Dechlorinated Analogues of Dechlorane Plus

Subscriber access provided by UNIV OF NEW ENGLAND ARMIDALE

Characterization of Natural and Affected Environments

Dechlorinated Analogues of Dechlorane Plus Allison L Brazeau, Miren Pena Abaurrea, Li Shen, Nicole Riddell, Eric J Reiner, Alan J. Lough, Robert McCrindle, and Brock Chittim Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.8b00545 • Publication Date (Web): 16 Apr 2018 Downloaded from http://pubs.acs.org on April 17, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 18

Environmental Science & Technology

1

Dechlorinated Analogues of Dechlorane Plus

2

Allison L. Brazeau,*,† Miren Pena-Abaurrea,§,ǁ,‡ Li Shen, ǁ Nicole Riddell,† Eric J. Reiner,§,ǁ Alan

3

J. Lough,§ Robert McCrindle,†,♯ Brock Chittim†

4

†

5

§

6 7 8

ǁ

Wellington Laboratories Inc., Research Division, Guelph, ON, Canada, N1G 3M5

Department of Chemistry, University of Toronto, Toronto, ON, Canada, M5S 3H6

Ontario Ministry of the Environment and Climate Change, Toronto, ON, Canada, M9P 3V6 ‡

Department of Analysis, CEPSA Research Center, Alcala de Henares, 28805, Spain ♯

Department of Chemistry, University of Guelph, Guelph, ON, Canada, N1G 2W1

9

10

Abstract

11

Degradation products of the chlorinated additive flame retardant Dechlorane Plus (DP) have

12

been discovered globally. However, the identity of many of these species remains unknown due

13

to a lack of available analytical standards, hindering the ability to quantitatively measure the

14

amounts of these compounds in the environment. In the present study, synthetic routes to

15

possible dechlorinated DP derivatives were investigated in an effort to identify the

16

environmentally significant degradation products. The methano-bridge chlorines of anti- and

17

syn-DP were selectively replaced by hydrogen atoms to give six new hydrodechlorinated DP

18

analogues. The identity and absolute configuration of all of these compounds were confirmed by

19

GC-MS, NMR spectroscopy, and x-ray diffraction studies. These compounds were observed in

ACS Paragon Plus Environment

1


Page 2 of 18

20

sediment samples from streams and rivers in relatively rural areas of Ontario and are thus

21

environmentally relevant.

22

Introduction

23

Dechlorane Plus (DP, C18H12Cl12) is the product of a Diels–Alder cycloaddition of 1,5-

24

cyclooctadiene (1,5-COD) with two equivalents of hexachlorocyclopentadiene (HCCP). It has

25

been manufactured since the 1960’s in the USA by OxyChem (Niagara Falls, NY)1 and more

26

recently (2003) in Huai’an, China by Jiangsu Anpon Electrochemical Company.2

27

synthesized as an isomeric mixture of anti- and syn-DP with an approximate 3:1 anti:syn ratio.3

28

It is distributed globally as a highly chlorinated additive flame retardant and has been

29

incorporated into materials with uses spanning a variety of industries, for example: plastic

30

roofing in construction; industrial polymers used for coating electrical wires and cables; and, in

31

hardware connectors for computers.3 DP has been frequently detected in environmental samples

32

world-wide and is a growing environmental concern.

DP is

33

Dechlorane Plus was first reported in the environment in 2006 by Hoh et al. when it was

34

detected in air, fish, and sediment samples in the Great Lakes region.1 Since this initial report,

35

the halogenated flame retardant has been reported in many other areas and matrices.3-18 A large

36

number of studies have been conducted in regions of China where electronic waste recycling is

37

prevalent. Many of these facilities use primitive methods without taking appropriate safety

38

measures or ensuring proper ventilation causing workers and local residents to be exposed to

39

DP.2,4,19 Such studies have identified the presence of DP in human serum19,20 and hair,10 indoor

40

dust,10 fish,21 breast milk,20 and even reported prenatal DP exposure by transplacental transfer.11

41

Disturbingly, DP has also been detected in air, seawater and biota in remote regions of the Artic,

42

speaking to its susceptibilities for long-range atmospheric transport.17,18,22


2

Page 3 of 18


43

Dechlorinated DP species were first discovered in the environment in 2008 by Sverko et al.23

44

Since then, DP derivatives with fewer than twelve chlorines have been observed worldwide in

45

air,24 sediments,23,25-27 sewage sludge,7,28 seawater,17 marine6,8,9,12,21,29,30 and terrestrial15,31,32

46

biota, bird eggs,15,33 human serum19,34 and hair,10,34 placental tissue,11 breast milk,20 and dust.10,35

47

The ubiquitous presence of these related compounds in environmental samples is troubling given

48

that research has shown some degradation products to be more toxic than a parent compound, as

49

is the case for the hydrodechlorinated analogues of the chlorinated pesticides aldrin and mirex.36

