Occurrence and seasonal variations of antibiotic micro-pollutants in the Wei River, China.

In this study, a systematic monitoring campaign of 30 antibiotics belonging to tetracyclines (TCs), macrolides (MLs), fluoroquinolones (FQs) and sulfonamides (SAs) was performed in the Xi'an section of the Wei River during three sampling events (December 2021, June 2022, and September 2022). The total concentrations of antibiotics in water ranged from 297 to 461 ng/L with high detection frequencies ranging from 45% to 100% for the various antibiotics. A marked seasonal variation in concentrations was found with total antibiotic concentrations in winter being 1.5 and 2 times higher than those in the summer and autumn seasons, respectively. The main contaminants in both winter and summer seasons were FQs, but in the autumn SAs were more abundant, suggesting different seasonal sources or more effective runoff for certain antibiotics during periods of rainfall. Combined analysis using redundancy and clustering analysis indicated that the distribution of antibiotics in the Wei River was affected by the confluence with dilution of tributaries and outlet of domestic sewage. Ecological risk assessment based on risk quotient (RQ) showed that most antibiotics in water samples posed insignificant risk to fish and green algae, as well as insignificant to low risk to Daphnia. The water-sediment distribution coefficients of SAs were higher than those of other antibiotics, indicating that particle-bound runoff could be a significant source for this class of antibiotics.

Photodegradation of hydroxyfluorenes in ice and water: A comparison of kinetics, effects of water constituents, and phototransformation by-products.

The photochemical behavior of organic pollutants in ice is poorly studied in comparison to aqueous photochemistry. Here we report a detailed comparison of ice and aqueous photodegradation of two representative OH-PAHs, 2-hydroxyfluorene (2-OHFL) and 9-hydroxyfluorene (9-OHFL), which are newly recognized contaminants in the wider environment including colder regions. Interestingly, their photodegradation kinetics were clearly influenced by whether they reside in ice or water. Under the same simulated solar irradiation (λ > 290 nm), OHFLs photodegraded faster in ice than in equivalent aqueous solutions and this was attributed to the specific concentration effect caused by freezing. Furthermore, the presence of dissolved constituents in ice also influenced photodegradation with 2-OHFL phototransforming the fastest in 'seawater' ice (k = (11.4 ± 1.0) × 10-2 min-1) followed by 'pure-water' ice ((8.7 ± 0.4) × 10-2 min-1) and 'freshwater' ice ((8.0 ± 0.7) × 10-2 min-1). The presence of dissolved constituents (specifically Cl-, NO3-, Fe(III) and humic acid) influences the phototransformation kinetics, either enhancing or suppressing phototransformation, but this is based on the quantity of the constituent present in the matrixes, the specific OHFL isomer and the matrix type (e.g., ice or aqueous solution). Careful derivation of key photointermediates was undertaken in both ice and water samples using tandem mass spectrometry. Ice phototransformation exhibited fewer by-products and 'simpler' pathways giving rise to a range of hydroxylated fluorenes and hydroxylated fluorenones in ice. These results are of importance when considering the fate of PAHs and OH-PAHs in cold regions and their persistence in sunlit ice.

Increasing Accumulation of Perfluorocarboxylate Contaminants Revealed in an Antarctic Firn Core (1958-2017).

Perfluoroalkyl acids (PFAAs) are synthetic chemicals with a variety of industrial and consumer applications that are now widely distributed in the global environment. Here, we report the measurement of six perfluorocarboxylates (PFCA, C4-C9) in a firn (granular compressed snow) core collected from a non-coastal, high-altitude site in Dronning Maud Land in Eastern Antarctica. Snow accumulation of the extracted core dated from 1958 to 2017, a period coinciding with the advent, use, and geographical shift in the global industrial production of poly/perfluoroalkylated substances, including PFAA. We observed increasing PFCA accumulation in snow over this time period, with chemical fluxes peaking in 2009-2013 for perfluorooctanoate (PFOA, C8) and nonanoate (PFNA, C9) with little evidence of a decline in these chemicals despite supposed recent global curtailments in their production. In contrast, the levels of perfluorobutanoate (PFBA, C4) increased markedly since 2000, with the highest fluxes in the uppermost snow layers. These findings are consistent with those previously made in the Arctic and can be attributed to chlorofluorocarbon replacements (e.g., hydrofluoroethers) as an inadvertent consequence of global regulation.

