Substituted Diphenylamine Antioxidants and Benzotriazole UV

For herring gull eggs, the samples from upper Great Lakes contained ... lake trout, and biodilution of C8C8 was observed in a Lake Superior lake trout...
0 downloads 0 Views 810KB Size
Subscriber access provided by READING UNIV

Article

Substituted Diphenylamine Antioxidants and Benzotriazole UV Stabilizers in Aquatic Organisms in the Great Lakes of North America: Terrestrial Exposure and Biodilution Zhe Lu, Amila O. De Silva, Daryl McGoldrick, Wenjia Zhou, Thomas E. Peart, Cyril J Cook, Gerald Tetreault, Pamela A. Martin, and Shane Raymond de Solla Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.7b05214 • Publication Date (Web): 29 Dec 2017 Downloaded from http://pubs.acs.org on December 31, 2017

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 free 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 accessible to all readers and 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.

Environmental Science & Technology 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 31

Environmental Science & Technology

1

Substituted Diphenylamine Antioxidants and Benzotriazole UV Stabilizers in

2

Aquatic Organisms in the Great Lakes of North America: Terrestrial Exposure and

3

Biodilution

4

Zhe Lu,† Amila O. De Silva,†* Daryl J. McGoldrick,† Wenjia Zhou,† Thomas E. Peart,† Cyril Cook,†

5

Gerald R. Tetreault,† Pamela A. Martin,# Shane R. de Solla,#

6



7

Ontario, L7S 1A1Canada

8

#

9

Ontario, L7S 1A1 Canada

Water Science & Technology Directorate, Environment and Climate Change Canada, Burlington,

Ecotoxicology and Wildlife Health Division, Environment and Climate Change Canada, Burlington,

10

Email addresses:

11

[email protected] (Zhe Lu);

12

[email protected] (Amila De Silva)

13

[email protected] (Daryl McGoldrick)

14

[email protected] (Wenjia Zhou)

15

[email protected] (Thomas Peart)

16

[email protected] (Cyril Cook)

17

[email protected] (Gerald Tetreault)

18

[email protected] (Pamela Martin)

19

[email protected] (Shane de Solla)

20 21

*Corresponding author: Amila O. De Silva, Tel.: 1-905-336-4407, E-mail: [email protected] 
 Words: 5600(from Abstract to Acknowledgements) + 2 tables + 2 figures = 6800. 1 Environment ACS Paragon Plus

Environmental Science & Technology

22

TOC Art

23 24

2 Environment ACS Paragon Plus

Page 2 of 31

Page 3 of 31

25 26

Environmental Science & Technology

ABSTRACT Substituted diphenylamine antioxidants (SDPAs) and benzotriazole UV stabilizers (BZT-UVs) are

27

industrial

28

biomagnification and spatial distribution of these contaminants in the Great Lakes of North America

29

are unknown. The present study addresses these knowledge gaps by reporting SDPAs and BZT-UVs in

30

herring gull (Larus argentatus) eggs, lake trout (Salvelinus namaycush) and their food web in the Great

31

Lakes for the first time. Herring gull eggs showed much higher detection frequency and concentrations

32

of target SDPAs and 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol(UV328) than that of the whole

33

body fish homogenate. For herring gull eggs, the samples from upper Great Lakes contained

34

significantly greater levels of SDPAs than those eggs from lower lakes, possibly due to the differences

35

in terrestrial food in diet. Interestingly, the predominant SDPAs in herring gull eggs were dinonyl-

36

(C9C9) and monononyl-diphenylamine (C9) which were previously shown to be less bioaccumulative

37

than other SDPAs in fish. In contrast, dioctyl-diphenylamine(C8C8) was the major SDPA in lake trout

38

and biodilution of C8C8 was observed in a Lake Superior lake trout food web. Such variations in

39

herring gull eggs and fish indicate the differences in accumulation and elimination pathways of SDPAs

40

and BZT-UVs and require further elucidation of these mechanisms.

additives

of

emerging

environmental

concern.

