50 ppm 655,922 32.8
PCNB 500 ppm 627,338 313.7
Chlorothalonil 40 ppm 4,928,591 197.1
Lindane 50 ppm 51,345 2.6
Pentachlorophenol 50 ppm 4,000,000 12.0 (see text)

R.E. Bailey / Chemosphere 43 (2001) 167±182

Pesticides sub total 1270.0
Chlorinated solvent usage 1 ppb 282,600,000 0.3
Manufacturing

US chemical manufacturing 399

Low HCB Mean HCB High HCB Product (kg/yr) Calculated HCB Calculated HCB Calculated HCB
emissions factor emissions factor emissions factor emissions using emissions using emissions using
(kg HCB/kg) (kg HCB/kg) (kg HCB/kg) low factors (kg/yr) mean factors (kg/yr) high factors (kg/yr)
Metals
Aluminum casting 8.6´10 2.2E-03 4.3E-03 HCE 58,800 51 129 253
Secondary copper 3.9E-09 3.9E-08 3.9E-07 695,000,000 3 27 271
Metals sub totals 53 156 524
Combustion
Municipal 2.9E-09 2.9E-08 2.9E-07 29,350,000,000 85 851 8512
Hazardous wastes 1.9E-09 1.9E-08 1.9E-07 1,500,000,000 3 29 285
Medical 2.9E-09 2.9E-08 2.9E-07 770,000,000 2 22 223
Coal 1.3E-12 1.3E-11 1.3E-10 791,877,000,000 1 10 103
Cement 1.7E-11 1.7E-10 1.7E-09 67,600,000,000 1 11 115
Iron sintering 1.5E-10 1.5E-09 1.5E-08 12,200,000,000 2 18 183
Sewage sludge 4.7E-10 4.7E-09 4.7E-08 865,000,000 0 4 41
Biomass 6.0E-12 6.0E-11 6.0E-10 228,000,000,000 1 14 137
Combustion sub totals 96 960 9598
US total HCB emissions (kg/yr) 1818 2785 11,791

171
Table 2

172
Canadian hexachlorobenzene emissions summary, mid 1990s
HCB concentration Annual canadian use (kg/yr) HCB emissions (kg/yr)
Products containing HCB
Pesticides
DCPA (dacthal) 1000 ppm 7245 7.2
Atrazine 1 ppm 893,130 0.9
Simazine 1 ppm 67,870 0.1
Picloram 50 ppm 433
PCNB 500 and 1000 ppm Not listed
Chlorothalonil 40 ppm 244,440 9.8
Lindane 50 ppm 284,500 14.2
Pentachlorophenol 50 ppm 500,000 1.5 (see text)
Pesticides sub total 33.7

R.E. Bailey / Chemosphere 43 (2001) 167±182

Chlorinated solvent usage 1 ppb 24,400,000 0.025
Manufacturing
Canadian chemical 0.1
manufacturing

