Remarks on Pesticides Guidelines by John Vijgen (SBC consultant), 13 August 2005:
7.
Mirex
(b)
Production
4th line aluminum should be aluminium
Toxaphene
(b)
Production
Para 33 has been modified as the information on Strobane has been as it
was occurring 2 times and looks now as follows:
33. Especially in the United States, the definition of “technical toxaphene”
was patterned after the Hercules Incorporated product (Hercules Code
Number 3956) marketed under the trademark name of “Toxaphene.” In
recent years, Hercules Incorporated has essentially let the name of
toxaphene lapse into the public domain so that many products with similar
properties are referred to as toxaphene. Other companies used slightly
different manufacturing processes, leading to a chlorinated camphene
mixture with degrees of total chlorination and a distribution of specific
congeners that are not the same as the Hercules Incorporated product. For
instance, the toxaphene-like product commonly marketed under names like
“Stroban(e)” had a slightly lowered degree of chlorination and used slightly
different camphene or pinene feedstocks. In 1996, toxaphene-like pesticide
agents were still produced and were widely used in many countries. While it
is impossible to quantify production figures or usage rates, India and many
countries in Latin America, Eastern Europe, the former Soviet Union, and
Africa are still using various toxaphene products as pesticides (ATSDR,
1996). From here on the strobane part has been deleted!!!
After para 40 propose to included new para 41
41. Annex I lists some of the wastes that may consist of, contain or be contaminated with
HCB as industrial chemical, these include:
Y5
Wastes from the manufacture, formulation and use of wood preserving
chemicals
Y6
Wastes from the production, formulation and use of organic solvents
Y15
Wastes of an explosive nature not subject to other legislation
Y41
Halogenated organic solvents
Y43
Y44
Any congenor of polychlorinated dibenzo-furan
Any congenor of polychlorinated dibenzo-p-dioxin
43. Annex VIII describes wastes that are “characterized as hazardous under
article 1 paragraph 1(a)” although “Designation of a waste on Annex VIII does
not preclude the use of Annex III (hazard characteristics) to demonstrate that a
waste is not hazardous.”-Annex IX lists wastes that will not be wastes covered by
article 1 paragraph 1(a), unless they contain Annex I material to an extent causing
them to exhibit an Annex III characteristic- The following wastes are applicable
to pesticide POPs:
(a)
A4010
Wastes from the production, preparation and use of
pharmaceutical products but excluding such wastes
specified on list B
A4030
Wastes from the production, formulation and use of
biocides and phytopharmaceuticals, including waste
pesticides and herbicides, which are off-specification,
outdated1, or unfit for their originally intended use
A4040
Wastes from the manufacture, formulation and use of
wood-preserving chemicals2
A4080
Wastes of an explosive nature (but excluding such
wastes specified on list B)
(b)
HCB as industrial chemical:
A4070
Wastes from the production, formulation and use of
inks, dyes, pigments, paints, lacquers, varnish
excluding any such waste specified on list B (note the
related entry on list B B4010)
A4080
1
2
Pesticide POPs
Wastes of an explosive nature (but excluding such
wastes specified on list B)
“Outdated” means unused within the period recommended by the manufacturer.
This entry does not include wood treated with wood-preserving chemicals.
44. Annex VIII includes a number of wastes or waste categories that have
the potential to contain or be contaminated with pesticide POPs and HCB as
industrial chemical owing to past applications of these substances, such as:
(a)
Pesticide POPs
A4130
Waste packages and containers containing Annex I
substances in concentrations sufficient to exhibit Annex
III hazard characteristics
A4140
Wastes consisting of or containing off specification or
outdated1 chemicals corresponding to Annex I categories
and exhibiting Annex III hazard characteristics
(b)
A4110
HCB as industrial chemical:
Wastes that contain, consist of or are contaminated with
Any of the following:
- Any congenor of polychlorinated dibenzo-furan
- Any congenor of polychlorinated dibenzo-dioxin
A4130
Waste packages and containers containing Annex I
substances in concentrations sufficient to exhibit Annex
III hazard characteristics
Consistency of HCB with other Pesticides
5. Hexachlorobenzene (HCB)
Hexachlorobenzene (HCB) (CAS No.: 118-74-1) is a chlorinated monocyclic
aromatic compound in which the benzene ring is fully substituted by chlorine.
