ECB – SUMMARY FACT SHEET PBT WO RKING GROUP – PBT LIST NO. 110

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## TC NES SUBGROUP ON IDENTI FICATION OF PBT AND VPVB SUBSTANCES

RESULTS OF THE EVALUATION OF THE PBT/VPVB PROPERTIES OF:

Substance name: Paraffin waxes and Hydrocarbon waxes, chloro
EC number: 264-150-0
CAS number: 63449-39-8 Molecular formula: not applicable Structural formula: not applicable

Summary of the evaluation: Paraffin waxes and hydrocarbon waxes, chloro is not considered as a PB T substance. It is not likely to meet the B criterion. The T criterion is not met as a borderline case. The substance may meet the P/vP criteria according to the available experimental data.ECB – SUMMARY FACT SHEET PBT WO RKING GROUP – PBT LIST NO. 110



## JUSTIFICATION

1 IDENTIFICATION OF THE SUBSTANC E AND PHYSICAL AND CHEMICAL PROPERTIES
Name: Paraffin waxes and Hydrocarbon waxes, chloro EC Number: 264-150-0 CAS Number: 63449-39-8 IUPAC Name: Molecular Formula: C n H 2n+2-y Cl y , where n=18 to 32 and y = ~4 to ~30 Structural Formula: Not applicable. Two st ructure examples of this multi-constituent substance are provided below.

(Environment Agency, 2006) Molecular Weight: Not applicable Synonyms: Hydrocarbon waxes, chlorinated; chloroparaffin; chlorinated paraffins; Alkanes, C 18-30 , chloro; ; long-chain chlorinated paraffins; LCCP (abbreviation). For more synonyms, see Environment Agency (2006)

1.1 Purity/impurities/additives The substance belongs to a group of long-chain chlo rinated paraffins (LCCPs) , which are also sold under other CAS numbers (e.g. CAS 85422-92-0). The substance contains chlorinated alkanes with a chain length C18 to C50. The products in liqui d form consist of C18- C20 alkyl chains with chlorine content of 40-50% w/w whereas the solid products mainly contain > C20 alkyl chains with a chlorination content of approximatley 70% w/w (source: confidential IUCL ID, company specific data sets) . According to Environment Agency ( 2006), chlorinated alkyl chains with a length of C16, C19 and C20 are expected to be present in LCCPs in a concen tration of < 1%, 0% and < 0.2%, respectively. A typical concentration of 17% (w ith a possible range of 10-20%) is reported for C17-constituents.

09.11.2007 2ECB – SUMMARY FACT SHEET PBT WO RKING GROUP – PBT LIST NO. 110

09.11.2007 3 1.2 Physico-chemical properties
Table 1 Summary of physico-chemical properties of the constituents groups. For details and references, see Environment Agency (2006).
REACH ref Annex, § Property C 18-20 liquids C >20 liquids C >20 solids Comments

V, 5.1 Physical state at 20 C and 101.3 Kpa Liquid Liquid Solid

V, 5.2 Melting / freezing point -30°C a 0°C b -30°C a 0°C b 100°C c

V, 5.3 Boiling point > 210°C (decomp.) > 210°C (decomp.) > 210°C (decomp.) V, 5.5 Vapour pressure 2.5×10 -4 Pa (at 25°C) 2.5×10 -5 Pa (at 25°C) 1.5×10 -14 Pa (at 25°C) V, 5.7 Water solubility 5 μg l -1 (at ca. 20°C) 5 μg l -1 (at ca. 20°C) 5 μg l -1 (at ca. 20°C) V, 5.8 Partition coefficient noctanol/water (log value) 9.7 10.3 17

VII, 5.19 Dissociation constant - - - a) For products with chlorine contents of 42-48% by weight. b) For products with chlorine contents of 50-52% by weight. c) For products with chlorine contents of around 70% by weight.



### 2 MANUFACTURE AND USES Eleven companies have notified the substa nce under Regulation 93/793/EEC. According to European Commission (2000), production and import volume is 10,000-50,000 tpa. Environment Agency (2006) estimated, that approximately 5,000 – 10,000 tons of l ong-chain chlorinated paraffins were used in the EU annually between 1998 and 2004. A variety of uses has been reported by Enviro nment Agency (2006) and European Commission (2000). These included, i.a., use as plasticiser in PVC, as flame reta rdant in rubber and textiles, as well as the use as plasticiser, binder and flame reta rdant in paints, coatings and sealants. LCCPs are also used in metalworking fluids and in fat liquors for leather treatment.



