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Analysis of tetrabromobisphenol A in a product and environmental samples
Chemosphere, Vol. 31, No. 4, pp. 3085-3092, 1995
Pergamon 0045-6535(95)00167-0
Copyright © 1995 Elsevier Science Ltd Printed in Great Britain. All rights reserved 0045-6535/95 $9,50+0.00
ANALYSIS OF TETRABROMOBISPHENOL A IN A PRODUCT AND ENVIRONMENTAL SAMPLES
Ulla Sellstrrm and Bo Jansson Laboratory for Analytical Environmental Chemistry Institute of Applied Environmental Research Stockholm University, S-106 91 Stockholm, Sweden
(Received in Germany 27 April 1995; accepted 6 June 1995)
ABSTRACT
Filings from a printed circuit board were extracted and analysed for unreacted tetrabromobisphenol A (TBBPA). About 0.7/ag free TBBPA per gram circuit board were found, corresponding to about 4 tag free TBBPA per gram of TBBPA used in the circuit board. These values are probably underestimates of the true levels due to incomplete extraction.
Surficial sediments taken upstream and downstream from a plastics industry where TBBPA is used were analysed for both TBBPA and its dimethylated derivative, MeTA. The TBBPA concentration was 34 ng/g dry weight upstream of the industry and 270 ng/g dry weight downstream. The corresponding concentrations of MeTA were 24 and 1500 ng/g dry weight respectively.
TBBPA was also found in two sewage sludge samples analysed. One sample was collected from the sewage treatment plant that receives leach water from a landfill with wastes from the investigated plastics industry The other sample was collected from a sewage treatment plant where no known users of TBBPA are connected. The levels of TBBPA in these samples were similar to those found in the samples upstream from the industry.
During the analysis of a number of biological samples for lipophilic brominated substances, MeTA has been screened, but so far no MeTA has been detected.
INTRODUCTION
TBBPA (Figure 1) is the most commonly used brominated flame retardant worldwide. Over 60 000 tonnes per year of TBBPA and its derivatives are used (1). In Sweden the use of TBBPA was about 280 tonnes in 1983 (2) and in 1990, one large industry used about 405 tonnes (3). It is used mainly as a reactive flame retardant, which 3085
3086
H3C4k' j , CEI 3
B r ~ c ~ .o
T Br
T
Br
H3C~, j C H 3
B r ~ c ~
Br
H3CO T
Br
OCH 3
Br
TBBPA
Br MeTA
Figure 1. Molecular structures for tetrabromobisphenol A (TBBPA), and the dimethylated derivative of tetrabromobisphenol A (Me TA).
means that it is covalently bound to polymers. It should therefore not leak to the environment but has nevertheless been found in environmental samples. In Japan, TBBPA has been found in sediments and mussels (4,5). The concentrations were highest in Osaka Bay (22-140 lag/kg sediment on a dry weight basis), probably due to discharges from nearby industries. In Arkansas, USA, TBBPA was found in sediment, soil, on air particulates and in human hair in the vicinity of TBBPA manufacturers (6,7,8).
TBBPA is toxic to fish (9) and has a log Pow 4.5 (10) thus having the potential to bioaccumulate. The presence of TBBPA in the environment may be due to discharges from industries producing or using this compound and/or from products containing TBBPA. To study this, and the possible presence of TBBPA in the Swedish environment, a product as well as sediments near a plastics industry using TBBPA were analysed. Two sewage sludge samples were also included. TBBPA can also be methylated in the environment to form the dimethylated derivative (MeTA in Figure 1) (5). This derivative is more lipophilic than the parent compound and even more likely to bioaccumulate. MeTA was therefore analysed in biological samples investigated for other lipophilic brominated flame retardants as well as in the sediments and sludge samples.