High Concentrations of Perfluoroalkyl Acids in Arctic Seawater Driven by Early Thawing Sea Ice.

Poly- and perfluoroalkyl substances are synthetic chemicals that are widely present in the global environment including the Arctic. However, little is known about how these chemicals (particularly perfluoroalkyl acids, PFAA) enter the Arctic marine system and cycle between seawater and sea ice compartments. To evaluate this, we analyzed sea ice, snow, melt ponds, and near-surface seawater at two ice-covered stations located north of the Barents Sea (81 °N) with the aim of investigating PFAA dynamics in the late-season ice pack. Sea ice showed high concentrations of PFAA particularly at the surface with snow-ice (the uppermost sea ice layer strongly influenced by snow) comprising 26-62% of the total PFAA burden. Low salinities (<2.5 ppt) and low δ18OH20 values (<1‰ in snow and upper ice layers) in sea ice revealed the strong influence of meteoric water on sea ice, thus indicating a significant atmospheric source of PFAA with subsequent transfer down the sea ice column in meltwater. Importantly, the under-ice seawater (0.5 m depth) displayed some of the highest concentrations notably for the long-chain PFAA (e.g., PFOA 928 ± 617 pg L-1), which were ≈3-fold higher than those of deeper water (5 m depth) and ≈2-fold higher than those recently measured in surface waters of the North Sea infuenced by industrial inputs of PFAAs. The evidence provided here suggests that meltwater arising early in the melt season from snow and other surface ice floe components drives the higher PFAA concentrations observed in under-ice seawater, which could in turn influence the timing and extent of PFAA exposure for organisms at the base of the marine food web.

Investigating the Uptake and Fate of Poly- and Perfluoroalkylated Substances (PFAS) in Sea Ice Using an Experimental Sea Ice Chamber.

Poly- and perfluoroalkyl substances (PFAS) are contaminants of emerging Arctic concern and are present in the marine environments of the polar regions. Their input to and fate within the marine cryosphere are poorly understood. We conducted a series of laboratory experiments to investigate the uptake, distribution, and release of 10 PFAS of varying carbon chain length (C4-C12) in young sea ice grown from artificial seawater (NaClsolution). We show that PFAS are incorporated into bulk sea ice during ice formation and regression analyses for individual PFAS concentrations in bulk sea ice were linearly related to salinity (r2 = 0.30 to 0.88, n = 18, p < 0.05). This shows that their distribution is strongly governed by the presence and dynamics of brine (high salinity water) within the sea ice. Furthermore, long-chain PFAS (C8-C12), were enriched in bulk ice up to 3-fold more than short-chain PFAS (C4-C7) and NaCl. This suggests that chemical partitioning of PFAS between the different phases of sea ice also plays a role in their uptake during its formation. During sea ice melt, initial meltwater fractions were highly saline and predominantly contained short-chain PFAS, whereas the later, fresher meltwater fractions predominantly contained long-chain PFAS. Our results demonstrate that in highly saline parts of sea ice (near the upper and lower interfaces and in brine channels) significant chemical enrichment (ε) of PFAS can occur with concentrations in brine channels greatly exceeding those in seawater from which it forms (e.g., for PFOA, εbrine = 10 ± 4). This observation has implications for biological exposure to PFAS present in brine channels, a common feature of first-year sea ice which is the dominant ice type in a warming Arctic.

Mechanistic Insight into the Uptake and Fate of Persistent Organic Pollutants in Sea Ice.