### 3 CLASSIFICATION AND LABELLING
The substance is not classifi ed under Directive 67/548/EEC.ECB – SUMMARY FACT SHEET PBT WO RKING GROUP – PBT LIST NO. 110

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### 4 ENVIRONMENTAL FATE PROPERTIES

4.1 Degradation (P)

4.1.1 Abiotic degradation Indirect photochemical degradati on in the atmosphere has been cal culated for several constituents from C 18 H 33 Cl 5 to C 30 H 35 Cl 27 by Environment Agency (2006). Half-lives between 30 and 112 hours were obtained for the reaction with OH-radicals using AOP v1.91 (24 h day -1 ; 5*10 5 OH - cm -3 ). Long-chain chlorinated alkylchains are not expected to undergo ab iotic degradation in aqueous media.

4.1.2 Biotic degradation No standard ready or inherent biodegradation test results are available for the substance. The available biodegradation data has been evaluate d by Environment Agency (2006). A brief overview of the reviewed information is provided below. There is evidence that some microorganisms may be capable of degrading LCCPs in the environment in acclimatised or co-metabolic systems. In a 25-day biochemical oxygen demand (BOD) test, acclimatised microorganisms showed approximately 23% biodegradation of a C 20-30 (42% chlorinated) product, comp ared with 7.5% biodegradation us ing a non-acclimatised inoculum (Madeley and Birtley, 1980). The same authors also s howed 11% mineralisation ( 14 CO 2 evolution) of centrally labelled 14 C-pentacosane (42% chlorinate d), mixed with the same C 20-30 product, by non-acclimatised microorganisms after 8 weeks. U nder anaerobic conditions, using several bacterial species isolated from soil, chlorinated C 24.5 (average) products showed up to 33% degr adation, as measured by chloride release, after 36 or 48 hour s incubation (Omori et al., 1987). The highest level of degradation was obtained for a 40.5% chlorinated substance in the presence of n-hexadecane as a co-metabolite. Other studies have shown, the potentia l for biodegradation appear ed to decrease with increasing chlorine content, although up to 15% degradation was observed for a 70% chlorinated product. Allpress and Gowland ( 1999) isolated a bacterium ( Rhodococcus sp.) from stream water that was able to utilise various chlorinated paraffins as the sole source of carbon and energy, with up to 14% degradation (measured as released chloride) after 71 days for a C >20 (42% chlorinated) product. It is not possible to deri ve rate constants for biodegradation in soil, surface water, marine water or sediment systems from the available data.

4.1.3 Other information 1
No data available.

1 For example, half life from field studies or monitoring dataECB – SUMMARY FACT SHEET PBT WO RKING GROUP – PBT LIST NO. 110

09.11.2007 5 4.1.4 Summary and discussion of persistence No standard ready or inherent biodegradation test results are av ailable for long-chain chlorinated paraffins. From the available data, long-chain chlo rinated paraffins can be considered to be not biodegradable in such systems. A bi odegradation rate constant of 0 day -1 has been used for all types of long-chain chlorinated paraffins in the ri sk assessment of Envi ronment Agency (2006).

4.2 Environmental distribution Data not reviewed for this report.

4.2.1 Adsorption

4.2.2 Volatilisation

4.2.3 Long-range environmental transport

4.3 Bioaccumulation (B)

4.3.1 Screening data LogKow values as summarised by Environment Agency (2006) in Table 1 are 9.7-17. The alkyl chain length has the most impact on the logKow -value.

4.3.2 Measured bioaccumulation data The available studies on bioconcentration and dietary accumulation cited below have been evaluated in detail by Environment Agency (2006). A bioconcentration factor (BCF) of 8 to 16 was obtained for a C 18-26 (49% chlorinated) substance after a 14-day exposure of bleak ( Alburnus alburnus ) to a concentration of 0.125 mg l -1 in brackish water (7% salinity) (Be ngtsson et al., 1979). In rainbow trout ( Oncorhynchus mykiss ), a maximum BCF of 9 (measured as parent compound) was observed after 60 days exposure to a C 22-26 (43% chlorinated) material, mixed with si milarly chlorinated n-pentacosane-13- 14 C; the corresponding BCF based on radiolabel measurem ent was 38, suggesting some metabolism within the fish tissues (Madeley and Maddock, 1983a). The measured expos ure concentrations in water were 0.97 and 4.0 mg l -1 . For a C >20 (70% chlorinated) material , mixed with 70% chlorinated n-pentacosane-13- 14 C, the maximum BCFs were 43 a nd 54, based on parent compound and radiolabel measurements, respectively (Madel ey and Maddock, 1983b). The measured exposure concentrations in water were 0.84, 1.9 and 3.8 mg l -1 . Although the exposure co ncentrations used for both of these LCCPs were above the solubili ty limit, in each case the highest BCFs were obtained at the highest exposure le vels, suggesting that adsorption of undissolved ma terial to the external surfaces of the fish may have contributed to the measured body burdens. The same two substances, with corresponding radiol abels, as used for th e rainbow trout studies above, were also tested in 60-da y exposures to marine mussels ( Mytilus edulis ) (Madeley andECB – SUMMARY FACT SHEET PBT WO RKING GROUP – PBT LIST NO. 110

