The degradation of organic micropollutants occurs via different reaction pathways. Compound specific isotope analysis is a valuable tool to identify such degradation pathways in different environmental systems. We propose a mechanism-based modeling approach that provides a quantitative framework to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. To demonstrate specific features of the modeling approach, we simulated the degradation of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model accurately reproduces the multi-element isotope data observed in previous experimental studies. Furthermore, it precisely captures the dual element isotope trends characteristic of different reaction pathways as well as their range of variation consistent with observed bulk isotope fractionation. It was also possible to directly validate the model capability to predict the evolution of position-specific isotope ratios with available experimental data. Therefore, the approach is useful both for a mechanism-based evaluation of experimental results and as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available.

There is an ongoing debate on the fate of mercury (Hg) in areas affected by artisanal and small-scale gold mining (ASGM). Over the last 30 years, ASGM has released 69 tons of Hg into the southeastern Peruvian Amazon. To investigate the role of suspended matter and hydrological factors on the fate of ASGM-Hg, we analysed riverbank sediments and suspended matter along the partially ASGM-affected Malinowski-Tambopata river system and examined Hg accumulation in fish. In addition, local impacts of atmospheric Hg emissions on aquatic systems were assessed by analysing a sediment core from an oxbow lake. Hg concentrations in riverbank sediments are lower (20–53 ng g−1) than in suspended matter (∼400–4000 ng g−1) due to differences in particle size. Elevated Hg concentrations in suspended matter from ASGM-affected river sections (∼1400 vs. ∼30–120 ng L−1 in unaffected sections) are mainly driven by the increased amount of suspended matter rather than increased Hg concentrations in the suspended matter. The oxbow lake sediment record shows low Hg concentrations (64–86 ng g−1) without evidence of any ASGM-related increase in atmospheric Hg input. Hg flux variations are mostly an effect of variations in sediment accumulation rates. Moreover, only 5% of the analysed fish (only piscivores) exceed WHO recommendations for human consumption (500 ng g−1). Our findings show that ASGM-affected river sections in the Malinowski-Tambopata system do not exhibit increased Hg accumulation, indicating that the released Hg is either retained at the spill site or transported to areas farther away from the ASGM areas. We suspect that the fate of ASGM-Hg in such tropical rivers is mainly linked to transport associated with the suspended matter, especially during high water situations. We assume that our findings are typical for ASGM-affected areas in tropical regions and could explain why aquatic systems in such ASGM regions often show comparatively modest enrichment in Hg levels.

Appalachian USA surface coal mines face public and regulatory pressure to reduce total dissolved solids (TDS) in discharge waters, primarily due to effects on sensitive macroinvertebrates. Specific conductance (SC) is an accurate surrogate for TDS and relatively low levels of SC (300–500 μS cm−1) have been proposed as regulatory benchmarks for instream water quality. Discharge levels of TDS from regional coal mines are frequently >1000 μS cm−1. The primary objectives of this study were to (a) determine the effect of rock type and weathering status on SC leaching potentials for a wide range of regional mine spoils; (b) to relate leachate SC from laboratory columns to actual measured discharge SC from field sites; and (c) determine effective rapid lab analyses for SC prediction of overburden materials. We correlated laboratory unsaturated column leaching results for 39 overburden materials with a range of static lab parameters such as total-S, saturated paste SC, and neutralization potential. We also compared column data with available field leaching and valley fill discharge SC data. Leachate SC is strongly related to rock type and pre-disturbance weathering. Fine-textured and non-weathered strata generally produced higher SC and pose greater TDS risk. High-S black shales produced the highest leachate SC. Lab columns generated similar range and overall SC decay response to field observations within 5–10 leaching cycles, while actual reduction in SC in the field occurs over years to decades. Initial peak SC can be reliably predicted (R2 > 0.850; p < 0.001) by simple lab saturated paste or 1:2 spoil:water SC procedures, but predictions of longer-term SC levels are less reliable and deserve further study. Overall TDS release risk can be accurately predicted by a combination of rock type + S content, weathering extent, and simple rapid SC lab measurements.

Superfund sites with sediments contaminated by hydrophobic organic compounds (HOCs) can be difficult to characterize because of the complex nature of sorption to sediments. Porewater concentrations, which are often used to model transport of HOCs from the sediment bed into overlying water, benthic organisms, and the larger food web, are traditionally estimated using sediment concentrations and sorption coefficients estimated using equilibrium partitioning (EqP) theory. However, researchers have begun using polymeric samplers to determine porewater concentrations since this method does not require knowledge of the sediment's sorption properties. In this work, polyethylene passive samplers were deployed into sediments in the field (in situ passive sampling) and mixed with sediments in the laboratory (ex situ active sampling) that were contaminated with polychlorinated biphenyls (PCBs). The results show that porewater concentrations based on in situ and ex situ sampling generally agreed within a factor of two, but in situ concentrations were consistently lower than ex situ porewater concentrations. Imprecision arising from in situ passive sampling procedures does not explain this bias suggesting that field processes like bioirrigation may cause the differences observed between in situ and ex situ polymeric samplers.

