Metal pollution in estuaries represents a serious environmental challenge, especially in areas affected by industrial and mining activities. This study investigates the metal partitioning and availability of rare earth elements (REE), Y and other trace metals (Ag, Tl, U and Cs) in the Ria of Huelva estuary (SW Spain), strongly affected by mining and industrial activities. A 30 h monitoring campaign was performed collecting periodic water samples and deploying diffusive gradient in thin films (DGTs) devices to determine the main factors controlling metal availability. The dissolved concentrations of U (3118–3952 ng/L) and Cs (284–392 ng/L) were in the same order of magnitude than those reported in other estuaries and coastal waters worldwide, however, REE (26–380 ng/L), Y (15–109 ng/L), Ag (14–307 ng/L) and Tl (29–631 ng/L) concentrations exceeded these values for the same salinities. Unlike most metals (i.e. Ag, Tl, U, Cs), which were mainly found in the dissolved form (87–100% of total), REE and Y were found in the particulate phase (22–36% of total). Metal lability was mainly related to the concentration in the water column following this order: U>REE>Y>Ag>Tl. A similar binding mechanism was observed for Tl and Cd, due to its chemical affinity. This relationship between chemical properties and absorption by DGT-resin was also observed for REE (and Y), Rb and Sr, which may cause bioaccumulation upon persistent exposure, considering the ability of these metals to cross the biological membranes. The lability of metals predicted by geochemical codes did not coincide with absorption of labile metals by DGTs due probably to the instability of complexes in contact with the DGT membranes, the inability of metals to form thermodynamically stable complexes or the absorption of colloids. From this work it can be concluded that DGT passive sampling should complement traditional sampling to monitor metal availability in aquatic environments.

The metalloid arsenic is one of the most conspicuous groundwater contaminants in the Indian subcontinent and its removal from aqueous medium is the main focus of this study. The study aims at functionalising melanin using iron and copper for the efficient removal of arsenic and rendering water fit for consumption. Melanin obtained from the marine bacteria Pseudomonas stutzeri was functionalised by iron impregnation (Fe-melanin) and copper impregnation (Cu-melanin). Morphological studies using FESEM portrayed the impregnated iron and copper granules on the surface of melanin, while XRD analysis confirmed the presence of Fe₂O₃ and CuO on melanin. Adsorption studies on As (V) and As (III) were conducted using Fe-melanin and Cu-melanin for different operating variables like pH, temperature and contact time. More than 99% per cent of As (III) and As (V) from water was removed at a pH range between 4 and 6 within 50 min in the case of Fe-melanin and 80 min for Cu-melanin. Adsorption equilibrium studies showed better fit with Langmuir adsorption isotherm and had good agreement with Redlich-Peterson’s three-parameter model. The maximum adsorption capacities of Fe-melanin and Cu-melanin obtained from Langmuir adsorption model are 50.12 and 20.39 mg/g, respectively, for As (V) and similarly 39.98 and 19.52 mg/g, respectively, for As (III). Arsenic-binding to the functionalised melanin was confirmed using FT-IR and the XPS analysis. Reuse of the adsorbent was effectively done by desorbing the iron and copper together with the bound As (III) and As (V) and further re-impregnation of iron and copper in melanin. Re-functionalised melanin showed 99% adsorption efficiency up to four cycles of adsorption/desorption.

