ARTICLE pubs.acs.org/est
Concentration and Bioaccumulation of Dechlorane Compounds in Coastal Environment of Northern China Hongliang Jia,*,† Yeqing Sun,‡ Xianjie Liu,† Meng Yang,† Degao Wang,† Hong Qi,§ Li Shen,|| Ed Sverko,^ Eric J. Reiner,|| and Yi-Fan Li*,^,†,§ †
International Joint Research Center for Persistent Toxic Substances (IJRC-PTS), Dalian Maritime University, Dalian, P. R. China Institute of Environmental Systems Biology, Dalian Maritime University, Dalian, P. R. China § IJRC-PTS, State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin, P. R. China Ontario Ministry of the Environment, Toronto, Ontario, Canada ^ Science and Technology Branch, Environment Canada, Toronto/Burlington, Ontario, Canada
)
‡
bS Supporting Information ABSTRACT: Dechloranes, including Dechlorane Plus (DP), Mirex (Dechlorane), Dechlorane 602 (Dec 602), Dechlorane 603 (Dec 603), and Dechlorane 604 (Dec 604), were determined using GC-MSD for water, sediment and oyster samples collected at 15 sampling sites near the Bohai and Huanghai Sea shore area of northern China in 2008. DP and Mirex were detected in most water, sediment, and oyster samples, which indicated widespread distribution of these two compounds. The mean concentrations in water, sediment and oyster samples, respectively, were 1.8 ng/L, 2.9 ng/g dry weight (dw) and 4.1 ng/g wet weight (ww) for total DP, and 0.29 ng/L, 0.90 ng/g dw, and 2.0 ng/g ww for Mirex. Dec 602 and Dec 603 were not detected in water but in small portions of the sediment and oyster samples, showing a low level of contamination by these two chemicals in the region. Strong and significant correlations were found between total DP and Mirex concentrations in water, sediment and oyster samples, probably suggesting similar local sources of these two chemicals. Dec 604 was not found in any samples. The biota-sediment accumulation factor (BSAF) of DP, Mirex, and Dec 602 declined along with the increase of their logarithm of octanol-water partition coefficients (log Kow), possibly indicating that compounds with lower log Kow (like Mirex and Dec 602) accumulated more readily in biota. The mean fractional abundance of syn-DP (fsyn) was 0.34 in water samples, a value lower than that in Chinese commercial mixture (0.41), while the mean fsyn for surface sediment (0.44) and oyster (0.45) samples were higher than technical values. Enrichment of syn-DP in oyster was in agreement with previously reported findings in Great Lakes fish. Enrichment of syn-DP in marine surface sediments, however, is contrary to data reported for fresh water sediments. To our knowledge this is the first report of Dec 602, Dec 603, and Dec 604 in a marine environment and also the first report of Dechloranes in marine biota.
’ INTRODUCTION Dechloranes, including Mirex (also used under the trade name Dechlorane), Dechlorane Plus (DP, C18H12Cl12; also called Dechlorane 605), Dechlorane 602 (Dec 602, C14H4Cl12O), Dechlorane 603 (Dec 603, C17H8Cl12), and Dechlorane 604 (Dec 604, C13H4Br4Cl6), were reported to have flame retardant properties.1 Mirex was developed by Hooker Chemical, now known as OxyChem. Starting in the mid-1960s, it was used as pesticide and also as flame retardant in plastics, rubber, paint, paper, and electrical goods. The nonagricultural uses of this chemical were banned in the 1970s because of toxicity2 and partially replaced by other Dechloranes, DP in particular.3 r 2011 American Chemical Society
DP exists as two stereoisomers (syn- and anti-DP) in commercial products, and has been classified as a high production volume substance by the United States Environmental Protection Agency4 but received little attention until recently. DP was first reported in air, sediment, and fish samples from the Great Lakes in 2006,5 and Dec 602, 603, and 604 were first reported in sediment and fish samples from the Great Lakes in 2010.3 DP has Received: November 4, 2010 Accepted: February 9, 2011 Revised: January 18, 2011 Published: February 25, 2011 2613
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Environmental Science & Technology since been detected in North America and China in diverse environmental matrices including air,5-7 indoor dust,8 water,9,10 sediment,3,5,9-14 and biota.3,5,9,10,14-19 Recently Wang et al.20 reported DP and other Dechloranes in water, soil, and air near a DP manufacturer in China, and high DP concentrations were found in the area. Liu and co-workers21 presented DP, Decs 602, 603, and 604 in surface soil across China, and the soil-air exchange of DP was first studied. Just recently, M€oller et al. reported DP in air and seawater sampled along an oceanic transect from Greenland to Antarctica, and the results indicated that DP is subject to long-range atmospheric transport.22 The current study investigates Dechloranes concentrations in seawater, sea sediment, and oyster along the coast of the northern Chinese sea. The objectives of this study are primarily (i) to examine the extent and potential source of contaminations, (ii) to assess the bioaccumulation of these Decloranes, and (iii) to study the differences in fractional abundances of DP isomers values among the different media in a coastal marine environment. To our knowledge this is the first report of Dec 602, Dec 603, and Dec 604 in a marine environment and also the first report of Dechloranes in marine biota.