EXPERIMENTAL SAMPLES
A printed circuit board (epoxy laminate coated with copper) was bought in a local store in Solna, Sweden. Surficial sediments (1 cm) were taken with a core sampler. The sampling sites were located approximately 2 kilometers upstream and 5 kilometers downstream from a plastics factory using TBBPA. The sediments had high organic contents. The samples taken downstream were black with a strong smell of hydrogen sulphide.
3087 Sewage sludge was obtained from a treatment plant receiving leach water from the land fill where this industry's wastes are placed. A sewage sludge sample was also obtained from a plant having no known sources of TBBPA connected to it.
CHEMICALS
Tetrabromobisphenol A, (Firemaster BP4A, Michigan Chem. Corp.), dimethylated tetrabromobisphenol A and diacetylated tetrabromobisphenol A (Alasdair Neilson, IVL, Sweden) were used as standards. Other chemicals used were dechlorane®603 (Hooker), sodium hydroxide (Elektrokemiska aktiebolaget), sodium chloride (Baker Chemicals B.V.), hydrochloric acid (Kebo AB), tetrabutyl ammonium hydrogen sulphate, TBA (Labkemi AB), sulphuric acid (BDH), diethyl ether (Labscan Ltd), 2-propanol, sodium sulphite (water free), acetic acid anhydride and pyridine (Merck). n-Hexane, acetone and 2,2,4-trimethylpentane were all glass distilled and checked for impurities before use.
TBA-sulphite reagent was prepared by dissolving tetrabutyl ammonium hydrogen sulphate (3.39 g) in water (100 ml). This solution was extracted with n-hexane (3 x 20 ml) to remove impurities and then saturated with sodium sulphite (25 g).
SAMPLE TREATMENT
A file was used to remove a subsample of the plastic from the electric circuit board. 0.5 g of filings were extracted with 10 ml of a water solution containing NaOH (0.01 M) and NaCI (0.2 M) in a glass tube that was rotated for 20 hours. The water phase was removed and acidified with 1 ml of HCl (1 M) and then extracted with 4 ml oftrimethylpentane. This extract was concentrated to 2 ml, derivatised and dechlorane was added as injection standard. A solvent blank followed the sample. Standard solutions of TBBPA were derivatised for quantitative analysis.
The water content of the sediment was determined after heating an aliquot of the centrifuged sample at 105°C overnight. The content of organic material, ignition loss, was determined after heating the dried sample at 550°C for two hours.
Extraction and clean-up of the sediment and sewage sludge samples were according to Nylund et al (I l), with some changes. The clean-up procedure for the samples is shown in Figure 2. In short it can be described as follows:
Sediment or sewage sludge corresponding to 0.5 - 1 g dry weight was centrifuged and the water phase was discarded. The sample was first extracted with 40 ml of acetone and then with a mixture of 10 ml of acetone and
3088
30 ml of n-hexane. The extracts were combined and shaken with 50 ml of a water solution containing NaOH (0.01 M) and NaCI (0.2 M). The water phase was washed with 20 ml of n-hexane and the organic phases were combined and used for analysis of neutral components, such as MeTA. The water phase was acidified with 2 ml ofHCl (IM), extracted with first 30 ml of n-hexane and then 20 ml of a mixture of n-hexane and diethyl ether (1:1). These extracts were combined to create fraction 2. Both fraction 1 and fraction 2 were concentrated to 2 ml before removal of sulphur.
Sulphur was removed by shaking the hexane solution with a mixture of 2 ml of 2-propanol and 2 ml of TBAsulphite reagent in a test tube for at least 1 minute at 50°C. 6 mi of HCl (1 M) was added and the sample was shaken for at least 1 minute. It is important that the water phase is acidic to avoid loss of TBBPA. The test tube was centrifuged and the organic phase was removed for treatment with concentrated sulphuric acid (fraction 1) or with sulphuric acid monohydrate (fraction 2). Before analysis fraction 2 was derivatised.