50

Halogenated compounds may sustain physical, chemical, biological, or photochemical

51

degradation leading to dehalogenated derivatives.37

52

dechlorinated DP derivatives in animals (marine or terrestrial) has been that they were not the

53

result of metabolism, but were likely already present in the environment prior to uptake.6,8-

54

10,15,21,29,32

55

significantly higher ratios of anti-endo-Cl11-DP (aCl11DP) in the liver compared to muscle

56

tissues, suggesting hepatic dechlorination of anti-DP.21

57

synthesized industrially by the Diels–Alder cycloaddition of HCCP with 1,5-COD, and therefore,

58

any pentachloro- or tetrachloro- impurities in the HCCP reagent could result in contamination of

59

DP with derivatives containing fewer than 12 chlorines. Photodegradation of DP has been

60

investigated in the literature by three different research groups, each using different wavelengths,

61

solvents, concentrations, and lamp power.23,35,38

62

observed in all cases but the common conclusion was that exposure to UV light does cause

63

dechlorination of DP. A hydrodechlorination decomposition route has also been confirmed to

64

occur by anaerobic digestion of DP in sewage sludge.28 Dechlorination by microbes under

65

anaerobic conditions has also been observed for other chlorinated hydrocarbons such as dieldrin,

The general concensus on finding

One exception to this trend has been reported for the northern snakehead, which had

As previously mentioned, DP is

Not surprisingly, different results were


3


Page 4 of 18

66

endrin, aldrin, isodrin, heptachlor, mirex, toxaphene, lindane, and DDT.39-46 Identification of the

67

dechlorinated species will be vital to studying, monitoring, and understanding DP’s

68

environmental fate.

69

In this context, we report on the identification and thorough characterization of six formerly

70

unknown dechlorinated analogues of DP. Our studies have allowed us to ascertain the identity of

71

dechlorinated (Cl10 and Cl11) DP compounds that were previously observed in sediment

72

samples.26

73 74

Experimental Section

75

General Synthesis

76

Compounds 1-6 (see Figure 1) were synthesized at Wellington Laboratories Inc. using

77

proprietary methods. The compounds were isolated and purified using chromatographic and

78

recrystallization techniques. Each new compound was analyzed by gas chromatography (GC)

79

combined with mass spectrometry (MS), proton (1H) nuclear magnetic resonance (NMR)

80

spectroscopy, and single crystal x-ray diffraction (XRD) studies. Crystalline materials suitable

81

for XRD were grown at room temperature by slow diffusion of methanol into concentrated

82

dichloromethane or toluene solutions of the bulk material. Reference standards aCl11DP and

83

aCl10DP were previously synthesized by Wellington Laboratories Inc. and are commercially

84

available as certified reference materials.

85

Sample Analysis

86

A purified extract of rural sediment that had shown unknown dechlorinated (Cl11 and Cl10) DP

87

species by GC×GC-TOF MS26 was chosen as a respresentative environmental sample for

88

comparison to our six synthesized dechlorinated dechloranes.


4

Page 5 of 18


89

Instrumentation

90

GC-LRMS analysis was performed on a Shimadzu GCMS-QP2010 mass spectrometer

91

equipped with a 30 m DB-5 capillary column (0.25 mm i.d. × 0.25 µm film thickness; Agilent

92

J&W GC column, Folsom, CA). A full scan range of 50 – 1000 atomic mass units (amu) was

93

used in positive ion electron ionization (EI) mode. Splitless injections of 1 µL were made with a

94

250 °C injector temperature. The initial oven temperature was set to 100 °C with a 5 min hold

95

time. The temperature was ramped at 10 °C/min to 325 °C and held for 30 min. The source and

96

quadrupole temperature were set to 230 °C and 150 °C, respectively.

97

High resolution mass spectrometry (HRMS) experiments were carried out using a Waters

98

AutoSpec PremierTM (Milford, MA) HRMS equipped with an Agilent (Wilmington, DE) 6890N

99

gas chromatograph using a 15 m DB-5HT column (0.25 mm i.d, 0.10 µm film thickness, J&W

100

Scientific, Folsom, CA). The temperature program was: 120 °C for 1 min, ramp to 240 °C at 30

101

°C/min, ramp to 275 °C at 5 °C/min, ramp to 320 °C at 40 °C/min hold for 3 min. The HRMS

102

system was operated in EI positive mode with electron energy of 40 eV and was tuned to 10 000

103

resolving power (10% valley definition).

104

1

H NMR spectra were collected on a Bruker Avance 400 or 600 MHz spectrometer (400.13 or

105

600.13 MHz for 1H). Spectra were recorded at room temperature (22 °C) in chloroform-d

106

(CDCl3) with tetramethylsilane (TMS) added as an internal reference standard (0 ppm). The

107

number of scans varied between 8 and 16 scans depending on the sample and a delay time of 1

108

second was used.

