Copper export and mobility in acid mine drainage are difficult to understand with conventional approaches. Within this context, Cu isotopes could be a powerful tool and here we have examined the relative abundance of dissolved (<0.22 μm) Cu isotopes (δ⁶⁵Cu) in the Meca River which is an outlet of the Tharsis mine, one of the largest abandoned mines of the Iberian Pyrite Belt, Spain. We followed the chemical and isotopic composition of the upstream and downstream points of the catchment during a 24-h diel cycle. Additional δ⁶⁵Cu values were obtained from the tributary stream, suspended matter (>0.22 μm) and bed sediments samples. Our goals were to 1) assess Cu sources variability at the upstream point under contrasted hydrological conditions and 2) investigate the conservative vs. non conservative Cu behavior along a stream. Average δ⁶⁵Cu values varied from −0.47 to −0.08‰ (n = 9) upstream and from −0.63 to −0.31‰ downstream (n = 7) demonstrating that Cu isotopes are heterogeneous over the diel cycle and along the Meca River. During dry conditions, at the upstream point of the Meca River the Cu isotopic composition was heavier which is in agreement with the preferential release of heavy isotopes during the oxidative dissolution of primary sulfides. The more negative values obtained during high water flow are explained by the contribution of soil and waste deposit weathering. Finally, a comparison of upstream vs. downstream Cu isotope composition is consistent with a conservative behavior of Cu, and isotope mass balance calculations estimate that 87% of dissolved Cu detected downstream originate from the Tharsis mine outlet. These interpretations were supported by thermodynamic modelling and sediment characterization data (X-ray diffraction, Raman Spectroscopy). Overall, based on contrasted hydrological conditions (dry vs flooded), and taking the advantage of isotope insensitivity to dilution, the present work demonstrates the efficiency of using the Cu isotopes approach for tracing sources and processes in the AMD regions.

Eating fish provides numerous health benefits, but it is also a dominant pathway for human exposure to contaminants. Many studies have examined mercury (Hg) accumulation in fish, but fewer have considered other elements, such as arsenic (As) and chromium (Cr). Recently, freshwater fish from several pristine boreal systems across northern Ontario, Canada, have been reported with elevated concentrations of As and Cr for reasons that are not well understood. Our goal was to investigate the ecological and environmental influences over concentrations of As, Cr, and other elements in these fish to better understand what affects metal uptake and the risk to consumers. We measured 10 elements (including As, Cr, Hg) as well as carbon (δ¹³C), nitrogen (δ¹⁵N), and sulfur (δ³⁴S) stable isotopes in 388 fish from 25 lake and river sites across this remote region. These data were used to determine the effect of: 1) trophic ecology; and 2) watershed geology on piscine elemental content. Overall, most element concentrations were low, often below provincial advisory benchmarks (ABs). However, traces of Hg, As, Cr, and selenium (Se) were detected in most fish. Based on their exceedance of their respective ABs, the most restrictive elements on fish consumption in these boreal systems were Hg > As > Cr. Arsenic and Se, but not Cr concentrations were related to fish size and trophic ecology (inferred from δ¹³C and δ¹⁵N), suggesting bioaccumulation of the former elements. Fish with enriched δ³⁴S values, suggestive of anadromous behaviour, had marginally lower Hg but higher Se concentrations. Modeling results suggested a strong effect of site-specific factors, though we found weak trends between piscine elemental content and geological features (e.g., mafic intrusions), potentially due to the broad spatial scale of this study. Results from this study address gaps in our understanding of As and Cr bioaccumulation and will help to inform fish consumption guidelines.

