A full-factorial test design was applied to systematically investigate the contribution and significance of water chemistry parameters (pH, divalent cations and dissolved organic carbon (DOC) concentration) and their interactions on the behavior and fate of copper nanoparticles (CuNPs). The total amount of Cu remaining in the water column after 48 h of incubation was mostly influenced by divalent cation content, DOC concentration and the interaction of divalent cations and DOC. DOC concentration was the predominant factor influencing the dissolution of CuNPs, which was far more important than the effect of pH in the range from 6 to 9 on the dissolution of the CuNPs. The addition of DOC at concentrations ranging from 5 to 50 mg C/L resulted in a 3–5 fold reduction of dissolution of CuNPs after 48 h of incubation, as compared to the case without addition of DOC. Divalent cation content was found to be the most influential factor regarding aggregation behavior of the particles, followed by DOC concentration and the interaction of divalent cations and DOC. In addition, the aggregation behavior of CuNPs rather than particulate dissolution explained most of the variance in the sedimentation profiles of CuNPs. These results are meaningful for improved understanding and prediction of the behavior and fate of metallic NPs in aqueous environments.

By identifying the main sources of nitrate (NO3−) can obtain useful information to support the management of NO3− pollution, particularly in subtropical catchments with shallow drinking water wells. This study used water chemistry and dual stable isotopes δ15N and δ18O methods to assess seasonal and spatial variations of NO3− in precipitation, surface water, and groundwater in an agricultural and forest subtropical catchment in Jiangxi Province, China. The maximum concentrations of nitrate-nitrogen (NO3−-N) and ammonium-nitrogen (NH4+-N) were 10.4 and 10.8 mg L−1in samples collected from 221 rainfall events from 2011 to 2013. About 4.4% and 12.3% NH4+-N concentrations of surface water and groundwater exceeded the thresholds of 1.0 and 0.2 mg L−1. The NO3−-N concentrations in surface water were closely correlated with NH4+-N concentrations in surface water and groundwater (r = −0.71 and r = −0.71, P < 0.05). The concentrations of NH4+-N and NO3−-N were significantly higher in a fishery pond and nearby drinking wells than in other monitoring points. Annual exports of NO3−-N and NH4+-N were 4.06 × 104 and 8.14 × 103 kg yr−1, respectively and NO3−-N is the main form of N loss. The δ15N values ranged from 0‰ to 20‰ in surface water and groundwater, and the δ18O values ranged from 0‰ to 15‰ and 1‰–13‰, respectively. Dual stable isotope natural abundance distribution and water chemistry [NO3−]/[Cl−] molar ratio information suggested that manure and sewage and soil N were the main sources of NO3− in surface water and manure and sewage in groundwater in summer and winter. In spring, water occurred denitrification and ammonium fertilizer, manure and sewage were the main sources of NO3− in surface water and groundwater which sampling points were closer residential area and fish ponds than paddy field and local farmers used more Manure. Manure applications should be reasonable around drinking water wells to protect the drinking water quality.

Bisphenol A (BPA) is a widely concerned endocrine disrupting chemical and hard to be removed through conventional wastewater treatment processes. In this study, we developed a TiO2 decorated titanate nanotubes composite (TiO2/TNTs) and used for photocatalytic degradation of BPA. TEM and XRD analysis show that the TiO2/TNTs is a nano-composite of anatase and titanate, with anatase acting as the primary photocatalytic site and titanate as the skeleton. TiO2/TNTs exhibited excellent photocatalytic reactivity and its easy-settling property leaded to good reusability. After 5 reuse cycles, TiO2/TNTs also could photo-degrade 91.2% of BPA with a high rate constant (k1) of 0.039 min⁻¹, which was much better than TiO2 and TNTs. Higher pH facilitated photocatalysis due to more reactive oxygen species produced and less material aggregation. The presence of NaCl and CaCl2 showed negligible effects on BPA degradation, but NaHCO3 caused an inhibition effect resulting from consumption of ·OH. Humic acid inhibited degradation mainly due to blockage of the active sites of TiO2/TNTs. Degradation pathway was well interpreted through theoretical calculation. Hydroxyl radical played the dominate role in BPA photodegradation, and the atoms of BPA with high Fukui index based on density-functional theory (DFT) calculation are the radical easy-attacking (f⁰) sites. Considering the good photocatalytic reactivity, reusability, stability and settle property, TiO2/TNTs promises to be an efficient alternative for removal of organic compounds from wastewaters.

