A monitoring network was established in streams within a catchment near the Costa Rican Pacific coast (2008–2011) to estimate the impact of pesticides in surface water (84 samples) and sediments (84 samples) in areas under the influence of melon and watermelon production. A total of 66 (water) and 47 (sediment) pesticides were analyzed, and an environmental risk assessment (ERA) was performed for four taxa (algae, Daphnia magna, fish and Chironomus riparius). One fungicide and seven insecticides were detected in water and/or sediment; the fungicide azoxystrobin (water) and the insecticide cypermethrin (sediments) were the most frequently detected pesticides. The insecticides endosulfan (5.76 μg/L) and cypermethrin (301 μg/kg) presented the highest concentrations in water and sediment, respectively. The ERA revealed acute risk in half of the sampling points of the melon-influenced area and in every sampling point from the watermelon-influenced area. Safety levels were exceeded within and around the crop fields, suggesting that agrochemical contamination was distributed along the catchment, with potential influence of nearby crops. Acute risk was caused by the insecticides chlorpyrifos, cypermethrin and endosulfan to D. magna, fish and C. riparius; the latter was the organism with the overall highest/continuous risk. High chronic risk was determined in all but one sampling point, and revealed a higher number of pesticides of concern. Cypermethrin was the only pesticide to pose chronic risk for all benchmark organisms. The results provide new information on the risk that tropical crops pose to aquatic ecosystems, and highlight the importance of including the analysis of sediment concentrations and chronic exposure in ERA.

The use of reclaimed water in agriculture represents a promising alternative to relieve pressure on freshwater supplies, especially in arid or semiarid regions facing water scarcity. However, this implies introducing micropollutants such as pharmaceutical residues into the environment. The fate and the ecotoxicological impact of valsartan, an antihypertensive drug frequently detected in wastewater effluents, were evaluated in soil-earthworm microcosms. Valsartan dissipation in the soil was concomitant with valsartan acid formation. Although both valsartan and valsartan acid accumulated in earthworms, no effect was observed on biomarkers of exposure (acetylcholinesterase, glutathione S-transferase and carboxylesterase activities). The geometric mean index of soil enzyme activity increased in the soils containing earthworms, regardless of the presence of valsartan. Therefore, earthworms increased soil carboxylesterase, dehydrogenase, alkaline phosphatase, β-glucosidase, urease and protease activities. Although bacterial richness significantly decreased following valsartan exposure, this trend was enhanced in the presence of earthworms with a significant impact on both alpha and beta microbial diversity. The operational taxonomic units involved in these changes were related to four (Proteobacteria, Bacteroidetes, Actinobacteria and Firmicutes) of the eight most abundant phyla. Their relative abundances significantly increased in the valsartan-treated soils containing earthworms, suggesting the presence of potential valsartan degraders. The ecotoxicological effect of valsartan on microbes was strongly altered in the earthworm-added soils, hence the importance of considering synergistic effects of different soil organisms in the environmental risk assessment of pharmaceutical active compounds.

The developing nervous system is highly vulnerable to environmental toxicants especially pesticides. Glyphosate pesticide induces neurotoxicity both in humans and rodents, but so far only when exposed to higher concentrations. A few studies, however, have also reported the risk of general toxicity of glyphosate at concentrations comparable to allowable limits set up by environmental protection authorities. In vitro data regarding glyphosate neurotoxicity at concentrations comparable to maximum permissible concentrations in drinking water is lacking. In the present study, we established an in vitro assay based upon neural stem cells (NSCs) from the subventricular zone of the postnatal mouse to decipher the effects of two maximum permissible concentrations of glyphosate in drinking water on the basic neurogenesis processes. Our results demonstrated that maximum permissible concentrations of glyphosate recognized by environmental protection authorities significantly reduced the cell migration and differentiation of NSCs as demonstrated by the downregulation of the expression levels of the neuronal ß-tubulin III and the astrocytic S100B genes. The expression of the cytoprotective gene CYP1A1 was downregulated whilst the expression of oxidative stresses indicator gene SOD1 was upregulated. The concentration comparable to non-toxic human plasma concentration significantly induced cytotoxicity and activated Ca²⁺ signalling in the differentiated culture. Our findings demonstrated that the permissible concentrations of glyphosate in drinking water recognized by environmental protection authorities are capable of inducing neurotoxicity in the developing nervous system.

