| 1. |
- Bidleman, Terry, 1942-, et al.
(author)
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A review of halogenated natural products in Arctic, Subarctic and Nordic ecosystems
- 2019
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In: Emerging Contaminants. - : Elsevier. - 2405-6650 .- 2405-6642. ; 5, s. 89-115
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Journal article (peer-reviewed)abstract
- Halogenated natural products (HNPs) are organic compounds containing bromine, chlorine, iodine, andrarely fluorine. HNPs comprise many classes of compounds, ranging in complexity from halocarbons tohigher molecular weight compounds, which often contain oxygen and/or nitrogen atoms in addition tohalogens. Many HNPs are biosynthesized by marine bacteria, macroalgae, phytoplankton, tunicates,corals, worms, sponges and other invertebrates. This paper reviews HNPs in Arctic, Subarctic and Nordicecosystems and is based on sections of Chapter 2.16 in the Arctic Monitoring and Assessment Program(AMAP) assessment Chemicals of Emerging Arctic Concern (AMAP, 2017) which deal with the highermolecular weight HNPs. Material is updated and expanded to include more Nordic examples. Much ofthe chapter is devoted to “bromophenolic” HNPs, viz bromophenols (BPs) and transformation productsbromoanisoles (BAs), hydroxylated and methoxylated bromodiphenyl ethers (OH-BDEs, MeO-BDEs) andpolybrominated dibenzo-p-dioxins (PBDDs), since these HNPs are most frequently reported. Othersdiscussed are 2,20-dimethoxy-3,30,5,50-tetrabromobiphenyl (2,20-dimethoxy-BB80), polyhalogenated 10-methyl-1,20-bipyrroles (PMBPs), polyhalogenated 1,10-dimethyl-2,20-bipyrroles (PDBPs), polyhalogenatedN-methylpyrroles (PMPs), polyhalogenated N-methylindoles (PMIs), bromoheptyl- and bromooctylpyrroles, (1R,2S,4R,5R,10E)-2-bromo-1-bromomethyl-1,4-dichloro-5-(20-chloroethenyl)-5-methylcyclohexane (mixed halogenated compound MHC-1), polybrominated hexahydroxanthene derivatives(PBHDs) and polyhalogenated carbazoles (PHCs). Aspects of HNPs covered are physicochemicalproperties, sources and production, transformation processes, concentrations and trends in the physicalenvironment and biota (marine and freshwater). Toxic properties of some HNPs and a discussion of howclimate change might affect HNPs production and distribution are also included. The review concludeswith a summary of research needs to better understand the role of HNPs as “chemicals of emergingArctic concern”.
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| 2. |
- Bidleman, Terry, et al.
(author)
-
Atmospheric pathways of chlorinated pesticides and natural bromoanisoles in the northern Baltic Sea and its catchment
- 2015
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In: Ambio. - : Springer Science and Business Media LLC. - 0044-7447 .- 1654-7209. ; 44, s. 472-483
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Journal article (peer-reviewed)abstract
- Long-range atmospheric transport is a major pathway for delivering persistent organic pollutants to the oceans. Atmospheric deposition and volatilization of chlorinated pesticides and algae-produced bromoanisoles (BAs) were estimated for Bothnian Bay, northern Baltic Sea, based on air and water concentrations measured in 2011-2012. Pesticide fluxes were estimated using monthly air and water temperatures and assuming 4 months ice cover when no exchange occurs. Fluxes were predicted to increase by about 50 % under a 2069-2099 prediction scenario of higher temperatures and no ice. Total atmospheric loadings to Bothnian Bay and its catchment were derived from air-sea gas exchange and bulk'' (precipitation ? dry particle) deposition, resulting in net gains of 53 and 46 kg year(-1) for endosulfans and hexachlorocyclohexanes, respectively, and net loss of 10 kg year(-1) for chlordanes. Volatilization of BAs releases bromine to the atmosphere and may limit their residence time in Bothnian Bay. This initial study provides baseline information for future investigations of climate change on biogeochemical cycles in the northern Baltic Sea and its catchment.
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| 3. |
- Bidleman, Terry, et al.
