the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
The atmospheric fate of 1,2-Dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH): Spatial patterns, seasonal variability, and deposition to Canadian coastal regions
Abstract. Brominated flame retardants (BFRs) that are gradually phased out are being replaced by emerging BFRs. Here, we report the concentration of the α- and β-isomers of 1,2-Dibromo-4-(1,2-dibromoethyl) cyclo–hexane (TBECH) in over 300 air, water, and precipitation samples collected between 2019 and 2022 using active air and deposition sampling as well as networks of passive air and water samplers. The sampling region includes Canada's most populated cities and areas along the St. Lawrence River and Estuary, Quebec, as well as around the Salish Sea, British Columbia. TBECH was detected in over 60 % of air samples at levels comparable to those of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47). Concentrations of TBECH and BDE-47 were typically higher in urban areas, with stronger correlations with population density during warmer deployments. Uniform α/β-TBECH ratios across space, time and environmental media indicate highly similar atmospheric fate of the two isomers. Although TBECH air concentrations were strongly related to temperature in urban Toronto and a remote site on the East coast, the lack of such dependence at a remote site on the West coast can be explained by the small seasonal temperature range and summertime air mass transport from the Pacific Ocean. Despite there being no evidence that TBECH has been produced, or imported for use, in Canada, it is now one of the most abundant gaseous BFRs in the Canadian atmosphere. The recorded spatial and temporal variability of TBECH suggest that its emissions are not constrained to specific locations but are generally tied to the presence of humans. The most likely explanation for its environmental occurrence in Canada is the release from imported consumer products containing TBECH. Chiral analysis suggests that despite its urban origin, at least some fraction of TBECH has experienced enantioselective processing, i.e., has volatilized from reservoirs where it has undergone microbial transformations. Microbial processes in urban soils and in marine waters may have divergent enantioselectivity.
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Notice on discussion status
The requested preprint has a corresponding peer-reviewed final revised paper. You are encouraged to refer to the final revised version.
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The requested preprint has a corresponding peer-reviewed final revised paper. You are encouraged to refer to the final revised version.
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Interactive discussion
Status: closed
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CC1: 'Comment on egusphere-2023-1151', Terry Bidleman, 26 Jun 2023
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AC1: 'Reply to comments by Terry Bidleman', Frank Wania, 01 Jul 2023
We would like to thank Terry Bidleman for taking the time to send his insightful and constructive feedback. We have taken the feedback in consideration and prepared responses for each comment in the atached document.
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RC1: 'Reply on AC1', Terry Bidleman, 10 Jul 2023
Thanks to the authors for thorough and thoughtful responses to my comments. I am satisfied with these responses and enthusiastically recommend the paper for final publication.
Citation: https://doi.org/10.5194/egusphere-2023-1151-RC1
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RC1: 'Reply on AC1', Terry Bidleman, 10 Jul 2023
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AC1: 'Reply to comments by Terry Bidleman', Frank Wania, 01 Jul 2023
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RC2: 'Comment on egusphere-2023-1151', Anonymous Referee #2, 11 Jul 2023
In summary, I find this to be an excellent paper. It is very well written and is also a very significant contribution to our knowledge on the environmental presence of the emerging contaminant, TBECH and stands to influence its regulatory review. I recommend accepting it. I list a few minor comments for the authors to consider below, but would not insist on any of them be done.
Keywords: I did not actually see the keywords, but, consider including the other name to TBECH there: DBE-DBCH
Line 50 - it could be mentioned that toxicity & effects can still occur with non-persistent contaminants - if they are continuously released.
Line 71-74 - There are a few other toxic effects - you could simply point readers to a recent review which covers many of them (Marteinson et al 2021: A review of 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane in the environment and assessment of its persistence, bioaccumulation and toxicity, Environmental Research, 195. https://can01.safelinks.protection.outlook.com/?url=https%3A%2F%2Fdoi.org%2F10.1016%2Fj.envres.2020.110497&data=05%7C01%7CSarah.Marteinson%40dfo-mpo.gc.ca%7C8cea1b93e57d4f681fd608db81059958%7C1594fdaea1d94405915d011467234338%7C0%7C0%7C638245633299908122%7CUnknown%7CTWFpbGZsb3d8eyJWIjoiMC4wLjAwMDAiLCJQIjoiV2luMzIiLCJBTiI6Ik1haWwiLCJXVCI6Mn0%3D%7C3000%7C%7C%7C&sdata=m%2BwLPfK8PoZZwmKf2GV2DfUUphjgbnkHw9ri1Zo9oKI%3D&reserved=0)
102 - 2019 - 22 - should any potential impacts of change human behaviour during the pandemic be mentioned? I am not sure what these might be given TBECH is likely emitted from finished imported products. However, it does come to the reader's mind that this might not be a representative period of time. There is no need to speculate, but it could simply be acknowledged a an unknown; perhpas there is some trend data on other similar air pollutants to indicate any changes (or not) during the pandemic that could be mentioned?
Line 181-183 - I think it would be beneficial to summarize in a few lines what these tables show - otherwise the results for all of these other BFRs measured are only found in the supplemental information and that is unfortunate.
Paragraph beginning line 185 - Note that concentrations of TBECH have already been reviewed (Marteinson et al 2020) which includes most of these same references - this should be acknowledged.