Owing to the substantial consumption of caffeinated food, beverages, and medicines worldwide, caffeine is considered the most representative pharmaceutically active compound (PhAC) pollutant based on its high abundance in the environment and its suitability as an indicator of the anthropogenic inputs of PhACs in water bodies. This review presents a worldwide analysis of 132 reports of caffeine residues in freshwater environments. The results indicated that more than 70% of the studies reported were from Asia and Europe, which have densely populated and industrially developed areas. However, caffeine pollution was also found to affect areas isolated from human influence, such as Antarctica. In addition, the maximum concentrations of caffeine in raw wastewater, treated wastewater, river, drinking water, groundwater, lake, catchment, reservoir, and rainwater samples were reported to be 3.60 mg/L, 55.5, 19.3, 3.39, 0.683, 174, 44.6, 4.87, and 5.40 μg/L, respectively. The seasonal variation in caffeine residues in the freshwater environment has been demonstrated. In addition, despite the fact that there was a small proportion of wastewater treatment plants in which the elimination rates of caffeine were below 60%, wastewater treatment is generally believed to have a high caffeine removal efficiency. From a pharmacy perspective, we proposed to adopt effective measures to minimize the environmental risks posed by PhACs, represented by caffeine, through a new concept known as ecopharmacovigilance (EPV). Some measures of EPV aimed at caffeine pollution have been advised, as follows: improving knowledge and perceptions about caffeine pollution among the public; listing caffeine as a high-priority PhAC pollutant, which should be targeted in EPV practices; promoting green design and production, rational consumption, and environmentally preferred disposal of caffeinated medicines, foods, and beverages; implementing intensive EPV measures in high-risk areas and during high-risk seasons; and integrating EPV into wastewater treatment programs.

Organisms and ecosystems are generally exposed to mixtures of chemicals rather than to individual chemicals, but there have been relatively few detailed analyses of the mixtures of pesticides that occur in surface waters. This study examined over 2600 water samples, analysed for between 21 and 47 pesticides, from 15 waterways that discharge to the lagoon of the Great Barrier Reef in Queensland, Australia between July 1, 2011 and June 30, 2015. Essentially all the samples (99.8%) contained detectable concentrations (>limit of detection) of pesticides and pesticide mixtures. Approximately, 10% of the samples contained no quantifiable (>limit of reporting) pesticides, 10% contained one quantifiable pesticide and 80% contained quantifiable mixtures of 2–20 pesticides. Approximately 82% of samples that contained quantifiable mixtures had more than two modes of action (MoAs), but only approximately 6% had five or more MoAs. The mode, average and median number of quantifiable pesticides in all the samples were 2, 5.1 and 4, respectively. The most commonly detected compounds both individually and in mixtures were the pesticides atrazine, diuron, imidacloprid, hexazinone, 2,4-D, and the degradation product desethylatrazine. The number of pesticides and modes of action of pesticides in mixtures differed spatially and were affected by land use. Waterways draining catchments where sugar cane was a major land use had mixtures with the most pesticides.

The Sürgü Stream, located in the Euphrates River basin of Turkey, is used for drinking water source, agricultural irrigation and rainbow trout production. Therefore, water quality of the stream is of great importance. In this study, multivariate statistical techniques (MSTs) and water quality index (WQI) were applied to assess water quality of the stream affected by multiple stressors such as untreated domestic sewage, effluents from fish farms, agricultural runoff and streambank erosion. For this, 16 water quality parameters at five sites along the stream were monitored monthly during one year. Most of parameters showed significant spatial variations, indicating the influence of anthropogenic activities. All parameters except TN (total nitrogen) showed significant seasonal differences due to high seasonality in WT (water temperature) and water flow. The spatial variations in the WQI were significant (p < 0.05) and the mean WQI values ranged from 87.6 to 95.3, indicating “good” to “excellent” water quality in the stream. Cluster analysis classified five sites into three groups, that is, clean region, low polluted region and very clean region. Stepwise temporal discriminant analysis (DA) identified that pH, WT, Cl⁻, SO₄²⁻, COD (chemical oxygen demand), TSS (total suspended solids) and Ca²⁺ are the parameters responsible for variations between seasons, and stepwise spatial DA identified that DO (dissolved oxygen), EC (electrical conductivity), NH₄–N, TN (total nitrogen) and TSS are the parameters responsible for variations between the regions. Principal component analysis/factor analysis revealed that the parameters responsible for water quality variations were mainly associated with suspended solids (both natural and anthropogenic), soluble salts (natural) and nutrients and organic matter (anthropogenic).

