| 1. |
- Okeme, Joseph, et al.
(författare)
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Gas chromatographic estimation of vapor pressures and octanol-air partition coefficients of semivolatile organic compounds of emerging concern
- 2020
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Ingår i: Journal of Chemical and Engineering Data. - Washington, DC, USA : American Chemical Society (ACS). - 0021-9568 .- 1520-5134. ; 65:5, s. 2467-2475
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Tidskriftsartikel (refereegranskat)abstract
- The subcooled liquid-phase vapor pressures (pL298/Pa) and octanol–air partition coefficients (KOA298) at T/K = 298, enthalpies of vaporization (ΔVAPH/kJ·mol–1), and internal energies of phase transfer from octanol to air (ΔOAU/kJ·mol–1) were estimated for synthetic musks, novel brominated flame retardants (N-BFR), organophosphate esters, and ultraviolet filters using the capillary gas chromatographic retention time (GC-RT) method. These compounds, which spanned approximately six and three orders of magnitude for pL298/Pa and KOA298, respectively, were co-chromatographed with one of three reference compounds to give initial estimates of properties at T/K = 298. The initial GC-RT property estimates were subsequently calibrated using 18 compounds that spanned 6 log units for pL298/Pa and 13 compounds covering 4 log units for KOA298. The calibrated log10pL298/Pa values estimated here ranged from 0.14 ± 0.19 to −9.19 ± 0.29 for cyclopentadecanone to syn-dechlorane plus (syn-DDC-CO), respectively, while the range of log10KOA298 values was 6.59 ± 0.26 to 11.40 ± 0.23 for cyclopentadecanone to 2,2′,4,4′,5-pentabromodiphenyl ether (BDE-99), respectively. The calibrated GC-RT-derived values were highly correlated with, and were within an average of 0.70 log units of, the literature data for compounds with well-established pL298/Pa and KOA298 measured or derived using non-GC-RT methods. Nonpolar compounds were used in this study to estimate the target polar compound data, which may introduce systematic errors. However, the comparison of our GC-RT results against the literature non-GC-RT values shows that the GC-RT methods performed similarly well for estimating both polar and nonpolar target compounds studied in this work.
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| 2. |
- Rodgers, Timothy F.M., et al.
(författare)
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Novel Bayesian Method to Derive Final Adjusted Values of Physicochemical Properties : Application to 74 Compounds
- 2021
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 55:18, s. 12302-12316
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Tidskriftsartikel (refereegranskat)abstract
- Accurate values of physicochemical properties are essential for screening semivolatile organic compounds for human and environmental hazard and risk. In silico approaches for estimation are widely used, but the accuracy of these and measured values can be difficult to ascertain. Final adjusted values (FAVs) harmonize literature-reported measurements to ensure consistency and minimize uncertainty. We propose a workflow, including a novel Bayesian approach, for estimating FAVs that combines measurements using direct and indirect methods and in silico values. The workflow was applied to 74 compounds across nine classes to generate recommended FAVs (FAVRs). Estimates generated by in silico methods (OPERA, COSMOtherm, EPI Suite, SPARC, and polyparameter linear free energy relationships (pp-LFER) models) differed by orders of magnitude for some properties and compounds and performed systematically worse for larger, more polar compounds. COSMOtherm and OPERA generally performed well with low bias although no single in silico method performed best across all compound classes and properties. Indirect measurement methods produced highly accurate and precise estimates compared with direct measurement methods. Our Bayesian method harmonized measured and in silico estimated physicochemical properties without introducing observable biases. We thus recommend use of the FAVRs presented here and that the proposed Bayesian workflow be used to generate FAVRs for SVOCs beyond those in this study.
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| 3. |
- Bidleman, Terry F., et al.
(författare)
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Air-water exchange of brominated anisoles in the northern baltic sea
- 2014
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 48:11, s. 6124-6132
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Tidskriftsartikel (refereegranskat)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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| 4. |
- Bidleman, Terry F., et al.
(författare)
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Atmospheric transport and deposition of bromoanisoles along a temperate to arctic gradient
- 2017
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Ingår i: Environmental Science and Technology. - Washington : American Chemical Society (ACS). - 1086-931X .- 1520-6912 .- 0013-936X .- 1520-5851. ; 51:19, s. 10974-10982
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Tidskriftsartikel (refereegranskat)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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| 5. |
- Bidleman, Terry F., et al.
(författare)
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Biannual cycles of organochlorine pesticide enantiomers in arctic air suggest changing sources and pathways
- 2014
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Ingår i: Atmospheric Chemistry and Physics Discussions. - : Copernicus GmbH. - 1680-7367 .- 1680-7375. ; 14:17, s. 25027-25050
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Tidskriftsartikel (refereegranskat)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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| 6. |
- Bidleman, Terry F., et al.
(författare)
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Breakthrough during air sampling with polyurethane foam : What do PUF 2/PUF 1 ratios mean?
- 2018
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Ingår i: Chemosphere. - : Elsevier. - 0045-6535 .- 1879-1298. ; 192, s. 267-271
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Tidskriftsartikel (refereegranskat)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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| 7. |
- Bidleman, Terry F., et al.