Pharmaceuticals and personal care products (PPCPs) are a class of emerging contaminants commonly detected in environmental waters worldwide. Although reports about their detection in aquatic environments are increasing, limited studies show their effects on holometabolous insects. In this study, acute and chronic exposure to naproxen (0.02, 41, 82, 164, 382, 656, and 1312 mg L⁻¹) and propylparaben (0.02, 25, 50, 100, 250, 500, and 1000 mg L⁻¹) were evaluated in Aedes aegypti L. Acute exposure to naproxen (≥0.02 mg L⁻¹) and propylparaben (≥0.02 mg L⁻¹) reduced egg eclosion. Propylparaben (≥250 mg L⁻¹) caused significant larval mortality but naproxen did not even at the highest experimental concentration used. LC₅₀ for naproxen and propylparaben in larvae were 1100 mg L⁻¹ and 182.6 mg L⁻¹, respectively. Naproxen (≥0.02 mg L⁻¹) and propylparaben (≥0.02 mg L⁻¹) reduced pupation. Emergence was also reduced by naproxen (≥164 mg L⁻¹) and propylparaben (≥0.02 mg L⁻¹). The fecundity of females was significantly reduced due to chronic exposure to naproxen (≥0.02 mg L⁻¹). There was also a reduction in the fecundity of females due to chronic propylparaben exposure but it was statistically insignificant in the concentrations used. In the F1 generation eggs, only 100 mg L⁻¹ propylparaben reduced eclosion. Eclosion and larval survival were sensitive to acute exposure, particularly to propylparaben. The reduced pupation and emergence indicated a delay in the progression of the life cycle. Chronic exposure also indicated a reduction in fecundity. F1 eggs exhibited tolerance to the negative effect of subsequent exposure. Our findings suggest that propylparaben can affect Ae. aegypti more negatively than naproxen.

Among the most used non-steroidal anti-inflammatory drugs (NSAIDs), ketoprofen (KTF) assumes an important position. Nevertheless, its ecotoxicological effects in non-target organisms are poorly characterized, despite its use and frequency of occurrence in aquatic matrices. Thus, the aim of this study was to evaluate the possible toxicological effects of KTF contamination, in two freshwater species, Lemna minor and Daphnia magna, by measuring biochemical, physiological and population parameters. To attain this objective, both species were exposed to KTF at the same concentrations (0, 0.24, 1.2, 6 and 30 μg/L). L. minor plants were exposed during 4 d to these levels of KTF, and the enzymatic activity (catalase (CAT), glutathione S-transferases (GSTs) and carbonic anhydrase (CA)), and pigments content (chlorophylls a, b and total and carotenoids) were analyzed to evaluate the toxicity of this drug. D. magna was acutely and chronically exposed to KTF, and enzymatic activities (CAT, GSTs and cyclooxygenase (COX)), the feeding rates, and reproduction traits were assessed. In L.minor, KTF provoked alterations in all enzyme activities, however, it was not capable of causing any alteration in any pigment levels. On the other hand, KTF also provoked alterations in all enzymatic activities in D. magna, but did not affect feeding rates and life-history parameters. In conclusion, exposure to KTF, provoked biochemical alterations in both species. However, these alterations were not reflected into deleterious effects on physiological and populational traits of L. minor and D. magna.

After the exploitation of coal mines in the 19th and 20th centuries in northern France, many mining slag heaps (SH) were left without any particular management or monitoring. Currently, the influence of these SHs on the quality of surrounding wetlands is hardly known.The purpose of this work is to determine the water quality in the neighbourhood of two SHs located near the city of Douai and its influence on the distribution of aquatic invertebrates in local wetlands. Our approach involves (1) the spatial and temporal characterization of the water composition (anions, major elements, sulphide, DOC and alkalinity) and of the biological diversity (aquatic invertebrates) and (2), based on this chemical and biological screening, the establishment of relationships between water quality and biodiversity distribution through multivariate data analysis. The results clearly indicate that substantial leaching from the slag heaps occurs, given the very high concentrations of dissolved sulphates (in the range of 2 g L⁻¹). While the pH remains weakly basic, indicating that the leaching water has been neutralized by the highly carbonated regional substratum, high levels of biodegradable organic matter and sulphate contents have been noticed. They sporadically cause significant drops in dissolved oxygen and the occurrence of dissolved sulphides that massively reduce biodiversity, qualitatively and quantitatively. In Summer, oxygen saturation is generally lower due to the higher rate of organic matter degradation, and the risk of anoxic episodes therefore increases. Finally, as wetlands are vulnerable environments, these preliminary results suggest that monitoring and management of these sites must be attempted quickly to avoid the degradation of those valuable habitats.