’ EXPERIMENTAL PROCEDURES Sampling. Between October and December of 2008, water, sediment, and oyster samples were collected at 15 sites (1 industrial, 2 urban, and 12 rural) in proximity to the shore around Dalian, Northeast China. Among the 15 sampling sites, 8 were from Bohai Sea (R01-R08) and 7 were from Huanghuai Sea (the rest sampling sites). Locations of sampling sites are shown in Figure SI-1, Supporting Information (SI). All samples (water, sediment, and oyster) were packed in solvent-rinsed glass bottles with Teflon-lined caps. Surface sediment (0-5 cm) was collected using a bucket grab. An acetone rinsed bistoury was used to harvest edible parts from oyster shells and at least 15 individual samples were thus collected from each site (details can also be found in SI Table SI-1). Each water or sediment sample was composed of well-mixed five subsamples collected from different locations at each site. After collection, samples were sent to the laboratory of the International Joint Research Center for Persistent Toxic Pollutants (IJRC-PTS), Dalian Maritime University, Dalian, China, for processing and analysis. Sediment and oyster samples were stored at -20 C and l L seawater samples were mixed with 100 mL dichloromethane (DCM) for storage at 4 C until extraction. Chemical and Reagents. All solvents used were of pesticide grade purity (J.T. Baker, Phillipsburg, NJ). Silica gel (100-200 mesh) was purchased from Merck (Merck, Germany). Standards for individual anti- and syn-DP (CAS# 13560-89-9) was purchased from Wellington Laboratories (Guelph, Ontario, Canada). Dechlorane (CAS# 2385-85-5) was purchased from Cambridge Isotope Laboratories Inc. (Andover, MA). Dec 602 (95%, CAS# 31107-44-5), Dec 603 (98%, CAS# 13560-92-4), and Dec 604 (98%, CAS# 34571-16-9) were supplied by Toronto Research Chemicals Inc. Polychlorinated biphenyls 155 (CB-155) and octachloronaphthalene (OCN) purchased from Accustandard Inc. (New Haven, CT) were used as the surrogate and internal standards for all compounds. Extraction and Analyses. Samples were extracted and analyzed according to the methods established at the National Laboratory for Environmental Testing (NLET), Environment Canada. After spiking with CB 155 surrogate, water samples were
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extracted with 100 mL DCM in a separatory funnel with agitation followed by a 1 h settling time. Extraction was thrice repeated, followed by DCM collection and rotary-evaporation to 1 mL. Ten grams of sediment and 10 g anhydrous sodium sulfate were measured into a precleaned extraction thimble and spiked with a CB155 surrogate standard. After mixing, samples were Soxhlet extracted for 24 h with 100 mL mixed solvent (hexane/acetone, 1:1 v/v). Following extraction, the extract was added to a separatory funnel and washed 3 times using 98% H2SO4, which was subsequently discarded. Extracts were then rotary evaporated to 1 mL. The extraction method for oyster was similar with the additional step of gravimetric lipid determination for 10% of the extract after Soxhlet extraction. Further details can be found elsewhere.23 The 1 mL extracts were passed through a 5.5 g silica gel column after a 25 mL hexane prerinse and eluted with 40 mL of hexane/DCM mixture (1:1, v/v). The extract was rotary-evaporated to 2 mL, then solvent-exchanged into isooctane and reduced to 1 mL under nitrogen. The internal standard OCN was added to correct volume difference prior to GC-MS analysis. All samples were quantified using an Agilent 6890 GC coupled to an Agilent 5973N mass spectrometer detector (GC/MSD) equipped with a 60 m 0.25 mm 0.25 μm DB-5 MS capillary column (J&W Scientific, Folsom, CA) in selected ion monitoring (SIM) mode. The