(författare)
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Bromoanisoles and Methoxylated Bromodiphenyl Ethers in Macroalgae from Nordic Coastal Regions
- 2019
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Ingår i: Environmental Science. - London : Royal Society of Chemistry. - 2050-7887 .- 2050-7895. ; , s. 881-892
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Tidskriftsartikel (refereegranskat)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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| 8. |
- Bidleman, Terry F, et al.
(författare)
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Chiral persistent organic pollutants as tracers of atmospheric sources and fate : review and prospects for investigating climate change influences
- 2012
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Ingår i: Atmospheric Pollution Research. - 1309-1042. ; 3:4, s. 371-382
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Tidskriftsartikel (refereegranskat)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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| 9. |
- Bidleman, Terry F, et al.
(författare)
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Chiral Pesticides in Soil and Water and Exchange with the Atmosphere
- 2002
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Ingår i: TheScientificWorldJOURNAL. - : Hindawi Limited. ; 2, s. 357-373
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Tidskriftsartikel (refereegranskat)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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| 10. |
- Bidleman, Terry F., et al.
(författare)
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Chlorinated pesticides and natural brominated anisoles in air at three northern Baltic stations
- 2017
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Ingår i: Environmental Pollution. - : Elsevier. - 0269-7491 .- 1873-6424. ; 225, s. 381-389
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Tidskriftsartikel (refereegranskat)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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| 11. |
- Bidleman, Terry F., et al.
(författare)
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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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Ingår i: Chemosphere. - : Elsevier. - 0045-6535 .- 1879-1298. ; 347
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Tidskriftsartikel (refereegranskat)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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| 12. |
- Bidleman, Terry F., et al.
(författare)
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Field estimates of polyurethane foam : air partition coefficients for hexachlorobenzene, alpha-hexachlorocyclohexane and bromoanisoles
- 2016
-
Ingår i: Chemosphere. - : Elsevier. - 0045-6535 .- 1879-1298. ; 159, s. 126-131
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Tidskriftsartikel (refereegranskat)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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| 13. |
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| 14. |
- Bidleman, Terry F., et al.
(författare)
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Is There Still “New” DDT in North America? An Investigation Using Proportions of DDT Compounds
- 2013
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Ingår i: 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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Bokkapitel (refereegranskat)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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| 15. |
- Bidleman, Terry F., et al.
(författare)
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Lake Superior Has Lost over 90% of Its Pesticide HCH Load since 1986
- 2021
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 55:14, s. 9518-9526
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Tidskriftsartikel (refereegranskat)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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| 16. |
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| 17. |
- Bidleman, Terry F., et al.
(författare)
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Sea-air exchange of bromoanisoles and methoxylated bromodiphenylethers in the Northern Baltic
- 2016
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Ingår i: Marine Pollution Bulletin. - : Elsevier. - 0025-326X .- 1879-3363. ; 112:1-2, s. 58-64
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Tidskriftsartikel (refereegranskat)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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| 18. |
- Bidleman, Terry F., et al.
(författare)
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Will Climate Change Influence Production and Environmental Pathways of Halogenated Natural Products?
- 2020
-
Ingår i: Environmental Science and Technology. - Washington, DC, USA : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 54:11, s. 6468-6485
-
Tidskriftsartikel (refereegranskat)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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| 19. |
- Chartrand, Michelle, et al.
(författare)
-
Compound specific isotope analysis of hexachlorocyclohexane isomers : a method for source fingerprinting and field investigation of in situ biodegradation
- 2015
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Ingår i: Rapid Communications in Mass Spectrometry. - : John Wiley & Sons. - 0951-4198 .- 1097-0231. ; 29:6, s. 505-514
-
Tidskriftsartikel (refereegranskat)abstract
- RATIONALE: The manufacturing and uses of hexachlorocyclohexane (HCH) have resulted in a serious environmentalchallenge and legacy. This study highlights the ability of compound specific isotope analysis (CSIA) to distinguishamong various HCH sources and to support the evaluation of the potential for in situ biodegradation in contaminatedgroundwater.METHODS: Tests were conducted to verify the absence of significant isotope fractionation during HCH sample preconcentrationincluding dichloromethane extraction, solvent exchange into iso-octane, and H2SO4 clean-up, and analysisby gas chromatography/combustion-isotope ratio mass spectrometry (GC/C-IRMS). The method was then applied tofour Technical Grade (TG) HCH mixtures procured from different sources and to groundwater samples from acontaminated site.RESULTS: The pre-concentration method enabled determination of carbon isotope ratios (δ13C values) of HCH isomerswith no significant isotopic fractionation. The TG-HCH mixtures had significantly different δ13C values. Moreover, forany given TG-HCH, all isomers had δ13C values within 1.1‰ of each other – a distinctly uniform fingerprint. At theHCH-contaminated field site, compared with source wells, downgradient wells showed significant (up to 5.1‰)enrichment in 13C and the δ13C values of the HCH isomers were significantly different from each other.CONCLUSIONS: A method was successfully developed for the CSIA of HCH isomers that showed potential for HCHsource differentiation and identification of HCH in situ biodegradation. At the HCH-contaminated site, the observedpreferential isotopic enrichment of certain isomers relative to others for a given source allows differentiation betweenbiodegraded and non-biodegraded HCH.
