Elevated manganese (Mn) in drinking water has been reported worldwide. While, naturally occurring Mn in groundwater is generally the major source, anthropogenic contamination by Mn-containing fungicides such as mancozeb may also occur. The main objective of this study was to examine factors associated with Mn and ethylenethiourea (ETU), a degradation product of mancozeb, in drinking water samples from villages situated near banana plantations with aerial spraying of mancozeb. Drinking water samples (n = 126) were obtained from 124 homes of women participating in the Infants' Environmental Health Study (ISA, for its acronym in Spanish), living nearby large-scale banana plantations. Concentrations of Mn, iron (Fe), arsenic (As), lead (Pb), cadmium (Cd) and ethylenethiourea (ETU), a degradation product of mancozeb, were measured in water samples. Only six percent of samples had detectable ETU concentrations (limit of detection (LOD) = 0.15 μg/L), whereas 94% of the samples had detectable Mn (LOD = 0.05 μg/L). Mn concentrations were higher than 100 and 500 μg/L in 22% and 7% of the samples, respectively. Mn was highest in samples from private and banana farm wells. Distance from a banana plantation was inversely associated with Mn concentrations, with a 61.5% decrease (95% CI: −97.0, −26.0) in Mn concentrations for each km increase in distance. Mn concentrations in water transported with trucks from one village to another were almost 1000 times higher than Mn in water obtained from taps in houses supplied by the same well but not transported, indicating environmental Mn contamination. Elevated Mn in drinking water may be partly explained by aerial spraying of mancozeb; however, naturally occurring Mn in groundwater, and intensive agriculture may also contribute. Drinking water risk assessment for mancozeb should consider Mn as a health hazard. The findings of this study evidence the need for health-based World Health Organization (WHO) guidelines on Mn in drinking water.

Sewage sludge applied to soil may be a valuable fertiliser but can also introduce poorly degradable and highly adsorptive wastewater-born residues of pharmaceuticals and personal care products (PPCPs) to the soil, posing a potential risk to the receiving environment. Three azole antimycotics (climbazole, ketoconazole and fluconazole), and one quaternary ammonium compound (benzyldimethyldodecylammonium chloride, BDDA) that are frequently detected in municipal sewage sludge and/or treated wastewater were therefore characterised in their toxicity toward terrestrial (Brassica napus) and aquatic (Lemna minor) plants. Fluconazole and climbazole showed the greatest toxicity to B. napus, while toxicity of ketoconazole and BDDA was by one to two orders of magnitude lower. Sludge amendment to soil at an agriculturally realistic rate of 5 t/ha significantly reduced the bioconcentration of BDDA in B. napus shoots compared to tests without sludge amendment, although not significantly reducing phytotoxicity. Ketoconazole, fluconazole and BDDA proved to be very toxic to L. minor with median effective concentrations ranging from 55.7 μg/L to 969 μg/L. In aquatic as well as terrestrial plants, the investigated azoles exhibited growth-retarding symptoms presumably related to an interference with phytohormone synthesis as known for structurally similar fungicides used in agriculture. While all four substances exhibited considerable phytotoxicity, the effective concentrations were at least one order of magnitude higher than concentrations measured in sewage sludge and effluent. Based on preliminary hazard quotients, BDDA and climbazole appeared to be of greater environmental concern than the two pharmaceuticals fluconazole and ketoconazole.

This work forwards new insights into the risk-assessment of multi-walled carbon-nanotubes (MWCNTs) while analysing the role of quantum-mechanical interactions between the electrons in the adsorption of probe compounds and biomolecules by MWCNTs. For this, the quantitative models are developed using quantum-chemical descriptors and their electron-correlation contribution. The major quantum-chemical factors contributing to the adsorption are found to be mean polarizability, electron-correlation energy, and electron-correlation contribution to the absolute electronegativity and LUMO energy. The proposed models, based on only three quantum-chemical factors, are found to be even more robust and predictive than the previously known five or four factors based linear free-energy and solvation-energy relationships. The proposed models are employed to predict the adsorption of biomolecules including steroid hormones and DNA bases. The steroid hormones are predicted to be strongly adsorbed by the MWCNTs, with the order: hydrocortisone > aldosterone > progesterone > ethinyl-oestradiol > testosterone > oestradiol, whereas the DNA bases are found to be relatively less adsorbed but follow the order as: guanine > adenine > thymine > cytosine > uracil. Besides these, the developed electron-correlation based models predict several insecticides, pesticides, herbicides, fungicides, plasticizers and antimicrobial agents in cosmetics, to be strongly adsorbed by the carbon-nanotubes. The present study proposes that the instantaneous inter-electronic interactions may be quite significant in various physico-chemical processes involving MWCNTs, and can be used as a reliable predictor for their risk assessment.