109

Single crystal x-ray diffraction data were collected on a Bruker Kappa APEX-DUO CCD

110

using Mo Kα radiation (λ = 0.71073 Å) at a temperature of 147(2) K. Structures were solved and

111

refined using SHELXL-2014/7.


5


Page 6 of 18

112

Results and Discussions

113

Structure Determination

114

The terms exo and endo will be employed to define the orientation of the hydrogens on the

115

bridging carbons of the chlorinated norbornene moieties of the DP analogues.

116

demonstrates this naming convention.

Chart 1

117 118

Chart 1. Molecular configuration of DP derivatives. Exo (x) and endo (n) positions indicated

119

on the bridging carbons.

120 121 122

X-ray Diffraction Studies

123

The solid-state structures of 1-6 (Figure 1) were unequivocally determined by XRD studies.47

124

This technique provides concrete evidence on the extent and locations of chlorine replacement

125

by hydrogen. The anti (1-3) and syn (4-6) DP analogues contain a central eight-membered ring

126

in chair- and boat-type conformations, respectively. A single hydrodechlorination in an exo

127

position yielded Cl11 compounds 1 and 4.

128

hydrodechlorinations occur on the two opposite norbornene moieties, producing Cl10 species.

129

For compounds 3 and 6 the hydrodechlorinations occurred in the x1 and x2 positions, while for 2

130

and 5 the dechlorination took place at x1 and n2 positions. This was in contrast to the Wellington

131

Laboratories Cl10 reference standard, aCl10DP, in which protonation exists within a single

Compounds 2, 3, 5 and 6 had single


6

Page 7 of 18


132

norbornene moiety on x1 and n1.48 There are no significant intermolecular interactions and bond

133

lengths and bond angles were determined as expected (see Supporting Information). Solid-state

134

structures for aCl11DP49 and aCl10DP48 have been published previously. anti

syn

exo-Cl11-DP

1

4

2

5

3

6

exo-endo-Cl10-DP

exo-exo-Cl10-DP

135

Figure 1. Solid-state structures of 1-6. Ellipsoids are drawn to 50% probability. Non-essential

136

hydrogen atoms and solvates are removed for clarity.

137

NMR Spectroscopy Analysis


7


Page 8 of 18

138

Proton NMR spectroscopy provided corroborating evidence as to the extent and location of

139

dechlorination (see ESI for detailed descriptions). According to NMR spectroscopy studies on

140

dechlorinated analogues of dieldrin,50 isodrin,51 and 1,2,3,4,7,7-hexachloro-5-endo-acetoxy-

141

bicyclo[2.2.1]-2-heptene,52 which all contain the HCCP moiety, a proton in an endo position has

142

a slightly higher chemical shift than a proton in an exo position of a chlorinated ring in an

143

otherwise identical structure. The same trend is observed in the case of dechlorinated DP

144

products (Table 1). A single resonance for exo protons was observed in the 1H NMR spectra of

145

compounds 1, 3, 4 and 6 as singlets. The singlet for compounds 1 and 4 integrate for one proton,

146

while those for 3 and 6 integrate for two.

147

Table 1. 1H NMR spectroscopy chemical shifts (ppm) of DP analogues.

148 149

Substitution Pattern Additional Compound x1 n1 x2 n2 proton(s) 1 anti-DP Cl Cl Cl Cl – § aCl11DP Cl Cl Cl H 4.28 H Cl Cl Cl 4.07 1 H Cl Cl H 4.06, 4.28 2 H Cl H Cl 4.07 3 § aCl10DP Cl Cl H H 2.45, 2.41 1 syn-DP Cl Cl Cl Cl – H Cl Cl Cl 4.12 4 H Cl Cl H 4.12, 4.41 5 H Cl H Cl 4.11 6 § Commercially available reference standards. † Peak for H4 overlaps or is equivalent with H1.

H1 2.86 2.88 2.83 2.83 2.82 2.86 3.01 2.97 2.96 3.00

Proton # in central ring H2/H2′ H3/H3′ 0.86 2.23 0.89 2.26 0.87 2.22 0.89 2.23 0.88 2.19 0.84 2.23 1.50 2.07 1.49 2.05 1.50 2.06 1.48 2.02

H4 2.86† 2.65 2.83† 2.65 2.82† 2.65 3.01† 3.04 2.79 3.00†

150 151

GC/LRMS Analysis

152

A comparison of the chromatographic behaviour of anti-DP (Cl12), aCl11DP, aCl10DP and the

153

decomposition compounds (1, 2, 3) was completed (Figure 2).