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| 20. |
- Hites, Ronald, et al.
(författare)
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Atmospheric Concentrations of Hexachlorobenzene and Octachlorostyrene Are Uniform across the Great Lakes Region and Have Not Changed Much in 25 Years
- 2022
-
Ingår i: Environmental Science and Technology Letters. - : American Chemical Society (ACS). - 2328-8930. ; 9:8, s. 660-665
-
Tidskriftsartikel (refereegranskat)abstract
- Hexachlorobenzene (HCB) was used in the United States from 1945 to 1966 as a fungicide on wheat, while octachlorostyrene (OCS) was never marketed. However, both HCB and OCS continue to be emitted into the atmosphere as byproducts of several industrial processes. We have measured the atmospheric concentrations of HCB and OCS in samples collected every 12 days at five sites on the shores of the North American Great Lakes since 1991. The geometric mean concentrations of HCB and OCS are ∼60 and 0.7 pg/m3, respectively, at all sites regardless of the local population, and these concentrations have not changed significantly over time. The concentrations of HCB measured here are similar to those reported by other studies of the northern troposphere and are ∼3 times those reported in the southern troposphere, suggesting that HCB sources are largely in the Northern Hemisphere. It is apparent that direct and recycled emissions of HCB and OCS into the northern troposphere are widespread in scope and, despite the elimination of HCB as a fungicide, have not changed in a meaningful way in the past 20–30 years. This is unlike the case for other legacy chemicals, for which global restrictions on their use have been more effective.
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| 21. |
- Jantunen, Liisa, et al.
(författare)
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20 Years of Air-Water Gas Exchange Observations for Pesticides in the Western Arctic Ocean
- 2015
-
Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 49:23, s. 13844-13852
-
Tidskriftsartikel (refereegranskat)abstract
- The Arctic has been contaminated by legacy organochlorine pesticides (OCPs) and currently used pesticides (CUPs) through atmospheric transport and oceanic currents. Here we report the time trends and air−water exchange of OCPs and CUPs from research expeditions conducted between 1993 and 2013. Compounds determined in both air and water were trans- and cis-chlordanes (TC, CC), trans- and cis-nonachlors (TN, CN), heptachlor exo-epoxide (HEPX), dieldrin (DIEL), chlorobornanes (ΣCHBs and toxaphene), dacthal (DAC), endosulfans and metabolite endosulfan sulfate (ENDO-I, ENDO-II, and ENDO SUL), chlorothalonil (CHT), chlorpyrifos (CPF), and trifluralin (TFN). Pentachloronitrobenzene (PCNB and quintozene) and its soil metabolite pentachlorothianisole (PCTA) were also found in air. Concentrations of most OCPs declined in surface water, whereas some CUPs increased (ENDO-I, CHT, and TFN) or showed no significant change (CPF and DAC), and most compounds declined in air. Chlordane compound fractions TC/(TC + CC) and TC/(TC + CC + TN) decreased in water and air, while CC/(TC + CC + TN) increased. TN/(TC + CC + TN) also increased in air and slightly, but not significantly, in water. These changes suggest selective removal of more labile TC and/or a shift in chlordane sources. Water−air fugacity ratios indicated net volatilization (FR > 1.0) or near equilibrium (FR not significantly different from 1.0) for most OCPs but net deposition (FR < 1.0) for ΣCHBs. Net deposition was shown for ENDO-I on all expeditions, while the net exchange direction of other CUPs varied. Understanding the processes and current state of air−surface exchange helps to interpret environmental exposure and evaluate the effectiveness of international protocols and provides insights for the environmental fate of new and emerging chemicals.
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| 22. |
- Kupryianchyk, Darya, et al.
(författare)
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Industrial and natural compounds in filter-feeding black fly larvae and water in 3 tundra streams
- 2018
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Ingår i: Environmental Toxicology and Chemistry. - : John Wiley & Sons. - 0730-7268 .- 1552-8618. ; 37:12, s. 3011-3017
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Tidskriftsartikel (refereegranskat)abstract
- We report concentrations of polychlorinated biphenyls, polybrominated diphenyl ethers, novel flame retardants, and naturally occurring bromoanisoles in water and filter-feeding black fly (Simuliidae) larvae in 3 tundra streams in northern Sweden. The results demonstrate that black fly larvae accumulate a wide range of organic contaminants and can be used as bioindicators of water pollution in Arctic streams.
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| 23. |
- Kurt-Karakus, Perihan Binnur, et al.