Nitric oxide (NO) plays a critical role in atmospheric chemistry and also is a precursor of nitrate, which affects particle matter formation and nitrogen deposition. Agricultural soil has been recognized as a main source of atmospheric NO. However, quantifying the NO fluxes emitted from croplands remains a challenge and in situ long-term measurements of NO are still limited. In this study, we used an automated sampling system to measure NO fluxes with a high temporal resolution over two years (April 2017 to March 2019) from a rainfed maize field in the Northeast China. The cumulative annual NO emissions were 8.9 and 2.3 kg N ha⁻¹ in year 1 (April 2017 to March 2018) and year 2 (April 2018 to March 2019), respectively. These interannual differences were largely related to different weather conditions encountered. In year 1, a month-long drought before and after the seeding and fertilizing reduced plant N uptake and dramatically increased soil N concentration. The following moderate rainfalls promoted large amount of NO emissions, which remained high until late September. The NO fluxes in both years showed clearer seasonal patterns, being highest after fertilizer application in summer, and lowest in winter. The seasonal patterns of NO fluxes were mainly controlled by soil available N concentrations and soil temperatures. The contribution of NO fluxes during the spring freeze-thaw in both years was no more than 0.2% of the annual NO budget, indicating that the freeze-thaw effect on agricultural NO emissions was minimal. In addition, with high-resolution monitoring, we found that soil not only act as a NO source but also a sink. Long-term and high-resolution measurements help us better understand the diurnal, seasonal, and annual dynamics of NO emissions, build more accurate models and better estimate global NO budget and develop more effective policy responses to global climate change.

Trace organic compounds (TOrCs) and microplastics (MPs) have been recognized as emerging pollutants that cause severe water pollution related problems due to their non-degradable and bio-accumulative nature. Many studies on oxidation processes such as ozone have been conducted to efficiently remove TOrCs in water treatment. However, there has been a lack of research on the removal efficiency of TOrCs in the oxidation process when they co-exist with MPs and form transformation byproducts (TBPs) during this process. This study evaluates the effects of MPs on TOrC removal during ozonation at various ozone concentrations and based on the mass of MP particles in distilled water. The adsorption of TBPs and TOrCs was also evaluated using the Freundlich and Langmuir isotherm equations. The toxicity of these compounds was evaluated to confirm the risk to aquatic ecosystems. The results show that triclosan (TCS) had the highest absorption capacity amongst the TOrCs and TBPs tested. Polyvinylchloride exhibited the highest adsorption efficiency compared with polyethylene and polyethyleneterephthalate (TCS 0.341 mg/g) due to its high adsorption capacity and hydrophobicity. In the toxicity test, 2,4-dichlorophenol and 4-chloroaniline as TBPs had a relatively higher toxicity to Vibrio fischeri (a marine bacterial species) than Daphnia magna (a freshwater plankton species).

Microplastic (MP) pollution in the environment has aroused great concern. However, our knowledge of MP abundance and distribution in soil environment is scarce. This work investigated the MPs in the farmland and grassland at a remote area of China, namely, the eastern area of the Qinghai–Tibet Plateau (QTP). The average numbers of MPs were 53.2 ± 29.7 and 43.9 ± 22.3 items/kg in shallow and deep soil, respectively, from 35 soil samples. A remarkable difference in MP abundances was observed among soil samples from mulch farmland, greenhouses, farmland without covering, and grassland. The MPs were mostly in the form of a film and transparent in color in this study. The dominant polymers of MPs in the soil samples were polyester (PE) and polypropylene (PP). This study revealed the characteristics of MP distribution among different land use at the QTP, and MPs may stem from the fragmentation of plastic mulch in farmland soil. Notably, MP abundance increased with the increase in mulching time in facility agriculture. Additionally, human disturbances and increased mulching time in facility agriculture promote the fragmentation of soil MPs. This study provides important data for follow-up research on MPs in a plateau terrestrial ecosystem.

Rice plants accumulate Hg from the soil and ambient air, however, evaluating the contribution of Hg from these two sources remains challenging. Here, we proposed a practical method to predict the contribution of total gaseous mercury (TGM) to Hg in white rice in Wanshan Hg mine area (WMM). In this study, rice was planted in the same low-Hg soil at different sites of WMM with varying TGM levels. Comparing to the control sites at IG (Institute of Geochemistry, Guiyang), TGM is the dominant source of Hg in rice leaves and white rice at TB (Tianba) and ZJW (Zhangjiawan) sites of WMM. Subsequently, a good correlation between the Hg concentrations in rice leaves and the concentration contributions of TGM to Hg in white rice was obtained. Such a correlation enabled feasible quantification of the contribution of TGM to Hg in white rice collected from the Wanshan Hg mine. The contribution of TGM to Hg in white rice across the WMM area was also estimated, demonstrating that white rice receives 14–83% of Hg from the air. Considering the high contribution of TGM to Hg in white rice, we compared the relative health risks of Hg via inhalation and rice consumption and found that inhalation, rather than rice consumption, was the major pathway for bioaccessible Hg exposure in adults at high-TGM sites. This study provides new knowledge of Hg biogeochemistry in Hg-mining areas.