Low HCB Mean HCB High HCB Product Calculated HCB Calculated HCB Calculated HCB
emissions factor emissions factor emissions factor (kg/yr) emissions using emissions using emissions using
(kg HCB/kg) (kg HCB/kg) (kg HCB/kg) low factors (kg/yr) mean factors (kg/yr) high factors (kg/yr)
Metals
Aluminum casting 8.6E-04 2.2E-03 4.3E-03 HCE 4840 4 11 21
Secondary copper 3.9E-09 3.9E-08 3.9E-07 112,000,000 0 4 44
Metals sub totals 5 15 64
Combustion
Municipal 2.9E-09 2.9E-08 2.9E-07 1,461,000,000 4 42 424
Hazardous wastes 1.9E-09 1.9E-08 1.9E-07 361,000,000 1 7 69
Medical 2.9E-09 2.9E-08 2.9E-07 79,400,000 0 2 23
Coal 1.3E-12 1.3E-11 1.3E-10 46,174,000,000 0 1 6
Cement 1.7E-11 1.7E-10 1.7E-09 10,740,000,000 0 2 18
Iron sintering 1.5E-10 1.5E-09 1.5E-08 644,000,000 0 1 10
Sewage sludge 4.7E-10 4.7E-09 4.7E-08 131,000,000 0 1 6
Biomass 6.0E-12 6.0E-11 6.0E-10 60,600,000,000 0 4 36
Combustion sub totals 6 59 592
Canadian total HCB 44 108 690
emissions (kg/yr)
 R.E. Bailey / Chemosphere 43 (2001) 167±182
factors are about the same. The ratio of North American
to global solvent production was estimated to be 0.305
(307,000,000±1,005,000,000 kg) based on estimated 1992
solvent emissions taken from McCulloch and Midgley
(1996). Thus the estimation of global HCB emissions
from the production of chlorinated chemicals was cal-
culated as follows:
(TRI + Canadian mfr. HCB)/0.305 ˆ Global HCB
(399 kg/year + 0.1 kg/year)/0.305 ˆ 1,308 kg HCB/
year.
With global HCB emissions from chlorinated chemical
manufacturing thereby estimated as 1308 kg/yr, non-
North American HCB emissions were then estimated as
1308 …399 ‡ 0:1† ˆ 909 kg/yr. An uncertainty range of
a factor of 3 was assigned, based on the range of HCB
emissions reported by Carpenter et al. (1986) for chlo-
rinated chemical manufacture outside North America,
Table 3. The European HCB emissions inventory com-
piled by Berdowski and Bloos (1997) lists 557 kg/year
for HCB emissions to the atmosphere from organic
chemical manufacturing, about the same as that esti-
mated for Europe by the above procedure.
Manufacturing emissions factors for HCB in coun-
tries with few enforced health and environmental laws
may be greater than those used in this report, which are
based on current North American manufacturing prac-
tices, and may be similar to those in the US of some
years ago. For example, Wu et al. (1997) report exten-
sive contamination of Lake Ya-Er (China) sediments
and surrounding soil with HCB, HCH, and other chlo-
rinated compounds from a major pesticide production
plant between the years 1960 and 1987, perhaps from the
production of pentachlorophenol by the reaction of
HCB with NaOH. Fedorov (1993) also reports the
production of pentachlorophenol from HCB in Chap-
aevsk, Russia. This process can be used as an outlet for
waste a-HCH from the manufacture of lindane. (HCH is
thermally dehydrohalogenated to trichlorobenzene and
then chlorinated to produce HCB which is treated with
NaOH to produce pentachlorophenol.) As no informa-
tion was found on HCB emissions from these processes,
their emissions have not been included in the tables.
The pulp and paper industry often uses chlorine or
chlorine dioxide for pulp bleaching. HCB does not seem
to be formed under the mild conditions employed
(Rantio, 1996; LaFleur, 1999), more vigorous conditions
degrade the pulp quality. The manufacture of chlorine
using carbon anodes is known to produce small amounts
of HCB, which accumulates in the piping and chlorine
compressor ta€y. Much of the global chlorine capacity
has switched to metallic anodes over the past 25 years so
that this source has become much smaller. The heavy
material-containing HCB would be treated along with
the other byproduct HCB and incinerated or placed in
secure underground disposal facilities. Land®lled HCB-
containing wastes from chlorine manufacture may have
173
contributed to contamination of the Great Lakes before
the 1970s.
4.2. Metals industry
Molten aluminum reacts with atmospheric moisture
to form aluminum oxide and hydrogen gas bubbles
which lead to voids in castings. Among the compounds,
which have been used for removing the hydrogen are
chlorine gas, aluminum chloride mixed with other
chlorides and hexachloroethane. Hexachloroethane is
currently in use by a few foundries in the US (Strieter,
1998). Westberg and Selden (1994) and Westberg et al.
(1997) have studied the products of aluminum degassing
with hexachloroethane. They found a variety of hydro-
carbons along with the expected HCl and small amounts
of a series of chloro-organics, including HCB. They re-
ported an HCB yield of 4300 lg/g hexachloroethane
used. If their estimate of global hexachloroethane use,
3,500,000 kg/yr, is correct, then it could lead to global
HCB emissions of 15,050 kg/yr. Since the o€ gases
contain a variety of materials, the emissions are usually
treated, which is expected to remove a portion of the
HCB. Aittola et al. (1996) report a 54% reduction in
HCB emissions concentration from an aluminum sec-
ondary smelter by a baghouse ®lter.
Tables 1±3 assume that 80%, 50% or 0% of the HCB
is captured and not released into the environment in the
low, mean and high emission factors for aluminum
casting, respectively. The global total amount of hexa-
chloroethane used, 3,500,000 kg/yr (Westberg and Sel-
den, 1994), was allocated to the US based on the data
collected by the EPA for implementation of MACT re-
quirements under the Clean Air Act (Strieter, 1998) and
to Canada on the basis of its Gross Domestic Product
(GDP) for 1994 (United Nations, 1996) relative to that
of the US, 8.2%. In the US, the capacity of aluminum
furnaces reporting the use of hexachloroethane is 53,922
tons/yr (Strieter, 1998). Assuming a hexachloroethane
use rate of 0.12% the weight of aluminum, the lower end
of the application rates suggested for di€erent aluminum
alloys (Foseco, 1975; Scottish, 2000), US use of hexa-
chloroethane would be 58,800 kg/yr. Calculated poten-
tial HCB emissions are shown in Tables 1±3.
Oehme et al. (1989) reported the emission of about 7
kg/week (350 kg/yr) HCB along with other chlorinated
compounds from the magnesium and nickel plants at
Porsgrunn, Norway. Emissions of PCDD/Fs were to
have been reduced from these plants since this 1989 re-
port; however no information on current HCB emissions
in Norwegian Mg/Ni plants was found. Because of the
variety of processes used for magnesium and other
metals, these emissions have not been extrapolated to
the rest of the world.
Cohen et al. (1995) assigned HCB emission factors,
with a range of 2 orders of magnitude, to secondary
Table 3

174
Global hexachlorobenzene emissions summary, including the US and Canada, mid 1990s, all quantities in kg/year
HCB concentration Annual pesticide usage (kg/yr) HCB emissions (kg/yr)
Products containing HCB

Pesticides
DCPA (dacthal) 1000 ppm 946,601 947
Atrazine 1 ppm 53,168,653 53
Simazine 1 ppm 5,703,261 6
Picloram 50 ppm 1,194,850 60
PCNB 500 and 1000 ppm 1,007,298 694
Chlorothalonil 40 and 100 ppm 15,342,541 1224
Lindane 50 ppm 3,936,045 197
Technical HCH 100 ppm 29,102,000 2910
Pentachlorophenol (used as 100 ppm 3,500,000 350

R.E. Bailey / Chemosphere 43 (2001) 167±182

molluscicide in water)
Pentachlorophenol (used in 50 & 100 ppm 6,000,000 23 (see text)
wood treatment) (see text)
Pesticides sub total 6463
Chlorinated solvent usage 1 ppb 1,005,000,000 1
Manufacturing
US chemical manufacturing 399
Canadian chemical 0.1
manufacturing
Non-North American 909
chemical manufacturing
(see text)

Low HCB Mean HCB High HCB Product Calculated HCB Calculated HCB Calculated HCB
emissions factor emissions factor emissions factor (kg/yr) emissions using emissions using emissions using
(kg HCB/kg) (kg HCB/kg) (kg HCB/kg) low factors (kg/yr) mean factors (kg/yr) high factors (kg/yr)
Metals
Aluminum casting 8.6E-04 2.2E-03 4.3E-03 HCE 3,500,000 3010 7700 15,050
Secondary copper 3.9E-09 3.9E-08 3.9E-07 2,673,000,000 10 104 1042
Magnesium 350 350 350
Metals sub totals 3370 8154 16,442
Combustion
Municipal 2.9E-09 2.9E-08 2.9E-07 194,000,000,000 563 5626 56,260
Hazardous wastes 1.9E-09 1.9E-08 1.9E-07 5,000,000,000 10 95 950
 R.E. Bailey / Chemosphere 43 (2001) 167±182 175

copper recovery and scrap electric wire recovery. No

experimental data on HCB emissions from copper re-
covery processes was found. In Table 1, the HCB
emissions factors for secondary copper smelters from
Cohen et al. (1995) were applied to the US quantity of
3495

4956
858

431
704
119

67,774
91,988
secondary copper from the draft dioxin source inventory
for the US (USEPA, 1998a) 695,000,000 kg/yr. For
Table 2, the Canadian quantity of secondary copper was
taken from Cohen et al. (1995). For Table 3, the global
total of secondary copper recovery was estimated from
6777
350