HCB is a white crystalline solid that is virtually insoluble in water, but is soluble
in ether, benzene and chloroform (NTP, 1994). It has a high octanol/water
partition coefficient, low vapour pressure, moderate Henry's Law constant and
low flammability. HCB is found almost exclusively in the gas phase (as is
predicted by its vapour pressure), with less than 5% associated with particles in all
seasons except winter, where levels are still less than 10% particle-bound (Cortes
et al, 1998).
References used:
NTP (1994) Seventh annual report on carcinogens. Summary, 1994. Research
Triangle Park North Carolina, US Department of Health and Human Services,
National Toxicology Program.
Cortes, D.R.; Basu, I.; Sweet, C.W.; Brice, K.A.; Hoff, 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.
(b)
Production
Here added some valuable information see yellow coloured text
26. The industrial production of HCB is normally by the direct chlorination of
benzene at 150-200°C over a ferric chloride catalyst. Other routes that are
believed to have been used to some extent are: (a) the chlorination of
hexachlorocyclohexane (HCH) isomers with sulphuryl chloride or
chlorosulphonic acid in the presence of a ferric chloride or other catalyst, and (b)
the distillation of heavy-end residues from perchloroethylene production (Brooks,
1984). Most of the HCB produced was of “technical grade” material for pesticide
use. This contained about 98 % of HCB. Known impurities in “technical grade”
HCB include 1,2,4,5-tetrachlorobenzene, pentachlorobenzene,
decachlorobiphenyl and the higher congeners (octachloro-) of the PCDDs and
PCDFs (IPCS, 1997). Smaller quantities, usually of purer HCB, were produced
for other industrial uses and as a chemical intermediate for the production of other
chemicals. See annex I for a more detailed list of trade names and synonyms and
section IV.D of this guideline for considerations regarding precautions to take
when using trade names in inventory exercises.
Industrial production of HCB began in 1945 in the USA. It was subsequently
produced in Canada, Mexico, Europe (Czech Republic, Germany), India and the
former USSR – and possibly elsewhere. Global production reached 1,000-2,000
Mg/a by the early 1970s and is believed to have peaked at some 10,000 Mg/a in
the late 1970s and early 1980s (Rippen, 1986).
Approximately 80% of HCB production in 1978 is believed to have been in
Europe (Rippen and Frank, 1986). Production of HCB has declined as a result of
restrictions on its use starting in the 1970s. In the US, 360000 kg/year was used
around 1960 and an estimated 300 tonnes was produced by three manufacturers in
the US in 1973 (IARC, 1979). US production in 1977 was 454 tonnes (SMOC
Mexico, 1998). HCB was produced at a maximum rate of 3500 tonnes/year in
Mexico in the 1970s, with a total of 39000 tonnes produced between 1970 and the
end of production in 1991 (SMOC Mexico, 1998). The majority of this HCB was
used within Mexico for agricultural purposes, with significant use continuing
right up until it was banned in 1992 (SMOC Mexico, 1998). Approximately 1500
tonnes of HCB were manufactured annually in Germany for the production of the
rubber auxiliary, PCTP (IPCS, 1997), but this production was discontinued in
1993. In Germany HCB was produced at rates of approximately 4000 tonnes/year
in 1974 and 2600 tonnes/year in 1976 (Rippen, 1989). No further centres of HCB
manufacture in Europe or North America have been identified. In the Czech
Republic, HCB production was terminated in Spolana Neratovice in 1968. India
produced 42612 tonnes of technical grade HCB during 1995-97 (Ministry of
Chemicals and Fertilisers, 2000). About 15390 tonnes of HCB were imported by
Pakistan during 1970-92 and 12162 tonnes was used (1979-88).