(författare)
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CURRENT-USE PESTICIDES IN INLAND LAKE WATERS, PRECIPITATION, AND AIR FROM ONTARIO, CANADA
- 2011
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Ingår i: Environmental Toxicology and Chemistry. - : WILEY-BLACKWELL. - 0730-7268 .- 1552-8618. ; 30:7, s. 1539-1548
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Tidskriftsartikel (refereegranskat)abstract
- Concentrations of current-use pesticides (CUPs) in water, zooplankton, precipitation, and air samples as well as stereoisomer fractions (SF; herbicidally active/total stereoisomers) of metolachlor were determined in water samples collected from 10 remote inland lakes in Ontario, Canada, between 2003 and 2005. The most frequently detected chemicals in lake water, precipitation, and air were alpha-endosulfan, atrazine, metolachlor, chlorpyrifos, chlorothalonil, and trifluralin, and alpha-endosulfan and chlorpyrifos were the chemicals detected frequently in zooplankton. Air concentrations of these CUPs were within the range of previously reported values for background sites in the Great Lakes basin. High detection frequency of CUPs in lake water and precipitation was attributed to high usage amounts, but some CUPs such as ametryn and disulfoton that were not used in Ontario were also detected. Mean bioaccumulation factors (wet wt) in zooplankton for endosulfan ranged from 160 to 590 and from 20 to 60 for chlorpyrifos. The overall median SF of metolachlor in precipitation samples (0.846) was similar to that of the commercial S-metolaehlor (0.882). However, the median SF of metolachlor in water from all sampled inland lakes (0.806) was significantly lower compared with Ontario rivers (0.873) but higher compared with previous measurements in the Great Lakes (0.710). Lakes with smaller watershed areas showed higher SFs, supporting the hypothesis of stereoselective processing of deposited metolachlor within the watersheds, followed by transport to the lakes. Environ. Toxicol. Chem. 2011;30:1539-1548. (C) 2011 SETAC
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| 24. |
- Lohmann, Rainer, et al.
(författare)
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Passive-sampler-derived PCB and OCP concentrations in the waters of the world : first results from the AQUA-GAPS/MONET network
- 2023
-
Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 57:25, s. 9342-9352
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Tidskriftsartikel (refereegranskat)abstract
- Persistent organic pollutants (POPs) are recognized as pollutants of global concern, but so far, information on the trends of legacy POPs in the waters of the world has been missing due to logistical, analytical, and financial reasons. Passive samplers have emerged as an attractive alternative to active water sampling methods as they accumulate POPs, represent time-weighted average concentrations, and can easily be shipped and deployed. As part of the AQUA-GAPS/MONET, passive samplers were deployed at 40 globally distributed sites between 2016 and 2020, for a total of 21 freshwater and 40 marine deployments. Results from silicone passive samplers showed α-hexachlorocyclohexane (HCH) and γ-HCH displaying the greatest concentrations in the northern latitudes/Arctic Ocean, in stark contrast to the more persistent penta (PeCB)- and hexachlorobenzene (HCB), which approached equilibrium across sampling sites. Geospatial patterns of polychlorinated biphenyl (PCB) aqueous concentrations closely matched original estimates of production and use, implying limited global transport. Positive correlations between log-transformed concentrations of Σ7PCB, ΣDDTs, Σendosulfan, and Σchlordane, but not ΣHCH, and the log of population density (p < 0.05) within 5 and 10 km of the sampling sites also supported limited transport from used sites. These results help to understand the extent of global distribution, and eventually time-trends, of organic pollutants in aquatic systems, such as across freshwaters and oceans. Future deployments will aim to establish time-trends at selected sites while adding to the geographical coverage.
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| 25. |
- Pućko, Monika, et al.
(författare)
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Current use pesticide and legacy organochlorine pesticide dynamics at the ocean-sea ice-atmosphere interface in resolute passage, Canadian Arctic, during winter-summer transition
- 2017
-
Ingår i: Science of the Total Environment. - : Elsevier BV. - 0048-9697 .- 1879-1026. ; 580, s. 1460-1469
-
Tidskriftsartikel (refereegranskat)abstract
- Here, we present the first detailed analysis of processes by which various current use pesticides (CUPs) and legacy organochlorine pesticides (OCPs) are concentrated in melt ponds that form on Arctic sea ice in the summer, when surface snow is melting and ice eventually breaks up. Four current use pesticides (dacthal, chlorpyrifos, trifluralin, and pentachloronitrobenzene) and one legacy organochlorine pesticide (α-hexachlorocyclohexane) were detected in ponds in Resolute Passage, Canadian Arctic, in 2012. Melt-pond concentrations changed over time as a function of gas exchange, precipitation, and dilution with melting sea ice. Observed increases in melt-pond concentrations for all detected pesticides were associated with precipitation events. Dacthal reached the highest concentration of all current use pesticides in ponds (95 ± 71 pg L− 1), a value exceeding measured concentrations in the under-ice (0 m) and 5 m seawater by > 10 and > 16 times, respectively. Drainage of dacthal-enriched pond water to the ocean during ice break-up provides an important ice-mediated annual delivery route, adding ~ 30% of inventory in the summer Mixed Layer (ML; 10 m) in the Resolute Passage, and a concentrating mechanism with potential implications for exposures to organisms such as ice algae, and phytoplankton.