496
86

43
70
12

22,703

the ratio of the US quantity of secondary copper re-

covery to the US fraction of global gross domestic
product (GDP). For this, with the US comprising 26%
of the global GDP (United Nations, 1996), the global
total of secondary copper is estimated to be
2,673,000,000 kg/yr. The draft dioxin source inventory
for the US (USEPA, 1998a) estimated dioxin emissions
from secondary lead and iron to be minor. Thus, HCB
emissions from these sources have also been assumed to
be minor and not included here.
678
35

50
9

4
7
1

11,820

5. Combustion processes
2,960,000,000

46,900,000,000
2,540,000,000
4,369,000,000,000

8,260,000,000,000
253,800,000,000

Hexachlorobenzene has been reported as a product

of incomplete combustion in many studies where chlo-
rine is present. Unfortunately, the quantitative results on
yield of HCB from combustion under di€erent condi-
tions are scattered so that it is impossible to assign
factors with much con®dence. Thus, a 100-fold range of
HCB emissions from combustion processes is used in
2.9E-07
8.0E-10
1.7E-09
1.5E-08
4.7E-08
6.0E-10

this report unless there were reasons to believe com-

bustion conditions are relatively uniform for a particular
process.
While it seems logical that the amount of HCB would
be related to the amount of chlorine plus chloride in the
fuel as well as combustion conditions, Faengmark et al.
(1993, 1994) have shown that the major e€ect on yield of
2.9E-08
8.0E-11
1.7E-10
1.5E-09
4.7E-09
6.0E-11

HCB (and other chloroaromatics) is residence time in

the postcombustion zone. Halonen et al. (1994, 1997),
Akimoto et al. (1997), and Froese and Hutzinger (1997)
suggest that heterogeneous catalytic processes may be
active in the formation of HCB and other chlorinated
benzenes. Iron and copper have both been reported to
2.9E-09
8.0E-12
1.7E-11
1.5E-10
4.7E-10
6.0E-12

catalyze the formation of HCB in combustion. Halonen

et al. (1994) reported little e€ect of increasing chlorine
content of the fuel, either organic or inorganic, on the
Global total HCB emissions

yield of chlorobenzenes under their combustion condi-

tions. However, Oberg and Bergstrom. (1985) reported a
Combustion sub totals

direct relationship between HCB formation and chlorine

content with about 3  10 6 g HCB/g chlorine in a
Sewage sludge

hazardous waste incinerator.

Iron sintering

There appears to be a qualitative correlation between

Biomass
Medical

Cement

HCB and PCDD/Fs from combustion based on studies,

(kg/yr)
Coal

where both HCB and PCDD/Fs have been reported.