Spatial and seasonal variations in nitrate contamination are a globally concern. While numerous studies have used δ¹⁵N-NO₃ and δ¹⁸O-NO₃ to elucidate the dominant sources of nitrate in groundwater, this approach has significant limitations due to the overlap of nitrate isotopic ranges and the occurrence of nitrate isotopic fractionation. This study quantitatively assessed the spatial and seasonal variations in the proportional contributions of nitrate sources from different land uses in the Tarom watershed in North-West Iran. To achieve this aim, orthogonal projection of the hydrochemical and isotopic dataset of the principal component analysis (PCA) as well as correlation coefficient matrix (Corr-PCA) were evaluated to reduce the dimensionality of the inter-correlated dataset. Next, a nitrate isotopic biplot accompanied with a Bayesian isotope mixing model (SIAR) were applied to specify the spatial and seasonal trends in the proportional contribution of three dominant sources of nitrate (fertilizers, animal manure and residential waste) in the watershed. Finally, in order to provide a sensitive framework for nitrate source appointment and overcome the associated limitations of dual nitrate isotope application, the integration of boron isotope (δ¹¹B) and strontium isotopic ratio (⁸⁷Sr/⁸⁶Sr) was introduced. The results revealed that the mean contribution of residential sewage increased (17%–27.5%), while the mean contribution of fertilizers decreased (28.3%–19%), from late spring to early autumn. Also, fertilizer was the highest contributor (42.1% ± 3.2) during late spring, especially in regions with more than 75% agricultural land. Meanwhile, the mean contribution of sewage was highest in early autumn (32.1% ± 2.8) in the areas with more than 20% residential land. These results were confirmed by coupled application of δ¹¹B and ⁸⁷Sr/⁸⁶Sr. This study provides a useful insight for environmental managers to verify groundwater pollution contributors and to better apply remedial solutions.

The Laurentian Great Lakes are a valuable natural resource that is affected by contaminants of emerging concern (CECs), including sex steroid hormones, personal care products, pharmaceuticals, industrial chemicals, and new generation pesticides. However, little is known about the fate and biological effects of CECs in tributaries to the Great Lakes. In the current study, 16 sites on three rivers in the Great Lakes basin (Fox, Cuyahoga, and Raquette Rivers) were assessed for CEC presence using polar organic chemical integrative samplers (POCIS) and grab water samplers. Biological activity was assessed through a combination of in vitro bioassays (focused on estrogenic activity) and in vivo assays with larval fathead minnows. In addition, resident sunfish, largemouth bass, and white suckers were assessed for changes in biological endpoints associated with CEC exposure. CECs were present in all water samples and POCIS extracts. A total of 111 and 97 chemicals were detected in at least one water sample and POCIS extract, respectively. Known estrogenic chemicals were detected in water samples at all 16 sites and in POCIS extracts at 13 sites. Most sites elicited estrogenic activity in bioassays. Ranking sites and rivers based on water chemistry, POCIS chemistry, or total in vitro estrogenicity produced comparable patterns with the Cuyahoga River ranking as most and the Raquette River as least affected by CECs. Changes in biological responses grouped according to physiological processes, and differed between species but not sex. The Fox and Cuyahoga Rivers often had significantly different patterns in biological response Our study supports the need for multiple lines of evidence and provides a framework to assess CEC presence and effects in fish in the Laurentian Great Lakes basin.

We conducted an exposure experiment with Diffusive Gradients in Thin- Films (DGT), fathead minnow (Pimephales promelas), and yellow lampmussel (Lampsilis cariosa) to estimate bioavailability and bioaccumulation of Cu. We hypothesized that Cu concentrations measured by DGT can be used to predict Cu accumulation in aquatic animals and alterations of water chemistry can affect DGT's predict ability. Three water chemistries (control soft water, hard water, and addition of natural organic matter (NOM)) and three Cu concentrations (0, 30, and 60 μg/L) were selected, so nine Cu-water chemistry combinations were used. NOM addition treatments resulted in decreased concentrations of DGT-measured Cu and free Cu ion predicted by Biotic Ligand Model (BLM). Both hard water and NOM addition treatments had reduced concentrations of Cu ion and Cu-dissolved organic matter complexes compared to other treatments. DGT-measured Cu concentrations were linearly correlated to fish accumulated Cu, but not to mussel accumulated Cu. Concentrations of bioavailable Cu predicted by BLM, the species complexed with biotic ligands of aquatic organisms and, was highly correlated to DGT-measured Cu. In general, DGT-measured Cu fit Cu accumulations in fish, and this passive sampling technique is acceptable at predicting Cu concentrations in fish in waters with low NOM concentrations.