Plastic, and especially microplastic, contamination of soils has become a novel research field. After the detection of microplastics in soils, spatial distribution and dynamics are still unknown. However, the potential risks associated with plastic particles in soils cannot be sufficiently assessed without knowledge about the spatial distribution of these anthropogenic materials. Based on a spatial research approach, including soil surveys, this study quantified the mesoplastic (MEP, > 5.0 mm) and coarse microplastics (CMP, 2.0–5.0 mm) content of twelve floodplain soils. At four transects in the catchment area of the Lahn river (Germany), soils down to a depth of 2 m were examined for plastic content for the first time. MEP and CMP were detected through visual examination after sample preprocessing and ATR-FTIR analyses. Average MEP and CMP concentrations range between 2.06 kg⁻¹ (±1.55 kg⁻¹) and 1.88 kg⁻¹ (±1.49 kg⁻¹) with maximal values of 5.37 MEP kg⁻¹ to 8.59 CMP kg⁻¹. Plastic particles are heterogeneously distributed in samples. Both plastic size classes occur more frequently in topsoils than in soil layers deeper than 30 cm. The maximal depth of CMP occurrence lies between 75 and 100 cm. Most common CMP polymer type was PE-LD, followed by PP and PA. MEP and CMP particles occur frequently at near channel sides and more often on riparian strips or grassland than on farmland. Vertical distribution of CMP indicates anthropogenic relocation in topsoils and additional deep displacement through natural processes like preferential flow paths or bioturbation. By comparing sedimentation rates of the river with the maximum age of plastic particles, sedimentation as a deposition process of plastic in floodplains becomes probable. From our findings, it can be concluded that an overall widespread but spatial heterogenous contamination occurs in floodplain soils. Additionally, a complex plastic source pattern seems to appear in floodplain areas.

The present study is the first comprehensive monitoring of 13 selected endocrine disrupting compounds (EDCs) in untreated urban and industrial wastewater in Serbia to assess their impact on the Danube River basin and associated freshwaters used as sources for drinking water production in the area. Results showed that natural and synthetic estrogens were present in surface and wastewater at concentrations ranging from 0.1 to 64.8 ng L⁻¹. Nevertheless, they were not detected in drinking water. For alkylphenols concentrations ranged from 1.1 to 78.3 ng L⁻¹ in wastewater and from 0.1 to 37.2 ng L⁻¹ in surface water, while in drinking water concentrations varied from 0.4 to 7.9 ng L⁻¹. Bisphenol A (BPA) was the most abundant compound in all water types, with frequencies of detection ranging from 57% in drinking water, to 70% in surface and 84% in wastewater. Potential environmental risks were characterized by calculating the risk quotients (RQs) and the estrogenic activity of EDCs in waste, surface and drinking water samples, as an indicator of their potential detrimental effects. RQ values of estrone (E1) and estradiol (E2) were the highest, exceeding the threshold value of 1 in 60% of wastewater samples, while in surface water E1 displayed potential risks in only two samples. Total estrogenic activity (EEQₜ) surpassed the threshold of 1 ng E2 L⁻¹ in about 67% of wastewater samples, and in 3 surface water samples. In drinking water, EEQₜ was below 1 ng L⁻¹ in all samples.

