Isomer Profiles Research Articles

Atmospheric perfluoroalkyl acid occurrence and isomer profiles in Beijing, China

The airborne occurrence, isomer profiles, and phase distribution of perfluoroalkyl acids (PFAAs), including perfluoroalkyl carboxylates (PFCAs) and sulfonates (PFSAs), have received little scientific attention to date. Here we collected gaseous and particulate phase (PM2.5) samples in China, between June and November 2013, using alkalized annular denuders and downstream filters toavoid sampling artefacts associated with traditional air sampling. We analysed the concentrations of 18 linear PFAAs and the branched isomers of perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS). Concentrations of total PFAAs were dominated by PFCAs, with a range of 6.6–610 pg/m3 in the gaseous phase and 2.3–290 pg/m3 in the particulate phase. Concentrations of total PFCAs were higher in summer than winter in both phases. Branched PFOA isomers accounted for 10–22% of total PFOA in the gaseous phase and 13–24% in the particulate phase, which is close to, but slightly lower than, their abundance in the commercial PFOA mixtures manufactured using the electrochemical fluorination (ECF) process. In contract, branched PFOS isomers accounted for 26-63% of total PFOS in the gaseous phase and 39-77% in the particulate phase, which is much higher than their abundance in commercial PFOS mixtures manufactured by ECF. Most PFCAs had mean particle-associated fractions (Φ) higher than 0.5. PFHxS had a much higher mean Φ (0.65) than linear PFOS (0.31). We hypothesise that PFAAs observed in Beijing air may originate from the local water bodies through processes such as aerosol generation, although transformation of precursors also contribute.

Spatiotemporal distribution and isomer profiles of perfluoroalkyl acids in airborne particulate matter in Chengdu City, China

Airborne particulate matter (APM) was collected in four seasons at five different areas of the city of Chengdu, China to study the spatial and seasonal contamination pattern of perfluoroalkyl acids (PFAAs). The results showed that ∑PFAA concentrations in Downtown Chengdu (mean value: 297 ± 238 pg/m3) were higher than concentrations in suburban areas. The highest concentrations of PFAAs occurred during spring (97.5–709 pg/L; arithmetic mean concentration: 297 ± 191 pg/L) while the lowest concentration occurred during autumn (9.27–105 pg/L; arithmetic mean concentration 41.1 ± 24.8 pg/L). Perfluorooctanoic acid (PFOA) was the main PFAA quantified during winter, summer and autumn, and perfluorononanoic acid (PFNA) was the predominant PFAA in spring. Relative humidity (RH) and average daily precipitation (PRE) showed significant negative correlations with PFAA concentrations in winter and summer, suggesting that they played an important role in controlling PFAA concentrations in APM. The linear structural isomer of PFOA (n-PFOA) was the most abundant isomer in APM in Chengdu, with the average proportion of 85.6% ± 6.13%, higher than the proportion in ECF PFOA commercial products (74.3–77.6%). However, the consistent fingerprint of branched PFOA in the APM implies that ECF PFOA makes a significant contribution to the PFOA in APM. PFOS in the APM collected throughout the year had a mean proportion of 54.0 ± 8.81% of n-PFOS. This proportion of n-PFOS is lower than commercial ECF products (62.9–78.2%), suggesting an additional proportion of branched PFOS isomers in APM in Chengdu.

Levels, spatial distribution and isomer profiles of perfluoroalkyl acids in soil, groundwater and tap water around a manufactory in China

In this study, 32 surface soil samples, 24 groundwater samples, and 6 tap water samples were collected around a perfluorosulfonates (PFSAs) manufactory in China to analyze the distributions of perfluoroalkyl acids (PFAAs) including linear and branched isomers. The total concentrations of PFAAs (∑PFAAs) ranged from 1.30 to 913 ng/g on a dry weight basis (dw), 31.4–15656 ng/L, and 11.8–59.7 ng/L in soil, groundwater and tap water samples respectively. Perfluorooctanesulfonate (PFOS) and perfluorobutanoic acid (PFBA) were the predominant PFAAs in the soil whereas PFBA was the predominant congener in groundwater. PFAA concentrations in the soil and groundwater decreased with increasing distance from the manufactory. Shorter-chain PFAAs showed higher proportions in groundwater than in soil samples and that shorter-chain PFAAs exhibited faster decreasing rates in soil samples, which may be due to the differences in the polarity and hydrophobicity of these molecules. For isomer profiles, n-PFHxS, n-PFOS, and n-PFOA were the main isomer in soil samples and groundwater samples. Direct exposure to PFOS and PFOA via the soil and tap water posed relatively low risk to the residents’ health.