The sample in 2 ml of trimethylpentane was derivatised with 100 jal acetic acid anhydride and pyridine (1:1) at 60°C for 30 minutes. Alter derivatisation the organic phase was extracted with 2 ml of water to remove some contaminants. Dechlorane (500 ng) was added as injection standard and the samples were analysed with GC/MS-NCI. A solvent blank followed the sample through the entire process. Recovery experiments were performed on sediments spiked with known amounts of TBBPA and MeTA at three levels: 2.6, 11.5 and 134 ng/g dry weight for both substances.
GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS)
Samples were analysed by GC/MS using the negative ions formed at chemical ionisation (NCI). A Finnigan 4021 mass spectrometer equipped with a 4500 ion source was used. Methane (99.95 %, AGA, Stockholm) was used as reaction gas at a pressure of 0.40 torr. Ion source temperature was 150°C. The emission current was 02 mA, the electron multiplier was held at 1600 V and the electron energy was 70 eV. The mass fragments mcnitored were m/z -79 and -81 for the brominated compounds. For the injection standard (dechlorane) the ions m/z -237 and -239 were used.
A Finnigan Model 9610 gas chromatograph was used with the split-splitless injector kept at 250°C The GC column was a Hewlett Packard Ultra-2 (0.33 lam) fused silica capillary column (25 m X 02 mm i.d.) directly coupled into the ion source.
The following temperature program was used. The injection temperature was 80°C, held for I 5 minutes with the split valve closed, followed by a rapid increase of the temperature by 25°C/minute up to 220"C Thereatter the temperature was increased by 5°C/minute up to 310°C and held there for 10 minutes. The carrier gas was helium (AGA, Stockholm). Data were collected using an Incos data system.
3089
sediment ~_ extraction HCI
~~--
NaOH
...............
\'!t
+
sulphur removal sulphur removal
H2SO4
H2SO4"H20 derivatisation %J
FR 1 GC/MS-NCI
FR 2 GC/MS-NCI Figure 2. Clean-upprocedurefor sediment and sewage sludge samples.
RESULTS AND DISCUSSION
The extraction method used for the product sample probably only extracts the fraction of the acidic compounds present on the surface of the filings. No recovery experiments were made. The levels of unreacted TBBPA were determined to be at least 700 ng per gram filings with this method. According to the producer, a circuit board contains about 8 to 12 % bromine which corresponds to 14 to 20 % TBBPA. If 20 % TBBPA was used for the circuit board, this would imply that there is at least 4 lag free TBBPA per gram of TBBPA used.
The results from the analyses of sediment and sewage sludge are shown in Table 1. The concentrations are not
3090
SAMPLE
TBBPA (ng/g)
MeTA (ng/g)
ig.
d.w.
ig.
d.w.
Sediment upstream Sediment downstream
50 430
34 270
36 2400
24 1500
Sewage sludge I Sewage sludge II
100 65
56 31
< 3.7 < 3.7
< 19 < 1.9
Table 1. Concentrations of TBBPA and MeTA in sediment and sewage sludge given in ng/g ignition loss (ig.) and ng/g dry weight (d.w.).
corrected for losses during clean-up. The recoveries of TBBPA were between 79 and 86 % The recoveries of MeTA were between 18 and 72 % with the lower values found in the samples spiked with low levels of MeTA Losses due to concentrated sulphuric acid treatment is probably one explanation for the low recovery The sediments were very rich in organic material and sulphuric acid monohydrate was not sufficient for the clean-up Extraction of standard solutions of MeTA with concentrated sulphuric acid showed about 60 % recovery at five concentrations between 7.5 and 200 pg/lal.
Downstream from the factory, the concentration of TBBPA was about 10 times higher than upstream, whereas MeTA was about 70 times higher downstream than upstream.
A brominated compound with the same retention time as the derivatised TBBPA was seen in both of the sewage sludge samples. NCIMS gives mainly bromide ions and the concentrations were too low to confirm this with another ionisation technique. MeTA was not found in the sewage sludge at a detection limit of 3 7 ng/g ignition loss. Nothing was found in the blank.