(author)
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Chapter 2: Properties, sources, global fate and transport
- 2013
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In: Canadian Arctic Contaminants Assessment Report III 2013. - Ottawa : Northern Contaminants Program, Aboriginal Affairs and Northern Development Canada. - 9781100546520 ; , s. 19-146
-
Book chapter (peer-reviewed)abstract
- Part II of the second Canadian Arctic Contaminants Assessment Report (CACAR-II) began with a section on “Physicochemical Properties of Persistent Organic Pollutants”, which identified key physicochemical (pchem) properties, provided the rationale for their measurement or prediction and tabulated literature citations for chemicals that are of concern to the NCP (Bidleman et al. 2003). The section also discussed temperature dependence of pchem properties and their applications to describing partitioning in the physical environment.There is, and will continue to be, emphasis on predictive approaches to screening chemicals for persistence, bioaccumulation and toxic (PB&T)properties, as well as long-range atmospheric transport (LRAT) potential (Brown and Wania 2008, Czub et al. 2008, Fenner et al. 2005, Gouin andWania 2007, Howard and Muir 2010, Klasmeier et al. 2006, Matthies et al. 2009, Muir and Howard 2006). This has created the need for determining pchem properties of new and emerging chemicals of concern.Predicting gas exchange cycles of legacy persistent organic pollutants (POPs) and new and emerging chemicals of concern places a high demand on the accuracy of pchem properties, particularly the air/water partition coefficient, KAW. Hexachlorocyclohexanes (HCHs) in Arctic Ocean surface waters are close to air-water equilibrium, with excursions toward net volatilization or deposition that vary with location and season (Hargrave et al. 1993, Jantunen et al. 2008a, Lohmann et al. 2009, Su et al. 2006, Wong et al. 2011) while hexachlorobenzene (HCB) (Lohmann et al. 2009, Su et al. 2006, Wong et al. 2011) and some current use pesticides (CUPs) (Wong et al. 2011) are undergoing net deposition. The predicted Arctic Contamination Potential (ACP) for persistent organic chemicals is strongly influenced by ice cover due to its effect on air-water gas exchange (Meyer and Wania 2007).Many advances have taken place and numerous papers have been published since CACAR-II, which present new measurements and predictions of pchem properties. This section does not attempt to provide a comprehensive review of the field, or to compile pchem properties from the many studies. The approach taken is to highlight the reports which are most relevant to polar science, particularly in areas of improving reliability of pchem properties for POPs, improving experimental techniques and comparing predictive methods. The section ends with a discussion of polyparameter linear free energy relationships (pp-LFERs), which goes beyond partitioning descriptions based on single pchem properties by taking into account specific chemical interactions that can take place in airsurface and water-surface exchange processes. A detailed list of chemical names and nomenclature are provided in the Glossary.
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| 4. |
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| 5. |
- Bidleman, Terry F., et al.
(author)
-
Air-water exchange of brominated anisoles in the northern baltic sea
- 2014
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In: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 48:11, s. 6124-6132
-
Journal article (peer-reviewed)abstract
- Bromophenols produced by marine algae undergo O-methylation to form bromoanisoles (BAs), which are exchanged between water and air. BAs were determined in surface water of the northern Baltic Sea (Gulf of Bothnia, consisting of Bothnian Bay and Bothnian Sea) during 2011-2013 and on a transect of the entire Baltic in September 2013. The abundance decreased in the following order: 2,4,6-tribromoanisole (2,4,6-TBA) > 2,4-dibromoanisole (2,4-DBA) ≫ 2,6-dibromoanisole (2,6-DBA). Concentrations of 2,4-DBA and 2,4,6-TBA in September were higher in the southern than in the northern Baltic and correlated well with the higher salinity in the south. This suggests south-to-north advection and dilution with fresh riverine water enroute, and/or lower production in the north. The abundance in air over the northern Baltic also decreased in the following order: 2,4,6-TBA > 2,4-DBA. However, 2,6-DBA was estimated as a lower limit due to breakthrough from polyurethane foam traps used for sampling. Water/air fugacity ratios ranged from 3.4 to 7.6 for 2,4-DBA and from 18 to 94 for 2,4,6-TBA, indicating net volatilization. Flux estimates using the two-film model suggested that volatilization removes 980-1360 kg of total BAs from Bothnian Bay (38000 km(2)) between May and September. The release of bromine from outgassing of BAs could be up to 4-6% of bromine fluxes from previously reported volatilization of bromomethanes and bromochloromethanes.
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| 6. |
- Bidleman, Terry Frank, et al.
(author)
-
Annual cycles of organochlorine pesticide enantiomers in Arctic air suggest changing sources and pathways
- 2015
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In: Atmospheric Chemistry And Physics. - : Copernicus GmbH. - 1680-7316 .- 1680-7324. ; 15:3, s. 1411-1420
-
Journal article (peer-reviewed)abstract
- Air samples collected during 1994-2000 at the Canadian Arctic air monitoring station Alert (82 degrees 30'N, 62 degrees 20'W) were analysed by enantiospecific gas chromatography-mass spectrometry for alpha-hexachlorocyclohexane (alpha-HCH), trans-chlordane (TC) and cis-chlordane (CC). Results were expressed as enantiomer fractions (EF = peak areas of (+)/[(+) + (-)] enantiomers), where EFs = 0.5, <0.5 and >0.5 indicate racemic composition, and preferential depletion of (+) and (-) enantiomers, respectively. Long-term average EFs were close to racemic values for alpha-HCH (0.504 +/- 0.004, n = 197) and CC (0.505 +/- 0.004, n = 162), and deviated farther from racemic for TC (0.470 +/- 0.013, n = 165). Digital filtration analysis revealed annual cycles of lower alpha-HCH EFs in summer-fall and higher EFs in winter-spring. These cycles suggest volatilization of partially degraded alpha-HCH with EF < 0.5 from open water and advection to Alert during the warm season, and background transport of alpha-HCH with EF > 0.5 during the cold season. The contribution of sea-volatilized alpha-HCH was only 11% at Alert, vs. 32% at Resolute Bay (74.68 degrees N, 94.90 degrees W) in 1999. EFs of TC also followed annual cycles of lower and higher values in the warm and cold seasons. These were in phase with low and high cycles of the TC / CC ratio (expressed as F-TC = TC/(TC + CC)), which suggests greater contribution of microbially "weathered" TC in summer-fall versus winter-spring. CC was closer to racemic than TC and displayed seasonal cycles only in 1997-1998. EF profiles are likely to change with rising contribution of secondary emission sources, weathering of residues in the environment, and loss of ice cover in the Arctic. Enantiomer-specific analysis could provide added forensic capability to air monitoring programs.