Lycopene presence in facial skin corneocytes and sebum and its association with circulating lycopene isomer profile: Effects of age and dietary supplementation.

Lycopene is a dietary antioxidant known to prevent skin photodamage. This study aimed to examine age‐dependent presence of this carotenoid on the surface of the facial skin and in the serum as well as to measure the same parameters during supplementation with lycopene. Serum samples and samples from facial skin surface were obtained from 60 young (under 25 years old) and 60 middle‐aged (over 50 years old) volunteers. Similar samples were taken from 15 middle‐aged subjects during 4‐week supplementation with lycopene (7 mg/day). Serum lycopene levels and isomer profiles were analyzed by HPLC. Lycopene in desquamated corneocytes and the sebum from facial skin surface was determined using lycopene‐specific fluorescent monoclonal antibodies. The results demonstrated that there was no age‐related difference in serum lycopene levels, but a higher proportion of (all‐E)‐lycopene was detected in the “young” group (37.5% vs 26.2% in the “middle‐aged” group; p < 0.0001). “Young” volunteers also had a higher lycopene level in both corneocytes (p = 0.0071) and the sebum (p = 0.0139) from the skin surface. Supplementation with lycopene resulted in a sharp increase of lycopene concentrations in both serum and skin surface samples. There was also a clear change in the pattern of lycopene isomers in the serum manifested by a significant increase in the proportion of (all‐E)‐lycopene (from 22.1% to 44.0% after supplementation, p < 0.0001). It can be concluded that dietary supplementation with lycopene results in its accumulation in the serum and skin. This process is accompanied by significant changes in the circulating lycopene isomer profile which becomes similar to that typical for young individuals.

Novel isomeric metabolite profiles correlate with warfarin metabolism phenotype during maintenance dosing in a pilot study of 29 patients.

: For this pilot study, we leveraged metabolite patterns for warfarin patients to more accurately assess clinically relevant differences in drug metabolism. We tested our hypothesis that plasma metabolite levels correlate with the influence of clinical factors on R-warfarin and S-warfarin metabolism (warfarin metabolic phenotype). We recruited 29 patients receiving a maintenance dose and testing within targeted therapeutic range. We determined their CYP2C9 and vitamin K epoxide reductase genotype and profiled 14 isomeric forms of warfarin and its metabolites. We employed three novel types of clearance ratios using analyte levels to perform multiple-linear regression analyses with clinical factors impacting drug metabolism and dose-responses. Competitive clearance ratios correlated with seven clinical factors including lifestyle choices (smoking), genetics (CYP2C9 and vitamin K epoxide reductase 1), and drug interactions (omeprazole) along with age, weight, and malignancy. Significant competitive clearance ratio correlations (P = 0.04 to < 0.001) explained 21-95% variability. Their performances surpassed that of oxidative and metabolic clearance ratios based on the number and significance of correlations. Competitive clearance ratios may accurately assess significance of factors on maintaining levels of pharmacologically active forms of the drug and metabolites related to dose-responses and thus provide a strategy to minimize adverse events and improve safety during anticoagulant therapy. This unique capacity could provide a strategy in a future, higher power study with a larger cohort of patients to more accurately assess the significance of clinical factors on active drug levels contributing to warfarin dose-responses.

Hexabromocyclododecane: concentrations and isomer profiles from sources to environmental sinks.