These results show that a small fraction of TBBPA is unreacted in the plastic and therefore can leak out of the product. The electric circuit board analysed was of the same kind that is found in most electronic equipment TBBPA and MeTA were found in sediments both upstream and downstream of a factory using TBBPA This, and the indications of TBBPA in the sludge samples, implies that TBBPA is released to the environment.
Determination of the log P~, for MeTA was performed on a TLC plate with C~x-phase according to Renberg et ai (12). In this method, retention values for reference substances with known log Pow are used to calculate log Po~ for the unknown. The retention of MeTA on the TLC plate was outside the calibration range. A log Pow of 7.6 for MeTA was obtained by extrapolation and is therefore somewhat tentative (13), but indicates a very high ability for MeTA to bioconcentrate. The log Pow for MeTA has also been reported to be 6 4 (14).
3091 In the process of analysing biological samples for polybrominated diphenyl ethers, we also screened for the presence of MeTA. These samples include rabbit, moose, reindeer, starling, guillemot, osprey, whitefish, arctic char, herring, bream, pike, perch, trout, ringed seal and grey seal (15). So far no MeTA has been detected at a detection limit of 2 ng/g lipid weight. TBBPA was not analysed in biological samples.
ACKNOWLEDGEMENTS
We are indebted to Susanne Zakrisson for helping us determine the log Po~ for MeTA, to Lars Renberg and Cynthia de Wit for valuable discussions and to local authorities in Kristianstad, Sweden for helping with the sediment sampling. This project was supported financially by the National Swedish Chemicals Inspectorate and the Swedish Environmental Protection Agency.
REFERENCES
OECD, Brominated Flame Retardants - November 1993 - draft status report. Paris, Organisation for Economic Cooperation and Development, (1993). 2.
Jansson, E., Report to Chemicals lnspectorate, Sweden, 1983-02-15.
3.
Environment Report, 1990, Perstorp AB, Perstorp, Sweden.
4.
Watanabe, I., Kashimoto, T. and Tatsukawa, R., "Identification of the flame retardant tetrabromobisphenol A in the river sediment and the mussel collected in Osaka", Bull Environ Contain Toxicol 31, (1983), 48-52.
5.
Watanabe, I., Kashimoto, T. and Tatsukawa, R., "The flame retardant tetrabromobisphenol A and its metabolite found in river and marine sediments in Japan", Chemosphere 12, (1983), 1533-1539
6.
DeCarlo, V.J., "Studies on brominated chemicals in the environment", New York Academy of sciences, Annals, Vol 320, (1979), 678-681.
7.
Zweidinger, R.A., Cooper, S.D. and Pellizzari, ED., "Identification and quantitation ofbrominated fire retardants", ASTM Special Technical Publications 686, (1979), Meas. Org Pollut. Water Wastewater, 234-250.
8.
Zweidinger, RA., Cooper, S.D, Erickson, M.D., Michael, L.C. and Pellizzari, ED., "Sampling and analysis for semivolatile brominated organics in ambient air", ACS Symposium Series, 94, (1979), 217231.
9.
Margler, L.W., "Environmental implications of changes in the brominated chemicals industry", US.EPA 600/8-82-020, NTIS PB82-247594, 1982.
10.
Kover, F.D., Letter to Warren R Muir, US.EPA, May 3, 1978, (Revised May I 0, 1979)
11.
Nylund, K., Asplund, L., Jansson, B., Jonsson, P., Litzen K. and Sellstrom, U, "Analysis of some polyhalogenated organic pollutants in sediment and sewage sludge", Chemosphere 24, (1992), 17211730.
12.
Renberg, L.O., SundstrOm, S.G and Rosen-Olofsson, A-C., "The determination of partition coefficients
3092
of organic compounds in technical products and waste waters for the estimation of their bioaccumulation potential using reversed phase thin layer chromatography", Tox. Environ. Chem. 10, (1985), 333-349. 13.