09.11.2007 6 Thompson, 1983a and 1983b). The maximum BCFs obtained, by parent co mpound analysis, were 1,000 and 157 for the 40.5% and 70% chlorinated ma terials, respectively; by radiolabel the corresponding BCFs were 1158 and 341. It is possible th at the filter feeding activity of the mussels may have resulted in the ingestion of particles of undissolved test substance, which may account for the higher BCFs than observed for fish. Although the measured fish BCFs (above) were obtaine d using exposure concentr ations in excess of the water solubility of the substances, they are consistent with the results of reliable studies for short-chain and medium-chain chlorinated para ffins that were obtained by testing below the solubility limit. BCFs of 7,816 and 1,087 were determined for short-chain ( 14 C-C 11 ) and medium-chain ( 14 C-C 15 ) chlorinated paraffins, respec tively (Madeley and Maddock, 1983c; Thompson et al, 2000). Thus, based on a comparison with the available data for other chlorinated paraffins, the fish BCF for long-ch ain chlorinated paraffins would be expected to further reduce with increasing carbon chain length. This trend of declining BCF with increasing chai n length is further confirmed by QSAR estimation based on the octanol-water partition coefficient (K ow). Using a QSAR for substances of log Kow > 6 (EU Technical Guidance Document, 2003), the es timated BCFs in fish for the three types of LCCP are as follows:
C 18-20 liquid LCCP BCF = 1,096
C >20 liquid LCCP BCF = 192
C >20 solid LCCP BCF <1 There is evidence from feeding studies that LCCP s can be taken up via the diet. The accumulation of a C 18 , 49% chlorinated paraffin has been st udied in juvenile rainbow trout ( Oncorhynchus mykiss ) by Fisk et al. (2000). The uptake and accumulation of a C 20-30 , 42% chlorinated product has been investigated using both rainbow trout ( Oncorhynchus mykiss ) and mussel ( Mytilus edulis ) (Madeley and Birtley, 1980). Zitko (1974) looked at the uptake of two long-chain chlorinated paraffins in the diet of j uvenile Atlantic salmon ( Salmo salar ) over 181 days. A further feeding study with fish has been carried out by Bengtsson and Baumann Ofst ad (1982). In this experiment, bleak ( Alburnus alburnus ) were exposed to a C 18-26 , 49% chlorinated product via food for 91 days, followed by a 316-day depuration period. Dietary uptak e in rats has been re viewed in BUA (1992) and WHO (1996). In all dietary studies the concentr ations reached in the an imals were less than those in the diet. This indicates that although uptake of the subs tance can occur via the food, the levels do not increase through the food chain.

4.3.3 Other supporting information 2
No data available.

2 For example, measured co ncentrations in biotaECB – SUMMARY FACT SHEET PBT WO RKING GROUP – PBT LIST NO. 110

09.11.2007 7 4.3.4 Summary and discussion of bioaccumulation Environment Agency (2006) summarises th e data on bioaccumulation as follows:
the available bioconcentration results on long-chain chlorinated paraffins are not reliable as much of the data were obtained using exposu re concentrations well in excess of the water solubility of the substance and it is genera lly not clear if the length of the studie s was sufficient for steady state to be reached. Therefore, although these studi es show that uptake does occur, it is not possible to obtain a reliable BCF value from them. As a result, the estimated data for the fish bioconcentration factor will be considered in the assessment as a precau tionary approach. The following values will be used for the fish bioconcentration factor.