In this paper, the degradation of three endocrine-disrupting chemicals (EDCs): bisphenol A (BPA), 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) by manganite (γ-MnOOH) activated peroxymonosulfate (PMS) was investigated. Preliminary optimisation experiments showed that complete degradation of the three EDCs was achieved after 30 min of reaction using 0.1 g L⁻¹ of γ-MnOOH and 2 mM of PMS. The degradation rate constants were determined to be 0.20, 0.22 and 0.15 min⁻¹ for BPA, E2 and EE2, respectively. Combining radical scavenging approaches, Electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS) analyses, we revealed for the first time that about 40% of EDCs degradation can be attributed to heterogeneous electron transfer reaction involving freshly generated Mn(IV), and 60% to sulfate radical degradation pathway. The influence of various inorganic ions on the γ-MnOOH/PMS system indicated that removal efficiency was slightly affected by chloride and carbonate ions, while nitrate and nitrite ions had negligible impacts. The application of γ-MnOOH/PMS system in real sewage treatment plant water (STPW) showed that degradation rate constants of EDCs decreased to 0.035–0.048 min⁻¹ and complete degradation of the three EDCs after 45 min. This study provides new insights into the reactivity of combined γ-MnOOH and PMS, and opens new ways for the application of Mn-bearing species in wastewater treatment technologies.

Phosphorus (P) discharges from human activities result in eutrophication of lakes. We investigated whether the forms of phosphorus (P) in rivers with high effluent loads flowing through urban areas of Sapporo, Japan, were transformed when transported downstream into a eutrophic lake, namely Lake Barato. We hypothesized that the inorganic P supplied from the rivers might be transformed to organic forms in the lake. The results showed that soluble reactive phosphorus (SRP) and particulate inorganic phosphorus (PIP) dominated in the river discharge to the lake. Suspended solids in the rivers were rich in iron (Fe) so PIP was associated with Fe. A comparison of the concentrations at the river mouth and 4.5 km downstream showed that the concentrations of SRP and PIP were lower at 4.5 km downstream than at the river mouth, whereas the concentrations of organic P (i.e., dissolved organic phosphorus and particulate organic phosphorus) were similar. The results from solution ³¹P nuclear magnetic resonance spectroscopy of lake water showed that pyrophosphate was only present in the particulate fraction, while orthophosphate diesters (DNA-P) were only present in the dissolved fraction. Riverine samples contained orthophosphate (ortho-P) only, while lake samples contained ortho-P, orthophosphate monoesters, and DNA-P. The results suggest that the P forms, particularly those of dissolved P, shifted from inorganic to organic forms as the water was discharged from the river to the lake.

Fish meal (FM) is an industrial product, mainly obtained from whole wild-caught fish, that is used as a high protein feedstuff component in aquaculture and intensive animal farming. Contamination of FM by microplastics (MPs), the synthetic polymer particles known to be nearly ubiquitous in the marine environment, is a likely consequence of their ingestion by zooplankton and other small marine animals that through the food chain end up in the fish commercialized not only for direct human consumption but also for the industrial production of FM. Unfortunately, analytical tools for quantifying contamination of FM by synthetic polymers are not available. A newly developed procedure described here allows quantification of the total amounts of polyolefins (including ethene and propene homo- and copolymers), polystyrene (PS), and poly(ethylene terephthalate) (PET), respectively, in FM. The multi-step procedure involves a sequence of solvent extractions, hydrolytic treatments to remove the biogenic matrix mainly consisting of proteins and some lipids, and selective depolymerization for PET. The gravimetric and SEC-UV techniques employed for the quantification of polyolefins and PS, respectively, only allowed to estimate their concentration in FM at around or below 100 mg/kg each, a more accurate quantification being prevented by the interference from the organic matrix and, in the case of polyolefins, by the limited sensitivity of the quantification by gravimetry. On the other hand, the contamination by PET MPs could accurately be quantified at 12.9 mg/kg based on the dry FM mass. Ways to overcome the sensitivity limitations for PS and polyolefins by using e.g. pyrolysis-GC/MS are highlighted.