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| 7. |
- Bidleman, Terry F., et al.
(author)
-
Atmospheric transport and deposition of bromoanisoles along a temperate to arctic gradient
- 2017
-
In: Environmental Science and Technology. - Washington : American Chemical Society (ACS). - 1086-931X .- 1520-6912 .- 0013-936X .- 1520-5851. ; 51:19, s. 10974-10982
-
Journal article (peer-reviewed)abstract
- Bromoanisoles (BAs) arise from O-methylation of bromophenols, produced by marine algae and invertebrates. BAs undergo sea-air exchange and are transported over the oceans. Here we report 2,4-DiBA and 2,4,6-TriBA in air and deposition on the Swedish west coast (Råö) and the interior of arctic Finland (Pallas). Results are discussed in perspective with previous measurements in the northern Baltic region in 2011−2013. BAs in air decreased from south to north in the order Råö > northern Baltic > Pallas. Geometric mean concentrations at Pallas increased significantly (p < 0.05) between 2002 and 2015 for 2,4-DiBA but not for 2,4,6-TriBA. The logarithm of BA partial pressures correlated significantly to reciprocal air temperature at the coastal station Råö and over the Baltic, but only weakly (2,4-DiBA) or not significantly (2,4,6-TriBA) at inland Pallas. Deposition fluxes of BAs were similar at both sites despite lower air concentrations at Pallas, due to greater precipitation scavenging at lower temperatures. Proportions of the two BAs in air and deposition were related to Henry’s law partitioning and source regions. Precipitation concentrations were 10−40% of those in surface water of Bothnian Bay, northern Baltic Sea. BAs deposited in the bay catchment likely enter rivers and provide an unexpected source to northern estuaries. BAs may be precursors to higher molecular weight compounds identified by others in Swedish inland lakes.
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| 8. |
- Bidleman, Terry F., et al.
(author)
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Biannual cycles of organochlorine pesticide enantiomers in arctic air suggest changing sources and pathways
- 2014
-
In: Atmospheric Chemistry and Physics Discussions. - : Copernicus GmbH. - 1680-7367 .- 1680-7375. ; 14:17, s. 25027-25050
-
Journal article (peer-reviewed)abstract
- Air samples collected during 1994–2000 at the Canadian arctic air monitoring stationAlert (82300 N, 62200 W) were analyzed by enantiospecific gas chromatography –mass spectrometry for -hexachlorocyclohexane (-HCH), trans-chlordane (TC) and5 cis-chlordane (CC). Results were expressed as enantiomer fractions (EF = quantitiesof (+)/[(+)+(−)] enantiomers), where EFs=0.5, < 0.5 and > 0.5 indicate racemic composition,and preferential depletion of (+) and (−) enantiomers, respectively. Long-termaverage EFs were close to racemic values for -HCH (0.504±0.004, n =197) andCC (0.505±0.004, n =162), and deviated farther from racemic for TC (0.470±0.013,10 n =165). Digital filtration analysis revealed biannual cycles of lower -HCH EFs insummer-fall and higher EFs in winter-spring. These cycles suggest volatilization ofpartially degraded -HCH with EF < 0.5 from open water and advection to Alert duringthe warm season, and background transport of -HCH with EF> 0.5 during the coldseason. The contribution of sea-volatilized -HCH was only 11% at Alert, vs. 32%15 at Resolute Bay (74.68 N, 94.90W) in 1999. EFs of TC also followed biannual cyclesof lower and higher values in the warm and cold seasons. These were in phasewith low and high cycles of the TC/CC ratio (expressed as FTC =TC/(TC+CC)), whichsuggests greater contribution of microbially “weathered” TC in summer-fall vs. winterspring.CC was closer to racemic than TC and displayed seasonal cycles only in 1997–20 1998. EF profiles are likely to change with rising contribution of secondary emissionsources, weathering of residues in the environment, and loss of ice cover in the Arctic.Enantiomer-specific analysis could provide added forensic capability to air monitoringprograms.
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| 9. |
- Bidleman, Terry F., et al.
(author)
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Breakthrough during air sampling with polyurethane foam : What do PUF 2/PUF 1 ratios mean?
- 2018
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In: Chemosphere. - : Elsevier. - 0045-6535 .- 1879-1298. ; 192, s. 267-271
-
Journal article (peer-reviewed)abstract
- Frontal chromatography theory is applied to describe movement of gaseous semivolatile organic compounds (SVOCs) through a column of polyurethane foam (PUF). Collected mass fractions (FC) are predicted for sample volume/breakthrough volume ratios (τ = VS/VB) up to 6.0 and PUF bed theoretical plate numbers (N) from 2 to 16. The predictions assume constant air concentrations and temperatures. Extension of the calculations is done to relate the collection efficiency of a 2-PUF train (FC1+2) to the PUF 2/PUF 1 ratio. FC1+2 exceeds 0.9 for PUF 2/PUF 1 ≤ 0.5 and lengths of PUF commonly used in air samplers. As the PUF 2/PUF 1 ratio approaches unity, confidence in these predictions is limited by the analytical ability to distinguish residues on the two PUFs. Field data should not be arbitrarily discarded because some analytes broke through to the backup PUF trap. The fractional collection efficiencies can be used to estimate air concentrations from quantities retained on the PUF trap when sampling is not quantitative.