The recent Canadian inventory (Government of Cana-
176 R.E. Bailey / Chemosphere 43 (2001) 167±182
da, 1999) reports an HCB to PCDD/PCDF (TEQ) ratio
of 350, based on analyses at two municipal incinerators
and di€erent ratios for other types of combustion. The
e€orts in many countries to reduce emissions of PCDD/
Fs from combustion processes can be expected to reduce
HCB emissions as a result of improved combustion
conditions. Kaune et al. (1994) found that addition of
air pollution equipment to an incinerator that reduced
the PCDD/Fs by more than a factor of 10, however, had
little e€ect on the concentration of pentachlorobenzene,
and presumably HCB.
6. Municipal waste incineration
The reported measurements of HCB yield from
municipal incineration experiments cover a wide range,
as shown below. Unless the ratio of ¯ue gas to waste
was explicitly stated, it was taken as 7000 m3 /metric
ton of waste to convert from mass of HCB/m3 of ¯ue
gas to kg HCB/kg waste (Carpenter et al., 1986). A
lower ratio of ¯ue gas to waste would yield lower
factors for the emission of HCB, and could reduce the
values by 50%.
The geometric mean of these municipal incinerator
mean values is 2:9  10 8 kg HCB/kg waste with a range
of three orders of magnitude. Cohen et al. (1995), in
their summary of HCB emissions, listed a range
3:3  10 9 ±3:3  10 8 kg HCB/kg waste with a mean of
1:0  10 8 kg HCB/kg waste, without any air pollution
control equipment. Since the HCB emission factors for
open burning and incineration are insigni®cantly di€er-
ent, open burning and incineration are combined with
one factor in Tables 1±3. An uncertainty factor of 100
was assigned to the municipal combustion in the tables.
Canadian HCB emissions calculated using the mean
factor and the waste amount reported in OECD (1991)
is 42 kg/yr, fortuitously close to the 50 kg/yr reported in
the Canadian inventory (Government of Canada, 1999).
Incineration of municipal waste in Ôhigh tech incin-
eratorsÕ is largely con®ned to the OECD (Organization
for Economic Cooperation and Development) countries.
The volume of municipal waste incinerated during the
late 1980s in the OECD countries, 75,000,000,000 kg, is
from OECD (1991) and represents about 18% of the
Authors Range of HCB (kg HCB/kg waste)
8 6
Samuelsson and Lindskog (1983) 9 ´ 10 ±1.7 ´ 10
Oberg and Bergstrom (1985) 2.9 ´ 10 10 ±2.5 ´ 10 8
Oberg and Bergstrom (1987) 5.7 ´ 10 9 ±7.7 ´ 10 7
Tiernan et al. (1983) 2.2 ´ 10 8 ±4.6 ´ 10 6
Jay and Stieglitz (1995) 7.7 ´ 10 10
Lemieux (1997) (open burning) 3.5 ´ 10 8
municipal waste in those countries. The volume of US
municipal waste incinerated in 1995 was taken from the
draft dioxin inventory (USEPA, 1998a) and is nearly
twice the amount reported by the OECD. Domestic
waste is at least partially burned in many developing
countries in open ®res, either at the city dump or indi-
vidual trash piles. To estimate the total amount of mu-
nicipal waste outside the OECD, the municipal waste
from China, 285 kg/capita/yr (Henderson and Chang,
1996), was added to an estimated 200 kg/capita/yr for
the remainder of the world, which is consistent with the
observations of Rathje (1998). This yields an estimate of
1,039,000,000,000 kg/yr municipal waste. If it is assumed
that 10% of this is actually burned in the open, there
would be an additional 103,900,000,000 kg/yr of mu-
nicipal waste burned. The low fraction estimated by this
author to be actually burned re¯ects the fact that while
®res are often present at land®lls, there is often extensive
scavenger activity and the ®res are not raging but only
smoldering in parts of the land®ll. No data on the extent
of waste burned was found, and the percentage burned
could be di€erent.
6.1. Hazardous waste incineration
Hazardous waste is more variable than municipal
waste. It may contain higher or lower chlorine content
than municipal waste and in fact may contain a high
concentration of HCB. Extensive pollution control
equipment is usually installed on modern hazardous
waste incinerators. The amount of hazardous waste is
hard to de®ne because it is a regulatory classi®cation
and varies from country to country. Oberg and Berg-
strom (1985) reported a wide range of HCB emission
factors from hazardous waste incineration, 2:1  10 10 ±
3:6  10 8 kg HCB/kg waste, with a range of fuel chlo-
rine concentration from 0.01% to 4%. Wienecke et al.
(1995) reported very low emissions factors both for
HCB, approximately 1:2  10 11 kg HCB/kg waste, and
for other chlorinated chemicals in the ¯ue gas of a
hazardous waste incinerator. This HCB emissions factor
was not used because it is much less than reported in
other studies. Because of the ill-de®ned nature of haz-
ardous waste, Cohen et al. (1995) divided hazardous
waste into Ôgeneric hazardous wasteÕ and speci®c wastes
Geometric mean (kg HCB/kg waste)
7
5.1 ´ 10
3.6 ´ 10 9
9.1 ´ 10 8
1.3 ´ 10 7
7.7 ´ 10 10
3.5 ´ 10 8
 R.E. Bailey / Chemosphere 43 (2001) 167±182
from production of di€erent chlorinated chemicals,
which may contain signi®cant concentrations of HCB.
Because much of the emissions from the HCB-contain-
ing wastes are included under manufacturing in Tables
1±3, the Cohen et al. (1995) mean HCB emissions factor
for generic hazardous waste, 7:1  10 8 kg HCB/kg
waste, was averaged with the Oberg and Bergstrom
(1985) factor to give 1:9  10 8 as the mean HCB
emissions factor from generic hazardous waste for cal-
culations in this report.
The quantity of US hazardous waste, 1,500,000,000
kg/yr, was taken from the draft dioxin source inventory
(USEPA, 1998a). The global total of hazardous waste
was estimated from the ratio of the US quantity of
hazardous waste to the US fraction of the global GDP.
Thus, with the US comprising 26% of the global GDP
(United Nations, 1996), the global total of hazardous
waste is estimated to be 5,000,000,000 kg/yr. Tables 1
and 3 show the mean HCB emissions from hazardous
waste for the US and world of 25 and 95 kg/yr, re-
spectively. Canadian HCB emissions were taken from
the Canadian inventory (Government of Canada, 1999)
based on tests of most of the hazardous waste facilities
in Canada, 0.02 kg/yr, Table 2.
6.2. Medical waste incineration
The quantity of US medical waste, 770,000,000 kg/yr,
was taken from the draft dioxin source inventory
(USEPA, 1998a), and the amount of Canadian medical
waste was taken from Cohen et al. (1995). The global
total of medical waste was estimated from the ratio of
the US quantity of medical waste to the US fraction of