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| 26. |
- Pućko, Monika, et al.
(författare)
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The delivery of organic contaminants to the Arctic food web : why sea ice matters
- 2015
-
Ingår i: Science of the Total Environment. - : Elsevier. - 0048-9697 .- 1879-1026. ; 506–507, s. 444-452
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Tidskriftsartikel (refereegranskat)abstract
- For decades sea ice has been perceived as a physical barrier for the loading of contaminants to the Arctic Ocean. We show that sea ice, in fact, facilitates the delivery of organic contaminants to the Arctic marine food web through processes that: 1) are independent of contaminant physical–chemical properties (e.g. 2–3-fold increase in exposure to brine-associated biota), and 2) depend on physical–chemical properties and, therefore, differentiate between contaminants (e.g. atmospheric loading of contaminants to melt ponds over the summer, and their subsequent leakage to the ocean). We estimate the concentrations of legacy organochlorine pesticides (OCPs) and current-use pesticides (CUPs) in melt pond water in the Beaufort Sea, Canadian High Arctic, in 2008, at near-gas exchange equilibrium based on Henry's law constants (HLCs), air concentrations and exchange dynamics. CUPs currently present the highest risk of increased exposures through melt pond loading and drainage due to the high ratio of melt pond water to seawater concentration (Melt pond Enrichment Factor, MEF), which ranges from 2 for dacthal to 10 for endosulfan I. Melt pond contaminant enrichment can be perceived as a hypothetical ‘pump’ delivering contaminants from the atmosphere to the ocean under ice-covered conditions, with 2–10% of CUPs annually entering the Beaufort Sea via this input route compared to the standing stock in the Polar Mixed Layer of the ocean. The abovementioned processes are strongly favored in first-year ice compared to multi-year ice and, therefore, the dynamic balance between contaminant inventories and contaminant deposition to the surface ocean is being widely affected by the large-scale icescape transition taking place in the Arctic.
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| 27. |
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| 28. |
- Sánchez-Osorio, José Luis, et al.
(författare)
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Organochlorine pesticides in residential soils and sediments within two main agricultural areas of northwest Mexico : concentrations, enantiomer compositions and potential sources
- 2017
-
Ingår i: Chemosphere. - : Elsevier BV. - 0045-6535 .- 1879-1298. ; 173, s. 275-287
-
Tidskriftsartikel (refereegranskat)abstract
- The agricultural Mexicali and Yaqui valleys (MV, YV) in northwest Mexico were heavily treated with organochlorine pesticides in the past. Residential soils and agricultural drain sediments were sampled in 2008–2009 and analyzed for DDTs (o,p′- and p,p′- isomers of DDE, DDD and DDT); hexachlorocyclohexanes (α-, β-, γ- and δ-HCH) and chlordanes (trans-chlordane, cis-chlordane, heptachlor and heptachlor exo-epoxide). Geometric means (GMs) (ng g−1 dry weight) were: MV soils (n = 27) ΣDDT 22, ΣHCH 0.80, ΣCHL 0.88; YV soils (n = 25) ΣDDT 5.0, ΣHCH 0.23, ΣCHL 0.67; MV sediments (n = 3) ΣDDT 5.0, ΣHCH 0.23, ΣCHL 0.53; YV sediments (n = 8) ΣDDT 2.6, ΣHCH 0.12, ΣCHL 0.090. GMs were significantly higher (p < 0.05) in MV than YV soils for ΣDDT and ΣHCH, but not for ΣCHL. Comparison to worldwide regulatory guideline values (RGVs) for residential soils showed all compounds below mean or GM RGVs, but above the lowest RGV in some cases. Low p,p′-DDT/(p,p′-DDT + p,p′-DDE) in most soils indicated aged residues. Lack of p,p′-DDT metabolism might account for its dominance in a few soils. HCH isomer profiles suggested aged technical HCH in the YV, and technical HCH + lindane in the MV. Heptachlor dominated the ΣCHL, probably from application of technical heptachlor as well as chlordane. Chiral compounds were nonracemic in soils and sediments and indicated enantioselective microbial degradation of (+)α-HCH, (−)trans-chlordane, (−)cis-chlordane and (+)o,p′-DDT. Depletion of (+)o,p′-DDT in soils may account for similar enantiomer signatures previously reported in air of northwest Mexico.
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| 29. |
- Tysklind, Mats, et al.
(författare)
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A Baltic mystery
- 2014
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Annan publikation (refereegranskat)abstract
- HNPs are produced by macroalgae (seaweeds), phytoplankton, worms, sponges and other marine organisms. HNPs in the Baltic comprise halocarbons, bromophenols and their transformation products, and other compounds with diverse chemical structures. The HNPs derived from bromophenols are widespread in Baltic algae, fi sh and mussels, and include bromoanisoles, hydroxylated and methoxylated bromodiphenyl ethers (OH- and MeO-BDEs) and polybrominated dibenzo-p-dioxins (PBDDs). Some of these also have anthropogenic origins; bromophenols are used as industrial compounds, while MeO-BDEs and OH-BDEs are metabolites and photolysis products of polybrominated diphenyl ether fl ame retardants. Nonetheless, radiocarbon-14 dating has shown that most of the OH-BDEs and MeO-BDEs found in marine mammals and sponges are natural. The bromophenolderived HNPs have toxic properties which add to the ‘soup’ of anthropogenic toxic chemicals present in the Baltic.