41 42 43 44 45 46 47 48 49 3 Environment ACS Paragon Plus

However,

the

bioaccumulation,

Environmental Science & Technology

50

Page 4 of 31

INTRODUCTION

51

Substituted diphenylamine antioxidants (SDPAs) and benzotriazole UV stabilizers (BZT-UVs) are

52

industrial additives applied in industrial and consumer products such as fuel, lubricant, plastics and

53

rubber to minimize theoxidative degradation or UV radiation-induced color change of materials.1-

54

3

55

(Table S1).1,3-6Therefore, many SDPAs and BZT-UVs have been identified and managed as High

56

Production Volume chemicals (e.g., as defined by Toxic Substances Control Act in the U.S.) and may

57

pose risks to ecosystems and human health.5,6In Europe, some SDPAs and BZT-UVs have been

58

considered as PBT (Persistent, Bioaccumulative and Toxic) chemicals and managed as Substances of

59

Very High Concern (Table S1). 6

SDPAs and BZT-UVs are produced and consumed in large volumes in North America and Europe

60

Many of these contaminants have been detected in environmental compartments such as

61

wastewater, biosolids, surface water, sediments and biota samples, and they tend to partition to organic

62

carbon and lipids.1-3The estimated log n-octanol/water partition coefficient (log Kow) of the target

63

SDPAs and BZT-UVs in the present study ranged between 5.3-12.2 and 5.6-7.7, respectively;1,3given

64

that many hydrophobic compounds with log Kow≥ 5 tend to biomagnify in aquatic ecosystems,7 some

65

of these compounds are expected to biomagnify in food web and result in high exposure risks in top

66

predators. In addition, SDPAs and BZT-UVs preferentially accumulate in the fish liver compared to

67

other tissues and the biliary excretion of these contaminants is very limited in fish.8Although the

68

information on their toxicity is limited, they may have chronic adverse effects on endocrine systems

69

based on available mammalian and fish evaluations.9-12For example, BZT-UVs could lead to sex-

70

specific chronic toxicities in rats9 and may have endocrine disruption properties in humans10 and

71

fish.11,12 To date, there are no published studies on SDPA toxicity. However, U.S. EPA assessments

72

reported some chronic adverse effects such as liver, blood, reproductive and developmental toxicities

73

of SDPAs in rats.13-15As such, there is a strong rationale for studying the distribution, fate and toxicities

4 Environment ACS Paragon Plus

Page 5 of 31

Environmental Science & Technology

74

of these contaminants in the environment for ecological risk assessment and informed management of

75

these chemicals.

76

Lu et al.1 recently reported the occurrence and distribution of SDPAs and BZT-UVs in water,

77

sediment and biota from an urban creek in the Great Lakes region. High levels of these contaminants

78

were detected in the crayfish (Orcoescties spp.) (up to 5.5 µg g-1for total (Ʃ) SDPAs and 1.3 µg g-1 for

79

UV328, lipid weight (lw)).1The organisms in Great Lakes may also accumulate high levels of SDPAs

80

and BZT-UVs because the Great Lakes receive water and particulate from an abundance of

81

creeks/rivers affected by human activity (e.g., the effluent of wastewater treatment plant (WWTPs)).1,3

82

However, the occurrence and environmental fate of these contaminants in the biota in the Great

83

Lakes have never been reported. Great Lakes contain 21% of the surface freshwater on Earth and a

84

human population exceeding 30 million in this region.16To protect the water resources and ecosystems

85

in the Great Lakes, the updated U.S.-Canada Great Lakes Water Quality Agreement specifically

86

recommends efforts on the identification and monitoring of chemicals of emerging concern in this

87

region.17In the present study, the distribution of SDPAs and BZT-UVs in top predators in the Great

88

Lakes was investigated, and their food web biomagnification potential.