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| 10. |
- Bidleman, Terry F., et al.
(author)
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Bromoanisoles and Methoxylated Bromodiphenyl Ethers in Macroalgae from Nordic Coastal Regions
- 2019
-
In: Environmental Science. - London : Royal Society of Chemistry. - 2050-7887 .- 2050-7895. ; , s. 881-892
-
Journal article (peer-reviewed)abstract
- Marine macroalgae are used worldwide for human consumption, animal feed, cosmetics and agriculture. In addition to beneficial nutrients, macroalgae contain halogenated natural products (HNPs), some of which have toxic properties similar to those of well-known anthropogenic contaminants. Sixteen species of red, green and brown macroalgae were collected in 2017–2018 from coastal waters of the northern Baltic Sea, Sweden Atlantic and Norway Atlantic, and analyzed for bromoanisoles (BAs) and methoxylated bromodiphenyl ethers (MeO-BDEs). Target compounds were quantified by gas chromatography-low resolution mass spectrometry (GC-LRMS), with qualitative confirmation in selected species by GC-high resolution mass spectrometry (GC-HRMS). Quantified compounds were 2,4-diBA, 2,4,6-triBA, 2′-MeO-BDE68, 6-MeO-BDE47, and two tribromo-MeO-BDEs and one tetrabromo-MeO-BDE with unknown bromine substituent positions. Semiquantitative results for pentabromo-MeO-BDEs were also obtained for a few species by GC-HRMS. Three extraction methods were compared; soaking in methanol, soaking in methanol–dichloromethane, and blending with mixed solvents. Extraction yields of BAs did not differ significantly (p > 0.05) with the three methods and the two soaking methods gave equivalent yields of MeO-BDEs. Extraction efficiencies of MeO-BDEs were significantly lower using the blend method (p < 0.05). For reasons of simplicity and efficiency, the soaking methods are preferred. Concentrations varied by orders of magnitude among species: ∑2BAs 57 to 57 700 and ∑5MeO-BDEs < 10 to 476 pg g−1 wet weight (ww). Macroalgae standing out with ∑2BAs >1000 pg g−1 ww were Ascophyllum nodosum, Ceramium tenuicorne, Ceramium virgatum, Fucus radicans, Fucus serratus, Fucus vesiculosus, Saccharina latissima, Laminaria digitata, and Acrosiphonia/Spongomorpha sp. Species A. nodosum, C. tenuicorne, Chara virgata, F. radicans and F. vesiculosus (Sweden Atlantic only) had ∑5MeO-BDEs >100 pg g−1ww. Profiles of individual compounds showed distinct differences among species and locations.
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| 11. |
- Bidleman, Terry Frank, et al.
(author)
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Chiral Chemicals as Tracers of Atmospheric Sources and Fate Processes in a World of Changing Climate
- 2013
-
In: Mass Spectrometry. - 2186-5116. ; 2:19, Special Issue: Proceedings of 19th International Mass Spectrometry Conference, s. S0019-
-
Journal article (peer-reviewed)abstract
- Elimination of persistent organic pollutants (POPs) under national and international regulations reduces “primary” emissions, but “secondary” emissions continue from residues deposited in soil, water, ice and vegetation during former years of usage. In a future, secondary source controlled world, POPs will follow the carbon cycle and biogeochemical processes will determine their transport, accumulation and fate. Climate change is likely to affect mobilisation of POPs through e.g., increased temperature, altered precipitation and wind patterns, flooding, loss of ice cover in polar regions, melting glaciers, and changes in soil and water microbiology which affect degradation and transformation. Chiral compounds offer advantages for following transport and fate pathways because of their ability to distinguish racemic (newly released or protected from microbial attack) and nonracemic (microbially degraded) sources. This paper discusses the rationale for this approach and suggests applications where chiral POPs could aid investigation of climate-mediated exchange and degradation processes. Multiyear measurements of two chiral POPs, trans-chlordane and α-HCH, at a Canadian Arctic air monitoring station show enantiomer compositions which cycle seasonally, suggesting varying source contributions which may be under climatic control. Large-scale shifts in the enantioselective metabolism of chiral POPs in soil and water might influence the enantiomer composition of atmospheric residues, and it would be advantageous to include enantiospecific analysis in POPs monitoring programs.
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| 12. |
- Bidleman, Terry F, et al.
(author)
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Chiral persistent organic pollutants as tracers of atmospheric sources and fate : review and prospects for investigating climate change influences
- 2012
-
In: Atmospheric Pollution Research. - 1309-1042. ; 3:4, s. 371-382
-
Journal article (peer-reviewed)abstract
- Elimination of persistent organic pollutants (POPs) under national and international controls reduces “primary” emissions, but “secondary” emissions continue from residues deposited in soil, water, ice and vegetation during former years of high usage. Secondary sources are expected to dominate in the future, when POPs transport and accumulation will be controlled by air–surface exchange and the biogeochemical cycle of organic carbon. Climate change is likely to affect mobilization of POPs through, e.g., increased temperature, loss of ice cover in polar regions, melting glaciers and changes in soil and water microbiology which affect degradation and transformation. Chiral compounds offer advantages for following transport and fate pathways because of their ability to distinguish racemic (newly released or protected from microbial attack) and nonracemic (microbially altered) sources. Here we explain the rationale for this approach and suggest applications where chiral POPs could aid investigation of climate–mediated exchange and degradation processes. Examples include distinguishing agricultural vs. non–agricultural and recently used vs. residual pesticides, degradation and sequestration processes in soil, historical vs. recent atmospheric deposition, sources in arctic air and influence of ice cover on volatilization.