global GDP. Thus, with the US comprising 26% of the
global GDP (United Nations, 1996), the global total of
medical waste is estimated to be 14,310,000,000 kg/yr. In
the absence of any speci®c experimental information on
the emissions of HCB from medical waste incinerators,
the same emissions factor as for municipal waste was
used in Tables 1±3. The Canadian inventory (Govern-
ment of Canada, 1999) reports a total of 7 g HCB/yr
from hospital incinerators implying a lower emission
factor than used in Tables 1±3.
6.3. Coal combustion
Utilities normally are operated under good com-
bustion conditions because of the economic advanta-
ges. The Electric Power Research Institute (EPRI) has
tested 14 coal burning power plants for HCB with
occasional detection and average values less than the
detection limit. Di€erent studies used di€erent detec-
tion limits. If the most sensitive detection limit is used
as the concentration, then the factor is 1:3  10 11 kg
177
HCB/kg coal. The US HCB inventory (USEPA, 1998c)
treated the data di€erently, using the highest detection
limit and concluded utilities are major emitters of
HCB. Ontario Hydro tested three coal-®red facilities
with no HCB detected. Oberg and Bergstrom (1985)
have the only laboratory experimental factor found for
HCB emissions from coal combustion, 4:9  10 10 kg
HCB/kg coal, which is used here as representative of
small-scale coal combustion. Globally, the total
amount of coal burned is 4,369,000,000,000 kg/year
(Marland and Boden, 1995) with about half in small-
scale furnaces and ®res and the remainder in large-scale
power plants. The utility emission factor was used for
Tables 1 and 2 for the US and Canada with the
Marland and Boden (1995) reported quantity of coal.
A geometric average of the laboratory and utility
emission factors, 8:0  10 11 kg HCB/kg coal, was used
in Table 3 for global emissions.
6.4. Cement production
The production of cement worldwide is a very large
industry. In the production of cement, coal and other
fuels are burned to fuse the raw materials lime, sand,
alumina, and other minerals at high temperature to form
the ÔclinkerÕ, which is ground to make the ®nished ce-
ment. Hazardous wastes are used to supplement the fuel
in some cement kilns because the controlled high tem-
perature, 1400±1510°C, destroys the waste completely
and the alkaline material traps liberated chloride. The
Canadian Portland Cement Association has sponsored
emission studies of several cement kilns. Averaging all
the emission factors, taking non-detected at the detec-
tion level, yielded an emission factor of 1:7  10 7 kg/
metric ton of clinker or 1:7  10 10 kg HCB/kg cement
(Cornelissen, 1998).
US cement production was taken from the draft di-
oxin source inventory (USEPA, 1998a) and Canadian
cement production from Cornelissen (1998). For the US,
this is calculated to lead to the emission of about 11.2 kg
HCB. On the global scale this equates to 43 kg/yr as-
suming that US cement production is about 26% of
world total, based on the US fraction of the global
GDP, and emissions corresponding to Canadian tech-
nology. In Canada, the amount of HCB calculated to be
emitted from cement production is 2.4 kg. This larger
quantity of HCB emissions for Canada was used in
Table 2 in preference to the 0.1 kg reported in the
Canadian Inventory (Government of Canada, 1999).
6.5. Iron ore sintering
Cohen et al. (1995) reported estimated emissions of
HCB from iron ore sintering plants in the US and
178 R.E. Bailey / Chemosphere 43 (2001) 167±182
Canada. Using CohenÕs emission factors and production
value for Canada, and the draft dioxin source inventory
for the US (USEPA, 1998a) the calculated emissions for
the US and Canada are listed in Tables 1 and 2. For
Table 3, US ore sintering was assumed to be 26% of the
world total, based on the US fraction of the global
GDP. This yields global HCB emissions of 70 kg HCB/
yr.
6.6. Sewage sludge incineration
The Canadian inventory (Government of Canada,
1999) reports 0.6 kg HCB/yr emitted from sewage
sludge incineration based on tests at several facilities.
Using the amount of Canadian sewage sludge from
Cohen, 131,000,000 kg and the 0.6 kg HCB emitted
gives a factor of 4:7  10 9 kg HCB/kg sludge, ap-
proximately 0.01 of the factor used by Cohen et al.
(1995). Using these factors and the amount of sewage
sludge from the draft dioxin source inventory for the
US (USEPA, 1998a) for the US, HCB emissions from
sewage sludge incineration are calculated to be 4 kg/
yr. Sewage sludge incineration is practiced primarily
in the most highly developed countries. Thus, to es-
timate global HCB emissions from this source, the US
sewage sludge quantity was multiplied by the ratio of
the GDP for Western Europe plus Japan and Aus-
tralia to the US GDP, to yield a global estimate of
2,540,000,000 kg sewage sludge incinerated per year,
which could lead to global HCB emissions of 12 kg/
yr.
6.7. Biomass burning
A great amount of biomass is burned each year.
This includes not only the wood that we think of in
North America but also the grass in savanna ®res in
the tropics and other agricultural and accidental bio-
mass burning. The quantity of biomass burning in the
US was taken from the draft dioxin source inventory
(USEPA, 1998a) for use in Table 1. Canadian biomass
burning was estimated in two parts: (a) 0.17 of the
global temperate and boreal forest and shrubland
burning based on the land surface area of Canada, and
(b) 59 million metric tons of wood burned both in-
dustrially and for residential heating. The latter quan-
tity was back calculated from information in the
Dioxins and Furans and HCB Inventory (Government
of Canada, 1998). Global biomass burned was taken
from Lobert et al. (1999).
The average chlorine content of wood is about 110
ppm (Lobert et al., 1999). Other biomass, i.e., grass and
leaves, is reported to contain many times as much
chlorine, up to 4685 ppm (Lobert et al., 1999). No ex-
perimental data on HCB emissions from burning wood
or other biomass were found. Cohen et al. (1995), re-
ported an average factor of 6:0  10 11 kg HCB/kg
wood with a range from 1:9  10 11 to 1:9  10 10 kg
HCB/kg wood. For use in Tables 1±3, the emission
factor range has been increased to 6:0  10 12 ±
6:0  10 10 kg HCB/kg wood.
6.8. Motor fuel
Because of the low chlorine content of unleaded
motor fuels and lack of HCB emissions information,
HCB emissions from motor fuel use were judged to be
insigni®cant.
7. Summary