As a signatory of the Stockholm Convention and the largest developing country, China plays a very important role in implementation of the convention to reduce and finally eliminate persistent organic pollutants (POPs) in the world. In the past ten years after the enforcement in 2004, Chinese Government and scientists have made great progress on the study of POPs. The present work aims to provide an overview on recent studies on POPs in China, with particular focus on usage/emission inventory, residue inventory, and pollution status of POPs on national scale. Several legend (old) and new target POPs were comprehensively summarized with progress on inventory. Furthermore, several national scale monitoring programs have been selected for the occurrence, spatial and temporal trends of POPs in China, which are compared with Asian data and Global data. Based on the observed results, some important scientific issues, such as the primary and secondary distribution patterns, the primary and secondary fractionations, and air-soil exchange of POPs, are also discussed. It is proposed that more studies should be carried out for the new targeted POPs in future for both the national and global interests.

Although phosphorus (P) is an essential element needed for all lives, excess P can be harmful to the environment. The objective of this study aims to determine P flows in the fisheries sector of Thailand consisting of both sea and freshwater activities of captures and cultures. Currently, the annual fisheries catch averages 3.44 ± 0.50 Mt. Most comes from marine capture 1.95 ± 0.46 Mt, followed by coastal aquaculture 0.78 ± 0.09 Mt, freshwater aquaculture 0.49 ± 0.05 Mt, and inland capture 0.22 ± 0.01 Mt. Of this total, about 11% is contained in fresh products directly sold in local markets for consumption, while 89% is sent to processing factories prior to being sold in local markets and exported. The quantities of P entering the fisheries sector come from captures, import of fisheries products and feed produced from agriculture. This P input to the fisheries sector is found to average 28,506 t P.y−1 based on the past ten-year records. Of this total, P input from captures accounts for 76%; while, 11% represents aquatic feeds from agriculture and animal manures. About 13% is obtained from the imports of fishery products. Coastal and freshwater aquacultures are found to be P consumers because their feeds are almost all produced from agricultural crops grown inland. Moreover, these activities cause most of P losses, approximately 10,188 t P·y−1, which account for 89% of the total P loss from the fisheries sector. Overall, P in the fisheries sector is found to mobilize through three channels: (a) 44% is consumed within the country; (b) about 16% is exported; and, (c) 40% is lost from the ecosystem. Based on the results of this work it is recommended that future research be directed on ways to minimize P loss and maximize P recycle in Thailand's fisheries sector as to enhance its food security and curtail water pollution.

In recent years measurable concentrations of non-steroidal anti-inflammatory drugs (NSAIDs) have been shown in the aquatic environment as a result of increasing human consumption. Effects of five frequently used non-steroidal anti-inflammatory drugs (diclofenac, diflunisal, ibuprofen, mefenamic acid and piroxicam in 0.1 mg ml−1 concentration) in batch cultures of cyanobacteria (Synechococcus elongatus, Microcystis aeruginosa, Cylindrospermopsis raciborskii), and eukaryotic algae (Desmodesmus communis, Haematococcus pluvialis, Cryptomonas ovata) were studied. Furthermore, the effects of the same concentrations of NSAIDs were investigated in natural algal assemblages in microcosms. According to the changes of chlorophyll-a content, unicellular cyanobacteria seemed to be more tolerant to NSAIDs than eukaryotic algae in laboratory experiments. Growth of eukaryotic algae was reduced by all drugs, the cryptomonad C. ovata was the most sensitive to NSAIDs, while the flagellated green alga H. pluvialis was more sensitive than the non-motile green alga D. communis. NSAID treatments had weaker impact in the natural assemblages dominated by cyanobacteria than in the ones dominated by eukaryotic algae, confirming the results of laboratory experiments. Diversity and number of functional groups did not change notably in cyanobacteria dominated assemblages, while they decreased significantly in eukaryotic algae dominated ones compared to controls. The results highlight that cyanobacteria (especially unicellular ones) are less sensitive to the studied, mostly hardly degradable NSAIDs, which suggest that their accumulation in water bodies may contribute to the expansion of cyanobacterial mass productions in appropriate environmental circumstances by pushing back eukaryotic algae. Thus, these contaminants require special attention during wastewater treatment and monitoring of surface waters.