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| 13. |
- Bidleman, Terry F, et al.
(author)
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Chiral Pesticides in Soil and Water and Exchange with the Atmosphere
- 2002
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In: TheScientificWorldJOURNAL. - : Hindawi Limited. ; 2, s. 357-373
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Journal article (peer-reviewed)abstract
- The enantiomers of chiral pesticides are often metabolised at different rates in soil and water, leading to nonracemic residues. This paper reviews enantioselective metabolism of organochlorine pesticides (OCPs) in soil and water, and the use of enantiomers to follow transport and fate processes. Residues of chiral OCPs and their metabolites are frequently nonracemic in soil, although exceptions occur in which the OCPs are racemic. In soils where enantioselective degradation and/or metabolite formation has taken place, some OCPs usually show the same degradation preference — e.g., depletion of (+)trans-chlordane (TC) and (-)cis-chlordane (CC), and enrichment of the metabolite (+)heptachlor exo-epoxide (HEPX). The selectivity is ambivalent for other chemicals; preferential loss of either (+) or (-)o,p?-DDT and enrichment of either (+) or (-)oxychlordane (OXY) occurs in different soils. Nonracemic OCPs are found in air samples collected above soil which contains nonracemic residues. The enantiomer profiles of chlordanes in ambient air suggests that most chlordane in northern Alabama air comes from racemic sources (e.g., termiticide emissions), whereas a mixture of racemic and nonracemic (volatilisation from soil) sources supplies chlordane to air in the Great Lakes region. Chlordanes and HEPX are also nonracemic in arctic air, probably the result of soil emissions from lower latitudes. The (+) enantiomer of a-hexachlorocyclohexane (a-HCH) is preferentially metabolised in the Arctic Ocean, arctic lakes and watersheds, the North American Great Lakes, and the Baltic Sea. In some marine regions (the Bering and Chukchi Seas, parts of the North Sea) the preference is reversed and (-)a-HCH is depleted. Volatilisation from seas and large lakes can be traced by the appearance of nonracemic a-HCH in the air boundary layer above the water. Estimates of microbial degradation rates for a-HCH in the eastern Arctic Ocean and an arctic lake have been made from the enantiomer fractions (EFs) and mass balance in the water column. Apparent pseudo first-order rate constants in the eastern Arctic Ocean are 0.12 year-1 for (+)a-HCH, 0.030 year-1 for (-)a-HCH, and 0.037 year-1 for achiral ?-HCH. These rate constants are 3–10 times greater than those for basic hydrolysis in seawater. Microbial breakdown may compete with advective outflow for long-term removal of HCHs from the Arctic Ocean. Rate constants estimated for the arctic lake are about 3–8 times greater than those in the ocean.
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| 14. |
- Bidleman, Terry F., et al.
(author)
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Chlorinated pesticides and natural brominated anisoles in air at three northern Baltic stations
- 2017
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In: Environmental Pollution. - : Elsevier. - 0269-7491 .- 1873-6424. ; 225, s. 381-389
-
Journal article (peer-reviewed)abstract
- Abstract Polyurethane foam (PUF) disk passive samplers were deployed at one inland and two island locations in the Bothnian Bay region of the northern Baltic Sea. Uptake was linear over 81–147 d and a temperature range of −2.6 to 14.2 °C for organochlorine pesticides (OCPs) and current-use pesticides (CUPs) having log KOA ≥9 at ambient temperatures. Partial saturation of the PUF disks occurred for the more volatile OCPs hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB), and for bromoanisoles (BAs), which are products of bromophenols released by natural and anthropogenic sources. Correction for nonlinear uptake of these was made using experimentally measured PUF-air partition coefficients. Passive-derived air concentrations of pesticides were uniform over the bay and agreed within a factor of 2 or better with levels determined by active (pumped) sampling at one of the island stations. Levels of OCPs were similar to those reported at background sites in the European and Canadian Arctic and at monitoring stations in the central Baltic and southern Scandinavia, indicating long-range transport. The insecticide chlorpyrifos was 10 times lower at bay stations than in the Canadian Arctic. Insight to sources and processes was gained by examining compound profiles. Fractions Falpha = α-HCH/(α-HCH + γ-HCH) and FTC = trans-chlordane/(trans-chlordane + cis-chlordane) at bay stations were higher than in the Norwegian and Finnish Arctic and similar to those at the southern monitoring stations. Volatilization of chlordanes from Baltic seawater may also modify FTC. Higher FTriBA = 2,4,6-TriBA/(2,4,6-TriBA + 2,4-DiBA) distinguished local volatilization from the Baltic Sea versus lower FTriBA found at the inland site and reported in air on the Norwegian coast, suggesting westerly transport from the Atlantic across Norway and Sweden.
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| 15. |
- Bidleman, Terry F., et al.