The fate of persistent organic pollutants in sea ice is a poorly researched area and yet ice serves as an important habitat for organisms at the base of the marine foodweb. This study presents laboratory-controlled experiments to investigate the mechanisms governing the fate of organic contaminants in sea ice grown from artificial seawater. Sea ice formation was shown to result in the entrainment of chemicals from seawater, and concentration profiles in bulk ice generally showed the highest levels in both the upper (ice-atmosphere interface) and lower (ice-ocean interface) ice layers, suggesting their incorporation and distribution is influenced by brine advection. Results from a 1-D sea ice brine dynamics model supported this, but also indicated that other processes may be needed to accurately model low-polarity compounds in sea ice. This was reinforced by results from a melt experiment, which not only showed chemicals were more enriched in saltier brine, but also revealed that chemicals are released from sea ice at variable rates. We use our results to demonstrate the importance of processes related to the occurrence and movement of brine for controlling chemical fate in sea ice which provides a pathway for exposure to ice-associated biota at the base of the pelagic food web.

Accumulation of perfluoroalkyl compounds in tibetan mountain snow: temporal patterns from 1980 to 2010.

The use of snow and ice cores as recorders of environmental contamination is particularly relevant for per- and polyfluoroalky substances (PFASs) given their production history, differing source regions and varied mechanisms driving their global distribution. In a unique study perfluoroalkyl acids (PFAAs) were analyzed in dated snow-cores obtained from high mountain glaciers on the Tibetan Plateau (TP). One snow core was obtained from the Mt Muztagata glacier (accumulation period of 1980-1999), located in western Tibet and a second core from Mt. Zuoqiupo (accumulation period: 1996-2007) located in southeastern Tibet, with fresh surface snow collected near Lake Namco in 2010 (southern Tibet). The higher concentrations of ∑PFAAs were observed in the older Mt Muztagata core and dominated by perfluorooctanesulfonic acid (PFOS) (61.4-346 pg/L) and perfluorooctanoic acid (PFOA) (40.8-243 pg/L), whereas in the Mt Zuoqiupu core the concentrations were lower (e.g., PFOA: 37.8-183 pg/L) with PFOS below detection limits. These differences in PFAA concentrations and composition profile likely reflect the upwind sources affecting the respective sites (e.g., European/central Asian sources for Mt Muztagata and India sources for Mt Zuoqiupu). Perfluorobutanoic acid (PFBA) dominated the recent surface snowpack of Lake Namco which is mainly associated with India sources where the shorter chain volatile PFASs precursors predominate. The use of snow cores in different parts of Tibet provides useful recorders to examine the influence of different PFASs source regions and reflect changing PFAS production/use in the Northern Hemisphere.

The influence of climate change on the global distribution and fate processes of anthropogenic persistent organic pollutants.

The effect of climate change on the global distribution and fate of persistent organic pollutants (POPs) is of growing interest to both scientists and policy makers alike. The impact of warmer temperatures and the resulting changes to earth system processes on chemical fate are, however, unclear, although there are a growing number of studies that are beginning to examine these impacts and changes in a quantitative way. In this review, we examine broad areas where changes are occurring or are likely to occur with regard to the environmental cycling and fate of chemical contaminants. For this purpose we are examining scientific information from long-term monitoring data with particular emphasis on the Arctic, to show apparent changes in chemical patterns and behaviour. In addition, we examine evidence of changing chemical processes for a number of environmental compartments and indirect effects of climate change on contaminant emissions and behaviour. We also recommend areas of research to address knowledge gaps. In general, our findings indicate that the indirect consequences of climate change (i.e. shifts in agriculture, resource exploitation opportunities, etc.) will have a more marked impact on contaminants distribution and fate than direct climate change.

Climate change influence on the levels and trends of persistent organic pollutants (POPs) and chemicals of emerging Arctic concern (CEACs) in the Arctic physical environment - a review.