Concentrations and isomer compositions of hexabromocyclododecane (HBCD) were measured in six matrices in the Czech Republic (HBCD technical mixture; consumer products; indoor and outdoor air at industrial, urban and background locations; soils; and sediments) to provide insight into changes in concentrations and isomer profiles between environmental sources and environmental sinks. A distinct gradient of air concentrations was observed, from 1600ng/m3 in the industrial area to < 10pg/m3 in urban and background air. Isomer profiles also showed a distinct gradient in air, from 95% γ-HBCD in industrial air to 40% γ-HBCD in background air, suggesting the influence of differential atmospheric transport and phototransformation of γ- to α-HBCD. Concentrations and isomer compositions in consumer products were highly variable and indicated differences between products with intentional addition of HBCD as a flame retardant versus those with HBCD as an impurity, e.g., from recycled plastic. Understanding the isomer-specific environmental distributions and processes remains important for risk assessment and toxicology, considering the continued use of HBCD and the isomer-specific differences in uptake, metabolism, and toxicity, and further, demonstrates the utility of isomer profiles to better understand environmental processes of HBCDs.

LC-MS/MS glycomics of idiopathic rapid eye movement sleep behavior disorder.

Idiopathic REM sleep behavior disorder (iRBD) is now considered a prodromal stage of an α-synucleinopathy-related to neurodegenerative disease such as Parkinson's diseases. Emerging evidence has shown that post-translational modification or glycosylation are implicated in dynamic disease mechanisms and the onset of many pathological conditions. We hypothesized that the characterization of the glycosylation pattern of patients with RBD would be of great value to understand the pathophysiology and underlying mechanisms and represent potentially useful biomarkers for disease-associated molecular changes. To test this hypothesis, we assessed the serum glycome of patients with RBD and compared to that of healthy controls. NanoRPLC-MS was used to generate quantitative N-glycan profiles while high-temperature PGC-LC-MS platform was employed to generate quantitative isomeric N-glycan profiles. By analyzing permethylated glycans derived from human blood sera on C18-LC-MS/MS, we identified 59 N-glycan structures in healthy (control) cohort, 56 N-glycans in RBD cohort. Sixteen N-glycans structures were found to be significantly altered in the RBD cohort (p<0.05). N-glycans with the composition of HexNAc4 Hex5 Fuc1 , HexNAc5 Hex5 , and HexNAc4 Hex5 Fuc1 NeuAc1 presented the most substantial difference between controls and RBD patients (p<0.01). HexNAc4 Hex5 Fuc1 NeuAc1 showed a relatively high abundance (3.1±0.7% in the control cohort versus 4±3% in the idiopathic RBD cohort). These N-glycans can be potential diagnostic biomarker candidates and provide a window into underlying neurodegenerative processes in patients with idiopathic RBD. In addition, 7 N-glycan isomers were significantly different between controls and RBD patients (p<0.05). HexNAc4 Hex5 Fuc1 NeuAc1 (4511-2) and HexNAc4 Hex5 Fuc1 NeuAc2 (4512-2) showed the most substantial difference between the control and idiopathic RBD cohorts (p<0.001). Levels of both these two isomeric structures were higher in the idiopathic RBD cohort. Further larger studies are required to assess the reproducibility of these findings and to elucidate the role played by the changes in glycan structures in the pathogenetic mechanisms of RBD. This information will be instrumental in developing molecular therapeutic targets to promote neuroprotection and prevention of neurodegeneration.

Coverage and composition of cuticular waxes on the fronds of the temperate ferns Pteridium aquilinum, Cryptogramma crispa, Polypodium glycyrrhiza, Polystichum munitum and Gymnocarpium dryopteris.