Cyanobacterial blooms are an increasing problem in a more eutrophic world. It is still a challenge to fully understand the influence of cyanobacteria on the interactions between predator and prey at higher trophic levels. The present study was mainly undertaken to understand the inducible anti-predator responses of cladocerans while using cyanobacteria as part of food. Specifically speaking, we focused on the anti-predator strategies of Ceriodaphnia cornuta in response to different predators (fish and Chaoborus larvae) under food with different proportions of Microcystis aeruginosa. The morphological (i.e., body size and the induction of horns) and life history traits (e.g., time to first reproduction, offspring number, and survival time) responses were measured under different proportions of M. aeruginosa (i.e., 0%, 20%, 40%, 60%, 80%, and 100%). Our results showed that both the life history and the inducible anti-predator responses of C. cornuta were significantly affected by different concentrations of M. aeruginosa. Specifically, lower concentrations of Microcystis (20%–60%) can significantly promote the horns induction under Chaoborus predation risks, and higher Microcystis concentrations (60%–100%) tend to enhance reproduction in response to fish predation risks, such as larger body size, decreased time to first reproduction, and increased total offspring number. Additionally, an increasing concentration of M. aeruginosa decreased the ability of C. cornuta to reverse horns when predation risks removed. Our findings indicated that cyanobacteria affecting life history traits and the subsequent indirect effects on anti-predator responses in cladocerans could impact the interactions between predator and prey at higher trophic levels and may consequently contribute to shaping the structure of the community in a cyanobacteria bloom area.

Malaysia is a tropical country that is highly dependent on surface water for its raw water supply. Unfortunately, surface water is vulnerable to pollution, especially in developed and dense urban catchments. Therefore, in this study, a methodology was developed for an extensive temporal water quality index (WQI) and classification analysis, simulations of various pollutant discharge scenarios using QUAL2K software, and maps with NH₃–N as the core pollutant using an integrated QUAL2K-GIS. It was found that most of the water quality stations are categorized as Class III (slightly polluted to polluted). These stations are surrounded by residential areas, industries, workshops, restaurants and wet markets that contribute to the poor water quality levels. Additionally, low WQI values were reported in 2010 owing to development and agricultural activities. However, the WQI values improved during the wet season. High concentrations of NH₃–N were found in the basin, especially during dry weather conditions. Three scenarios were simulated, i.e. 10%, 50% and 70% of pollution discharge into Skudai river using a calibrated and validated QUAL2K model. Model performance was evaluated using the relative percentage difference. An inclusive graph showing the current conditions and pollution reduction scenarios with respect to the distance of Skudai river and its tributaries is developed to determine the WQI classification. Comprehensive water quality maps based on NH₃–N as the core pollutant are developed using integrated QUAL2K-GIS to illustrate the overall condition of the Skudai river. High NH₃–N in the Skudai River affects water treatment plant operations. Pollution control of more than 90% is required to improve the water quality classification to Class II. The methodology and analysis developed in this study can assist various stakeholders and authorities in identifying problematic areas and determining the required percentage of pollution reduction to improve the Skudai River water quality.

Evaluating speciation of arsenic (As) is essential to assess its risk in paddy soils. In this study, effects of phosphate on speciation of As in six paddy soils differing in redox status were studied over a range of pH (pH 3-9) and different background calcium (Ca) levels by batch adsorption experiments and speciation modeling. Contrasting effects of phosphate on As speciation were observed in suboxic and anoxic soils. Under suboxic conditions, phosphate inhibited Fe and As reduction probably due to stabilization of Fe-(hydr)oxides, but increased soluble As(V) concentration as a result of competitive adsorption between As(V) and phosphate. In anoxic soils, phosphate stimulated Fe and As reduction and caused increases of As(III) in soil solution under both acidic and neutral/alkaline pH. The LCD (Ligand and Charge Distribution) and NOM-CD (Natural Organic Matter-Charge Distribution) model can describe effects of pH, calcium and phosphate on As speciation in these paddy soils. The results suggest that phosphatefertilization may decrease (at low pH) or increase (at neutral/alkaline pH) As mobility in paddy soils under (sub)oxic conditions, but under anoxic conditions and in phosphorus deficient soils phosphate fertilization may strongly mobilize As by promoting microbial activities.