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| 30. |
- Wiberg, Karin, et al.
(författare)
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Chiral analysis of organochlorine pesticides in Alabama soils
- 2001
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Ingår i: Chemosphere. ; 45:6-7, s. 843-8
-
Tidskriftsartikel (refereegranskat)abstract
- The enantiomeric composition of organochlorine (OC) pesticide residues was investigated in 32 agricultural and 3 cemetery soils from Alabama. The enantiomeric signatures were similar to those from other soils in US and Canada. The enantiomer fractions (EFs) of o,p′-DDT showed great variability, ranging from 0.41 to 0.57 while the EFs of chlordanes and chlordane metabolites were less variable and differed in general significantly from racemic. Enantioselective depletion of (+)trans-chlordane, (−)cis-chlordane, the first eluting enantiomer of MC5, and enrichment of (+)heptachlor-exo-epoxide and (+)oxychlordane was found in a large majority of the samples with detectable residues. The enantiomeric composition of α-hexachlorocyclohexane was racemic or close to racemic.
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| 31. |
- Wiberg, Karin, et al.
(författare)
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Concentrations and Fluxes of Hexachlorocyclohexanes and Chiral Composition of -HCH in Environmental Samples from the Southern Baltic Sea
- 2001
-
Ingår i: Environmental Science & Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 35:24, s. 4739-46
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Tidskriftsartikel (refereegranskat)abstract
- In summer 1997 and winter 1998, paired boundary air and surface water samples were collected during cruises in the southern Baltic Sea. Simultaneously, deposition samples were taken at Gotland Island, located close to the air-water sampling area. Water samples taken shortly after the flooding of Oder and Wisla Rivers in summer 1997 were also included in the study. Concentrations and gas exchange fluxes of - and -HCH and chiral composition of -HCH were determined. According to fugacity calculations, the HCHs were close to air-sea partitioning equilibrium. The net fluxes varied over time, particularly during summer. Importance of the air to sea removal routes "gross gas deposition" and "wet deposition" were about equal for -HCH, while the scavenging via precipitation was less important for -HCH. Enantiomer fractions were used to estimate the fraction of -HCH in the boundary air layer that had volatilized from the water. During summer, the fraction was approximately 60%, and wintertime significantly less (0-35%). Variations in air mass origin were clearly reflected in net air-sea gas exchange and isomeric and enantiomeric "signatures" in boundary air. The composition of boundary air and precipitation was also variable depending on season.
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| 32. |
- Wiberg, Karin, et al.
(författare)
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The Enantioselective Bioaccumulation of Chiral Chlordane and -HCH Contaminants in the Polar Bear Food Chain
- 2000
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Ingår i: Environmental Science & Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 34:13, s. 2668-74
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Tidskriftsartikel (refereegranskat)abstract
- The enantiomer ratios (ERs) of -HCH and chlordane related compounds (CHLs) were examined in the polar bear food chain (arctic cod-ringed seal-polar bear), using chiral gas chromatography-mass spectrometry (GC-MS). The cod showed near-racemic mixtures (ER = 1) for most of the compounds. In contrast, ERs in ringed seal and polar bear were frequently nonracemic (ER 1), due to enantiomer-specific biotransformation. As (+)--HCH was transferred up the food chain, it became more abundant relative to (-)--HCH. For the CHLs, there was no uniform trend for the ER changes and the increasing trophic level. Apparent chiral biomagnification factors (BFs) were calculated and up to a 20-fold difference in the BF between enantiomers was found. Analysis of chiral BFs relative to CB-153 indicated that oxychlordane was formed by ringed seal and metabolized by polar bears. However, the ERs did not change significantly as a result of these biotransformations. Multivariate statistical methods revealed the clustering of sample categories and were used to investigate the relationships between the ERs, chemical residue concentrations, and biological data. ERs were important variables for the sample groupings and for the class separation of male/female seals and fat/liver tissues. The variance in the cytochrome P450 CYP2B protein content of bear liver could be explained by the variances in chemical residue data. In this analysis the ERs were of secondary importance. The ERs of some highly recalcitrant CHLs in polar bear adipose showed linear relationships with the age of the bears.
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| 33. |
- Wong, Fiona, et al.