Line 204-5 "in this study, BDE-47 was also detected in the air in all sampling regions, with comparable levels to TBECH." This is a very significant and important finding, adding important evidence to that mounting which suggests TBECH is an contaminant of concern to consider further in risk assessment.
The figures are excellent.
Line 318 - can you verify this error before publication?
Paragraph beginning on line 354 - This is also a very interesting/novel finding and useful for understanding of TBECH enantiomers in the environment.
Section 4.1.2 - It was striking to me that air concentrations of TBECH changed with the season, but precipitation concentrations did not - some discussion of this here and how it relates to the scavenging rations you have calculated would be beneficial/interesting.
4.2 - this is the only heading phrased as a question which seems out of place - you may want to change it.
Citation: https://doi.org/10.5194/egusphere-2023-1151-RC2 - AC2: 'Reply on RC2', Frank Wania, 19 Jul 2023
Interactive discussion
Status: closed
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CC1: 'Comment on egusphere-2023-1151', Terry Bidleman, 26 Jun 2023
-
AC1: 'Reply to comments by Terry Bidleman', Frank Wania, 01 Jul 2023
We would like to thank Terry Bidleman for taking the time to send his insightful and constructive feedback. We have taken the feedback in consideration and prepared responses for each comment in the atached document.
-
RC1: 'Reply on AC1', Terry Bidleman, 10 Jul 2023
Thanks to the authors for thorough and thoughtful responses to my comments. I am satisfied with these responses and enthusiastically recommend the paper for final publication.
Citation: https://doi.org/10.5194/egusphere-2023-1151-RC1
-
RC1: 'Reply on AC1', Terry Bidleman, 10 Jul 2023
-
AC1: 'Reply to comments by Terry Bidleman', Frank Wania, 01 Jul 2023
-
RC2: 'Comment on egusphere-2023-1151', Anonymous Referee #2, 11 Jul 2023
In summary, I find this to be an excellent paper. It is very well written and is also a very significant contribution to our knowledge on the environmental presence of the emerging contaminant, TBECH and stands to influence its regulatory review. I recommend accepting it. I list a few minor comments for the authors to consider below, but would not insist on any of them be done.
Keywords: I did not actually see the keywords, but, consider including the other name to TBECH there: DBE-DBCH
Line 50 - it could be mentioned that toxicity & effects can still occur with non-persistent contaminants - if they are continuously released.
Line 71-74 - There are a few other toxic effects - you could simply point readers to a recent review which covers many of them (Marteinson et al 2021: A review of 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane in the environment and assessment of its persistence, bioaccumulation and toxicity, Environmental Research, 195. https://can01.safelinks.protection.outlook.com/?url=https%3A%2F%2Fdoi.org%2F10.1016%2Fj.envres.2020.110497&data=05%7C01%7CSarah.Marteinson%40dfo-mpo.gc.ca%7C8cea1b93e57d4f681fd608db81059958%7C1594fdaea1d94405915d011467234338%7C0%7C0%7C638245633299908122%7CUnknown%7CTWFpbGZsb3d8eyJWIjoiMC4wLjAwMDAiLCJQIjoiV2luMzIiLCJBTiI6Ik1haWwiLCJXVCI6Mn0%3D%7C3000%7C%7C%7C&sdata=m%2BwLPfK8PoZZwmKf2GV2DfUUphjgbnkHw9ri1Zo9oKI%3D&reserved=0)
102 - 2019 - 22 - should any potential impacts of change human behaviour during the pandemic be mentioned? I am not sure what these might be given TBECH is likely emitted from finished imported products. However, it does come to the reader's mind that this might not be a representative period of time. There is no need to speculate, but it could simply be acknowledged a an unknown; perhpas there is some trend data on other similar air pollutants to indicate any changes (or not) during the pandemic that could be mentioned?
Line 181-183 - I think it would be beneficial to summarize in a few lines what these tables show - otherwise the results for all of these other BFRs measured are only found in the supplemental information and that is unfortunate.
Paragraph beginning line 185 - Note that concentrations of TBECH have already been reviewed (Marteinson et al 2020) which includes most of these same references - this should be acknowledged.
Line 204-5 "in this study, BDE-47 was also detected in the air in all sampling regions, with comparable levels to TBECH." This is a very significant and important finding, adding important evidence to that mounting which suggests TBECH is an contaminant of concern to consider further in risk assessment.
The figures are excellent.
Line 318 - can you verify this error before publication?
Paragraph beginning on line 354 - This is also a very interesting/novel finding and useful for understanding of TBECH enantiomers in the environment.
Section 4.1.2 - It was striking to me that air concentrations of TBECH changed with the season, but precipitation concentrations did not - some discussion of this here and how it relates to the scavenging rations you have calculated would be beneficial/interesting.
4.2 - this is the only heading phrased as a question which seems out of place - you may want to change it.
Citation: https://doi.org/10.5194/egusphere-2023-1151-RC2 - AC2: 'Reply on RC2', Frank Wania, 19 Jul 2023
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The requested preprint has a corresponding peer-reviewed final revised paper. You are encouraged to refer to the final revised version.
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(5871 KB) - Metadata XML
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