Climate change brings about significant changes in the physical environment in the Arctic. Increasing temperatures, sea ice retreat, slumping permafrost, changing sea ice regimes, glacial loss and changes in precipitation patterns can all affect how contaminants distribute within the Arctic environment and subsequently impact the Arctic ecosystems. In this review, we summarized observed evidence of the influence of climate change on contaminant circulation and transport among various Arctic environment media, including air, ice, snow, permafrost, fresh water and the marine environment. We have also drawn on parallel examples observed in Antarctica and the Tibetan Plateau, to broaden the discussion on how climate change may influence contaminant fate in similar cold-climate ecosystems. Significant knowledge gaps on indirect effects of climate change on contaminants in the Arctic environment, including those of extreme weather events, increase in forests fires, and enhanced human activities leading to new local contaminant emissions, have been identified. Enhanced mobilization of contaminants to marine and freshwater ecosystems has been observed as a result of climate change, but better linkages need to be made between these observed effects with subsequent exposure and accumulation of contaminants in biota. Emerging issues include those of Arctic contamination by microplastics and higher molecular weight halogenated natural products (hHNPs) and the implications of such contamination in a changing Arctic environment is explored.

Pollution in the Arctic Ocean: An overview of multiple pressures and implications for ecosystem services.

The Arctic is undergoing unprecedented change. Observations and models demonstrate significant perturbations to the physical and biological systems. Arctic species and ecosystems, particularly in the marine environment, are subject to a wide range of pressures from human activities, including exposure to a complex mixture of pollutants, climate change and fishing activity. These pressures affect the ecosystem services that the Arctic provides. Current international policies are attempting to support sustainable exploitation of Arctic resources with a view to balancing human wellbeing and environmental protection. However, assessments of the potential combined impacts of human activities are limited by data, particularly related to pollutants, a limited understanding of physical and biological processes, and single policies that are limited to ecosystem-level actions. This manuscript considers how, when combined, a suite of existing tools can be used to assess the impacts of pollutants in combination with other anthropogenic pressures on Arctic ecosystems, and on the services that these ecosystems provide. Recommendations are made for the advancement of targeted Arctic research to inform environmental practices and regulatory decisions.

"Good Epidemiology Practice" Guidelines for Pesticide Exposure Assessment.

Both toxicology and epidemiology are used to inform hazard and risk assessment in regulatory settings, particularly for pesticides. While toxicology studies involve controlled, quantifiable exposures that are often administered according to standardized protocols, estimating exposure in observational epidemiology studies is challenging, and there is no established guidance for doing so. However, there are several frameworks for evaluating the quality of published epidemiology studies. We previously developed a preliminary list of methodology and reporting standards for epidemiology studies, called Good Epidemiology Practice (GEP) guidelines, based on a critical review of standardized toxicology protocols and available frameworks for evaluating epidemiology study quality. We determined that exposure characterization is one of the most critical areas for which standards are needed. Here, we propose GEP guidelines for pesticide exposure assessment based on the source of exposure data (i.e., biomonitoring and environmental samples, questionnaire/interview/expert record review, and dietary exposures based on measurements of residues in food and food consumption). It is expected that these GEP guidelines will facilitate the conduct of higher-quality epidemiology studies that can be used as a basis for more scientifically sound regulatory risk assessment and policy making.

A Survey of Systematic Evidence Mapping Practice and the Case for Knowledge Graphs in Environmental Health and Toxicology.

Systematic evidence mapping offers a robust and transparent methodology for facilitating evidence-based approaches to decision-making in chemicals policy and wider environmental health (EH). Interest in the methodology is growing; however, its application in EH is still novel. To facilitate the production of effective systematic evidence maps for EH use cases, we survey the successful application of evidence mapping in other fields where the methodology is more established. Focusing on issues of "data storage technology," "data integrity," "data accessibility," and "transparency," we characterize current evidence mapping practice and critically review its potential value for EH contexts. We note that rigid, flat data tables and schema-first approaches dominate current mapping methods and highlight how this practice is ill-suited to the highly connected, heterogeneous, and complex nature of EH data. We propose this challenge is overcome by storing and structuring data as "knowledge graphs." Knowledge graphs offer a flexible, schemaless, and scalable model for systematically mapping the EH literature. Associated technologies, such as ontologies, are well-suited to the long-term goals of systematic mapping methodology in promoting resource-efficient access to the wider EH evidence base. Several graph storage implementations are readily available, with a variety of proven use cases in other fields. Thus, developing and adapting systematic evidence mapping for EH should utilize these graph-based resources to ensure the production of scalable, interoperable, and robust maps to aid decision-making processes in chemicals policy and wider EH.