The use of some systemic insecticides has been banned in Europe because they are toxic to beneficial insects when these feed on nectar. A recent study shows that systemic insecticides can also kill beneficial insects when they feed on honeydew. Honeydew is the sugar-rich excretion of hemipterans and is the most abundant carbohydrate source for beneficial insects such as pollinators and biological control agents in agroecosystems. Here, we investigated whether the toxicity of contaminated honeydew depends on i) the hemipteran species that excretes the honeydew; ii) the active ingredient, and iii) the beneficial insect that feeds on it. HPLC-MS/MS analyses demonstrated that the systemic insecticides pymetrozine and flonicamid, which are commonly used in Integrated Pest Management programs, were present in honeydew excreted by the mealybug Planococcus citri. However, only pymetrozine was detected in honeydew excreted by the whitefly Aleurothixus floccosus. Toxicological studies demonstrated that honeydew excreted by mealybugs feeding on trees treated either with flonicamid or pymetrozine increased the mortality of the hoverfly Sphaerophoria rueppellii, but did not affect the parasitic wasp Anagyrus vladimiri. Honeydew contaminated with flonicamid was more toxic for the hoverfly than that contaminated with pymetrozine. Collectively, our data demonstrate that systemic insecticides commonly used in IPM programs can contaminate honeydew and kill beneficial insects that feed on it, with their toxicity being dependent on the active ingredient and hemipteran species that excretes the honeydew. Insecticides recommended in Integrated Pest Management programs reach honeydew and kill beneficial insects that feed on it.

Long-term trends (2004–2017) in the chemical composition and sources of PM₂.₅ (particulate matter smaller than 2.5 μm in diameter) in a metropolitan area were investigated using daily integrated PM₂.₅ chemical speciation data and continuous air pollution measurements. Eleven source factors were identified: coal combustion characterized by secondary sulphate, secondary nitrate, summertime organic carbon (OC), regional elemental carbon (EC), biomass burning, oil combustion, primary tailpipe emissions, non-tailpipe emissions related to road dust, non-tailpipe emissions related to brake wear, metal production, and road salt. Overall, coal combustion, secondary nitrate, regional EC, and oil combustion underwent marked decreases in concentrations with large reduction rates ranging from −8% yr⁻¹ to −18% yr⁻¹, contributing to an overall 34% decrease in annual PM₂.₅ over the past 14 years. Decreases in local tailpipe emissions (−3% yr⁻¹) were consistent with the reduction of traffic-related air pollutants. In contrast, non-tailpipe emissions remained constant until 2010–2011 and then increased with a range of rates of 21% yr⁻¹ to 27% yr⁻¹ from 2011 to 2016. The contribution of summertime OC increased to approximately 27% in the summer of 2013–2016, rising to become the largest PM₂.₅ source driven by the reduction of regional sources. The chemical composition of PM₂.₅ in the urban area drastically changed from inorganic-rich to organic- and metal-rich particles during 2013–2016. The depletion of ascorbic acid was measured using filter samples collected over one year to identify PM₂.₅ components and sources contributing to the oxidative potential (OP) of PM₂.₅. The OP was clearly associated with trace elements (e.g., Ba, Cu, Fe). Non-tailpipe emissions related to road dust and brake wear presented high redox activity per mass of PM₂.₅. This work suggests that summertime OC and non-tailpipe emissions in recent years have become increasingly important. As such, policies targeting traffic-related PM₂.₅ should focus on these sources for maximum impact.