Uncertainty assessment of parameters associated with non-point source pollution mechanism modeling are crucial for improving the effectiveness of pollution controlling. In this study, an approach based on Bayesian inference and integrated Markov chain Monte Carlo and multilevel factorial analysis has been developed, and it can not only apply straightforward Bayesian inference to assess parameter uncertainties, but also quantitatively investigate the main and interactive effects of multiple parameters on the model response variables by measuring the specific variations of model outputs. Its applicability and advantages are presented through the application of the Soil and Water Assessment Tool to Shitoukoumen Reservoir Catchment in northeast China. This study investigated the uncertainties of a set of sensitive parameters and their multilevel effects on model response variables, including average annual runoff (AAR), average annual sediment (AAS) and average annual total nitrogen (AAN). Results revealed that (i) soil conservation service runoff curve number for moisture condition II (CN2) had a positive effect on all response variables; (ii) available water capacity of the soil layer (SOL_AWC) had a negative effect on all response variables; (iii) the universal soil loss equation support practice (USLE_P) had a positive effect on AAS and AAN, and little effect on AAR; while the nitrate percolation coefficient (NPERCO) had a positive effect on AAN, and little effect on AAS and AAR; and (iv) the interactions amongst parameters had obvious interdependent effects on the model response variables, for example, the interaction between CN2 and SOL_AWC had a major impact on AAR. The above findings can improve the simulating and predicting capabilities of non-point source pollution mechanism model. Overall, this study highlights that the proposed approach represents a promising solution for uncertainty assessment of model parameters in non-point source pollution mechanism modeling.

Land use/Land cover (LULC) associated with Cryptosporidium sp. and Giardia sp. quantification and distribution can provide identification of the environmental circulation patterns of these parasites. The aim of this research was to relate the occurrence and circulation of these parasites to the LULC watershed with poor sanitation infrastructure and livestock as important economic activity. The study involved 11 municipalities in the state of São Paulo, located in southeastern Brazil. Sampling was carried out at the catchment sites of each water supply on a monthly basis, starting in December 2014 and lasting until November 2015, totalizing 128 samples. Protozoans were quantified according to the 1623.1 US. EPA Method. For watershed delimitation, the hydrographic network was extracted from the hydrology tool of ArcGIS 10.1. The frequency of occurrence of these pathogens and the high concentrations were evidenced in the municipality with the largest urban area (16.2%) and intense livestock activity (39%) near the catchment site. The municipality that showed the lowest frequency of occurrence presented the smallest urban area (0.87%) and absence of livestock activity near the catchment site. The high concentration of pathogens suggests a correlation between the impact on water supply networks and river basin degradation caused by urban activity and livestock.

The Arctic is subject to long-range atmospheric deposition of globally-distilled semi-volatile organic compounds (SVOCs) that bioaccumulate and biomagnify in lipid-rich food webs. In addition, locally contaminated sites may also contribute SVOCs to the arctic environment. Specifically, Alaska has hundreds of formerly used defense (FUD) sites, many of which are co-located with Alaska Native villages in remote parts of the state. The purpose of this study was to investigate the extent of SVOC contamination on Alaska’s St. Lawrence Island through the analysis of sentinel fish, the ninespine stickleback (Pungitius pungitius), collected from Troutman Lake located within the watershed of an FUD site and adjacent to the Yupik community of Gambell. We measured the concentrations of legacy and emerging SVOCs in 303 fish samples (81 composites), including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), organophosphate esters (OPEs) and their diester metabolites, and per- and poly-fluoroalkyl substances (PFAS). PBDEs and PCBs were the most abundant SVOC groups found in stickleback with ΣPBDE and ΣPCB median concentrations of 25.8 and 10.9 ng/g ww, respectively, followed by PFAS (median ΣPFAS 7.22 ng/g ww). ΣOPE and ΣOPE metabolite concentrations were lower with median concentrations of 4.97 and 1.18 ng/g ww, respectively. Chemical patterns and distributions based on correlations and comparison with SVOC concentrations in stickleback from other parts of the island suggest strong local sources of PCBs, PBDEs, and PFAS on St. Lawrence Island.