Susanne Zakrisson, ITM, Stockholm University, personal communication.
14.
Watanabe, I. and Tatsukawa, R., "Anthropogenic brominated aromatics in the Japanese environment", Proceedings from the Workshop on Brominated Aromatic Flame Retardants, Skokloster, Sweden, 24-26 October, 1989, Swedish National Chemicals Inspectorate.
15.
SellstrOm, U., Jansson, B., Kierkegaard, A., de Wit, C., OdsjO, T. and Olsson, M, "Polybrominated diphenyl ethers (PBDE) in biological samples from the Swedish environment", Chemosphere 26, (1993), 1703-1718.
Pergamon 0045-6535(95)00167-0
Copyright © 1995 Elsevier Science Ltd Printed in Great Britain. All rights reserved 0045-6535/95 $9,50+0.00
ANALYSIS OF TETRABROMOBISPHENOL A IN A PRODUCT AND ENVIRONMENTAL SAMPLES
Ulla Sellstrrm and Bo Jansson Laboratory for Analytical Environmental Chemistry Institute of Applied Environmental Research Stockholm University, S-106 91 Stockholm, Sweden
(Received in Germany 27 April 1995; accepted 6 June 1995)
ABSTRACT
Filings from a printed circuit board were extracted and analysed for unreacted tetrabromobisphenol A (TBBPA). About 0.7/ag free TBBPA per gram circuit board were found, corresponding to about 4 tag free TBBPA per gram of TBBPA used in the circuit board. These values are probably underestimates of the true levels due to incomplete extraction.
Surficial sediments taken upstream and downstream from a plastics industry where TBBPA is used were analysed for both TBBPA and its dimethylated derivative, MeTA. The TBBPA concentration was 34 ng/g dry weight upstream of the industry and 270 ng/g dry weight downstream. The corresponding concentrations of MeTA were 24 and 1500 ng/g dry weight respectively.
TBBPA was also found in two sewage sludge samples analysed. One sample was collected from the sewage treatment plant that receives leach water from a landfill with wastes from the investigated plastics industry The other sample was collected from a sewage treatment plant where no known users of TBBPA are connected. The levels of TBBPA in these samples were similar to those found in the samples upstream from the industry.
During the analysis of a number of biological samples for lipophilic brominated substances, MeTA has been screened, but so far no MeTA has been detected.
INTRODUCTION
TBBPA (Figure 1) is the most commonly used brominated flame retardant worldwide. Over 60 000 tonnes per year of TBBPA and its derivatives are used (1). In Sweden the use of TBBPA was about 280 tonnes in 1983 (2) and in 1990, one large industry used about 405 tonnes (3). It is used mainly as a reactive flame retardant, which 3085
3086
H3C4k' j , CEI 3
B r ~ c ~ .o
T Br
T
Br
H3C~, j C H 3
B r ~ c ~
Br
H3CO T
Br
OCH 3
Br
TBBPA
Br MeTA
Figure 1. Molecular structures for tetrabromobisphenol A (TBBPA), and the dimethylated derivative of tetrabromobisphenol A (Me TA).
means that it is covalently bound to polymers. It should therefore not leak to the environment but has nevertheless been found in environmental samples. In Japan, TBBPA has been found in sediments and mussels (4,5). The concentrations were highest in Osaka Bay (22-140 lag/kg sediment on a dry weight basis), probably due to discharges from nearby industries. In Arkansas, USA, TBBPA was found in sediment, soil, on air particulates and in human hair in the vicinity of TBBPA manufacturers (6,7,8).