The di€erent emissions sources reviewed in this study
have a wide range of uncertainties. Taking the mean
estimates of the various factors in Table 3, a total of
6500 kg could come from trace contamination of pesti-
cides, 9500 kg from manufacturing, 7000 kg from
combustion including 500 kg from biomass burning. All
this adds up to about 23,000 kg/yr of new HCB added to
the global environment. Canadian HCB emissions add
up to about 95 kg/yr and US HCB emissions add up to
about 2800 kg/yr. The overall uncertainty, because of
few measured emissions from most of the combustion
and manufacturing processes is substantial with a range
in global total HCB emissions of 14,000±73,000 kg/yr in
Table 3. The major uncertainties in HCB emissions are
as follows:
· HCB concentrations in pesticides in developing coun-
tries.
· Emissions from chemical process industries in devel-
oping countries.
· Emissions of HCB from combustion processes.
· Emissions from metals industries.
· HCB concentrations in soil and volatilization rate
from soil.
· HCB used or produced in military smokes.
· Processes for which no information was found and
which may emit HCB.
North American pesticides have been very well studied,
so there is a high level of con®dence in the reported
maximum HCB content and estimated potential HCB
emissions in North America. Major US chemical man-
ufacturing sites have been well regulated for some time
so that it is likely that the TRI estimated HCB emissions
for these sites are approximately correct. However, the
manufacture and use of HCB contaminated pesticides in
developing countries could be a major source of HCB in
the environment. The banning of technical HCH use in
 R.E. Bailey / Chemosphere 43 (2001) 167±182
India in January 1997 (Biegel, 1997) may have already
signi®cantly reduced HCB emissions.
Major conclusions of this review are as follows:
· HCB emissions from many processes have a large
range of uncertainty.
· No single overwhelming source of HCB was identi-
®ed.
· Pesticides in North America are not major sources of
HCB in the environment.
· Many chlorination processes in the chemicals and
metals manufacturing industries form traces of HCB.
· Most combustion processes emit traces of HCB.
· Past soil contamination by HCB used agriculturally
could be contributing to the currently observed at-
mospheric concentrations.
· North American environmental concentrations of
HCB are dropping rapidly.
HCB has very high thermodynamic stability and is
formed in small yield in a great variety of chemical re-
actions, where both chlorine and carbon are present,
especially at elevated temperatures. Thus, HCB is found
as a minor product of combustion of any carbonaceous
compound in the presence of inorganic chloride or
chloro-organic compounds. As HCB is produced as a
trace byproduct in so many chlorination and combus-
tion reactions, elimination of its production is not really
feasible. The vast majority of HCB produced as a
chemical byproduct in North America and Europe is
separated and incinerated.
The long-term trend of HCB emissions and envi-
ronmental concentrations is expected to be downward,
as observed in the 5±10% annual decreases in atmo-
spheric concentrations near the Great Lakes (Cortes et
al., 1998; Cortes, 1999). It is proposed that a signi®-
cant portion of the currently measured HCB in the
environment has been volatilized from soil and vege-
tation, the result of higher emissions and use of HCB
in the past. In addition, there are probably sources of
HCB in the developing countries, which have not been
counted in this inventory. As historical HCB volatilizes
from soil, the atmospheric concentration of HCB
would be expected to drop over a period of decades
toward an equilibrium concentration from current
atmospheric emissions. Also, the e€orts in many
countries to reduce emissions of dioxin-like compounds
from combustion processes may reduce HCB emis-
sions. At the same time, as developing countries
improve their chemical handling, HCB emissions can
be expected to decrease.
Acknowledgements
Assembly of the information in this review was
sponsored by the Chlorine Chemistry Council of the
Chemical Manufacturers Association.
179
References
Aittola, J.P., Paasivirta, J., Vattulainen, A., Sinkkonen, S., Koisti-
nen, J., Tarhanen, J., 1996. Formation of chloroaromatics at a
metal reclamation plant and eciency of stack ®lter in their
removal from emission. Chemosphere 32, 99±108.
Akimoto, Y., Nito, S., Inouye, Y., 1997. Comparative study on
formations of polychlorinated dibenzo-p-dioxins, polychlo-
rinated dibenzofurans and related compounds in a ¯uidized
bed solid waste incinerator using long term used sand and
fresh sand. Chemosphere 34, 791±799.
Axenfeld, F., Pacyna, J.M., Duiser, J., Munch, J., Veldt,
C., 1992. Test emission databases for trace elements
(As, Cd, Hg, Pb, Zn) and special organic compounds
(lindane, HCB, PCB, PAH) for air pollution modeling
in Europe. Unweltbundesamt Berlin, Report # UBA-FB
104 02 588.
Beall, M.L., 1976. Persistence of aerially applied hexachloro-
benzene on grass and soil. J. Environ. Qual. 5, 367±369.
Beck, U., 1986. Chlorobenzenes. In: Gerhartz, W. (Ed.),
UllmanÕs Encyclopedia of Industrial Chemistry, vol. A6,
p. 338.
Benazon, N., 1999. Hexachlorobenzene emissions/releases in-
ventory for Ontario 1988, 1998 and 2000, Draft Report for
Environment Canada, 17 February.
Berdowski, J., Bloos, J.J., 1997. European hexachlorobenzene
inventory prepared at TNO, Netherlands.
Biegel, W., 1997. Centre International DÕl du Lindane, personal
communication.
Bignert, A., Olsson, M., Persson, W., Jensen, S., Zakrisson, S.,
Litzen, K., Eriksson, U., Haeggberg, L., Alsberg, T., 1998.
Temporal trends of organochlorines in Northern Europe,
1967±1995. Relation to global fractionation, leakage from
sediments and international measures. Environ. Pollut. 99,
177±198.
Bishop, C.A., Weseloh, D.V., Burgess, N.M., Struger, J.,
Norstrom, R.J., Turle, R., Logan, K.A., 1992. An atlas of
contaminants in eggs of ®sh-eating colonial birds of the
Great Lakes (1970±1988). Technical Report Series No. 152,
Canadian Wildlife Service Ontario Region.
Boeckman, O.C., Haugeroed, O., Haver, E., Muerer, K., 1981.
Hexachlorobenzene and other organohalogens: results from
working with an environmental problem. Miljoevardsserien
(1981) (Organohalogener Akvat. Miljoe), 119±129 (Chem.
Abs., 96:168340).
Carpenter, C., Schweer, G., Stinnett, G., Gabel, N., 1986.
Exposure assessment for hexachlorobenzene. Prepared for