C 18-20 liquid BCF = 1,096 C >20 liquid BCF = 192 C >20 solid BCF <1
For the marine environment, there are data avai lable on the accumulation of long-chain chlorinated paraffins by mussels in salt water and fish in brackish water. These show similar patterns of uptake as found for freshwater species. Again, no reliable BCF can be deri ved from the data, and so the estimated BCFs are considered the most relevant for the marine environment as a precautionary approach. In addition to bioconcentration, the TGD also provides methods to take into account biomagnification in the assessment of secondary poisoning. The method requi res a biomagnification factor (BMF) for fish, preferably expressed on a lipid normalised ba sis. According to the TGD, an appropriate BMF for long chain ch lorinated paraffins would be 1 for all three types considered based on the fish BCF being < 2,000 and the log Kow being > 9. There is evidence from feeding st udies that the long-chai n chlorinated paraffins can be taken up via the diet, but in all cases the concentrations reached in the animals were less than those in the diet. This indicates that although uptak e of the substance can occur via the food, the levels should not increase through the food chain. These findings support the default BMF of 1 determined above. Uptake via diet or the undissolved phase may also explain some of the uptak e seen in the available bioconcentration studies.



### 5 HUMAN HEALTH HAZARD ASSESSMENT Data not reviewed for this report.



### 6 ENVIRONMENTAL HAZARD ASSESSMENT

6.1 Aquatic compartment (including sediment) The ecotoxicity data cited below have been ev aluated in more detail by Environment Agency (2006).ECB – SUMMARY FACT SHEET PBT WO RKING GROUP – PBT LIST NO. 110

09.11.2007 8 6.1.1 Toxicity test results

6.1.1.1 Fish

Acute toxicity For fish, numerous 96-hour LC 50 studies show no mortality at the highest concentrations tested, in many cases giving 96-hour LC 50 values >300 mg l -1 (see e.g., European Commission, 2000).

Long-term toxicity No mortalities or other sy mptoms of toxicity have been observe d in the long-term exposures of fish in the bioaccumulation studies. Th ese provide the following NOEC va lues, all showing no effects at concentrations well in excess of the solubility level of ≤ 0.005 mg l -1 : Species Substance Duration (days) NOEC (mg l- 1 )
Alburnus alburnus C 18-26 , 49% Cl 14 ≥ 0.125 Oncorhynchus mykiss C 22-26 , 43% Cl 60 ≥ 4 Oncorhynchus mykiss C >20 , 70% Cl 60 ≥ 3.8

6.1.1.2 Aquatic invertebrates

Acute toxicity For the marine crustacean, Nitocra spinipes , for both a C 22-26 , 42% chlorinated substance and a C 18-26 , 49% chlorinated substance, the 96-hour LC 50 s were greater than the highest concentrations tested, which were 1,000 and 10,000 mg l -1 , respectively (Tarkpea et al., 1981). Acute toxicity to Daphnia magna has been determined for a C 18-27 (60% chlorinated) product, with and without stabiliser, using both acetone and an emulsifier to pr epare the test solutions (BUA, 1992). All the 24-hour EC 50 values obtained were above 100 mg l -1

. The 48-hour EC 50 to Daphnia magna of a C 18-20 , 52% chlorinated material was found to be greater than the maximum solubility achieved as a “w ater-accomodated fractio n” (WAF) (Frank, 1993 and Frank and Steinhauser, 1994).

Long-term toxicity For invertebrates, there were no mo rtalities in the long-term mussel ( Mytilus edulis ) bioaccumulation studies available (see Section 4.3) . Effects were observed on the particle filtration rate at the higher exposure level fo r each substance but thes e effects were attributed to the physical effects of undissolved test substance. No such effects were seen at the lower exposure concentrations, which provide 60-day NOECs of 0.12 and 0.46 mg l -1 for the C 22-26 , 43% Cl and C >20 , 70% Cl substances, respectively, both in excess of solubility.
The effects of C 18-27 (60% chlorinated) on Daphnia reproduction were also determined, with a 21-day NOEC of 4.2 mg l -1 , well in excess of solubility. Inhibi tion observed above this level wereECB – SUMMARY FACT SHEET PBT WO RKING GROUP – PBT LIST NO. 110

09.11.2007 9 most probably due to the physical effects of undissolved material interfering with the organisms filter-feeding activity (BUA, 1992). Frank (1993) and Frank and Steinhauser (1994) found no effects of th e substance on survival and growth of Daphnia over 21 days at a nominal concentration of 1 mg l -1 , but reported effects of various dilutions of a WAF prepared at a loading rate of 10,000 mg l -1 . However, there are a number of reasons to doubt the validity of this result (Environm ent Agency, 2001). These include a failure of the temperature control system and a seri ous error in the statistical analysis that are not apparent from the published papers. The use of such a high loading when preparing the WAF is also likely to have preferentially dissolved any toxic impurities in the test substance that were more soluble than the LCCP. This may account for the a pparent measured concentration of approximately 0.5 mg l -1 in the filtered WAF, well in excess of LCCP solubility, since the analytical method was non-specific (adsorbable organic halogen determinati on). If these procedur al problems are ignored, but correcting the statistical analysis, th e 21-day NOEC from this study was 0.029 mg l -1

.