TBBPA is toxic to fish (9) and has a log Pow 4.5 (10) thus having the potential to bioaccumulate. The presence of TBBPA in the environment may be due to discharges from industries producing or using this compound and/or from products containing TBBPA. To study this, and the possible presence of TBBPA in the Swedish environment, a product as well as sediments near a plastics industry using TBBPA were analysed. Two sewage sludge samples were also included. TBBPA can also be methylated in the environment to form the dimethylated derivative (MeTA in Figure 1) (5). This derivative is more lipophilic than the parent compound and even more likely to bioaccumulate. MeTA was therefore analysed in biological samples investigated for other lipophilic brominated flame retardants as well as in the sediments and sludge samples.
EXPERIMENTAL SAMPLES
A printed circuit board (epoxy laminate coated with copper) was bought in a local store in Solna, Sweden. Surficial sediments (1 cm) were taken with a core sampler. The sampling sites were located approximately 2 kilometers upstream and 5 kilometers downstream from a plastics factory using TBBPA. The sediments had high organic contents. The samples taken downstream were black with a strong smell of hydrogen sulphide.
3087 Sewage sludge was obtained from a treatment plant receiving leach water from the land fill where this industry's wastes are placed. A sewage sludge sample was also obtained from a plant having no known sources of TBBPA connected to it.
CHEMICALS
Tetrabromobisphenol A, (Firemaster BP4A, Michigan Chem. Corp.), dimethylated tetrabromobisphenol A and diacetylated tetrabromobisphenol A (Alasdair Neilson, IVL, Sweden) were used as standards. Other chemicals used were dechlorane®603 (Hooker), sodium hydroxide (Elektrokemiska aktiebolaget), sodium chloride (Baker Chemicals B.V.), hydrochloric acid (Kebo AB), tetrabutyl ammonium hydrogen sulphate, TBA (Labkemi AB), sulphuric acid (BDH), diethyl ether (Labscan Ltd), 2-propanol, sodium sulphite (water free), acetic acid anhydride and pyridine (Merck). n-Hexane, acetone and 2,2,4-trimethylpentane were all glass distilled and checked for impurities before use.
TBA-sulphite reagent was prepared by dissolving tetrabutyl ammonium hydrogen sulphate (3.39 g) in water (100 ml). This solution was extracted with n-hexane (3 x 20 ml) to remove impurities and then saturated with sodium sulphite (25 g).
SAMPLE TREATMENT
A file was used to remove a subsample of the plastic from the electric circuit board. 0.5 g of filings were extracted with 10 ml of a water solution containing NaOH (0.01 M) and NaCI (0.2 M) in a glass tube that was rotated for 20 hours. The water phase was removed and acidified with 1 ml of HCl (1 M) and then extracted with 4 ml oftrimethylpentane. This extract was concentrated to 2 ml, derivatised and dechlorane was added as injection standard. A solvent blank followed the sample. Standard solutions of TBBPA were derivatised for quantitative analysis.
The water content of the sediment was determined after heating an aliquot of the centrifuged sample at 105°C overnight. The content of organic material, ignition loss, was determined after heating the dried sample at 550°C for two hours.
Extraction and clean-up of the sediment and sewage sludge samples were according to Nylund et al (I l), with some changes. The clean-up procedure for the samples is shown in Figure 2. In short it can be described as follows:
Sediment or sewage sludge corresponding to 0.5 - 1 g dry weight was centrifuged and the water phase was discarded. The sample was first extracted with 40 ml of acetone and then with a mixture of 10 ml of acetone and
3088
30 ml of n-hexane. The extracts were combined and shaken with 50 ml of a water solution containing NaOH (0.01 M) and NaCI (0.2 M). The water phase was washed with 20 ml of n-hexane and the organic phases were combined and used for analysis of neutral components, such as MeTA. The water phase was acidified with 2 ml ofHCl (IM), extracted with first 30 ml of n-hexane and then 20 ml of a mixture of n-hexane and diethyl ether (1:1). These extracts were combined to create fraction 2. Both fraction 1 and fraction 2 were concentrated to 2 ml before removal of sulphur.