EPA, Report No. EPA 560/5-86-019.
Cohen, M., Commoner, B., Eisl, H., Bartlett, P., Dickar, A.,
Hill, C., Quigley, J., Rosenthal, J., 1995. Quantitative
estimation of the entry of dioxins, furans and hexachloro-
benzene into the Great Lakes from airborne and waterborne
sources. CNBS ± Center for the Biology of Natural Systems,
Queens College, CUNY, Flushing, New York.
Cornelissen, A., 1998. Canadian Portland Cement Association,
personal communication.
Cortes, D.R., Basu, I., Sweet, C.W., Brice, K.A., Ho€,
R.M., Hites, R.A., 1998. Temporal trends in gas-phase
concentrations of chlorinated pesticides measured at the
shores of the Great Lakes. Environ. Sci. Technol. 32,
1920±1927.
180 R.E. Bailey / Chemosphere 43 (2001) 167±182
Cortes, D.R., 1999. Indiana University, personal communica-
tion.
Durham, R.W., Oliver, B.G., 1983. History of Lake Ontario
contamination from the Niagara River by sediment radio-
dating and chlorinated hydrocarbon analysis. J. Great
Lakes Res. 9 (2), 160±168.
Estreicher, H., 1999. Covington and Burling, personal commu-
nication.
Faengmark, I., Bavel, B., Marklund, S., Stroemberg, B., Berge,
N., Rappe, C., 1993. In¯uence of combustion parameters on
the formation of polychlorinated dibenzo-p-dioxins, dib-
enzofurans, benzenes, and biphenyls and polyaromatic
hydrocarbons in a pilot incinerator. Environ. Sci. Technol.
27, 1602±1610.
Faengmark, I., Stoemberg, B., Berge, B., Rappe, C., 1994.
In¯uence of postcombustion pro®les on the formation of
PCDDs, PCDFs, PCBzs, and PCBs in a pilot incinerator.
Environ. Sci. Technol. 28, 624±629.
Fedorov, L.A., 1993. Ecological problems in Russia caused by
dioxin emissions from chemical industry. Chemosphere 27,
91±95.
Fellin, P., Barrie, L.A., Dougherty, D., Toom, D., Muir, D.,
Grift, N., Lockhart, L., Billeck, B., 1996. Air monitoring in
the arctic: results for selected persistent organic pollutants
for 1992. Environ. Toxicol. Chem. 15, 253±261.
Foseco Services, 1975. The Foseco FoundrymanÕs Handbook.
Pergamon Press, Oxford.
Franke, B., Giegrich, J., Muller, F., 1996. Persistent organic
pollutants in Germany: release inventory and abatement
options. Progress Report, German Federal Environmental
Agency, Contract F + E 10402365.
Froese, K.L., Hutzinger, O., 1997. Mechanisms of the forma-
tion of polychlorinated benzenes and phenols by heteroge-
neous reactions of C2 aliphatics. Environ. Sci. Technol. 31,
542±547.
Gianessi, L., Anderson, J.E., 1995, Pesticide use in US crop
production, National Summary Report, National Center
for Food and Agricultural Policy, February 1995.
Gilding, T.J., 1996. American Crop Protection Association,
Letter to L. Driver, USEPA. 27 November 1996.
Government of Canada, 1999. Dioxins and furans and hexa-
chlorobenzene inventory of releases. Available from the
Environment Canada home page http://www.ec.gc.ca.
Halonen, I., Tarhanen, J., Ollikainen, S., Ruokojaervi, P.,
Tuppurainen, K., Ruuskanen, J., 1994. The e€ect of
inorganic and organic chlorine on formation of highly
chlorinated organic compounds during incineration: labo-
ratory pilot study. Chemosphere 28, 2129±2138.
Halonen, I., Tuppurainen, K., Ruuskanen, J., 1997. Formation
of aromatic chlorinated compounds catalyzed by copper
and iron. Chemosphere 34, 2649±2662.
Henderson, J.P., Chang, T.Y., 1996. Solid Waste Management
in China. Available at http://www.ecowaste.com/swanabc/
papers/hend01.htm.
Ho€, R.M., Strachan, W.M.J., Sweet, C.W., Chan, C.H.,
Shackleton, M., Bidleman, T.F., Brice, K.A., Burniston,
D.A., Cussion, S., Gatz, D.F., Harlin, K., Schroeder, W.H.,
1996. Atmospheric deposition of toxic chemicals to the
Great Lakes: a review of data through 1994. Atmos.
Environ. 30, 3505±3527.
IPCS, International Programme on Chemical Safety, 1997.
Environmental Health Criteria 195, Hexachlorobenzene.
World Health Organization, Geneva.
Jaco€, F.S., Scarberry, R., Rosa, D., 1986. Source assessment
of hexachlorobenzene from the organic chemical manufac-
turing industry. In: Morris, C.R., Cabral, J.R.P. (Eds.),
Hexachlorobenzene, Proceedings of an International Sym-
posium. IARC Scienti®c Publications No.77, pp. 31±37.
Jay, K., Stieglitz, L., 1995. Identi®cation and quanti®cation of
volatile organic components in emissions of waste inciner-
ation plants. Chemosphere 30, 1249±1260.
Kaune, A., Lenoir, D., Nikolai, U., Kettrup, A., 1994.
Estimating concentrations of polychlorinated dibenzo-p-
dioxins and dibenzofurans in the stack gas of a hazardous
waste incinerator from concentrations of chlorinated benz-
enes and biphenyls. Chemosphere 29, 2083±2096.
Knutzen, J., Oehme, M., 1989. Polychlorinated dibenzofuran
and dibenzo-p-dioxin levels in organisms and sediments
from the Frierfjord, Southern NorwayTrans PCDD. Che-
mosphere 19, 1897±1909.
LaFleur, L.E., 1999. In: Octachlorostyrene and suggested
industrial sources, A report to the Great Lakes Binational
Toxics Strategy OCS Workgroup. The Council of Great
Lakes Industries. Available at www.cgli.org.
Landell Mills Market Research, 1996 and 1997, Landell Mills
agrochemical database report for Bailey Associates: Chlo-
rothalonil, chlorthal and quintozene-(PCNB), November
1996 and Picloram, atrazine and simazine, May 1997.
Lemieux, P.M., 1997. Evaluation of emissions from the open
burning of household waste in barrels, vol. 1. Technical
Report, USEPA Report EPA-600/R-97-134a.
Li, Y.-F., McMillan, A., Scholtz, M.T., 1996. Global HCH
usage with 1°  1° longitude/latitude resolution. Environ.
Sci. Technol. 30, 3525±3533.
Lobert, J.M., Keene, W.C., Logan, J.A., Yevich, R., 1999.
Global chlorine emissions from biomass burning: reactive
chlorine emissions inventory. J. Geophys. Res. 104, 8373±
8390.
Mackay, D., Bentzen, E., 1997. The role of the atmosphere in
Great Lakes contamination. Atmos. Environ. 31, 4045±
4047.
Marland, G., Boden, T.A., 1995. Global, regional and national
CO2 emissions estimates from fossil fuel burning, cement
production, and gas ¯aring: 1950±1990, Database ®le NDP-
030/R4, Oak Ridge National Laboratory in CDIAC
Numeric data package collection, data from International
Energy Agency and the UN.
McConnell, L.L., Kucklick, J.R., Bidleman, T.F., Ivanov, G.P.,
Chernyak, S.M., 1996. Air±water gas exchange of orga-
nochlorine compounds in Lake Baikal, Russia. Environ.
Sci. Technol. 30, 2975±2983.
McCulloch, A., Midgley, P., 1996. The production and global
distribution of emissions of trichloroethene, tetrachloroeth-
ene and dichloromethane over the period. Atmos. Environ.
30, 601±608.