The cuticular waxes sealing plant surfaces against excessive water loss are complex mixtures of very-long-chain aliphatics, with compositions that vary widely between plant species. To help fill the gap in our knowledge about waxes of non-flowering plant taxa, and thus about the cuticle of ancestral land plants, this study provides comprehensive analyses of waxes on temperate fern species from five different families. The wax mixtures on fronds of Pteridium aquilinum, Cryptogramma crispa, Polypodium glycyrrhiza, Polystichum munitum and Gymnocarpium dryopteris were analysed using gas chromatography-mass spectrometry for identification, and gas chromatography-flame ionization detection for quantification. The wax mixtures from all five fern species contained large amounts of C36-C54 alkyl esters, with species-specific homologue distributions. They were accompanied by minor amounts of fatty acids, primary alcohols, aldehydes and/or alkanes, whose chain length profiles also varied widely between species. In the frond wax of G. dryopteris, C27-C33 secondary alcohols and C27-C35 ketones with functional groups exclusively on even-numbered carbons (C-10 to C-16) were identified; these are characteristic structures similar to secondary alcohols and ketones in moss, gymnosperm and basal angiosperm waxes. The ferns had total wax amounts varying from 3.9 μg cm-2 on P. glycyrrhiza to 16.9 μg cm-2 on G. dryopteris, thus spanning a range comparable with that on leaves of flowering plants. The characteristic compound class compositions indicate that all five fern species contain the full complement of wax biosynthesis enzymes previously described for the angiosperm arabidopsis. Based on the isomer profiles, we predict that each fern species, in contrast to arabidopsis, has multiple ester synthase enzymes, each with unique substrate specificities.

Dechlorane plus (DP) in indoor and outdoor air of an urban city in South China: Implications for sources and human inhalation exposure

ABSTRACTDechlorane Plus (DP) is a chemical of emerging concern due to the restrictions on brominated flame retardant formulations. However, very little information is known about the occurrence of DP in indoor and outdoor air and its associated health risk to the exposed human population. In this study, we examined the concentrations and isomer profiles of DP in archived air samples collected from 14 homes, 6 offices, and 10 public microenvironments in Guangzhou, China in 2004–2005. The average (median) value of atmospheric ΣDP (sum of anti-DP and syn-DP) concentration in the three indoor air was 5.73 ± 5.33 (3.62) for offices, 8.08 ± 5.17 (6.87) for homes, and 57.27 ± 83.08 (32.58) pg/m3 for public microenvironments, respectively. ΣDP concentration was significantly higher in the public microenvironments than those in homes and offices. The arithmetic mean and median concentrations of ΣDP in outdoor air were 36.00 and 28.76 pg/m3, respectively. Spatially and temporally consistent indoor and outdoor samples comparison suggested that outdoor air might be a relevant source of DP for indoor air. Average anti-DP fractional abundance (fanti = 0.65 ± 0.04) in all outdoor samples was similar to those reported in other studies and indistinguishable from that of the commercial mixture (fanti = 0.65). In contrast, a relatively large variation of fanti values was found in the indoor samples, suggesting a complex degradation process of DP existing in these microenvironments. The calculated average daily doses of ΣDP were in the range of 0.38–2.21 ng/day for people intake through air inhalation, which was in the same order of magnitude compared with other exposure pathways for the general publics.

Free Monoterpene Isomer Profiles of Vitis Vinifera L. cv. White Wines.

Monoterpene compounds contribute floral and fruity characters to wine and are desired by grape growers and winemakers for many white wines. However, monoterpene isomers, especially monoterpene enantiomers, have been little explored. It is possible to identify and quantitate 17 monoterpene isomers in 148 varietal wines from eight grape varieties; Chardonnay, Gewürztraminer, Muscat, Pinot gris, Riesling, Sauvignon blanc, Torrontes, and Viognier in two vintages by Headspace solidphase microextraction multidimensional gas chromatography mass spectrometry (HS-SPME-MDGC-MS). Results obtained from general linear models and discriminant analysis showed significant differences for the isomer profiles and enantiomer fractions among the eight grape varieties and four wine styles. The high R2 values from the fitted line show low variation in enantiomeric differences based on variety. These results provide an overview of the monoterpene isomers of wide varietal wines, and support that isomer profiles and enantiomer fractions could differentiate our wines by varietal and wine style.