References:
SMOC Mexico (1998) Nomination Dossier for Hexachlorobenzene. Sound
Management of Chemicals (SMOC) Working Group, 6th June 1998.
www.cec.org/files/pdf/POLLUTANTS/hcbmex_en.PDF
Rippen, G. (1989) Handbuch der Umwelt-Chemikalien. 4th Supplementary
Instalment, 11/89. Landsberg/Lech.
Ministry of Chemicals and Fertilisers (MC&F) (2000), Information compiled by
Plant Protection, Adviser, Department of Agriculture & Corporation, Ministry of
Agriculture and Corporation, New Delhi.
HCB is also produced as a by-product of the manufacture of perchloroethylene
(also known as tetrachloroethylene, PER or PERC), carbon tetrachloride and, to
some extent, trichloroethylene (TRI) (Government of Canada, 1993). In some
cases, there is a potential for the production of significant quantities. Historically,
when and where HCB had commercial value, the by-product stream was isolated
as a “heavy” fraction from distillation operations and purified to yield
intentionally produced technical grade HCB for sale as a pesticide. As a result,
substantial quantities of HCB may be contained in the wastes generated through
the past manufacture of such chlorinated solvents. In the 1980s, the concentration
of HCB in distillation “heavies” was estimated to be between 5 % and 25 % by
weight (Jacoff, 1986). There are at least two identified stockpiles of over 10,000
tonnes of waste HCB – one in Australia and the other in the Ukraine. It is
reasonable to assume there are other smaller such stockpiles elsewhere, associated
with similar historical manufacturing operations. However, the present day
manufacture of chlorinated solvents only gives rise to trace quantities of HCB.
(c)
Use
Here added some valuable information see yellow coloured text
26. Historically, the major use of HCB has been as a fungicide. It was used
worldwide as an agricultural fungicide from early in the twentieth century,
particularly as a seed dressing to prevent fungal diseases of grain and other field
crops. Use in the former Soviet Union was particularly extensive and has given
rise to significant environmental concerns in the countries of that region. The
pesticide uses have now been virtually discontinued in most countries, with
reductions beginning in the 1970s and virtually complete by the early 1990s.
Emissions of “old” pesticide HCB is, however, believed to be continuing from
soils, stockpiles and wastes.
26. HCB was used extensively as a fungicide to control Bunt (Tilletia caries, T.
tritici and T. foetida) in wheat, representing a major breakthrough for this disease.
HCB was applied as a dust that contained 10-40% active ingredient (FAO/WHO, 1970),
and reported application rates range from 0.2oz of HCB per bushel of seed (US EPA,
1991) to 1-3oz of 30% HCB dust per bushel (330-990 ppm on the seed) (FAO/WHO,
1970). There is little information available about the amount of HCB that was used for
this purpose, however. HCB was used briefly as a fungicide in small quantities in
Australia and New Zealand in the 1960s and 1970s. In the 1960s in Australia, 12 million
bushels of seed wheat were treated annually with HCB dust, requiring 200 tons of
technical HCB (FAO/WHO, 1970). A smaller proportion of the total crop was probably
treated in the US, Canada, UK and some other European countries, but there was
extensive use in Turkey, Italy, Spain, Netherlands, Germany, France and some Eastern
European countries (FAO/WHO, 1970). It has been reported that a company in Spain
produced an estimated 150 tonnes of HCB annually (IARC, 1979), and this resulted in
particularly high levels being detected in that area (Grimalt et al, 1994; see Section 5.2).
Approximately 610 tonnes were used in the former USSR until HCB was banned for
agricultural purposes in 1986. HCB was used in Canada as a seed dressing for several
crops from 1948 to 1972.
References:
FAO/WHO (1970) Hexachlorobenzene Evaluation session of the Codex Committee on
Pesticide Residues (JMPR).
Grimalt, J.O.; Sunyer, J; Moreno, V.; Amaral, O.C.; Sala, M.; Rosell, A.; Anto, J.M.;
Albaiges, J. (1994) Risk excess of soft-tissue sarcoma and thyroid cancer in a community
exposed to airborne organochlorinated compound mixtures with a high
hexachlorobenzene content. Internat. J. Canc. 56, 200-203.