154

dechlorinated products have shorter retention times than their parent compound and the exo


This revealed that the

8

Page 9 of 18


155

protonated species elute faster than their endo counterparts. For example, anti-exo-Cl11-DP (1)

156

has a lower retention time than anti-endo-Cl11-DP (aCl11DP) with ∆tR = 0.73 min. This trend

157

remains consistent with double hydrodechlorination where the Cl10 compound with two exo

158

hydrogens (3) has a shorter retention time than the molecule bearing hydrogen atoms in both an

159

exo and endo position (2), ∆tR = 0.63 min. An elution order of Cl10 < Cl11 < Cl12 was found,

160

which indicated that the higher the degree of dechlorination the faster they elute. Reference

161

standard aCl10DP, with dechlorination on a single norbornene moiety (Cl4 and Cl6 chlorinated

162

rings), has a shorter retention time compared to the other Cl10 compounds 2 and 3, which are

163

dechlorinated on two opposite norbornene moieties (Cl5 chlorinated rings).

164 165

Figure 2. Comparison of the gas chromatograms for all anti-DP derivatives: anti-DP (▬),

166

aCl11DP (▬), 1 (▬), 2 (▬), 3 (▬), and aCl10DP (▬).

167

Another noticeable trend was that in all cases, the syn-isomers elute prior to the corresponding

168

anti-isomers (Figure S1). However, co-elution was observed with the syn-isomers, syn-exo-Cl11-


9


Page 10 of 18

169

DP (4) and syn-exo-endo-Cl10-DP (5) while employing the DB-5 column (Figure 3). There is

170

possibly a fourth dechlorinated syn-DP species if the dechlorination of the syn isomer follows the

171

same trend as anti-DP. We have yet to successfully synthesize or isolate this elusive species, but

172

it will be reported in due course.

173 174

Figure 3. Comparison of the gas chromatograms for all syn-DP derivatives: syn-DP (▬), 4 (▬),

175

5 (▬), and 6 (▬).

176

The EI mass spectra of the dechlorinated analogues have subtle differences between the Cl11

177

and Cl10 species. All of the Cl11 and Cl10 (except aCl10DP) compounds exhibit a dominant

178

pentachlorinated cluster at m/z 238 and a low intensity tetrachlorinated cluster at m/z 203.26

179

Undecachlorinated DP analogues also show a minor cluster at m/z 272,26 indicative of

180

hexachlorocyclopentadiene (HCCP).

181

cluster at m/z 204, and a weak isotope pattern centred at m/z 237.

The EI mass spectrum for aCl10DP has a prominent


A cluster at m/z 237 10

Page 11 of 18


182

corresponds to the fragmentation of a C5Cl6 moiety, while that at m/z 238 originates from a

183

C5HCl5 unit. However, a cluster at m/z 203 can represent the fragmentation of a C5Cl6 or C5HCl5

184

moiety to C5HCl4+, while that at m/z 204 exclusively originates from a C5H2Cl4 unit. There are

185

no discernible differences in the EI mass spectra of the dechlorinated species to distinguish

186

between anti and syn isomers, or compounds containing exo or endo hydrodechlorination.

187

DP analogues identified in an environmental sample

188

A mixture of the synthesized DP analogues was compared to an environmental sample taken

189

from a stream sediment in a rural area of Ontario (sample 10 in reference 26). This was one of

190

six rural sediment samples from widely separated regions in Southern Ontario that were

191

observed, by non-targeted methods, to contain unidentified dechlorinated DP analogues.26

192

Figure 4 depicts a stacked plot for comparison of relevant channels (m/z 271.8102, 237.8491 and

193

203.8881) by EI-HRMS for the two samples. It is evident that the two samples have correlating

194

peaks for the dechlorinated DP products, indicating that the same species are present in both.

195


11


Page 12 of 18

196 197

Figure 4. Stacked plot for relevant masses comparing synthesized DP analogues to those found

198

in an environmental sample.

199

Six identified hydrodechlorinated DP species were found in the above representative DP

200

contaminated sediment sample. However, given that compounds 4 and 5 co-elute there are likely

201

seven hydrodechlorinated DP species in the environmental sample.

202

replacement of chlorine at the methylene bridge carbon atom by hydrogen is an environmentally

203

dominant mechanism of hydrodechlorination. Carbon atoms containing geminal chlorines are

204

often susceptible to replacement of chlorine by hydrogen. This has been observed in anaerobic

205

microbial hydrodehalogenation of DP,28 toxaphene,41,43,53

206

photolysis of aldrin;54 and the reduction by tri-n-butyl tin hydride and AIBN50 or alkoxide

207

bases51 for aldrin, isodrin, dieldrin and endosulfan.

208 209

This indicates that

mirex45 and dieldrin;42,45 the

The only current commercially available reference standards for dechlorinated DPs are aCl11DP and aCl10DP from Wellington Laboratories.