The presence of sulfonamide antibiotics in aquatic environments poses potential risks to human health and ecosystems. In the present study, a highly porous activated carbon was prepared by KOH activation of an anthracite coal (Anth-KOH), and its adsorption properties toward two sulfonamides (sulfamethoxazole and sulfapyridine) and three smaller-sized monoaromatics (phenol, 4-nitrophenol and 1,3-dinitrobenzene) were examined in both batch and fixed-bed adsorption experiments to probe the interplay between adsorbate molecular size and adsorbent pore structure. A commercial powder microporous activated carbon (PAC) and a commercial mesoporous carbon (CMK-3) possessing distinct pore properties were included as comparative adsorbents. Among the three adsorbents Anth-KOH exhibited the largest adsorption capacities for all test adsorbates (especially the two sulfonamides) in both batch mode and fixed-bed mode. After being normalized by the adsorbent surface area, the batch adsorption isotherms of sulfonamides on PAC and Anth-KOH were displaced upward relative to the isotherms on CMK-3, likely due to the micropore-filling effect facilitated by the microporosity of adsorbents. In the fixed-bed mode, the surface area-normalized adsorption capacities of Anth-KOH for sulfonamides were close to that of CMK-3, and higher than that of PAC. The irregular, closed micropores of PAC might impede the diffusion of the relatively large-sized sulfonamide molecules and in turn led to lowered fixed-bed adsorption capacities. The overall superior adsorption of sulfonamides on Anth-KOH can be attributed to its large specific surface area (2514 m²/g), high pore volume (1.23 cm³/g) and large micropore sizes (centered at 2.0 nm). These findings imply that KOH-activated anthracite coal is a promising adsorbent for the removal of sulfonamide antibiotics from aqueous solution.

The occurrence of POPs in remote areas, such as Antarctica, is the result of their ability to udergo Long Range Transport (LRT) in the atmosphere, precipitation and cold condensation.In this study, both recent levels of various POPs in Trematomus bernacchii and their changes in roughly three decades were determined in order to evaluate trends of POPs in Antarctic benthic seawaters. In fact, Trematomus bernacchii is considered a good sentinel bio-indicator for monitoring not only the extent of contamination by POPs in the Antarctic aquatic ecosystem, but also changes in Antarctic ecosystem quality and trends.A slight decreasing PCB trend was detected during 30-years time span (from early 1980's to 2010) in the circumantarctic seawaters. Two higher peaks of concentrations were reported in 2001 and 2005 in the Ross Sea and they may reflect the ice melting of icebergs.Because fire risk is very high in Antarctica due to the very dry air, a large use of flame retardants in buildings and furniture of stations is highly probable; moreover, many stations were built when there were no restrictions on flame retardants use. The PBDE levels in the T. bernacchii from 2001 to 2011 ranged 0.05–0.35 pg/g and were of the same order of magnitude in 2001/2011 and in 2002/2005, with a maximum value in 2005 (0.35 pg/g).Comparable concentrations of HCB, HCHs PCDDs and PCDFs are available only for few seasons: all these compounds showed a decreasing temporal trends and their concentrations were one or more order of magnitude lower in 2000s–2010s.

Increases in water temperature, as a result of climate change, may influence biogeochemical cycles, sediment-water fluxes and consequently environmental sustainability. Effects of rising temperature on dynamics of nitrate, nitrite, ammonium, dissolved inorganic nitrogen (DIN), dissolved reactive phosphorus (DRP), dissolved organic carbon (DOC) and gaseous nitrogen (N2 and N2O) were examined in a subtropical river (the Jiulong River, southeast China) by microcosm experiments. Slurry sediments and overlying water were collected from three continuous cascade reservoirs, and laboratory incubations were performed at four temperature gradients (5 °C, 15 °C, 25 °C and 35 °C). Results indicated: (1) warming considerably increased sediment ammonium, DIN and DOC fluxes to overlying water; (2) warming increased retention of nitrate, and to a lesser extent, nitrite, corresponding to increases in N2 and N2O emission; (3) DRP was retained but released from Fe/Al-P enriched sediments at high temperature (35 °C) due to enhanced coupled transformation of carbon and nitrogen with oxygen deficiency. Using relationships between sediment fluxes and temperature, a projected 2.3°C-warming in future would increase ammonium flux from sediment by 7.0%–16.8%, while increasing nitrate flux into sediment by 8.9%–28.6%. Moreover, substrates (e.g., grain size, carbon availability) influenced nutrient delivery and cycling across cascade reservoirs. This study highlights that warming would increase bioreactive nutrient (i.e., ammonium and phosphate) mobilization with limited gaseous N removal from sediments, consequently deteriorating water quality and increasing eutrophication with future climate change.