(författare)
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Aging of Organochlorine Pesticides and Polychlorinated Biphenyls in Muck Soil : Volatilization, Bioaccessibility, and Degradation
- 2011
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Ingår i: Environmental Science and Technology. - : AMER CHEMICAL SOC. - 0013-936X .- 1520-5851. ; 45:3, s. 958-963
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Tidskriftsartikel (refereegranskat)abstract
- An organic rich muck soil which is highly contaminated with native organochlorine pesticide (OCs) was spiked with known amounts of (13)C-labeled OCs and nonlabeled polychlorinated biphenyls (PCBs). Spiked soils were aged under indoor, outdoor, and sterile conditions and the change in volatility, surrogate bioaccessibility, and degradation of chemicals was monitored periodically over 730 d. Volatility was measured using a fugacity meter to characterize the soil-air partition coefficient (K(SA) = C(SOII)/C(AIR))). The fraction of bioaccessible residues was estimated by comparing recoveries of chemical with a mild extractant, hydroxylpropyl-beta-cyclodextrin (HPCD) vs a harsh extractant, DCM. K(SA) of the spiked OCs in the nonsterile (Indoor, Outdoor) soils were initially lower and approached the K(SA) of native OCs over time, showing reduction of volatility upon aging. HPCD extractability of spiked OCs and PCBs were negatively correlated with K(SA), which suggests that volatility can be used as a surrogate for bioaccessibility. Degradation of endosulfans, PCB 8 and 28 was observed in the nonsterile soils, and (13)C(6)-alpha-HCH showed selective degradation of the (+) enantiomer. Enantiomer fractions (EF) in air and HPCD extracts were lower than in nonsterile soils, suggesting greater sequestering of the (+) enantiomer in the soil during microbial degradation.
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| 34. |
- Wong, Fiona, et al.
(författare)
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Air-Water Exchange of Anthropogenic and Natural Organohalogens on International Polar Year (IPY) Expeditions in the Canadian Arctic
- 2011
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Ingår i: Environmental Science and Technology. - : AMER CHEMICAL SOC. - 0013-936X .- 1520-5851. ; 45:3, s. 876-881
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Tidskriftsartikel (refereegranskat)abstract
- Shipboard measurements of organohalogen compounds in air and surface seawater were conducted in the Canadian Arctic in 2007-2008. Study areas included the Labrador Sea, Hudson Bay, and the southern Beaufort Sea. High volume air samples were collected at deck level (6 m), while low volume samples were taken at 1 and 15 m above the water or ice surface. Water samples were taken within 7 m. Water concentration ranges (pg L-1) were as follows: alpha-hexachlorocyclohexane (alpha-HCH) 465-1013, gamma-HCH 150-254, hexachlorobenzene (HCB) 4.0-6.4, 2,4-dibromoanisole (DBA) 8.5-38, and 2,4,6-tribromoanisole (TBA) 4.7-163. Air concentration ranges (pg m(-3)) were as follows: alpha-HCH 7.5-48, gamma-HCH 2.1-7.7, HCB 48-71, DBA 4.8-25, and TBA 6.4 - 39. Fugacity gradients predicted net deposition of HCB in all areas, while exchange directions varied for the other chemicals by season and locations. Net evasion of alpha-HCH from Hudson Bay and the Beaufort Sea during open water conditions was shown by air concentrations that averaged 14% higher at 1 m than 15 m. No significant difference between the two heights was found over ice cover. The alpha-HCH in air over the Beaufort Sea was racemic in winter (mean enantiomer fraction, EF = 0.504 +/- 0.008) and nonracemic in late spring-early summer (mean EF = 0.476 +/- 0.010). This decrease in EF was accompanied by a rise in air concentrations due to volatilization of nonracemic alpha-HCH from surface water (EF = 0.457 +/- 0.019). Fluxes of chemicals during the southern Beaufort Sea open water season (i.e., Leg 9) were estimated using the Whitman two-film model, where volatilization fluxes are positive and deposition fluxes are negative. The means +/- SD (and ranges) of net fluxes (ng m(-2) d(-1)) were as follows: alpha-HCH 6.8 +/- 3.2 (2.7-13), gamma-HCH 0.76 +/- 0.40 (0.26-1.4), HCB -9.6 +/- 2.7 (-6.1 to -15), DBA 1.2 +/- 0.69 (0.04-2.0), and TBA 0.46 +/- 1.1 ng m(-2) d(-1) (-1.6 to 2.0).
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| 35. |
- Wong, Fiona, et al.
(författare)
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Comparison of micrometeorological and two-film estimates of air-water gas exchange for alpha-hexachlorocyclohexane in the Canadian archipelago
- 2012
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Ingår i: Environmental Science and Pollution Research. - : Springer Science and Business Media LLC. - 0944-1344 .- 1614-7499. ; 19:6, s. 1908-1914
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Tidskriftsartikel (refereegranskat)abstract
- The air-sea gas exchange of alpha-hexachlorocyclohexane (alpha-HCH) in the Canadian Arctic was estimated using a micrometeorological approach and the commonly used Whitman two-film model. Concurrent shipboard measurements of alpha-HCH in air at two heights (1 and 15 m) and in surface seawater were conducted during the Circumpolar Flaw Lead study in 2008. Sampling was carried out during eight events in the early summer time when open water was encountered. The micrometeorological technique employed the vertical gradient in air concentration and the wind speed to estimate the flux; results were corrected for atmospheric stability using the Monin-Obukhov stability parameter. The Whitman two-film model used the concentrations of alpha-HCH in surface seawater, in bulk air at 1 and 15 m above the surface, and the Henry's law constant adjusted for temperature and salinity to derive the flux. Both approaches showed that the overall net flux of alpha-HCH was from water to air. Mean fluxes calculated using the micrometeorological technique ranged from -3.5 to 18 ng m(-2) day(-1) (mean 7.4), compared to 3.5 to 14 ng m(-2) day(-1) (mean 7.5) using the Whitman two-film model. Flux estimates for individual events agreed in direction and within a factor of two in magnitude for six of eight events. For two events, fluxes estimated by micrometeorology were zero or negative, while fluxes estimated with the two-film model were positive, and the reasons for these discrepancies are unclear. Improvements are needed to shorten air sampling times to ensure that stationarity of meteorological conditions is not compromised over the measurement periods. The micrometeorological technique could be particularly useful to estimate fluxes of organic chemicals over water in situations where no water samples are available.