Fungicides in aquatic environments can impact non-target bacterial and fungal communities and the invertebrate detritivores responsible for the decomposition of allochthonous organic matter. Additionally, in some aquatic systems daily water temperature fluctuations may influence these processes and alter contaminant toxicity, but such temperature fluctuations are rarely examined in conjunction with contaminants. In this study, the shredding amphipod Hyalella azteca was exposed to the fungicide pyraclostrobin in three experiments. Endpoints included mortality, organism growth, and leaf processing. One experiment was conducted at a constant temperature (23 °C), a fluctuating temperature regime (18–25 °C) based on field-collected data from the S. Llano River, Texas, or an adjusted fluctuating temperature regime (20–26 °C) based on possible climate change predictions. Pyraclostrobin significantly reduced leaf shredding and increased H. azteca mortality at concentrations of 40 μg/L or greater at a constant 23 °C and decreased leaf shredding at concentrations of 15 μg/L or greater in the fluctuating temperatures. There was a significant interaction between temperature treatment and pyraclostrobin concentration on H. azteca mortality, body length, and dry mass under direct aqueous exposure conditions. In an indirect exposure scenario in which only leaf material was exposed to pyraclostrobin, H. azteca did not preferentially feed on or avoid treated leaf disks compared to controls. This study describes the influence of realistic temperature variation on fungicide toxicity to shredding invertebrates, which is important for understanding how future alterations in daily temperature regimes due to climate change may influence the assessment of ecological risk of contaminants in aquatic ecosystems.

The Mondego River estuary, located on the North Atlantic Ocean Ecoregion, is a basin affected by agricultural run-off with increasing signs of eutrophication. We evaluated the amounts and distribution of 56 priority pesticides belonging to distinct categories (insecticides, herbicides and fungicides). Temporal trends were considered and a total of 42 surface water samples were collected between 2010 and 2011. More than 55% of the GC–MS/MS-quantified pesticides were above the maximum amounts established by the European Directives (98/83/EC and 2013/39/EU). Based on the concentration addition (CA) and independent action (IA) models, we used a two-tiered approach to assess the hazard of the pesticide mixture, at the maximum concentration found, reflecting a potential risk. Short-term exposure using Artemia salina indicated a significant toxic effect where the locomotion of the animals was clearly affected.

Successive applications of copper-based (Cu) fungicides have increased Cu concentration in vineyard soils, inducing Cu toxicity in young vines and cover crops such as black oat, thus inhibiting growth and development. However, increasing soil phosphorus (P) content can reduce Cu toxicity symptoms. In this context, the aim of this study was to evaluate the effect of Cu toxicity and its alleviation by P fertilization in black oat cultivated in sandy soil. For the experiment, Typic Hapludalf soil samples were air-dried, prepared, and subjected to increasing doses of Cu (0, 30, and 60 mg kg⁻¹) and P (0 and 100 mg kg⁻¹). Subsequently, the soil was incubated and stored in pots, where black oat seedlings were grown for 30 days in a greenhouse. Plant roots subjected to Cu, especially with the highest Cu concentration and without P addition decreased the root cap size, showing early tissue differentiation and lateral root formation near the apical region. Decrease in dry matter (DM) production of roots (50 %) and shoots (67 %) was also observed in the highest Cu concentration. Plants without P addition, regardless of Cu concentration, also had lower root (33 %) and shoot (65 %) DM production. P addition in soil and its increased concentration reduced root anatomical changes and stimulated plant DM production. Therefore, we conclude that excessive Cu concentration alters black oat root anatomical structure, affecting plant growth, especially in sandy soils with low organic matter content. However, P supply can reduce root Cu toxicity symptoms, thus increasing plant dry matter production.

The potential of mayfly Ephemera orientalis McLachlan eggs and first-instar larvae in ecotoxicological testing was investigated. Both stages of E. orientalis showed high tolerance to various environmental variables, such as water temperature, pH, water hardness, and dissolved organic carbon. Toxicological assays were conducted with three insecticides (emamectin benzoate, endosulfan, and cypermethrin), one fungicide (mancozeb), and one herbicide (paraquat dichloride). The two toxicity endpoints for the assay were the 14-day egg median hatching rate (EHC₅₀) in static and renewal exposure systems and 24-h median larval mortality (LC₅₀). Cypermethrin was the most toxic to both eggs (EHC₅₀ in static system = 36.9 μg/L; EHC₅₀ in renewal system < 0.15 μg/L) and larvae (LC₅₀ = 4.5 μg/L), and paraquat dichloride was the least toxic to eggs (EHC₅₀ in static system = 54,359.8 μg/L; EHC₅₀ in renewal system = 49541.3 μg/L) and larvae (LC₅₀ = 9259.5 μg/L). The results were compared to literature data of Daphnia magna Straus and Cloeon dipterum Linnaeus to determine its relative sensitivity to pesticides. These three species had different toxicities to the tested pesticides, especially according to the exposure system. E. orientalis eggs in the static system were found to be less sensitive were D. magna and C. dipterum, but eggs in the renewal system and larvae had similar or higher sensitivities to the tested pesticides. The results revealed that this species has potential for use in ecotoxicological testing of pesticides. Because of its geographic distribution, E. orientalis may be used as an alternative or complementary test species for ecotoxicological studies in Northeast Asian countries, where natural populations of the international standard species, D. magna, are rarely found.