(author)
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Drosophilin a methyl ether (DAME) and other chlorinated dimethoxybenzenes in fungi and forest litter from Sweden
- 2023
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In: Chemosphere. - : Elsevier. - 0045-6535 .- 1879-1298. ; 347
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Journal article (peer-reviewed)abstract
- Fungi and substrates undergoing fungal decomposition were collected from forests in northern and southernSweden and analyzed for chlorinated dimethoxybenzenes (DMBs). Specimens were fungi fruiting bodies, rottingwood, forest litter and underlying humus. Targeted compounds were DAME (1,2,4,5-tetrachloro-3,6-DMB) andrelated fungal secondary metabolites. A screening procedure was developed which involved soaking the speci-mens in ethyl acetate followed by analysis by capillary gas chromatography – mass spectrometry with mass selec-tive detection (GC-MSD). DAME was the most frequently found (62% of 47 specimens) and often the most abun-dant target compound, with range and mean ± SD concentrations of <0.0017–3.81 and 0.21 ± 0.63 mg kg−1ww. Based on log-log correlations of partition coefficients of hydrophobic compounds between fungal biomass/water (KD) and octanol/water (KOW), five species of fungi are suggested to produce DAME de novo versus bioaccu-mulation from forest runoff water. Full-scan mass spectra of some high-concentration specimens indicated thepresence of a Cl2DMB and a Cl3DMB, which could not be identified further due to lack of standards, anddrosophilin A (DA = 2,3,5,6-tetrachloro-4-methoxyphenol), the precursor to DAME. Tetrachloroveratrole(TeCV = 1,2,3,4-tetrachloro-5,6-DMB) was found in only a few specimens. This study supports our hypothesis offungi as a source of DAME in terrestrial runoff and indicates that other chlorinated secondary metabolites arepresent. DAME is widely distributed globally, and it would be good to have a better understanding of its sourcesand pathways as a marker of terrestrial organochlorines and their availability for bioaccumulation
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| 16. |
- Bidleman, Terry F., et al.
(author)
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Field estimates of polyurethane foam : air partition coefficients for hexachlorobenzene, alpha-hexachlorocyclohexane and bromoanisoles
- 2016
-
In: Chemosphere. - : Elsevier. - 0045-6535 .- 1879-1298. ; 159, s. 126-131
-
Journal article (peer-reviewed)abstract
- Partition coefficients of gaseous semivolatile organic compounds (SVOCs) between polyurethane foam (PUF) and air (KPA) are needed in the estimation of sampling rates for PUF disk passive air samplers. We determined KPA in field experiments by conducting long-term (24-48 h) air sampling to saturate PUF traps and shorter runs (2-4 h) to measure air concentrations. Sampling events were done at daily mean temperatures ranging from 1.9 to 17.5 °C. Target compounds were hexachlorobenzene (HCB), alpha-hexachlorocyclohexane (α-HCH), 2,4-dibromoanisole (2,4-DiBA) and 2,4,6-tribromoanisole (2,4,6-TriBA). KPA (mL g(-1)) was calculated from quantities on the PUF traps at saturation (ng g(-1)) divided by air concentrations (ng mL(-1)). Enthalpies of PUF-to-air transfer (ΔHPA, kJ mol(-1)) were determined from the slopes of log KPA/mL g(-1) versus 1/T(K) for HCB and the bromoanisoles, KPA of α-HCH was measured only at 14.3 to 17.5 °C and ΔHPA was not determined. Experimental log KPA/mL g(-1) at 15 °C were HCB = 7.37; α-HCH = 8.08; 2,4-DiBA = 7.26 and 2,4,6-TriBA = 7.26. Experimental log KPA/mL g(-1) were compared with predictions based on an octanol-air partition coefficient (log KOA) model (Shoeib and Harner, 2002a) and a polyparameter linear free relationship (pp-LFER) model (Kamprad and Goss, 2007) using different sets of solute parameters. Predicted KP values varied by factors of 3 to over 30, depending on the compound and the model. Such discrepancies provide incentive for experimental measurements of KPA for other SVOCs.
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| 17. |
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| 18. |
- Bidleman, Terry F., et al.
(author)
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Is There Still “New” DDT in North America? An Investigation Using Proportions of DDT Compounds
- 2013
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In: Occurrence, fate and impact of atmospheric pollutants on environmental and human health. - Washington, DC : American Chemical Society (ACS). - 9780841228900 - 9780841228917 ; , s. 153-181
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Book chapter (peer-reviewed)abstract
- Usage of DDT ceased over four decades ago in Canada and the United States, and since 2000 in Mexico. Potential sources in the North American atmosphere today include emissions of legacy residues from soils and long-range transport from other countries where DDT is still used or recently banned. Distinction of source types is investigated here using proportions of p,p'-DDT, o,p'-DDT, p,p'-DDE and p,p'-DDD. The relative volatilization of DDT compounds can be accurately described by their subcooled liquid vapor pressures (PO; e.g., (p,p'-DDT/p,p'-DDE)AIR = (p,p'-DDT/p,p'-DDE)son. x PL, (DDT)/P-L,P-DDE. Using this model, the expected proportions in air due to volatilization from technical DDT and from soils in Canada, the U.S.A. and Mexico were estimated and expressed as the fractions F-DDTE = p,p'-DDT/(p,p'-DDT + P,P'-DDE), F-DDTO = p,p1-DDT/(p,p'-DDT + o,p'-DDT), and FDDTD = p,p1-DDT/(p,p'-DDT + p,p1-DDD). FDDTE, FDDTO and FDDTD predicted from soil emissions were compared to compound fractions in ambient air sampled at the Integrated Atmospheric Deposition Network (IADN) of stations on the Great Lakes between Canada and the U.S.A., and at arctic monitoring stations. FDDTE in air at IADN stations on lakes Erie, Ontario, Michigan and Huron were lower than in technical DDT vapor. This is consistent with emissions of aged residues from agricultural land and urban centers near these lakes. By comparison, FDDTE values were higher at stations on Lake Superior where atmospheric DDT is likely due to long-range transport rather than regional soil emissions. FDDTE increased from the early 1990s to 2005 at the Lake Superior stations and at the Canadian arctic station Alert between 2002-2005, whereas a significant decline in FDDTE was observed at the Norwegian arctic station Zeppelin Mountain. The mean FDDTO in air at IADN stations were consistent with either soil emissions or technical DDT composition, but annual values showed significant downward trends at two Canadian stations, and also decreased with time at Zeppelin Mountain (but not at Alert). These trends might signify contribution from dicofol-type DDT sources, which have a lower FDDTO than technical DDT or soil emissions, or preferential degradation of p,p'-DDT vs. o,p'-DDT over time. FDDTD in air at IADN stations were lower than in technical DDT vapor, showing the influence of soil sources. The enantiomer proportions of the chiral compounds o,p'-DDT and o,p1-DDD were nonracemic in some soils and ambient air, but enantiospecific analysis has not been done for IADN air samples. It is suggested that isomer, parent/metabolite and enantiomer composition information be incorporated into air monitoring programs to help identify sources.