HCH air levels derived from Bailín dumpsite dismantling (Sabiñánigo, Spain)

Remediation and management of dumpsites is a worldwide problem that must be addressed to protect human health and the environment. Aragon Government long-term objective is the control of air quality related to landfills used to dump organochlorine waste. The present study evaluated the influence of dismantling works performed in Bailín landfill, an hexachlorocyclohexane (1,2,3,4,5,6-hexaclorohexane; HCH) dumpsite located in the city of Sabiñánigo, Spain. A total of 65,000 t of HCH solid waste and 342,000 t of polluted soil were transferred to a new cell with additional isolating measures going beyond the Spanish legal requirements. To evaluate influence of excavation of the old cell, transfer of waste and the state once the works in Bailín area had finished, levels of α-, β-, γ-, δ- and ɛ- HCH isomers were analyzed in 112 air samples obtained from summer 2014 to autumn 2016 by using passive air samplers. Results showed that: i) the existence of the old landfill and/or the works performed during its dismantling were a source of HCH air contamination, ii) old landfill represented an HCH source even after dismantling work was completed, iii) other sources, tentatively associated to Sardas dumpsite and HCH production site (INQUINOSA Factory) were identified in the surroundings, where management should be addressed. Data comparison reflected a heavier contamination caused by the production, storage, and waste disposal than the corresponding to application of lindane and/or technical HCH in Spain. Meteorological dependence (temperature, solar radiation and relative humidity), α-/γ-HCH ratios and isomer profiles of HCH air concentrations were evaluated for temporal trends and geographic distribution.

The fingerprint nature of PCDD in iron ore sinter strand emissions, the effect of suppressants and alternative fuels, and the potential for comparison with the isomer profile of PCDF

It has been previously shown that the isomer profile of PCDF emissions from iron ore sinter plant only varies within limits even when suppressants or alternative fuels are added, to the extent that it can be said to have a 'fingerprint'. The isomer profiles of PCDD from tetra- to hexacholrodibenzo-p-dioxin from the same samples examined for PCDF emissions have been obtained, and show the same tendency for a 'fingerprint ' isomer distribution to occur. Occasional exceptionally high isomer abundances are observed, but these are uncommon. The potential for comparison of the abundances of PCDF and PCDD isomers with similar chlorination patterns to determine whether the same formation process is involved has been examined. It is found that co-elutions prevent extensive comparisons irrespective of whether the SP2331 or DB5ms column is used in the analyses for separation of isomers to provide the results used for comparisons, although they allow limited results to be obtained. It is suggested that analyses using the two chromatography columns to analyse the same sample in parallel could provide more resolution of the isomer profiles for use in comparisons. A pilot study using samples analysed using each column is limited because of detailed differences in the emissions profiles, but demonstrates that greater resolution is possible if the two columns are used to analyse one sample.

Caracterización comercial y nutricional de la grasa subcutánea de terneros y vacas de desvieje sacrificados en la Comunidad Autónoma del País Vasco

Este trabajo se ha llevado a cabo con el objetivo de comparar la calidad comercial de la canal y la composición de ácidos grasos de la grasa subcutánea de vacas de desvieje de raza Frisona de más de 30 meses de edad, y de terneros de 12 meses de edad de las razas Pirenaica y Salers sacrificados en un matadero comercial de la Comunidad Autónoma del País Vasco. Las vacas de raza Frisona presentaron canales de menor peso (p&lt;0,05), aunque similar al grupo de los terneros de raza Pirenaica y menor conformación (p&lt;0,001) y estado de engrasamiento (p&lt;0,01) en comparación con los grupos de terneros. La grasa subcutánea de las vacas de desvieje presentó un mayor contenido de ácidos grasos saturados (p&lt;0,001) y ramificados (p&lt;0,05), y un menor contenido de ácidos grasos monoinsaturados (p&lt;0,01) y poliinsaturados (p&lt;0,001) en comparación con la de los terneros de las razas Pirenaica y Salers. El porcentaje de ácidos grasos monoinsaturados de tipo trans fue significativamente superior en la grasa subcutánea de los terneros de raza Pirenaica (p&lt;0,001), mientras que el contenido de 10t-18:1 fue significativamente mayor en la grasa de terneros de raza Pirenaica, intermedio en la grasa de terneros de raza Salers, y menor en la grasa de las vacas de desvieje (p&lt;0,001). Esto dio lugar a una relación 10t/11t &lt;1 y un perfil isomérico relativo de trans-18:1 y ácidos linoleico conjugados más saludable en la grasa de las vacas de desvieje de raza Frisona en comparación con los grupos de terneros. Esta idea podría contribuir a la valorización de las canales procedentes de vacas de desvieje desde el punto de vista de su comercialización y de la rentabilidad de las explotaciones ganaderas de vacuno en la Comunidad Autónoma del País Vasco.