Sulphur was removed by shaking the hexane solution with a mixture of 2 ml of 2-propanol and 2 ml of TBAsulphite reagent in a test tube for at least 1 minute at 50°C. 6 mi of HCl (1 M) was added and the sample was shaken for at least 1 minute. It is important that the water phase is acidic to avoid loss of TBBPA. The test tube was centrifuged and the organic phase was removed for treatment with concentrated sulphuric acid (fraction 1) or with sulphuric acid monohydrate (fraction 2). Before analysis fraction 2 was derivatised.
The sample in 2 ml of trimethylpentane was derivatised with 100 jal acetic acid anhydride and pyridine (1:1) at 60°C for 30 minutes. Alter derivatisation the organic phase was extracted with 2 ml of water to remove some contaminants. Dechlorane (500 ng) was added as injection standard and the samples were analysed with GC/MS-NCI. A solvent blank followed the sample through the entire process. Recovery experiments were performed on sediments spiked with known amounts of TBBPA and MeTA at three levels: 2.6, 11.5 and 134 ng/g dry weight for both substances.
GAS CHROMATOGRAPHY/MASS SPECTROMETRY (GC/MS)
Samples were analysed by GC/MS using the negative ions formed at chemical ionisation (NCI). A Finnigan 4021 mass spectrometer equipped with a 4500 ion source was used. Methane (99.95 %, AGA, Stockholm) was used as reaction gas at a pressure of 0.40 torr. Ion source temperature was 150°C. The emission current was 02 mA, the electron multiplier was held at 1600 V and the electron energy was 70 eV. The mass fragments mcnitored were m/z -79 and -81 for the brominated compounds. For the injection standard (dechlorane) the ions m/z -237 and -239 were used.
A Finnigan Model 9610 gas chromatograph was used with the split-splitless injector kept at 250°C The GC column was a Hewlett Packard Ultra-2 (0.33 lam) fused silica capillary column (25 m X 02 mm i.d.) directly coupled into the ion source.
The following temperature program was used. The injection temperature was 80°C, held for I 5 minutes with the split valve closed, followed by a rapid increase of the temperature by 25°C/minute up to 220"C Thereatter the temperature was increased by 5°C/minute up to 310°C and held there for 10 minutes. The carrier gas was helium (AGA, Stockholm). Data were collected using an Incos data system.
3089
sediment ~_ extraction HCI
~~--
NaOH
...............
\'!t
+
sulphur removal sulphur removal
H2SO4
H2SO4"H20 derivatisation %J
FR 1 GC/MS-NCI
FR 2 GC/MS-NCI Figure 2. Clean-upprocedurefor sediment and sewage sludge samples.
RESULTS AND DISCUSSION
The extraction method used for the product sample probably only extracts the fraction of the acidic compounds present on the surface of the filings. No recovery experiments were made. The levels of unreacted TBBPA were determined to be at least 700 ng per gram filings with this method. According to the producer, a circuit board contains about 8 to 12 % bromine which corresponds to 14 to 20 % TBBPA. If 20 % TBBPA was used for the circuit board, this would imply that there is at least 4 lag free TBBPA per gram of TBBPA used.
The results from the analyses of sediment and sewage sludge are shown in Table 1. The concentrations are not
3090
SAMPLE
TBBPA (ng/g)
MeTA (ng/g)
ig.
d.w.
ig.
d.w.
Sediment upstream Sediment downstream
50 430
34 270
36 2400
24 1500
Sewage sludge I Sewage sludge II
100 65
56 31
< 3.7 < 3.7
< 19 < 1.9
Table 1. Concentrations of TBBPA and MeTA in sediment and sewage sludge given in ng/g ignition loss (ig.) and ng/g dry weight (d.w.).
corrected for losses during clean-up. The recoveries of TBBPA were between 79 and 86 % The recoveries of MeTA were between 18 and 72 % with the lower values found in the samples spiked with low levels of MeTA Losses due to concentrated sulphuric acid treatment is probably one explanation for the low recovery The sediments were very rich in organic material and sulphuric acid monohydrate was not sufficient for the clean-up Extraction of standard solutions of MeTA with concentrated sulphuric acid showed about 60 % recovery at five concentrations between 7.5 and 200 pg/lal.