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| 19. |
- Bidleman, Terry F., et al.
(author)
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Lake Superior Has Lost over 90% of Its Pesticide HCH Load since 1986
- 2021
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In: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 55:14, s. 9518-9526
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Journal article (peer-reviewed)abstract
- The time trend of α- and γ-hexachlorocyclohexane (HCH) isomers in Lake Superior water was followed from 1986 to 2016, the longest record for any persistent organic pollutant (POP) in Great Lakes water. Dissipation of α-HCH and γ-HCHs was first order, with halving times (t1/2) of 5.7 and 8.5 y, respectively. Loss rates were not significantly different starting a decade later (1996−2016). Concentrations of β-HCH were followed from 1996−2016 and dissipated more slowly (t1/2 = 16 y). In 1986, the lake contained an estimated 98.8 tonnes of α-HCH and 13.2 tonnes of γ-HCH; by 2016, only 2.7% and 7.9% of 1986 quantities remained. Halving times of both isomers in water were longer than those reported in air, and for γ-HCH, they were longer in water than those reported in lake trout. Microbial degradation was evident by enantioselective depletion of (+)α-HCH, which increased from 1996 to 2011. Volatilization was the main removal process for both isomers, followed by degradation (hydrolytic and microbial) and outflow through the St. Mary’s River. Sedimentation was minor. Major uncertainties in quantifying removal processes were in the two-film model for predicting volatilization and in microbial degradation rates. The study highlights the value of long-term monitoring of chemicals in water to interpreting removal processes and trends in biota.
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| 20. |
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| 21. |
- Bidleman, Terry Frank, et al.
(author)
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Scavenging amphipods : sentinels for penetration of mercury and persistent organic chemicals into food webs of the deep arctic ocean
- 2013
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In: Environmental Science and Technology. - Washington : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 47:11, s. 5553-5561
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Journal article (peer-reviewed)abstract
- Archived specimens of the scavenging amphipod Eurythenes gryllus, collected from 2075 to 4250 m below the surface on five expeditions to the western and central Arctic Ocean between 1983 and 1998, were analyzed for total mercury (∑Hg), methyl mercury (MeHg), polychlorinated biphenyls (PCBs) and other industrial or byproduct organochlorines (chlorobenzenes, pentachloroanisole, octachlorostyrene), organochlorine pesticides (OCPs), and polybrominated diphenyl ethers (PBDEs). Median ∑Hg concentrations ranged from 70 to 366 ng g(-1) wet weight (ww). MeHg concentrations (3.55 to 23.5 ng g(-1) ww) accounted for 1.7 to 20.1% (median 3.7%) of ∑Hg. ∑Hg and MeHg were positively and significantly correlated with ww (∑Hg r(2) = 0.18, p = 0.0004, n = 63; MeHg r(2) = 0.42, p = 0.0004, n = 25), but not significantly with δ(13)C nor δ(15)N. Median concentrations of total persistent organic pollutants (POPs) ranged from 9750 to 156 000 ng g(-1) lipid weight, with order of abundance: ∑TOX (chlorobornanes quantified as technical toxaphene) > ∑PCBs > ∑DDTs > ∑chlordanes > ∑mirex compounds > ∑BDEs ∼ ∑chlorobenzenes ∼ octachlorostyrene > α-hexachlorocyclohexane ∼ hexachlorobenzene ∼ pentachloroanisole. Enantioselective accumulation was found for the chiral OCPs o,p'-DDT, cis- and trans-chlordane, nonachlor MC6 and oxychlordane. Lipid-normalized POPs concentrations were elevated in amphipods with lipid percentages ≤10%, suggesting that utilization of lipids resulted in concentration of POPs in the remaining lipid pool. Multidimensional Scaling (MDS) analysis using log-transformed physiological variables and lipid-normalized organochlorine concentrations distinguished amphipods from the central vs western arctic stations. This distinction was also seen for PCB homologues, whereas profiles of other compound classes were more related to specific stations rather than central-west differences.