Recommendations for the conduct of systematic reviews in toxicology and environmental health research (COSTER).

BACKGROUND: There are several standards that offer explicit guidance on good practice in systematic reviews (SRs) for the medical sciences; however, no similarly comprehensive set of recommendations has been published for SRs that focus on human health risks posed by exposure to environmental challenges, chemical or otherwise. OBJECTIVES: To develop an expert, cross-sector consensus view on a key set of recommended practices for the planning and conduct of SRs in the environmental health sciences. METHODS: A draft set of recommendations was derived from two existing standards for SRs in biomedicine and developed in a consensus process, which engaged international participation from government, industry, non-government organisations, and academia. The consensus process consisted of a workshop, follow-up webinars, email discussion and bilateral phone calls. RESULTS: The Conduct of Systematic Reviews in Toxicology and Environmental Health Research (COSTER) recommendations cover 70 SR practices across eight performance domains. Detailed explanations for specific recommendations are made for those identified by the authors as either being novel to SR in general, specific to the environmental health SR context, or potentially controversial to environmental health SR stakeholders. DISCUSSION: COSTER provides a set of recommendations that should facilitate the production of credible, high-value SRs of environmental health evidence, and advance discussion of a number of controversial aspects of conduct of EH SRs. Key recommendations include the management of conflicts of interest, handling of grey literature, and protocol registration and publication. A process for advancing from COSTER's recommendations to developing a formal standard for EH SRs is also indicated.

A comparative study on the aqueous photodegradation of two organophosphorus pesticides under simulated and natural sunlight.

Aqueous solutions of fenitrothion and methyl parathion were photochemically degraded in an Atlas Suntest solar simulator (500 W m(-2)) as well as under ambient sunlight at Lancaster University (June & August 2007, 54 degrees N) and the degradation kinetics and disappearance quantum yields are reported. Fenitrothion degradation confirmed to first order kinetics (r(2) = 0.90-0.99) with a half-life range of 4.9 h-5.3 h, shorter than previously reported studies. In contrast, methyl parathion did not show significant degradation over the duration of these experiments. Light irradiances were monitored with a spectroradiometer during the Suntest simulator and outdoor experiments. The filtered-xenon arc lamp of the Suntest yielded spectral irradiances comparable to natural sunlight in the UVB and UVA wavelength range (280-400 nm), but with higher irradiances in the visible region (400-750 nm). Nonetheless, as both compounds have light absorption spectra at wavelengths < 400 nm, then the half-lives and disappearance quantum yields were similar between the Suntest and natural sunlight, and demonstrated that the Suntest is suitable for environmentally-relevant photochemical degradation experiments.

Systematic evidence maps as a novel tool to support evidence-based decision-making in chemicals policy and risk management.

BACKGROUND: While systematic review (SR) methods are gaining traction as a method for providing a reliable summary of existing evidence for health risks posed by exposure to chemical substances, it is becoming clear that their value is restricted to a specific range of risk management scenarios - in particular, those which can be addressed with tightly focused questions and can accommodate the time and resource requirements of a systematic evidence synthesis. METHODS: The concept of a systematic evidence map (SEM) is defined and contrasted to the function and limitations of systematic review (SR) in the context of risk management decision-making. The potential for SEMs to facilitate evidence-based decision-making are explored using a hypothetical example in risk management priority-setting. The potential role of SEMs in reference to broader risk management workflows is characterised. RESULTS: SEMs are databases of systematically gathered research which characterise broad features of the evidence base. Although not intended to substitute for the evidence synthesis element of systematic reviews, SEMs provide a comprehensive, queryable summary of a large body of policy relevant research. They provide an evidence-based approach to characterising the extent of available evidence and support forward looking predictions or trendspotting in the chemical risk sciences. In particular, SEMs facilitate the identification of related bodies of decision critical chemical risk information which could be further analysed using SR methods, and highlight gaps in the evidence which could be addressed with additional primary studies to reduce uncertainties in decision-making. CONCLUSIONS: SEMs have strong and growing potential as a high value tool in resource efficient use of existing research in chemical risk management. They can be used as a critical precursor to efficient deployment of high quality SR methods for characterising chemical health risks. Furthermore, SEMs have potential, at a large scale, to support the sort of evidence summarisation and surveillance methods which would greatly increase the resource efficiency, transparency and effectiveness of regulatory initiatives such as EU REACH and US TSCA.