initial oven temperature was set at 90 C for 0.5 min, ramped at 25 C min-1 to 240 C, then at 2 C min-1 to 260 C, 20 C min-1 to 285 C and held for 10 min. Helium gas was used as a carrier with a rate of 1 mL/min. The injector and transfer line were set isothermally at 280 C. The MS system was operated in an electron capture negative ionization (ECNI) mode using methane as the moderating gas. Source and quadrupole temperatures were both set to 150 C. Selected ion monitoring mode was applied (m/z 438.7/436.7/401.7/403.7 for Mirex; 613.6/611.6/615.6 for Dec 602; 404 for OCN; 637.6/ 635.6/639.6 for Dec 603; 541.6/543.6/463.7 for Dec 604; 653.5/651.5/655.5 for syn- and anti-DP). Organic Matter Fraction in Sediment. Ten grams of sediment from each sample were used for organic matter fraction (fOM) determination. Sediment samples were first oven-dried at 105 C for eight hours to a constant weight. After moisture elimination, the samples were placed in a muffle furnace and fOM determined by measuring their loss after baked at 550 C for five hours. Quality Assurance/Quality Control. Surrogate standard recoveries in samples ranged from 83% to 103% (mean 95 ( 12%). All compounds were identified within (0.05 min of the calibration standard and selected mass ions. One procedural blank was included for every batch of 10 samples by spiking deionized water for water samples, clean soil (solvent extracted five times) for sediment sample, and clean sodium sulfate (after baked 7 h at 500 C) for oyster that were treated as real samples through entire procedures. No Dechloranes were found in the procedural blanks. One spike sample was included for every batch of 10 samples by spiking clean sodium sulfate with the calibration standards of DP and treated as a real sample through entire procedures. The average spike recoveries were 72 ( 12% for synDP, 76 ( 16% for anti-DP. Final sample concentrations were not surrogate recovery corrected. The instrument detection limits (IDLs) were determined by assessing the injection amount that corresponded to a signal-to-noise value of 3:1, and then transfer this amount in the unit of concentration in the corresponding medium. IDL values are listed in SI Table SI-2. 2614
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Figure 1. Concentrations of Dechloranes measured at 15 sampling sites in (a) water (ng/L), (b) sediment (ng/g dw), and (c) oyster (ng/g ww).
’ RESULTS AND DISCUSSION Dechloranes in Water, Sediment, and Oyster. Concentrations of Dechloranes in seawater, sediment, and oyster samples are presented in Figure 1 with statistics listed in Table 1. Dec 604 was not detectable in any water, sediment, and oyster samples, and thus is not shown in either Figure 1 or Table 1. While Dec
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602 and Dec 603 were not detected in all seawater samples, DP (syn- and anti-isomer) and Mirex were detected in most seawater samples. In general, seawater concentrations of DP isomers in this study were higher than those at an e-waste recycling plant in South China9 (syn-DP: 0.27 ng/L, anti-DP: 0.53 ng/L, SI Table SI-3), and much higher than those in the fresh water (mean total DP = 0.03 ng/L, SI Table SI-3) of the Songhua River, China,10 and in seawater (syn-DP: ND-0.0009 ng/L, anti-DP: ND-0.0004 ng/L, SI Table SI-3) from East Greenland Sea and in the Northern and Southern Atlantic toward Antarctica.22 A further investigation has been arranged to understand the source of this high DP level in seawater in the area. DP concentrations in sediments have been widely reported for the Great Lakes,3,11-13 as well as the Songhua River.10 Dec 602, Dec 603, Dec 604, and Mirex concentrations have also been reported in Great Lake sediments.3 