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| 36. |
- Wong, Fiona, et al.
(författare)
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Fate of Brominated Flame Retardants and Organochlorine Pesticides in Urban Soil : Volatility and Degradation
- 2012
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Ingår i: Environmental Science and Technology. - Washington, DC : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 46:5, s. 2668-2674
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Tidskriftsartikel (refereegranskat)abstract
- As the uses of polybrominated diphenyl ethers (BDEs) are being phased out in many countries, soils could become a secondary emission source to the atmosphere. It is also anticipated that the demand for alternative brominated flame retardants (BFRs) will grow, but little is known about their environmental fate in soils. In this study, the volatility degradation of BFRs and organochlorine pesticides (OCPS) in soil was investigated. A low organic carbon (5.6%) urban soil was spiked with a suite of BFRs and OCPs, followed by incubation under laboratory condition for 360 days. These included BDE- 17, -28, -47, -99; alpha- and beta-1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), beta-1,2,5,6-tetrabromocyclooctane (TBCO), and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), OCPs: a-hexachlorocyclohexane (alpha-HCH) and C-13(6)-alpha-HCH, trans-chlordane (TC), and C-13(10)-TC. The volatility of spiked chemicals was investigated using a fugacity meter to measure the soil-air partition coefficient (K-SA). K-SA of some spiked BFRs and OCPs increased from Day 10 to 60 or 90 and leveled off afterward. This suggests that the volatility of BFRs and OCPs decreases over time as the chemicals become more strongly bound to the soil. Degradation of alternative BFRs (alpha- and beta-TBECH, beta-TBCO, DPTE), BDE-17, and alpha-HCH (C-13-labeled and nonlabeled) was evident in soils over 360 days, but no degradation was observed for the BDE-28, -47, -99, and TC (C-13-labeled and nonlabeled). A method to separate the enantiomers of alpha-TBECH and beta-TBCO was developed and their degradation, along with alpha-HCH (C-13-labeled and nonlabeled) was enantioselective. This is the first study which reports the enantioselective degradation of chiral BFRs in soils. Discrepancies between the enantiomer fraction (EF) of chemicals extracted from the soil by dichloromethane (DCM) and air were found. It is suggested that DCM removes both the sequestered and loosely bound fractions of chemicals in soil, whereas air accesses only the loosely bound fraction, and these two pools are subject to different degrees of enantioselective degradation. This calls for caution when interpreting EFs obtained from DCM extraction of soil with EFs in ambient air.
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| 37. |
- Zhang, Lin, et al.
(författare)
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Fate of chiral and achiral organochlorine pesticides in the North Atlantic Bloom experiment
- 2012
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 46:15, s. 8106-8114
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Tidskriftsartikel (refereegranskat)abstract
- Organochlorine pesticides (OCPs) were measured in the surface seawater and lower atmosphere during the North Atlantic Bloom Experiment in the spring 2008 from samples collected on the R/V Knorr. The gaseous concentration profiles resulted from both long-range transport (LRT) from the Arctic by polar easterlies and local biogeochemical processes. Relatively constant alpha/gamma-hexachlorocyclohexane (HCH) ratios and enantiomer fractions of alpha-HCH indicated that a single water mass was sampled throughout the cruise. Changes in dissolved phase concentrations were dominated by bloom processes (air-water exchange, partitioning to organic particles, and subsequent sinking) rather than LRT. alpha-HCH and dissolved phase trans-chlordanes showed depletion of (+) enantiomer, whereas depletion of the (-) enantiomer was observed for heptachlor exoepoxide (HEPX) and cis-chlordanes. Fugacity ratio calculations suggest that hexachlorobenzene (HCB) and gamma-HCH were depositing from air to water whereas heavier OCPs (chlordanes, HEPX) were evaporating. Dissolved phase concentrations did not decrease with time during the three-week bloom period; neither were lipophilic OCPs drawn down from air to water as previous studies hypothesized. Comparison with Arctic measurements suggested that the Arctic returned higher concentrations of alpha-HCH and HCB through both the atmospheric (polar easterlies) as well as oceanic transport (East Greenland Current) to the lower latitudes.
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