Of the articles investigating

12

Page 13 of 18


210

dechlorinated DP products in the literature, most report the occurrence of aCl11DP,6-11,15,17,21,24-

211

26,28-35

212

used above does not contain a detectable quantity of aCl10DP, therefore the mechanisms of

213

producing a C5H2Cl4 versus a C5HCl5 moiety are likely different.

however only a few confirm the presence of aCl10DP.8,15,17,21 The environmental sample

214

In summary, six new and environmentally relevant dechlorinated DP species have been

215

synthesized and comprehensively characterized. Hydrodechlorination of the geminal chlorides

216

on the methylene bridge of DP was found to be a major degradation route in sediment samples.

217

Identifying these DP degradation products is an important step towards monitoring the fate of

218

this ubiquitous chemical in the environment.

219 220

ASSOCIATED CONTENT

221

Supporting Information. GCs of corresponding syn- and anti-DP isomers, detailed NMR

222

analysis, stacked plots of 1H NMR spectra for anti- and syn-DP dechlorinated derivatives,

223

summary of XRD details for 1-6. This material is available free of charge via the Internet at

224

http://pubs.acs.org.

225

AUTHOR INFORMATION

226

Corresponding Author

227

*[email protected]

228

Notes

229

The authors declare no competing financial interest.

230

ACKNOWLEDGMENT


13


Page 14 of 18

231

Wellington Laboratories Inc. gratefully acknowledges the Natural Sciences and Engineering

232

Research Council of Canada (NSERC) for financial support through an Industrial Research and

233

Development Fellowship (IRDF) for AB (Application number: 6037-2014-468206).

234


14

Page 15 of 18


235

REFERENCES

236 237 238 239 240 241 242 243 244 245 246 247 248 249 250 251 252 253 254 255 256 257 258 259 260 261 262 263 264 265 266 267 268 269 270 271 272 273 274 275 276 277

1. Hoh, E.; Zhu, L.; Hites, R. A., Dechlorane Plus, a Chlorinated Flame Retardant, in the Great Lakes. Environ. Sci. Technol. 2006, 40 (4), 1184-1189. 2. Wang, D.-G.; Yang, M.; Qi, H.; Sverko, E.; Ma, W.-L.; Li, Y.-F.; Alaee, M.; Reiner, E. J.; Shen, L., An Asia-Specific Source of Dechlorane Plus: Concentration, Isomer Profiles, and Other Related Compounds. Environ. Sci. Technol. 2010, 44 (17), 6608-6613. 3. Sverko, E.; Tomy, G. T.; Reiner, E. J.; Li, Y.-F.; McCarry, B. E.; Arnot, J. A.; Law, R. J.; Hites, R. A., Dechlorane Plus and Related Compounds in the Environment: A Review. Environ. Sci. Technol. 2011, 45 (12), 5088-5098. 4. Sun, Y.-X.; Xu, X.-R.; Hao, Q.; Luo, X.-J.; Ruan, W.; Zhang, Z.-W.; Zhang, Q.; Zou, F.S.; Mai, B.-X., Species-specific accumulation of halogenated flame retardants in eggs of terrestrial birds from an ecological station in the Pearl River Delta, South China. Chemosphere 2014, 95, 442-447. 5. Jia, H.; Sun, Y.; Liu, X.; Yang, M.; Wang, D.; Qi, H.; Shen, L.; Sverko, E.; Reiner, E. J.; Li, Y.-F., Concentration and Bioaccumulation of Dechlorane Compounds in Coastal Environment of Northern China. Environ. Sci. Technol. 2011, 45 (7), 2613-2618. 6. Peng, H.; Wan, Y.; Zhang, K.; Sun, J.; Hu, J., Trophic Transfer of Dechloranes in the Marine Food Web of Liaodong Bay, North China. Environ. Sci. Technol. 2014, 48 (10), 54585466. 7. Zeng, L.; Yang, R.; Zhang, Q.; Zhang, H.; Xiao, K.; Zhang, H.; Wang, Y.; Lam, P. K. S.; Jiang, G., Current levels and composition profiles of emerging halogenated flame retardants and dehalogenated products in sewage sludge from municipal wastewater treatment plants in china. Environ. Sci. Technol. 2014, 48 (21), 12586-12594. 8. Wang, D.-G.; Guo, M.-X.; Pei, W.; Byer, J. D.; Wang, Z., Trophic magnification of chlorinated flame retardants and their dechlorinated analogs in a fresh water food web. Chemosphere 2015, 118, 293-300. 9. Wu, P.-F.; Yu, L.-L.; Li, L.; Zhang, Y.; Li, X.-H., Maternal transfer of dechloranes and their distribution among tissues in contaminated ducks. Chemosphere 2016, 150, 514-519. 10. Zheng, J.; Wang, J.; Luo, X.-J.; Tian, M.; He, L.-Y.; Yuan, J.-G.; Mai, B.-X.; Yang, Z.Y., Dechlorane Plus in Human Hair from an E-Waste Recycling Area in South China: Comparison with Dust. Environ. Sci. Technol. 2010, 44 (24), 9298-9303. 11. Ben, Y.-J.; Li, X.-H.; Yang, Y.-L.; Li, L.; Zheng, M.-Y.; Wang, W.-y.; Xu, X.-B., Placental Transfer of Dechlorane Plus in Mother-Infant Pairs in an E-Waste Recycling Area (Wenling, China). Environ. Sci. Technol. 2014, 48 (9), 5187-5193. 12. Sühring, R.; Freese, M.; Schneider, M.; Schubert, S.; Pohlmann, J.-D.; Alaee, M.; Wolschke, H.; Hanel, R.; Ebinghaus, R.; Marohn, L., Maternal transfer of emerging brominated and chlorinated flame retardants in European eels. Sci. Total Environ. 2015, 530, 209-218. 13. Brasseur, C.; Pirard, C.; Scholl, G.; De Pauw, E.; Viel, J.-F.; Shen, L.; Reiner, E. J.; Focant, J.-F., Levels of dechloranes and polybrominated diphenyl ethers (PBDEs) in human serum from France. Environ. Int. 2014, 65, 33-40. 14. Baron, E.; Rudolph, I.; Chiang, G.; Barra, R.; Eljarrat, E.; Barcelo, D., Occurrence and behavior of natural and anthropogenic (emerging and historical) halogenated compounds in marine biota from the Coast of Concepcion (Chile). Sci. Total Environ. 2013, 461, 258-264.