These chemicals, however, have never been reported in marine sediments. In this study, DP was detected in most sediment samples, Mirex and Dec 602 were detected in half of the samples, whereas Dec 603 in only two samples (Frequency of detection is 13%, Table 1). Mirex and DP concentrations in this study were higher than those in Lake Superior, Lake Michigan, Lake Huron, and Lake Erie, but lower than those in Lake Ontario, and concentrations of DP were a factor of magnitude lower than those measured in Lake Winnipeg sediments and much higher than those in the Songhua River (SI Table SI-3). In general, Dec 602 and Dec 603 in sediment were relatively low, similar to those in sediments from Lakes Superior, Michigan, Huron, and Erie, but much lower than that in Lake Ontario3 (SI Table SI-3). Recent studies have indicated that DP can bioaccumulate in biota, for example, in lake food webs, fish, and herring gull eggs,5,11,15 as well as freshwater food webs in south China.9 Shen et al.3 reported DP, Dec 602, Dec 603, Dec 604, and Mirex in fish samples from Great Lakes. In the present study, Dechloranes were widely detected in oyster samples and frequencies of detection were from 22% to 78% (Table 1). The mean concentrations of syn-DP, anti-DP, and Mirex were very similar, 1.9, 2.2, and 2.0 ng/g ww respectively. Much lower concentrations were observed for Dec 602 and Dec 603 in oyster samples. Concentrations of these chemicals in oyster in the units of both ng/g ww and ng/g lipid can be found in SI Table SI-4. It is worthwhile to compare concentrations of Dechloranes in seawater, sediment, and oyster among samples collected in Bohai and Huanghai areas. SI Figure SI-2 depicts the results of comparison, showing that, in general, concentrations of Dechloranes in rural areas in Bohai Sea were higher than those in Huanghai Sea. This is not surprising since the Bohai Sea is half closed internal sea of China, surrounded by the City of Tianjin, and three provinces of Shangdong, Hebei, and Liaoning (SI Figure SI-1), with an average residence time of about 580 days,24 while Huanghai Sea is an open sea directly connects the Pacific Ocean. The former areas receive pollutants from many other urban centers around the Bohai Sea. Therefore, the contamination status in Bohai Sea is much severer than that in Huanghai Sea. In fact, the mean DP concentration for water at rural sites along the Bohai Sea (1.7 ng/L) was 10 times higher than that along the Huanghai Sea (0.17 ng/L). Previous studies have associated high DP air concentrations with urban and industrial regions,5,7 which holds true in the present study. As shown in SI Figure SI-2, DP concentrations in water, sediment and oyster samples are higher in urban and industrial areas than in surrounding area for the samples along 2615
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Table 1. Concentrations of Mirex, Dec 602, Dec 603, syn-DP, and anti-DP in Water (ng/L), Sediment (ng/g Dry Weight), And Oyster (ng/g Wet Weight), Fractions of Lipid (flip) or Organic Mater (fOM)(%), and Frequencies of Detection (FD) (%) sample water
sediment
flip or fOM (%)
number 15
15
mean ( SD
0.29 ( 0.16
range FD (%)
BDL- 0.60 73
a
45
Dec 602 a
BDL 0
Dec 603
syn-DP
anti-DP
fsyn
BDL
0.54 ( 0.49
1.2 ( 1.1
0.34 ( 0.099
0
BDL - 1.5 67
BDL - 3.6 80
0.20- 0.55 67
mean ( SD
5.3 ( 2.1
0.90 ( 1.2
0.11 ( 0.20
0.028 ( 0.07
1.3 ( 1.5
1.6 ( 1.4
0.44 ( 0.086
range
3.2 - 10
BDL - 4.3
BDL - 0.66
BDL - 0.28
BDL - 5.4
0.017 - 4.9
0.33 - 0.6
60
53
13
87
100
80
FD (%) oyster
mirex
mean ( SD
2.0 ( 0.76
2.0 ( 2.1
0.21 ( 0.74
0.12 ( 0.547
1.9 ( 2.2
2.2 ( 2.6
0.45 ( 0.11
range FD (%)
0.97 - 4.0
BDL - 8.5 76
BDL - 5.0 62
BDL - 3.6 22
BDL - 8.1 78
BDL - 11 76
0.20 - 0.66 69
BDL: Below detection limit.