The importance of reactive oxygen species on the aqueous phototransformation of sulfonamide antibiotics: kinetics, pathways, and comparisons with direct photolysis.

Sulfonamide antibiotics (SAs) are increasingly detected as aquatic contaminants and exist as different dissociated species depending on the pH of the water. Their removal in sunlit surface waters is governed by photochemical transformation. Here we report a detailed examination of the hydroxyl radical (•OH) and singlet oxygen (1O2) mediated photooxidation of nine SAs: sulfamethoxazole, sulfisoxazole, sulfamethizole, sulfathiazole, sulfamethazine, sulfamerazine, sulfadiazine, sulfachloropyridazine and sulfadimethoxine. Both •OH and 1O2 oxidation kinetics varied depending on the dominant protonated states of the SA in question (H2SAs+, HSAs0 and SAs-) as a function of pH. Based on competition kinetic experiments and matrix deconvolution calculations, HSAs0 or SAs- (pH ∼5-8) were observed to be more highly reactive towards •OH, while SAs- (pH ∼8) react the fastest with 1O2 for most of the SAs tested. Using the empirically derived rates of reaction for the speciated forms at different pHs, the environmental half-lives were determined using typical 1O2 and •OH concentrations observed in the environment. This approach suggests that photochemical 1O2 oxidation contributes more than •OH oxidation and direct photolysis to the overall phototransformation of SAs in sunlit waters. Based on the identification of key photointermediates using tandem mass spectrometry, 1O2 oxidation generally occurred at the amino moiety on the molecule, whereas •OH reaction experienced multi-site hydroxylation. Both these reactions preserve the basic parent structure of the compounds and raise concerns that the routes of phototransformation give rise to intermediates with similar antimicrobial potency as the parent SAs. We therefore recommend that these phototransformation pathways are included in risk assessments concerning the presence and fate of SAs in waste and surface waters.

Exploring the aquatic photodegradation of two ionisable fluoroquinolone antibiotics - Gatifloxacin and balofloxacin: Degradation kinetics, photobyproducts and risk to the aquatic environment.

Fluoroquinolone antibiotics (FQs) are ubiquitous and ionisable in surface waters. Here we investigate gatifloxacin (GAT) and balofloxacin (BAL), two widely used FQs, and determine the photochemical reactivity of their respective dissociation species that arise at different pH to understand the relevance and pathways of phototransformation reactions. Simulated-sunlight experiments and matrix calculations showed that neutral forms (HFQs0) of the two antibiotics had the highest apparent photolytic efficiency and hydroxyl-radical oxidation reactivity. Based on the pH-dependent photochemical reactivities, the solar apparent photodegradation half-lives (t1/2) in sunlit surface waters ranged from 14.5-169min and was 1-2 orders of magnitude faster than hydroxyl-radical induced oxidation (t1/2=20.9-29.8h). The corresponding pathways were proposed based on the identification of key intermediates using HPLC-ESI-MS/MS. The apparent photodegradation induced defluorination, decarboxylation, and piperazinyl oxidation and rearrangement, whereas hydroxyl-radical oxidation caused hydroxylated defluorination and piperazinyl hydroxylation. The photomodified toxicity of GAT and BAL was examined using an Escherichia coli activity assay. E. coli activity was not affected by BAL, but was significantly affected by the photo-modified solutions of GAT, indicating that primary photo-degradates have a comparable or higher antibacterial activity than the parent GAT. In fresh water and seawater this antibacterial activity remained high for up to 24h, even after GAT had undergone significant photodegradation (>1 half-life), indicating the potential impact of this chemical on microbial communities in aquatic systems.

Assessing residual status and spatial variation of current-use pesticides under the influence of environmental factors in major cash crop growing areas of Pakistan.