Downstream from the factory, the concentration of TBBPA was about 10 times higher than upstream, whereas MeTA was about 70 times higher downstream than upstream.
A brominated compound with the same retention time as the derivatised TBBPA was seen in both of the sewage sludge samples. NCIMS gives mainly bromide ions and the concentrations were too low to confirm this with another ionisation technique. MeTA was not found in the sewage sludge at a detection limit of 3 7 ng/g ignition loss. Nothing was found in the blank.
These results show that a small fraction of TBBPA is unreacted in the plastic and therefore can leak out of the product. The electric circuit board analysed was of the same kind that is found in most electronic equipment TBBPA and MeTA were found in sediments both upstream and downstream of a factory using TBBPA This, and the indications of TBBPA in the sludge samples, implies that TBBPA is released to the environment.
Determination of the log P~, for MeTA was performed on a TLC plate with C~x-phase according to Renberg et ai (12). In this method, retention values for reference substances with known log Pow are used to calculate log Po~ for the unknown. The retention of MeTA on the TLC plate was outside the calibration range. A log Pow of 7.6 for MeTA was obtained by extrapolation and is therefore somewhat tentative (13), but indicates a very high ability for MeTA to bioconcentrate. The log Pow for MeTA has also been reported to be 6 4 (14).
3091 In the process of analysing biological samples for polybrominated diphenyl ethers, we also screened for the presence of MeTA. These samples include rabbit, moose, reindeer, starling, guillemot, osprey, whitefish, arctic char, herring, bream, pike, perch, trout, ringed seal and grey seal (15). So far no MeTA has been detected at a detection limit of 2 ng/g lipid weight. TBBPA was not analysed in biological samples.
ACKNOWLEDGEMENTS
We are indebted to Susanne Zakrisson for helping us determine the log Po~ for MeTA, to Lars Renberg and Cynthia de Wit for valuable discussions and to local authorities in Kristianstad, Sweden for helping with the sediment sampling. This project was supported financially by the National Swedish Chemicals Inspectorate and the Swedish Environmental Protection Agency.
REFERENCES
OECD, Brominated Flame Retardants - November 1993 - draft status report. Paris, Organisation for Economic Cooperation and Development, (1993). 2.
Jansson, E., Report to Chemicals lnspectorate, Sweden, 1983-02-15.
3.
Environment Report, 1990, Perstorp AB, Perstorp, Sweden.
4.
Watanabe, I., Kashimoto, T. and Tatsukawa, R., "Identification of the flame retardant tetrabromobisphenol A in the river sediment and the mussel collected in Osaka", Bull Environ Contain Toxicol 31, (1983), 48-52.
5.
Watanabe, I., Kashimoto, T. and Tatsukawa, R., "The flame retardant tetrabromobisphenol A and its metabolite found in river and marine sediments in Japan", Chemosphere 12, (1983), 1533-1539
6.
DeCarlo, V.J., "Studies on brominated chemicals in the environment", New York Academy of sciences, Annals, Vol 320, (1979), 678-681.
7.
Zweidinger, R.A., Cooper, S.D. and Pellizzari, ED., "Identification and quantitation ofbrominated fire retardants", ASTM Special Technical Publications 686, (1979), Meas. Org Pollut. Water Wastewater, 234-250.
8.
Zweidinger, RA., Cooper, S.D, Erickson, M.D., Michael, L.C. and Pellizzari, ED., "Sampling and analysis for semivolatile brominated organics in ambient air", ACS Symposium Series, 94, (1979), 217231.
9.
Margler, L.W., "Environmental implications of changes in the brominated chemicals industry", US.EPA 600/8-82-020, NTIS PB82-247594, 1982.
10.
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