IARC (1979) Hexachlorobenzene. In: IARC Monographs on the Evaluation of
Carcinogenic Risk of Chemicals to Humans. Vol 20: Some Halogenated Hydrocarbons.
Lyon, International Agency for Research on Cancer. 155-178.
US EPA (1991) Applying Pesticides Correctly: A Guide for Private and Commercial
Applicators. USEPA, USDA and Extension Service, revised 1991.
26. Industrial uses, including as a chemical intermediate, represent a relatively small
proportion of cumulative global production. However, these uses have not declined as
rapidly as the pesticide applications and the relatively small remaining production is
probably mostly for non-pesticide use, particularly as a chemical intermediate.
Historically there were a number of potentially dispersive non-pesticide end-uses for
HCB. It has been used as a wood preservative, for impregnating paper, as a means of
controlling porosity in the manufacture of graphite electrodes for electrolytic processes,
as a fluxing agent in the manufacture of aluminium and in the formulation of military
pyrotechnic products and tracer bullets. These uses have been almost completely
discontinued and the only reference found to end-product use since the year 2000 is in
pyrotechnic and smoke-generating products in the Russian Federation (Shekhovtsov,
2002).
HCB has also been used as a chemical intermediate in the manufacture of other
substances. It has been used as a peptising agent in the production of nitroso- and styrene
rubbers for use in vehicle tyres (Mumma, 1975). Other uses as a chemical intermediate
have included the manufacture of certain dyestuffs (ATSDR, 2002), the production of
pentachlorophenol, the production of aromatic fluorocarbons. It is believed that these
chemical intermediate applications have ceased in most countries (Bailey, 2001) except
for China (Kunisue, 2004) and Russia
6. Heptachlor
Foot note on Page 9 should be changed as follows:
A white to brown naturally occurring earthy substance, that has a substantial ability to adsorb impurities or colouring
bodies from fats, grease, or oils. Its name originated with the textile industry, in which textile workers (or fullers) cleaned
raw wool by kneading it in a mixture of water and fine earth that adsorbed oil, dirt, and other contaminants from the
clothing
D. Identifcation and inventories
1. Identification
Under (a) last part is eliminated and a new para 67 bis has been included. Under (f)
last word deleted
67. Pesticide POPs are typically found in the following locations:
(a) Storage and mixing places for agrochemicals (stores, farm sheds,
warehouses);
(b) Warehouses and stores of distributing agencies (central warehouses,
commercial shops, Government distribution warehouses);
(c) Contaminated spraying or application equipment (normally stored in
farmers’ stores, warehouses, etc.);
(d) Contaminated empty packaging materials (originally containing
pesticide POPs, like bags, bottles, metal drums, gas cylinders, etc.);
(e) Dumpsites (buried into the ground as –unsound- disposal practice);
(f) In and around (former) manufacturing plants (in stores, in the facility
as spillage and/or contamination, open air storage sites of
contaminated chemicals)
(g) Soil and groundwater (contaminated by spills);
(h) Sediment (contaminated by spills);
(i) Commercial products containing pesticide POPs (e.g. paints,
household insect spray, mosquito coils).
67bis. HCB as industrial chemical is typically found in the following
locations:
(a) (former) manufacturing plants for chlorinated solvents
(perchloroethylene (PER or PERC), carbon tetrachloride and, to some
extent, trichloroethylene (TRI)
(b) facilities for the formulation of military pyrotechnic products
(c) (former) manufacturing plants for graphite electrodes for
electrolytic processes
(d) Commercial pyrotechnic products containing HCB
H.
Remediation of contaminated sites
At the end of 119 eliminate empty space between Guidelines and the point.
119. Poor handling and storage practices may lead to releases of pesticide
POPs at sites storing these chemicals, resulting in contamination of sites
with high levels of pesticide POPs, which may pose serious health concerns.
For information on the identification and remediation of contaminated sites,
please refer to section IV.H of the General Technical Guidelines.