The response specificity of three metallothionein (MT) genes (CdMT, CuMT and Cd/CuMT) was assessed after long-term exposure (20 days) of Cantareus aspersus eggs to cadmium (Cd) (2 to 6 mg/L) or to the fungicide Bordeaux mixture (BM) (2.5 and 7.5 g/L). MT gene expression measured by quantitative real-time PCR (qRT-PCR) revealed that in the unexposed embryos, the transcript levels of the three MT genes decreased significantly through embryonic development. However, the CdMT gene was strongly upregulated with increasing Cd exposure concentration, whereas the transcript levels of the other two genes increased less pronouncedly, but significantly above an exposure concentration of 4 mg Cd/L. Upon exposure to BM, all three MT genes were significantly upregulated above a BM concentration of 2.5 g/L. It is concluded that long-term Cd exposure in hatched snails induced patterns of MT gene expression that differed from those obtained after short-term exposure (24 h).

The aqueous photodegradation of fluopyram was investigated under UV light (λ ≥ 200 nm) and simulated sunlight irradiation (λ ≥ 290 nm). The effect of solution pH, fulvic acids (FA), nitrate (NO₃ ⁻), Fe (III) ions, and titanium dioxide (TiO₂) on direct photolysis of fluopyram was explored. The results showed that fluopyram photodegradation was faster in neutral solution than that in acidic and alkaline solutions. The presence of FA, NO₃ ⁻, Fe (III), and TiO₂ slightly affected the photodegradation of fluopyram under UV irradiation, whereas the photodegradation rates of fluopyram with 5 mg L⁻¹ Fe (III) and 500 mg L⁻¹ TiO₂ were about 7-fold and 13-fold faster than that without Fe (III) and TiO₂ under simulated sunlight irradiation, respectively. Three typical products for direct photolysis of fluopyram have been isolated and characterized by liquid chromatography tandem mass spectrometry. These products resulted from the intramolecular elimination of HCl, hydroxyl-substitution, and hydrogen extraction. Based on the identified transformation products and evolution profile, a plausible degradation pathway for the direct photolysis of fluopyram in aqueous solution was proposed. In addition, acute toxicity assays using the Vibrio fischeri bacteria test indicated that the transformation products were more toxic than the parent compound.

Testing of effects on earthworms and non-target foliar arthropods is an integral part of the ecotoxicological risk assessment for the authorization of plant protection products. According to the new data requirements, which came into force in 2014 for active substances and in 2016 for plant protection products, the chronic earthworm toxicity test with Eisenia fetida based on reproductive, growth, and behavioral effects instead of the acute earthworm toxicity test based on mortality, has to be conducted routinely. Additional testing of effects on soil arthropods (Folsomia candida, Hyposaspis aculeifer) is required if the risk assessment of foliar applications raises concerns regarding non-target foliar arthropods (Aphidius rhopalosiphi, Typhlodromus pyri) or if the product is applied directly on or into the soil. Thus, it was investigated whether the sublethal earthworm endpoint is more sensitive than the sublethal soil arthropod endpoint for different types of pesticides and whether the risk assessment for non-target arthropods would trigger the testing of effects on soil arthropods in the cases where soil arthropods are more sensitive than earthworms. Toxicity data were obtained from Swiss ecotoxicological database, EFSA Conclusions and scientific literature. For insecticides and herbicides, no general conclusion regarding differences in sensitivity of either earthworms or soil arthropods based on sublethal endpoints were possible. For fungicides, the data indicated that in general, earthworms seemed to be more sensitive than soil arthropods. In total, the sublethal F. candida or H. aculeifer endpoint was lower than the sublethal E. fetida endpoint for 23 (34 %) out of 68 active substances. For 26 % of these 23 active substances, testing of soil arthropods would not have been triggered due to the new data requirement. These results based on sublethal endpoints show that earthworms and soil arthropods differ in sensitivity toward certain active substances and that the risk assessment for non-target foliar arthropods did not always trigger soil arthropod testing in the cases where soil arthropods were more sensitive than earthworms.