Huanghai Sea, indicating that the urban region of Dalian is a potential source of DP along the shore area of Huanghai Sea. Regression Analysis. Pearson correlation was performed for Dechlorane compounds and significant correlations were only found between total DP and Mirex concentrations in water, sediment and oyster samples (r = 0.81, p < 0.001 for water, 0.75, p < 0.001 for sediment, and r = 0.70, p < 0.005 for oyster) (SI Figure SI-3), which possibly suggest that DP and Mirex have the similar sources in the study area. While the source of DP in Dalian is still not fully understood, the source of Mirex seems clear. China started to produce Mirex in the 1960s, but production was low and ceased in 1975 due to the compound’s toxicity. It resumed however in 1997 after a serious termite disaster in southern China. Subsequent production until 2002 totalled 151 t.25 Mirex is used as a termicide for termite control in China, as is chlordane. A gridded usage inventory was produced based on the assumption of a use pattern similar to chlordane,26 and is shown in SI Figure SI-4. A total of 106 kg of Mirex was used in the city of Dalian from 1997 to 2002, possibly forming the sources of Mirex in the area. Organic matter fraction ( fOM) in sediment is an important variable that influences the concentration of hydrophobic organic compounds (HOCs). In this study, the values of fOM were measured for each sediment sample and ranged from 3.20% to 10.23%. It shows a statistically significant and strong correlation (r = 0.91, p < 0.001) between total Dechloranes and fOM in sediment (SI Figure SI-5). This finding indicates that fOM plays an important role in sediment absorption of Dechloranes. A statistically significant correlation (r = 0.64, p < 0.001) was observed between concentrations of total DP in oyster and oyster sample lipid content (flip) (n = 45) and a less significant relationship (r = 0.44, p < 0.01) was observed between Mirex concentrations and lipid content (SI Figure SI-6). No significant correlation between Dec 602, Dec 603 in oyster and lipid content was found, probably due to the relatively low concentrations of Dec 602 and Dec 603. Bioaccumulation Indication. The biota-sediment accumulation factor (BSAF) has been suggested as a simple approach to the prediction and estimation of the bioaccumulation potential of HOCs in aquatic biota.27,28 BSAF is based on equilibrium partitioning, which assumes that HOCs partition between the carbon pools of biotic tissue lipids and sediment organic carbon. This approach also assumes that there is no chemical transformation, mass transfer resistance, differential biotic uptake or
Figure 2. Box-Plot distributions of BSAFs depended on compounds.
depuration.28 Under these conditions, bioaccumulation can be assessed using the BSAF which is defined as BSAF ¼ ðCb =flip Þ=ðCs =fOM Þ
ð1Þ
where Cb is the biota HOC concentration (ng/g ww), flip is the organism lipid content, Cs is the sediment HOC concentration (ng/g dw), and fOM is the sediment organic carbon content. A theoretical BSAF value of 1.7 has been estimated based on partitioning of nonionic organic compounds between tissue lipids and sediment organic carbon. A value of less than 1.7 indicates less partitioning of an organic compound into lipids than predicted and a value greater than 1.7 indicates more uptake of the pollutant.29,30 In the present study, BSAFs were calculated for a total of 64 paired sediment and oyster samples that have both measurement values above IDL (15 for Dec 602, 26 for total DP and 23 for Mirex, SI Table SI-5). Figure 2 describes the range, mean, and median of the BSAF values for total DP, Dec 602, and Mirex depending on compounds. Individual compound BSAF values (mean and range in parentheses) are in the order: Mirex (9.1, 2.3-23) > Dec 602 (5.6, 2.1-12) > DP (4.6, 1.0-7.9). This sequence is contrary to the order of logarithm of octanol-water partition coefficients (log Kow), which is DP (11.3) > Dec 602 (8.05) > Mirex (7.01)3 and indicates that chemicals with higher log Kow are likely to be retained in sediment and that Mirex and Dec 602 have a higher accumulation potential in biota than DP.3 Interestingly, this trend is consistent with that found in PBDEs31 and PAHs.32 Fractional Abundances of DP Isomers. The stereoisomer ratios of DP can be described by the fractional abundance 2616
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and sediment in Harbin, a city in Northeast China. DP was detected in all media except water. The lower fsyn was also found in soil and sediment than in air. This result is in agreement to the depletion of syn-DP relative to anti-DP isomer in sediment samples from North America.13 It is interesting to note that, as shown in SI Figure SI-8, fsyn values of marine sediment decline with the increase in fsyn values of seawater at sampling sites. At this point, very little information exists on the transport and exchange of DP in water and sediment, and whether this finding is a reflection of the different transport and biodegradation process of DP isomers is still unclear. Further research is needed to investigate the physical and chemical properties of DP stereoisomers to obtain a full understanding of their behavior in the environment.