Fatty acid profile of goat milk in diets supplemented with chia seed (Salvia hispanica L.).

Chia seed (Salvia hispanica L.) is the greatest known plant source of n-3 α-linolenic acid. The present study evaluated the effects of 3 inclusion levels of chia seed [zero (control); low, 2.7% (CLow); and high, 5.5% (CHigh)] in diets of dairy goats on milk yield and fatty acid profile. Nine Saanen dairy goats in the last third of lactation period, live weight 38 ± 8.7 kg, housed in metabolic cages, were fed iso-proteic and iso-energetic (160 g of crude protein/d and 11 MJ of metabolizable energy/d) diets. Gas chromatography was used to analyze fatty acid profile and total conjugated linoleic acid (CLA). Silver ion HPLC was used to analyze the isomeric profile of CLA. The results were subjected to variance analysis using a Latin square design repeated 3 × 3. The CHigh treatment was higher for dry matter, neutral detergent fiber, and acid detergent fiber intake compared with CLow and control diets. Digestibility was not affected by the inclusion of chia seeds. The CHigh diet improved N intake with respect to the control and CLow diet. Milk yield and chemical composition were not affected by the treatment. The milk fatty acid profile of C18:0, C18:1, C18:2, and C:20 was higher for CHigh than the other treatments. The in vitro gas production (mL of gas/g of dry matter) was lower in CHigh than the control diet. In conclusion, the addition of chia seeds at the CHigh level in dairy goat diets negatively affected in vitro rumen fermentation, but increased the milk fatty acid profile of C18:0, C18:1n-9 cis, and C:20, monounsaturated fatty acids, and polyunsaturated fatty acids. The total CLA content increased from 0.33 to 0.73% with the supplementation of chia to the diet, as well as the isomers cis-9,trans-11, trans-7,cis-9, trans-11,cis-13, and trans-12,trans-14.

Perfluoroalkyl substances with isomer analysis in umbilical cord serum in China.

Perfluoroalkyl substances (PFASs) are a class of widely used chemicals that have been detected in the environment and general population. However, the isomer patterns in human are poorly characterized. Previous studies observed the isomer-specific maternal-fetal transfer of PFASs in human. In our current study, we first examined the profile of PFASs and isomers, including 17 linear PFASs and 10 branched PFOS/PFOA isomers by using isotopic internal standards in umbilical cord serum samples from Guangzhou, China. We collected a total of 321 of cord blood serum samples from July to October in 2013, and analyzed the PFASs concentration with isomer-specific PFASs analysis method. The results showed that 9 out of 17 PFASs (linear PFASs) were detected (>50% detection rate). Perfluorohexane sulfonate (PFHxS, median 3.87ng/mL) was the predominant, followed by total PFOS (median 2.99ng/mL) and total PFOA (median 1.23ng/mL) in cord serum. In addition, 1m-, iso-, ∑3+4+5m-PFOS and iso-PFOA were the branched PFASs detected in the current study. The proportion of linear PFOS (n-PFOS) was 75.16% of ∑PFOS which was similar to the proportion of electrochemical fluorination that produces ca. 70% linear PFOS and 30% branched. On the contrary, linear PFOA (n-PFOA) accounted for 98.69% ∑PFOA in cord serum samples. Our finding indicates distinct PFASs and PFOS/PFOA isomer profile in cord serum, suggesting there might be a different exposure pathway and metabolism of PFASs.