Morris, C.R., Cabral, J.R.P., (Eds.), 1986. Hexachloroben-
zene. In: Proceedings of an International Symposium,
Executive Summary ± Industrial chemistry and indirect
exposure assessments, IARC Scienti®c Publications No.
77, xiii±xviii.
 R.E. Bailey / Chemosphere 43 (2001) 167±182
Muir, D.C.G., Wagemann, R., Hargrave, B.T., Thomas, D.J.,
Peakall, D.B., Norstrom, R.J., 1992. Arctic marine ecosys-
tem contamination. Sci. Total Environ. 122, 75±134.
Nash, R.G., Gish, T.J., 1989. Halogenated pesticide volatiliza-
tion and dissipation from soil under controlled conditions.
Chemosphere 18, 2353±2362.
Oberg, T., Bergstrom, J.G.T., 1985. Hexachlorobenzene as an
indicator of dioxin production from combustion. Chemo-
sphere 14, 1081±1086.
Oberg, T., Bergstrom, J.G.T., 1987. Emission and chlorination
pattern of PCDD/PCDF predicted from indicator param-
eters. Chemosphere 16, 1221±1230.
OECD, 1991. OECD Environmental Data Compendium 1991,
Paris.
Oehme, M., Mano, S., Bjerke, B., 1989. Formation of
polychlorinated dibenzofurans and dibenzo-p-dioxins by
production processes for magnesium and re®ned nickel.
Chemosphere 18, 1379±1389.
Oliver, B.G., Nicol, K.D., 1982. Chlorobenzenes in sediments,
water, and selected ®sh from Lakes Superior, Huron, Erie,
and Ontario. Environ. Sci. Technol. 16, 532±536.
OMAFRA (Ontario Ministry of Agriculture, Food and Rural
A€airs), 1994. Survey of Pesticide Use in Ontario, 1993.
Pearson, F.J., 1999. Zeneca Ag Products, pers. commun.
Pekarik, C., Weseloh, D.V., Barrett, G.C., Simon, M., Bishop,
C.A., Petit, K.E., 1999. An atlas of contaminants in the eggs
of ®sh eating colonial birds of the Great Lakes. Technical
Report Series No. 321, Canadian Wildlife Service.
Petit, K.E., Bishop, C.A., Weseloh, D.V., Norstrom, R.J., 1994.
An atlas of contaminants in eggs of ®sh-eating colonial
birds of the Great Lakes (1989±1992). Technical Report
Series No. 193, Canadian Wildlife Service.
Quinlivan, S.C., Ghassemi, M., Leshendok, T.V., 1977. Sourc-
es, characteristics and treatment and disposal of industrial
wastes containing hexachlorobenzene. J. Hazardous Mater.
1, 343±359.
Rampy, L.W., 1998. Chemical Manufacturers Association,
personal communication.
Rantio, T., 1996. Chlorohydrocarbons in pulp mill e‚uent and
the environment III ± persistent chlorohydrocarbon pollu-
tants. Chemosphere 32, 253±265.
Rapaport, R.A., Eisenreich, S.J., 1988. Historical atmospheric
inputs of high molecular weight chlorinated hydrocarbons
to eastern North America. Environ. Sci. Technol. 22, 931±
941.
Rathje, W.L., 1998, University of Arizona, personal commu-
nication.
Rippen, G., Frank, R., 1986. Estimation of hexachlorobenzene
pathways from the technosphere into the environment. In:
Morris, C.R., Cabral, J.R.P. (Eds.), Hexachlorobenzene:
Proceedings of an International Symposium. IARC Scien-
ti®c Publications No. 77, pp. 45±52.
Samuelsson, U., Lindskog, A., 1983. Chlorinated compounds in
emissions from municipal incineration. Chemosphere 12,
665±668.
Santos-Burgoa, C., Downs, T., 1998. Nomination Dossier:
Hexachlorobenzene to the Working Group for the Sound
Management of Chemicals.
Sasamoto, T., 1997. SDS Biotech K.K., personal communica-
tion.
181
Schae€er, D.J., Kapila, S., Meadows, J.E., Hinderberger, E.,
Wentsel, R., 1988. Chemical characterization of residues
from military HC smokepots. J. Hazardous Mater. 17, 315±
328.
Scottish Chemical Industries, 2000. Web site http://www.scot-
tish-chem.com.
Simonich, S.L., Hites, R.A., 1995. Global distribution of
persistent organochlorine compounds. Science 269, 1851±
1854.
Strieter, R.P., 1998. The Aluminum Association, personal
communication.
Theisen, J., Maulshagen, A., Fuchs, J., 1993. Organic and
inorganic substances in the copper slag kieselrot. Chemo-
sphere 26, 881±896.
Tiernan, T.O., Taylor, M.L., Garrett, J.H., VanNess, G.F.,
Solch, J.G., Deis, D.A., Wagel, D.J., 1983. Chlorodibenzo-
dioxins, chlorodibenzofurans and related compounds in the
e‚uents from combustion processes. Chemosphere 12, 595±
606.
Tobin, P., 1986. Known and potential sources of hexachloro-
benzene. In: Morris, C.R., Cabral, J.R.P. (Eds.), Hexachlo-
robenzene: Proceedings of an International Symposium.
IARC Scienti®c Publications No. 77, pp. 3±11.
Tremolada, P., Notarianni, V., Fioretti, C., Cont, M., Cantu,
A., Calamari, D., 1996. Contaminazione regionale e globale
di alcuni idrocarburi clorurati in campioni vegetali di aree
fredde. Ingegneria Ambientale XXV, 469±479.
United Nations, 1996. Statistical Yearbook, Issue no. 41.
United Nations, NY, 1996.
USEPA, 1998a. The Inventory of Sources of Dioxin in the
United States, External Review Draft. April 1998.
USEPA, 1998b. 1990 Emissions inventory of section 112(c)(6)
pollutants: polycyclic organic matter (POM), TCDD,
TCDF, PCBs, Hexachlorobenzene, mercury and alkylated
lead. Final Report, April 1998.
USEPA, 1998c. Envirofacts Warehouse, Toxics Release Inven-
tory. Available at http://www.epa.gov:9966/envirodcd/owa/
tris_query.get_list.
Vogelsang, J., 1986. Hexachlorobenzene, octachlorostyrene and
other organochlorine compounds in wastewater from in-
dustrial high-temperature processes involving chlorine. Z.
Wasser Abwasser Forsch. 19, 140±144.
Wang, M.J., Jones, K.C., 1994. Behavior and fate of chloro-
benzenes in spiked and sewage sludge-amended soil. Envi-
ron. Sci. Technol. 28, 1843±1852.
Weber, K., Goerke, H., 1996. Organochlorine compounds in
®sh o€ the Antarctic peninsula. Chemosphere 33, 377±392.
Westberg, H., Selden, A., 1994. Organochlorine compounds in
aluminum degassing with hexachloroethane. Organohalo-
gen Compounds 20, 355±358.
Westberg, H.B., Selden, A.I., Bellander, T., 1997. Emissions of
some organochlorine compounds in experimental aluminum
degassing with hexachloroethane. Appl. Occup. Environ.
Hyg. 12, 178±183.
Wienecke, J., Kruse, H., Huckfeldt, U., Eickho€, W., Wasser-
man, O., 1995. Organic compounds in the ¯ue gas of a
hazardous waste incinerator. Chemosphere 30, 907±913.
Wu, W.Z., Schramm, K.W., Henkelmann, B., Xu, Y., Yediler,
A., Kettrup, A., 1997. PCDD/Fs, PCBs, HCHs and HCB in
sediments and soils of Ya-Er Lake area in China: results on
182 R.E. Bailey / Chemosphere 43 (2001) 167±182

residual levels and correlation to the organic carbon and the (HCB) and polychlorocamphenes (toxaphene) (PCC) in
particle size. Chemosphere 34, 191±202. biological samples. Fresenius Z. Anal. Chem. 300, 387±
Zell, M., Ballschmiter, K., 1980. Baseline studies of the global 402.
pollution, II. Global occurrence of hexachlorobenzene