15


278 279 280 281 282 283 284 285 286 287 288 289 290 291 292 293 294 295 296 297 298 299 300 301 302 303 304 305 306 307 308 309 310 311 312 313 314 315 316 317 318 319 320 321 322 323

Page 16 of 18

15. Guerra, P.; Fernie, K.; Jimenez, B.; Pacepavicius, G.; Shen, L.; Reiner, E.; Eljarrat, E.; Barcelo, D.; Alaee, M., Dechlorane Plus and Related Compounds in Peregrine Falcon (Falco peregrinus) Eggs from Canada and Spain. Environ. Sci. Technol. 2011, 45 (4), 1284-1290. 16. Klosterhaus, S. L.; Stapleton, H. M.; La Guardia, M. J.; Greig, D. J., Brominated and chlorinated flame retardants in San Francisco Bay sediments and wildlife. Environ. Int. 2012, 47, 56-65. 17. Möller, A.; Xie, Z.; Sturm, R.; Ebinghaus, R., Large-Scale Distribution of Dechlorane Plus in Air and Seawater from the Arctic to Antarctica. Environ. Sci. Technol. 2010, 44 (23), 8977-8982. 18. Wolschke, H.; Meng, X.-Z.; Xie, Z.; Ebinghaus, R.; Cai, M., Novel flame retardants (NFRs), polybrominated diphenyl ethers (PBDEs) and dioxin-like polychlorinated biphenyls (DLPCBs) in fish, penguin, and skua from King George Island, Antartica. Mar. Pollut. Bull. 2015, 96, 513-518. 19. Ren, G.; Yu, Z.; Ma, S.; Li, H.; Peng, P.; Sheng, G.; Fu, J., Determination of Dechlorane Plus in Serum from Electronics Dismantling Workers in South China. Environ. Sci. Technol. 2009, 43 (24), 9453-9457. 20. Ben, Y.-J.; Li, X.-H.; Yang, Y.-L.; Li, L.; Di, J.-P.; Wang, W.-Y.; Zhou, R.-F.; Xiao, K.; Zheng, M.-Y.; Tian, Y.; Xu, X.-B., Dechlorane Plus and its dechlorinated analogs from an ewaste recycling center in maternal serum and breast milk of women in Wenling, China. Environ. Pollut. 2013, 173, 176-181. 21. Zhang, Y.; Wu, J.-P.; Luo, X.-J.; Wang, J.; Chen, S.-J.; Mai, B.-X., Tissue distribution of Dechlorane Plus and its dechlorinated analogs in contaminated fish: High affinity to the brain for anti-DP. Environ. Pollut. 2011, 159 (12), 3647-3652. 22. Kim, J.-T.; Son, M.-H.; Kang, J.-H.; Kim, J.-H.; Jung, J.-W.; Chang, Y.-S., Occurence of Legacy and New Persistent Organic Pollutants in Avian Tissues from King George Island, Antartica. Environ. Sci. Technol. 2015, 49, 13628-13638. 23. Sverko, E.; Tomy, G. T.; Marvin, C. H.; Zaruk, D.; Reiner, E.; Helm, P. A.; Hill, B.; McCarry, B. E., Dechlorane Plus Levels in Sediment of the Lower Great Lakes. Environ. Sci. Technol. 2008, 42 (2), 361-366. 24. Chen, S.-J.; Tian, M.; Wang, J.; Shi, T.; Luo, Y.; Luo, X.-J.; Mai, B.-X., Dechlorane Plus (DP) in air and plants at an electronic waste (e-waste) site in South China. Environ. Pollut. 2011, 159 (5), 1290-1296. 25. Zhao, Z.; Zhong, G.; Möller, A.; Xie, Z.; Sturm, R.; Ebinghaus, R.; Tang, J.; Zhang, G., Levels and distribution of Dechlorane Plus in coastal sediments of the Yellow Sea, North China. Chemosphere 2011, 83 (7), 984-990. 26. Pena-Abaurrea, M.; Jobst, K. J.; Ruffolo, R.; Shen, L.; McCrindle, R.; Helm, P. A.; Reiner, E. J., Identification of Potential Novel Bioaccumulative and Persistent Chemicals in Sediments from Ontario (Canada) Using Scripting Approaches with GCxGC-TOF MS Analysis. Environ. Sci. Technol. 2014, 48 (16), 9591-9599. 27. Zhou, S. S.; Fu, J.; He, H.; Fu, J. J.; Tang, Q. Z.; Dong, M. F.; Pan, Y. Q.; Li, A.; Liu, W. P.; Zhang, L. M., Spatial distribution and implications to sources of halogenated flame retardants in riverine sediments of Taizhou, an intense e-waste recycling area in eastern China. Chemosphere 2017, 184, 1202-1208. 28. Sverko, E.; McCarry, B.; McCrindle, R.; Brazeau, A.; Pena-Abaurrea, M.; Reiner, E.; Smyth, S. A.; Gill, B.; Tomy, G. T., Evidence for Anaerobic Dechlorination of Dechlorane Plus in Sewage Sludge. Environ. Sci. Technol. 2015 49 (23), 13862-13867.