The status of seven currently used pesticides were assessed under the influence of soil parameters in surface soils of cash crop growing areas of Pakistan. Chlorpyrifos occurred in highest mean concentration (1.18 mg kg-1). Selected pesticides exhibited higher affinity towards both organic carbon and black carbon fractions. The δ13C stable carbon isotopic fraction of inorganic carbon was also used as a tracer and disclosed high retention of total organic carbon in Swat and Swabi sites. Statistical analysis revealed that carbon storage was primarily influenced by altitude and temperature. Soil clay mineral oxides of aluminum and iron positively correlated with organic carbon and selected pesticides (chlorpyrifos and cyprodinil). Soil to plant bio-concentration ratios predicted heightened uptake of azinfos and diazinon in major cash crop bio mass. Occupational risk via soil ingestion expressed no significant threat to the farmer community.

A contemporary assessment of polybrominated diphenyl ethers (PBDE) in the ambient air and soil of Azerbaijan.

PBDEs were measured in air and soil across Azerbaijan to establish contemporary concentrations at 13 urban and rural sites. Polyurethane foam passive air samplers (PUF-PAS) were deployed for a period of a month with surface soil samples collected at the same sites. Unlike organochlorine pesticides previously surveyed by our group, PBDE concentrations in both contemporary air and soil were low in comparison to recent European and Asian studies. For example, mean ∑9PBDE concentrations in air and soil were 7.13 ± 1.66 pg m-3 and 168 ± 57 pg g-1, respectively. The fully brominated BDE-209 was the most abundant congener observed in soil (174.8 ± 58.5 pg g-1), comprising ~ 96% of ∑10PBDE. However, the PAS-derived air concentrations for highly brominated congeners must be viewed with caution as there is uncertainty over the uptake rates of particle-bound chemicals using these devices. Some of the highest concentrations in air were observed at sites with the highest wind speeds and at several remote locations in the north of the country and this requires further research. Levels of BDE-47 and 99 (the two most abundant congeners in the widely used penta-formulation) were lower than levels reported elsewhere suggesting limited use/import of the penta-BDE formulation in Azerbaijan.

Aqueous multivariate phototransformation kinetics of dissociated tetracycline: implications for the photochemical fate in surface waters.

Antibiotics are ubiquitous pollutants in aquatic systems and can exist as different dissociated species depending on the water pH. New knowledge of their multivariate photochemical behavior (i.e., the photobehavior of different ionized forms) is needed to improve our understanding on the fate and possible remediation of these pharmaceuticals in surface and waste waters. In this study, the photochemical degradation of aqueous tetracycline (TC) and its dissociated forms (TCH20, TCH-, and TC2-) was investigated. Simulated sunlight experiments and matrix calculations indicated that the three dissociated species had dissimilar photolytic kinetics and photooxidation reactivities. TC2- photodegraded the fastest due to apparent photolysis with a kinetic constant of 0.938 ± 0.021 min-1, followed by TCH- (0.020 ± 0.005 min-1) and TCH20 (0.012 ± 0.001 min-1), whereas TCH- was found to be the most highly reactive toward •OH (105.78 ± 3.40 M-1 s-1), and TC2- reacted the fastest with 1O2 (344.96 ± 45.07 M-1 s-1). Water with relatively high pH (e.g., ~ 8-9) favors the dissociated forms of TCH- and TC2- which are most susceptible to photochemical loss processes compared to neutral TC. The calculated corresponding environmental half-lives (t1/2,E) in sunlit surface waters ranged from 0.05 h for pH = 9 in midsummer to 3.68 h for pH = 6 in midwinter at 45° N latitude. The process was dominated by apparent photolysis (especially in summer, 62-91%), followed by 1O2 and •OH oxidation. Adjusting the pH to slightly alkaline conditions prior to UV or solar UV light treatment may be an effective way of enhancing the photochemical removal of TC from contaminated water. Graphical abstract Aqueous multiple photochemical behavior of dissociated tetracycline (TCH20, TCH-, and TC2-) is first comprehensively reported on revealing the phototransformation kinetics and implications for the fate in surface waters.