89

The adult herring gull (Larus argentatus) is an ideal avian species to track the bioaccumulation of

90

organic contaminants in the Great Lakes region.18-20The herring gull is an opportunistic piscivore with

91

a high breeding colony fidelity that lives year round in the Great Lakes.18-20Therefore, their eggs have

92

been used as indicators of chemical contamination in the Great Lakes Herring Gull Contaminant

93

Monitoring program for more than 40 years.18-20These eggs have a relatively high lipid content and

94

may accumulate high levels of hydrophobic organic contaminants.19As hydrophobic compounds with

95

high production volume, some SDPAs and BZT-UVs may be accumulated in herring gull eggs. Thus

96

far, the occurrence of SDPAs has not been reported in any avian species, while BZT-UVs have been

97

detected in the liver of wild-caught spot-billed duck (Anas poecilorhyncha) and mallard (Anas

98

platyrhynchos) from Ariake Sea (Japan).21Nevertheless, no study has investigated the early-life 5 Environment ACS Paragon Plus

Environmental Science & Technology

Page 6 of 31

99

exposure of bird eggs to these contaminants. Lake trout (Salvelinus namaycush) and walleye (Sander

100

vitreus) are upper trophic level fish and are widely used in Fish Contaminants Monitoring and

101

Surveillance Program as indicators of environmental contamination.22Lake trout are consumed on a

102

regular basis by some communities in northern Canada23and are also a component of commercial and

103

sport fisheries, thereby presenting a route for human exposure to contaminants. These potential

104

exposure risks provide a rationale for determination of SDPAs and BZT-UVs in lake trout and

105

associated food webs. Furthermore, lake trout and walleye are likely representative of other

106

commercial and sport fisheries, and levels in those species provide some first information on potential

107

exposure levels of humans and piscivorous wildlife.

108

As the first study of SDPAs and BZT-UVs in Great Lakes organisms, we report the occurrence,

109

spatial distribution and composition of these contaminants in herring gull eggs and top predator fish,

110

lake trout and walleye, and evaluate the bioaccumulation of these contaminants in a food web in Lake

111

Superior. Further, we used stable isotopes (δ15N, δ13C) and essential fatty acids to elucidate feeding

112

ecology of the herring gulls throughout the Great Lakes, and how it affects body burdens of SDPAs and

113

BZT-UVs. Our hypotheses were: (1) biota samples near emissions from larger industrial and municipal

114

sources have higher levels of these contaminants; and (2) target compounds undergo biomagnification

115

or biodilution in Great Lakes food web, depending on their physicochemical properties and biological

116

half-life. Hence, we predict that biota from the lower Great Lakes (Lakes Ontario and Erie) would have

117

higher concentrations due to the proximity to larger and more abundant municipal and industrial

118

sources compared to the upper Great Lakes (Lakes Huron and Superior). Similarly, we predict that C4,

119

C4C4, C8, C9andall target BZT-UVs will biodilute (i.e., Biomagnification Factor (BMF)1) due to longer

121

biological half-life and higher estimated bioaccumulation factors (BAF) of these compounds in upper

122

trophic level fish (Table 1).

123 6 Environment ACS Paragon Plus

Page 7 of 31

124

Environmental Science & Technology

MATERIALS AND METHODS

125

Samples. Sampling sites for the Great Lakes herring gull eggs and fish are shown in Figure 1.

126

Fresh herring gull eggs were collected in 2014 from 7 colonies in Great Lakes under federal scientific

127

permits. The sampling sites included: Granite Island (GI; n = 10; site 1) and Agawa Rocks (AR; n = 10;

128

site 2) in Lake Superior, Chantry Island (CI; n = 10; site 3) in Lake Huron, Middle Island (MI; n = 10;

129

site 4) and Port Colborne (PC; n = 10; site 5) in Lake Erie, Weseloh Rocks (WR; n = 6; site 6) in

130

Niagara River, and Hamilton Harbour (HH; n = 10; site 7) in Lake Ontario.Lake Trout samples were

131

collected from Thunder Bay-Pie Island (TB; n=5, 2013; site 1), Marathon (MT; n=5; 2014; site 2) and

132

Whitefish Bay (WB; n=10; 2014; site 3) in Lake Superior, Goderich (GR; n=5; 2014; site 4) in Lake

133

Huron, Dunkirk (DK; n=5; 2014; site 6) in Lake Erie, and Niagara-on-the-Lakein Lake Ontario(NL;

134

n=5; 2014; site 7). In the western basin of Lake Erie, walleye occupy the top trophic level due to the

135

relative shallow and warm conditions that are inhospitable to lake trout, and were sampled accordingly