16

Page 17 of 18

324 325 326 327 328 329 330 331 332 333 334 335 336 337 338 339 340 341 342 343 344 345 346 347 348 349 350 351 352 353 354 355 356 357 358 359 360 361 362 363 364 365 366 367 368 369


29. Peng, H.; Zhang, K.; Wan, Y.; Hu, J., Tissue Distribution, Maternal Transfer, and AgeRelated Accumulation of Dechloranes in Chinese Sturgeon. Environ. Sci. Technol. 2012, 46 (18), 9907-9913. 30. Li, L.; Wang, W.; Lv, Q.; Ben, Y.; Li, X., Bioavailability and tissue distribution of Dechloranes in wild frogs (Rana limnocharis) from an e-waste recycling area in Southeast China. J. Environ. Sci.-China 2014, 26 (3), 636-642. 31. Sun, Y.; Luo, X.; Wu, J.; Mo, L.; Chen, S.; Zhang, Q.; Zou, F.; Mai, B., Species- and tissue-specific accumulation of Dechlorane Plus in three terrestrial passerine bird species from the Pearl River Delta, South China. Chemosphere 2012, 89 (4), 445-451. 32. Zheng, X.-B.; Luo, X.-J.; Zeng, Y.-H.; Wu, J.-P.; Mai, B.-X., Sources, gastrointestinal absorption and stereo-selective and tissue-specific accumulation of Dechlorane Plus (DP) in chicken. Chemosphere 2014, 114, 241-246. 33. Munoz-Arnanz, J.; Luis Roscales, J.; Vicente, A.; Ignacio Aguirre, J.; Jimenez, B., Dechlorane Plus in eggs of two gull species (Larus michahellis and Larus audouinii) from the southwestern Mediterranean Sea. Anal. Bioanal. Chem. 2012, 404 (9), 2765-2773. 34. Chen, K.; Zheng, J.; Yan, X.; Yu, L.; Luo, X.; Peng, X.; Yu, Y.; Yang, Z.; Mai, B., Dechlorane Plus in paired hair and serum samples from e-waste workers: Correlation and differences. Chemosphere 2015, 123, 43-47. 35. Wang, J.; Tian, M.; Chen, S.-J.; Zheng, J.; Luo, X.-J.; An, T.-C.; Mai, B.-X., Dechlorane Plus in House Dust from E-waste Recycling and Urban Areas in South China: Sources, Degradation, and Human Exposure. Environ. Toxicol. Chem. 2011, 30 (9), 1965-1972. 36. Zitko, V., Chlorinated Pesticides: Aldrin, DDT, Endrin, Dieldrin, Mirex. In The Handbook of Environmental Chemistry, Fiedler, H., Ed. Springer-Verlag: Berlin, 2003; Vol. 3, pp 47-90. 37. Shen, L.; Jobst, K. J.; Reiner, E. J.; Helm, P. A.; McCrindle, R.; Taguchi, V. Y.; Marvin, C. H.; Backus, S.; MacPherson, K. A.; Brindle, I. D., Identification and Occurrence of Analogues of Dechlorane 604 in Lake Ontario Sediment and their Accumulation in Fish. Environ. Sci. Technol. 2014, 48 (19), 11170-11177. 38. Wang, S.; Huang, J.; Yang, Y.; Yu, G.; Deng, S.; Wang, B., Photodegradation of Dechlorane Plus in n-nonane under the irradiation of xenon lamp. J. Hazard. Mater. 2013, 260, 16-23. 39. Chiu, T.-C.; Yen, J.-H.; Liu, T.-L.; Wang, Y.-S., Anaerobic Degradation of the Organochlorine Pesticides DDT and Heptachlor in River Sediment of Taiwan. Bull. Environ. Contam. Toxicol. 2004, 72 (4), 821-828. 40. Matsumoto, E.; Kawanaka, Y.; Yun, S.-J.; Oyaizu, H., Bioremediation of the organochlorine pesticides, dieldrin and endrin, and their occurrence in the environment. Appl. Microbiol. Biot. 2009, 84 (2), 205-216. 41. Fingerling, G.; Hertkorn, N.; Parlar, H., Formation and Spectroscopic Investigation of Two Hexachlorobornanes from Six Environmentally Relevant Toxaphene Components by Reductive Dechlorination in Soil under Anaerobic Conditions. Environ. Sci. Technol. 1996, 30 (10), 2984-2992. 42. Maule, A.; Plyte, S.; Quirk, A. V., Dehalogenation of organochlorine insecticides by mixed anaerobic microbial populations. Pestic. Biochem. Physiol. 1987, 27 (2), 229-236. 43. Ruppe, S.; Neumann, A.; Vetter, W., Anaerobic transformation of compounds of technical toxaphene. I. Regiospecific reaction of chlorobornanes with geminal chlorine atoms. Environ. Toxicol. Chem. 2003, 22 (11), 2614-2621.