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| 22. |
- Bidleman, Terry F., et al.
(author)
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Sea-air exchange of bromoanisoles and methoxylated bromodiphenylethers in the Northern Baltic
- 2016
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In: Marine Pollution Bulletin. - : Elsevier. - 0025-326X .- 1879-3363. ; 112:1-2, s. 58-64
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Journal article (peer-reviewed)abstract
- Halogenated natural products in biota of the Baltic Sea include bromoanisoles (BAs) and methoxylated bromodiphenyl ethers (MeO-BDEs). We identified biogenic 6-MeO-BDE47 and 2'-MeO-BDE68 in Baltic water and air for the first time using gas chromatography - high resolution mass spectrometry. Partial pressures in air were related to temperature by: log p/Pa=m/T(K)+b. We determined Henry's law constants (HLCs) of 2,4-dibromoanisole (2,4-DiBA) and 2,4,6-tribromoanisole (2,4,6-TriBA) from 5 to 30°C and revised our assessment of gas exchange in the northern Baltic. The new water/air fugacity ratios (FRs) were lower, but still indicated net volatilization in May-June for 2,4-DiBA and May - September for 2,4,6-TriBA. The net flux (negative) of BAs from Bothnian Bay (38,000km2) between May - September was revised from -1319 to -532kg. FRs of MeO-BDEs were >1, suggesting volatilization, although this is tentative due to uncertainties in their HLCs and binding to dissolved organic carbon.
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| 23. |
- Bidleman, Terry F., et al.
(author)
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Will Climate Change Influence Production and Environmental Pathways of Halogenated Natural Products?
- 2020
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In: Environmental Science and Technology. - Washington, DC, USA : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 54:11, s. 6468-6485
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Journal article (peer-reviewed)abstract
- Thousands of halogenated natural products (HNPs) pervade the terrestrial and marine environment. HNPs are generated by biotic and abiotic processes and range in complexity from low molecular mass natural halocarbons (nHCs, mostly halomethanes and haloethanes) to compounds of higher molecular mass which often contain oxygen and/or nitrogen atoms in addition to halogens (hHNPs). nHCs have a key role in regulating tropospheric and stratospheric ozone, while some hHNPs bioaccumulate and have toxic properties similar those of anthropogenic-persistent organic pollutants (POPs). Both chemical classes have common sources: biosynthesis by marine bacteria, phytoplankton, macroalgae, and some invertebrate animals, and both may be similarly impacted by alteration of production and transport pathways in a changing climate. The nHCs scientific community is advanced in investigating sources, atmospheric and oceanic transport, and forecasting climate change impacts through modeling. By contrast, these activities are nascent or nonexistent for hHNPs. The goals of this paper are to (1) review production, sources, distribution, and transport pathways of nHCs and hHNPs through water and air, pointing out areas of commonality, (2) by analogy to nHCs, argue that climate change may alter these factors for hHNPs, and (3) suggest steps to improve linkage between nHCs and hHNPs science to better understand and predict climate change impacts.
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| 24. |
- Bidleman, Terry, et al.
(author)
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Halogenated Natural Products
- 2017
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In: AMAP Assessment 2016: Chemicals of Emerging Arctic Concern. - Oslo, Norway : AMAP - Arctic Monitoring and Assessment Programme. - 9788279711049 ; , s. 243-267
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Book chapter (peer-reviewed)
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| 25. |
- Bidleman, Terry, et al.
(author)
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Halomethoxybenzenes in air of the Nordic region
- 2023
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In: Environmental Science and Ecotechnology. - : Elsevier. - 2666-4984. ; 13
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Journal article (peer-reviewed)abstract
- Halomethoxybenzenes (HMBs) are a group of compounds with natural and anthropogenic origins. Here we extend a 2002–2015 survey of bromoanisoles (BAs) in the air and precipitation at Råö on the Swedish west coast and Pallas in Subarctic Finland. New BAs data are reported for 2018 and 2019 and chlorinated HMBs are included for these and some previous years: drosophilin A methyl ether (DAME: 1,2,4,5-tetrachloro-3,6-dimethoxybenzene), tetrachloroveratrole (TeCV: 1,2,3,4-tetrachloro-5,6-dimethoxybenzene), and pentachloroanisole (PeCA). The order of abundance of HMBs at Råö was ΣBAs > DAME > TeCV > PeCA, whereas at Pallas the order of abundance was DAME > ΣBAs > TeCA > PeCA. The lower abundance of BAs at Pallas reflects its inland location, away from direct marine influence. Clausius-Clapeyron (CC) plots of log partial pressure (Pair)/Pa versus 1/T suggested distant transport at both sites for PeCA and local exchange for DAME and TeCV. BAs were dominated by distant transport at Pallas and by both local and distant sources at Råö. Relationships between air and precipitation concentrations were examined by scavenging ratios, SR = (ng m−3)precip/(ng m−3)air. SRs were higher at Pallas than Råö due to greater Henry's law partitioning of gaseous compounds into precipitation at colder temperatures. DAME is produced by terrestrial fungi. We screened 19 fungal species from Swedish forests and found seven of them contained 0.01–3.8 mg DAME per kg fresh weight. We suggest that the volatilization of DAME from fungi and forest litter containing fungal mycelia may contribute to atmospheric levels at both sites.
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