136

(EW; n = 5; 2014; site 5).The WB (2014) Lake Superior lake trout food web sampling consisted of

137

pooled plankton (>153µm; extracted in triplicate), pooled mysis (Mysis relicta) (extracted in triplicate),

138

slimy sculpin (Cottus cognatus; pooled from 20 fish, extracted in triplicate), rainbow smelt (Osmerus

139

mordax; pooled from 12 fish, measured in triplicate) and deep water sculpin (Myoxocephalus

140

thompsonii; 5 different pooled samples, consisting of 7 to 12 fish each). Though our previous data8

141

indicated liver as the predominant site of accumulation in fish, whole body homogenate is the

142

consistent

143

arepublished22,24and briefly described in the Supporting Information (SI). The biological parameters of

144

samples from the Great Lakes are shown in Table S2.

approach

for

studying

food

web

biomagnification.

Details

on

the

capture

145

Chemicals, Sample Preparation and Instrumental Analysis. Detailed information of target

146

SDPAs and BZT-UVs are shown in Table 1 and Figure S1.The details of other chemicals used in the

147

experiment, sample preparation methods and instrumental analysis are previously published1-3and

148

shown in SI (Table S3 and S4). The analyses of stable isotopes and fatty acids were based on published 7 Environment ACS Paragon Plus

Environmental Science & Technology

149

Page 8 of 31

methods25-27 as shown in the SI.

150

QA/QC. Glass materials were used in the experiment whenever possible to limit any possible

151

background contamination. Procedural blanks (n = 2 for egg samples; n= 1 for other biota samples) and

152

one spike-recovery sample (known amount of target compounds added to samples) were included for

153

each batch of samples. The recovery of the target compounds in spike-recovery egg samples ranged

154

from 68±26% (C9C9)to 112 ± 14% (diAMS) for SDPAs and from 74±11% (UV329) to 89±28%

155

(UV234) (mean ± standard deviation (SD)) for BZT-UVs (Table S4).For fish and other biota samples,

156

the recovery was in the range of 77±26% (C8C8) - 89 ± 21% (C8) and 73 ±18%(UV350)-78 ±17%

157

(UV328)for SDPAs and BZT-UVs, respectively (Table S4). The method limits of quantification

158

(MLOQs) were based on 3 times of standard deviation (SD) of the blanks (n= 6 for eggs; n = 12 for

159

fish and other biota samples). For analytes which were not observed in the method blanks, standard

160

concentration producing a signal with 10 times signal to noise ratio in acetonitrile were used to estimate

161

the MLOQ. In egg samples, the MLOQs were in the range of 0.001-0.01 ngg-1 (ww) for SDPAs and

162

0.03-0.66 ngg-1 (ww) for BZT-UVs (Table S4). The MLOQs in other biota samples were in the range

163

of 0.001-0.014 and 0.03-1.4 ngg-1 (ww) for SDPAs and BZT-UVs, respectively (Table S4).All

164

concentrations in samples were blank-subtracted.

165

Data Analysis. Data were analyzed using R 3.3.1 (with RStudio 0.99.903) (Boston, MA, USA),

166

GraphPad Prism 7.0 (La Jolla,CA, USA) and IBM SPSS Statistics (Version 23) to determine the

167

existence of possible differences in SDPAs and BZT-UVs levels in different samples and affecting

168

factors. Statistics for data with censored values (≤50% censoring and detects > 3) were conducted using

169

the robust regression on order statistics (ROS) method in R by the Nondetects and Data Analysis

170

(NADA) package (V1.5-6).28For the pooled samples (i.e., mixed plankton, mysis, slimy sculpin and

171

rainbow smelt) with small sample size (n=3), the censored values were substituted by 1/2 MLOQ when

172

contaminants were detected in two samples.28Concentration is reported as arithmetic mean±standard

8 Environment ACS Paragon Plus

Page 9 of 31

Environmental Science & Technology

173

error unless otherwise indicated.Data (Shapiro-Wilk test) were logarithmically transformed to

174

approximate a normal distribution before further statistical analysis. One-way ANOVA followed by

175

Tukey’s test were used for comparisons. Significance level was set as p