’ ASSOCIATED CONTENT Figure 3. fsyn values in water, sediment, and oyster samples as a function of total DP concentration.
given by13 fsyn ¼ ð½syn - DP þ ½anti - DPÞ
ð2Þ
Several previous studies have reported fsyn values of technical DP: 0.20,33 0.20-0.25,5 0.25,12,34 0.28,3 0.34,11 and 0.36.13 Recently Wang et al. measured fsyn in technical DP produced in China, and the value of 0.41 was found, which was higher than all reported fsyn values of technical DP.20 The fsyn values were calculated using eq 2 for water, sediment, and oyster samples in our study, and the mean values are shown in Table 1 and Figure 3 (The fsyn values for water, sediment, and oyster samples at each site are given in SI Figure SI-7) . The mean values of fsyn were 0.34 ( 0.10, 0.44 ( 0.086, and 0.45 ( 0.11 for water, sediment, and oyster samples respectively. Mean fsyn in surface seawater is significantly lower (p < 0.05) than the value of Chinese technical DP and similar to values found in Chinese air (0.34).7 An extraordinarily high fsyn value (0.55) in water samples of relatively low DP concentration (0.35 ng/L) was observed at R06 sampling sites. Values of fsyn higher than that of technical mixtures were observed in sea sediment and oyster samples, indicating an enrichment of syn-DP in these two matrices. Similar pattern was also found in fish in Great Lakes water.3,5 Fresh water and sediment fsyn data were usually lower than that found in technical DP.10 Values of fsyn higher than that of technical mixtures were also observed in both air and seawater in Arctic and Antarctica,22 possibly indicating different mechanism that affects the depletion/enrichment of syn- and anti-DP in seawater versus fresh water, but further studies are needed to achieve a full understanding of the phenomenon. The values of fsyn in Chinese matrices measured by our IJRCPTS research group are presented in SI Table SI-6. Previous air measurements in China7 showed higher fsyn values (0.34 ( 0.11) than in Chinese soil (0.29 ( 0.08),21 which indicated the stronger depletion of syn-DP relative to anti-DP isomer in soil than in air. A similar pattern was observed for the water and sediment samples in the Songhua River in northeastern China.10 The mean fsyn (0.31 ( 0.15) for all water samples in the urban section of the river was higher than that for sediment samples in the same section of the river (0.29 ( 0.03) and that in the rural section of the river (0.21 ( 0.04), showing higher depletion of syn-DP relative to anti-DP isomer in sediments than water. Ma et al.35 also measured DP in multimedia, including air, water, soil,
bS
Supporting Information. The location of study area and sampling sites (Figure SI-1); Comparing Dechloranes in different kind of sampling sites (Figure SI-2); Correlations between Dechloranes concentrations and relative (Figure SI-3, Figure SI-5, Figure SI-6, Figure SI-8); Gridded Chinese Mirex usage from 1997 to 2002 (Figure SI-4); Spacial distribution of fsyn values (Figure SI-7); Biological information of oyster samples (Table SI-1); IDL values of Dechloranes (Table SI-2); Summary concentrations of Dechloranes in water and sediment around world (Table SI-3); Concentrations of Dechloranes in oyster (Table SI-4); Details of field measurements that were used for BSAF value calculating (Table SI-5); fsyn values of DP in different media in China (Table SI-6). This material is available free of charge via the Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION Corresponding Author
*Phone: 86-411-8472-8489 (H.J.); 1-416-739-4892 (Y.-F.L.); fax: 86-411-8472-8489 (H.J.); 1-416-739-4288 (Y.-F.L.); e-mail:
[email protected] (H.J.);
[email protected] (Y.-F.L.).
’ ACKNOWLEDGMENT We are grateful to financial support from National Science & Technology Pillar Program of China in 2010 (2010BAC68B02), Dalian Maritime University (Supported by “the Fundamental Research Funds for the Central Universities”), and also the Science and Technology Branch, Ganjingzi District, the City of Dalian (Supported by Science & Technology Pillar Program of Dalian). Three anonymous reviewers are thanked for their valuable comments and Lindsay A.P. Smith from Environment Canada is thanked for reviewing and editing the manuscript. ’ REFERENCES (1) International Programme on Chemical Safety. Environmental Health Criteria 44, 341 Mirex. http://www.inchem.org/documents/ ehc/ehc44.htm (Accessed June 2009). (2) Kaiser, K. The rise and fall of mirex. Environ. Sci. Technol. 1978, 12, 520–528. (3) Shen, L.; Reiner, E. J.; Macpherson, K. A.; Kolic, T. M.; Sverko, E.; Helm, P. A.; Bhavsar, S. P.; Brindle, I. D.; Marvin, C. H. Identification and screening analysis of halogenated norbornene flame retardants in the laurentian Great Lakes: Dechloranes 602, 603, and 604. Environ. Sci. Technol. 2010, 44, 760–766. 2617
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