In this work, the results of hydrochemical studies aboard the R/V Iran Behshahr in southern Caspian Sea in late-winter 2014 were presented. Salinity, temperature, dissolved oxygen, pH, total dissolved inorganic carbon, total alkalinity, nitrate, phosphate and silicate concentrations in water column of Neka-Amir Kabir oil platform section in the southern Caspian Sea were measured to study the status of hydrochemistry of this area. Results showed that the hypoxia continues to intensify in the deep-water basin of the South Caspian Sea. Near-zero concentration of dissolved oxygen and accumulation of phosphate, silicate and total dissolved inorganic carbon in near-bottom layers in the study area showed that vertical winter mixing of water column did not reach the near-bottom layers at the time of this survey. Nitrate showed its maximum concentration at the intermediate maximum depth of 300m.

The most common lead (Pb) and zinc (Zn) ore minerals are galena (PbS) and sphalerite (ZnS). Milling and mining operations of these ores produce huge amounts of waste known as chat and tailings. Chat is composed of gravel, sand, and silt-sized rock materials, whereas tailings are often fine-grained and silt-sized particles with higher toxic element concentrations. Upon oxidation, tailings with high pyritic materials release Pb, Zn, Cadmium (Cd), and other elements associated with ores affecting plant productivity, the ecosystem, and human health. This article is an overview on utilizing the subsurface submergence technique for mitigating environmental impacts from abandoned mine waste materials. In the past, researchers have studied the influence of submergence on these elements; however, an emphasis on gathering a detailed understanding of such redox-based remediation processes is not that common. We reviewed literature that evaluated water chemistry, solid phases, and association of trace elements, and addressed utilization of surface amendments of mine tailings for predicting their interactions within sediments and overlying waters. Case studies specifically focused on mining of Pb and Zn, including a recent study conducted in the Tri-State mining district (Kansas, Missouri, and Oklahoma), are presented to add a more comprehensive understanding of biogeochemical transformations of trace elements present in mine waste materials under a long-term submergence. The purpose of this article is to present evidence on the viability of subsurface disposal of mine waste materials, in order to design effective remediation and mitigation strategies to protect human and environmental health in the global dimension.

Estuarine sediments can be a source of Phosphorus (P) to coastal waters, contributing to nutrient budgets and geochemical cycles. In this work, the concentration and speciation of P in 47 cores were examined from the inter-tidal mud flats of the tidal river Thames (~120km). Results of P concentration and speciation were combined with published data relating to known sediment dynamics and water chemistry (salinity) within the estuary to produce a conceptual model of sediment-P behaviour. Results demonstrated significant P desorption occurring after sediment passed through the Estuarine Turbidity Maximum and when the salinity of the river water exceeded ~6ppt. It was found that organic P was desorbed to a greater extent than inorganic P in the lower estuary. Models were used to identify those geochemical parameters that contributed to the Total P (R²=0.80), oxalate extractable P (R²=0.80) and inorganic P (R²=0.76) concentrations within the Thames estuary.

Acid deposition has led to acidification and loss of fish populations in thousands of lakes and streams in Norway. Since the peak in the late 1970s, acid deposition has been greatly reduced and acidified surface waters have shown chemical recovery. Biological recovery, in particular fish populations, however, has lagged behind. Long-term monitoring of water chemistry and fish populations in Lake Langtjern, south-eastern Norway, shows that around 2008, chemical recovery had progressed to the point at which natural reproduction of brown trout (Salmo trutta) reoccurred. The stocked brown trout reproduced in the period 2008–2014, probably for the first time since the 1960s, but reproduction and/or early life stage survival was very low. The results indicate that chemical thresholds for reproduction in this lake are approximately pH = 5.1, Alᵢ = 26 μg l⁻¹, ANC = 47 μeq l⁻¹, and ANCₒₐₐ = 10 μeq l⁻¹ as annual mean values. These thresholds agree largely with the few other cases of documented recovery of brown trout in sites in Norway, Sweden, and the UK. Occurrence and duration of acidic episodes have decreased considerably since the 1980s but still occur and probably limit reproduction success.