17


370 371 372 373 374 375 376 377 378 379 380 381 382 383 384 385 386 387 388 389 390 391 392 393 394 395 396 397 398

Page 18 of 18

44. Ruppe, S.; Neumann, A.; Braekevelt, E.; Tomy, G. T.; Stern, G. A.; Maruya, K. A.; Vetter, W., Anaerobic transformation of compounds of technical toxaphene. 2. Fate of compounds lacking geminal chlorine atoms. Environ. Toxicol. Chem. 2004, 23 (3), 591-598. 45. Mohn, W. W.; Tiedje, J. M., Microbial reductive dehalogenation. Microbiol. Rev. 1992, 56 (3), 482-507. 46. Baczynski, T. P.; Grotenhuis, T.; Knipscheer, P., The dechlorination of cyclodiene pesticides by methanogenic granular sludge. Chemosphere 2004, 55 (5), 653-659. 47. Crystallographic data for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre (1817447, 1817449, 1817450, 1817451, 1817452). The data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures. 48. Riddell, N.; McCrindle, R.; Arsenault, G.; Lough, A. J., (1R,2R,5R,6R,9S,10S,13S,14S)1,6,7,8,9,14,15,16,17,17-Decachloropentacyclo[12.2.1.16,9.02,13.05,10]octadeca-7,15-diene. Acta Crystallogr., Sect. E: Struct. Rep. Online 2008, 64 (7), o1249. 49. Riddell, N.; McCrindle, R.; Arsenault, G.; Lough, A. J., (1R,2R,5R,6S,9R,10S,13S,14S,18R)-1,6,7,8,9,14,15,16,17,17,18Undecachloropentacyclo[12.2.1.16,9.02,13.05,10]octadeca-7,15-diene. Acta Crystallogr., Sect. E: Struct. Rep. Online 2008, 64 (7), o1250. 50. Brooks, G. T., The Preparation of Some Reductively Dechlorinated Analogues of Dieldrin, Endosulfan and Isobenzan. J. Pesticide Sci. 1980, 5 (4), 565-574. 51. Adams, C. H. M.; Mackenzie, K., Dehalogenation of isodrin and aldrin with alkoxide bases. J. Chem. Soc. C 1969, (3), 480-486. 52. Williamson, K. L.; Fang Li Hsu, Y.; Young, E. I., The stereochemistry of reductive dehalogenation: The reduction of 1,2,3,4,7,7-hexachloro-5-endo-acetoxy-bicyclo[2.2.1]-2heptene. Tetrahedron 1968, 24 (18), 6007-6015. 53. Vetter, W.; Scherer, G., Persistency of Toxaphene Components in Mammals That Can Be Explained by Molecular Modeling. Environ. Sci. Technol. 1999, 33 (19), 3458-3461. 54. Dureja, P.; Mukerjee, S. K., Amine induced photodehalogenation of cyclodiene insecticides. Tetrahedron Lett. 1985, 26 (42), 5211-5212.

399 400

Table of Contents Graphic

401


18

Dechlorinated Analogues of Dechlorane Plus

Recommend Documents