Organochlorine pesticides in residential soils and sediments within two main agricultural areas of northwest Mexico: Concentrations, enantiomer compositions and potential sources

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.

Levels, Isomer Profiles, and Estimated Riverine Mass Discharges of Perfluoroalkyl Acids and Fluorinated Alternatives at the Mouths of Chinese Rivers.

An extensive sampling campaign was undertaken to study the levels, isomer profiles and riverine mass discharges of perfluoroalkyl acids (PFAAs) and fluorinated alternatives in 19 Chinese rivers. The levels and homologue profiles of Σ10PFAAs varied considerably among the 19 rivers (mean 106; median 16.3, range 8.9-1240 ng/L), indicating the influence of specific point sources. Highly branched isomer profiles of perfluorooctanoic acid (18-25% br-PFOA) in rivers with elevated concentrations (96-352 ng/L) indicate that releases during production of PFOA by electrochemical fluorination and/or its use in fluoropolymer manufacture were the dominant sources to these rivers. The fluorinated alternatives 6:2 fluorotelomer sulfonate (detection frequency 21%, < 0.1-3.1 ng/L) and chlorinated polyfluoroalkyl ether sulfonate F-53B (51%, < 0.56-78.5 ng/L) were also found in some rivers. The total Chinese riverine mass discharges of PFOA (mean 80.9; range 16.8-168 t/y) (including monitoring data from this and other studies) were in good agreement with theoretical PFOA emission estimates (17.3-203 t/y) whereas riverine mass discharges of PFOS (mean 3.6; range 1.9-5.6 t/y) could only account for a minor fraction of theoretically estimated PFOS releases (70 t/y). This study provides empirical evidence that emissions from Chinese point sources likely dominate the global emissions of several legacy PFASs (notably PFOA) and fluorinated alternatives (e.g., F-53B).

Study of dioxins formation in the basic oxygen furnace during organic waste disposal

Incineration is one of the most common methods used for organic waste utilization. However, there is a danger of the secondary generation of such supertoxicants as dioxins and furans. The results of the investigations of experimental and comparative converter meltings with the use of paper and plastic wastes under conditions of JSC “EVRAZ ZSMK” show the absence of influence of wastes on the concentration and isomeric profile of dioxins and furans in the converter gases.

Styrofoam Debris as a Source of Hazardous Additives for Marine Organisms.

There is growing concern over plastic debris and their fragments as a carrier for hazardous substances in marine ecosystem. The present study was conducted to provide field evidence for the transfer of plastic-associated chemicals to marine organisms. Hexabromocyclododecanes (HBCDs), brominated flame retardants, were recently detected in expanded polystyrene (styrofoam) marine debris. We hypothesized that if styrofoam debris acts as a source of the additives in the marine environment, organisms inhabiting such debris might be directly influenced by them. Here we investigated the characteristics of HBCD accumulation by mussels inhabiting styrofoam. For comparison, mussels inhabiting different substrates, such as high-density polyethylene (HDPE), metal, and rock, were also studied. The high HBCD levels up to 5160 ng/g lipid weight and the γ-HBCD dominated isomeric profiles in mussels inhabiting styrofoam strongly supports the transfer of HBCDs from styrofoam substrate to mussels. Furthermore, microsized styrofoam particles were identified inside mussels, probably originating from their substrates.

Freezing Properties of Alkenyl Succinic Anhydrides Derived from Linear Isomerized Olefins

Alkenyl succinic anhydrides are important specialty chemicals that are used in the paper, oilfield, and fuel additives industries. In this paper we investigate the link between the physical properties of alkenyl succinic anhydrides and the identities of their linear alkyl olefin precursors. We describe a straightforward GC analysis of olefin isomer distributions and show that these correlate well with the freezing temperatures of the subsequent alkenyl succinic anhydride products. This allows the identification of olefin isomer profiles that are required to give the desired physical properties in the alkenyl succinic anhydrides; it also provides a method to predict the freezing temperatures of alkenyl succinic anhydrides synthesized from a particular supply of olefin.