6.1.1.3 Algae and aquatic plants No data are available on the toxicity of LCCPs to freshwater algae. Crai gie and Hutzinger (1975) investigated the toxicity of a C >20 (50% chlorinated) product to three species of marine algae ( Dunaliella tertiole cta, Olisthodiscus sp. and Thalassiosira fluviatilis ). The substance was added to the test flasks as a solution in acetone to give nominal concentrations of 1 mg l -1 and 100 mg l -1 (in duplicate) and the acetone evaporated to dryness. A natural seawater medium was added to the flasks which were then sterilised by autoclaving a nd inoculated with the algae. No effects on algal biomass were seen in any of the exposed populations after 6 days growth at 20 o C (within 96-105% of the control values). Although no analytical m easurements of the exposur e concentrations were carried out, it is likely that, at l east at the higher nominal concentr ation, there was sufficient excess material present to ensure that the dissolved con centration was at or near the solubility limit. Therefore, although a precise NOEC cannot be determ ined, the results strong ly indicate that the substance was not toxic to these algal species.

6.1.2 Sediment organisms
No data available.

6.1.3 Other aquatic organisms Data not evaluated for this report.

6.2 Terrestrial compartment
No data available.

6.3 Atmospheric compartment
No data available.ECB – SUMMARY FACT SHEET PBT WO RKING GROUP – PBT LIST NO. 110

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### 7 PBT AND V P V B

7.1 PBT, vPvB assessment
Persistence: based on the laborat ory studies and other data available, long -chain chlorinated paraffins are considered to be unlikely readily or inherently biodegradable. Although there is some evidence that long-chain chlorina ted paraffins may biodegrade in th e environment it is considered likely that the rate will be sufficiently slow that long-chain chlorinated paraffins may meet the P/vP criteria. Bioaccumulation: although the bioconcentration of long-chain chlorinated paraffins has been investigated in laboratory studies, none of the available data are c onsidered sufficiently robust to allow a reliable BCF to be determined for long-cha in chlorinated paraffins. Based on estimates of BCF (calculated using the availa ble logKow –values), and consid eration of the known accumulation properties of structurally similar substances (sho rt and medium chain chlorinated paraffins), the BCF for long-chain chlorinated paraffins is consid ered to be < 2,000. In addition, the results of dietary uptake studies provide evid ences that no accumulation in the food chain is expected. Thus it is concluded that long-chain chlorinated paraffins are unlik ely to meet the B criterion. Toxicity: the majority of acute and chronic aquatic toxicity studies with LCCPs show that no lethal or sublethal effects are observed up to and substantially above th e solubility lim it, other than probable physical effects of undissolv ed material at concen trations two or more orders of magnitude in excess of solubility. This absence of aquatic toxicity is consistent with the evidence of low bioaccumulation potential indicating low bioavailabil ity. Only one study, on the chronic toxicity of a C 18-20 , 52% chlorinated material to Daphnia magna , reports any toxic effect s at levels potentially close to the solubility level (NOEC 0.029 mg l -1 ). Based on the experimental data, long-chain chlorinated paraffins do not meet the toxicity criteri on/are considered as not to fulfil the T criterion as a borderline case. Summary: paraffin waxes and hydrocarbon waxes, chlo ro is not likely to fulfil the B criterion. The substance may meet the P/vP criteria according to the screening data. Concerning the T criterion, the substances (esp. shorter chain constituents) may be regarded as a borderline case. It is concluded that these substances are not considered as PBT substances.

.ECB – SUMMARY FACT SHEET PBT WO RKING GROUP – PBT LIST NO. 110

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## INFORMATION ON USE AND EXPOSURE

Not relevant as the substance is not identified as a PBT.


## OTHER INFORMATION

The information and references used in this report were taken from the following sources: BUA (1992) Chlorinated Paraffins. GDCh-Advi sory Committee on Existing Chemicals of Environmental Relevance (B UA). BUA Report 93, June 1992. Environment Agency (2006) Environmental Risk Evaluation Report: long-chain chlorinated paraffins. Authors: Brooke, D.N. and Crookes, M.J. European Commission (2000). IUCLID Dataset, Paraffin waxes and Hydrocarbon waxes, chloro, CAS 63449-39-8, 18.2.2000. WHO (1996) Environmental Health Criteria 181. Chlorinated Paraffi ns. International Programme on Chemical Safety (IPCS).