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Biochar has received great attention as a biosorbent, but explanations of the underlying sorption mechanisms are still unclear. Here, batch sorption of cadmium (Cd(II)) and arsenate (As(V)) to Miscanthus biochar at different pH values and pyrolysis temperatures and the sorption mechanisms were comprehensively investigated. The maximum sorption capacities for both Cd(II) and As(V) were observed under alkaline conditions. Physisorption was identified as a common sorption mechanism for both Cd(II) and As(V) irrespective of pH; however, inner-sphere complexation with acidic functional groups (AFGs) and crystallized precipitation as otavite predominate at higher pH values for Cd(II), while hydrophobic attraction of arsenite and metallic As and electrostatic bridging with multivalent ions at deprotonated AFGs are presumed to be dominant sorption mechanisms for As(V). Inner-sphere complexes of Cd(II) (98.6%) and electrostatic bridging complexes of As(V) (89.5%) were the dominant sorption forms for B400, while inner-sphere complexes (45.9%) and precipitates (50.5%) of Cd(II) and physisorption and hydrophobic interactions of As (63.7%) were abundant. The results challenge the widely held notion that the sorption of anions decreases as pH increases, while that of cations increases with increasing pH. This unexpected phenomenon can be explained by reduction of As(V) and by the difference in the charge densities between As(V) and basic functional groups of the biochar. Such biochar-induced reduction would cause an unexpected risk of exposing human health and ecosystems to reduceable pollutants. These findings contribute to a better explanation for the environmental fate and behavior of inorganic pollutants in biochar applications., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The Mugan Plain is the most productive area in the Republic of Azerbaijan, but a previous study confirmed trace metal and metalloid (TM&M) contamination with Cr, Ni and Pb, and the potential ecological risk of As was estimated. However, no industrial activity was previously reported in this area; thus, a source apportionment model using positive matrix factorization (PMF) was employed to identify pollution sources, and a human health risk assessment was conducted to evaluate noncarcinogenic and carcinogenic risks. Surface soil samples were collected from 349 sites, and six major elements (Si, Ca, Cl, P, S and Sr) and 8 TM&Ms (As, Cd, Cr, Co, Cu, Ni, Pb and Zn) were analyzed by X-ray fluorescence and employed for further apportionment and risk assessment. As a result, the PMF model showed 7 factors, assigned to natural activity (12.9%), dry riverbed (13.6%), surface accumulation (3.1%), desalinization activity (3.2%), residential activity (12.3%), fossil fuel combustion (35.5%) and agricultural activity (19.3%). The PMF model characterized certain areas with desalinization activity in the previous Soviet period and with surface accumulation of salt, and these findings were confirmed by additional field surveys and historical Landsat satellite images. The risk assessment results showed that there was no risk for the adults, while for children, there was a noncarcinogenic risk, but no carcinogenic risk. Dermal contact was estimated to be the primary pathway, and Ni and As were identified as the most problematic TM&Ms for noncarcinogenic and carcinogenic risks, respectively. According to the results, fossil fuel combustion associated with heating and vehicle transportation was estimated to be the main source of pollution, contributing 42.6% of the noncarcinogenic and 48.0% of the carcinogenic risks. These results can provide scientific guidance to understand and prevent the risk of TM&Ms on the Mugan Plain., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Background: In 2018, the National Malaria Control Programme in Vietnam switched from prioritizing malaria control to elimination. However, with the ongoing elimination programme, there are still areas where residual malaria transmission persists, including the central highlands. This entomological survey was conducted to evaluate Anopheles diversity and host-seeking activity of Anopheles vectors in two communes with very low malaria transmission in Gia Lai Province., Methods: Anopheles species were collected in Ia DReh commune and Ia KDam commune, Gia Lai Province in the central highlands of Vietnam. Collections were conducted using human-baited double net trap, light trap and manual aspiration collections around cattle sheds, in the dry and rainy season. Mosquito specimens were identified morphologically, and members of species complexes were distinguished molecularly. Mosquito night-feeding patterns were investigated during the dry and rainy seasons., Results: Overall, 18,835 specimens including 19 taxa were collected in Ia KDam and Ia DReh communes. These included the primary malaria vectors, Anopheles dirus and Anopheles minimus, and other secondary vector species. Anopheles dirus was observed to be an anthropophilic species, whereas An. minimus and a number of secondary vectors were observed to be zoophilic. Anopheles vagus was the dominant species, followed by Anopheles sinensis and Anopheles peditaeniatus. The majority of specimens were collected in the rainy season due to the relatively large number of An. vagus, while An. peditaeniatus, An. dirus, Anopheles kochi, Anopheles monstrosus and Anopheles tessellatus were collected in greater numbers during the dry season. The peak of host-seeking activity for An. dirus, An. sinensis, and An. vagus was between 18.00 and 19.00 h., Conclusion: This study provided information on the diversity, seasonal prevalence and behaviour of Anopheles at the study sites. Identifying the diverse mosquito fauna in the central highlands of Vietnam allows species-specific control measures to be implemented by the National Programme to reduce malaria in areas of very low malaria transmission. The peak Anopheles host-seeking activity observed in this study was between 18.00 and 23.00 h, which highlights the need to better characterize Anopheles behaviour in this region of Vietnam to inform on vector control strategies., (© 2021. The Author(s).)

The Republic of Azerbaijan suffers from low agricultural productivity caused by soil salinization and erosion, and limited and insufficient soil data are available for economic and political reasons. In this study, soil salinity and heavy metal levels were assessed. Environmental risk assessment was conducted to evaluate the potential risk posed by soils to human health. Soil guideline values were proposed to monitor soil pollution in the Republic of Azerbaijan. Water extraction and spatial variability analysis were conducted to understand soil salinization and heavy metal pollution. Among the 20 studied elements, the elements Ca, Cl, and S and the heavy metals Cr, Ni, and Pb were classified as problematic on the basis of the geoaccumulation index, and As was also identified as posing a possible risk on the basis of the potential ecological risk index. Based on the developed soil guideline values for agricultural soil, the As, Cr, and Ni in the soil samples exceeded their respective guidelines by 31.3, 41.8, and 61.6%, respectively. Water extraction results confirmed that 99% of the leached ions were cationic salts, and the most problematic ion was Na, followed by Ca, Cl, and S. The extractability values of Cr and Ni were significantly lower than those of other heavy metals, which implies that their actual leaching potential may be overestimated. The linear regression and spatial variability analysis confirmed that leachable salts have accumulated in lowland areas due to the capillary rise of water and evaporation, but the distribution of heavy metals confirmed that As, Cr, and Ni were abundant in agricultural soils. Our results clearly showed that heavy metal soil contamination and high salinity levels are major problems that should be considered when assessing food safety and health hazards in the Mugan Plain of Azerbaijan. Therefore, future studies should be performed for additional environmental risk assessment, detailed hazard identification, and health risk assessment.

Recent developments in analytics using infrared spectroscopy have enabled us to identify the adsorption mechanism at interfaces, but such methods are applicable only for simple systems. In this study, the preferential adsorption of phosphate on binary goethite and maghaemite was investigated. As a result, monodentate and bidentate complexes were the major complexes on goethite and maghaemite, respectively. A shrinking effect in goethite and a swelling effect in maghaemite were identified, and environmental perturbations caused a significant decrease in the integrated absorbance of phosphate complexes on maghaemite, while no effect was observed on goethite, which implies that different adsorption mechanisms were involved. Based on the results, a bridging complex was proposed, and the swelling effect is explained by the negatively charged maghaemite surface resulting from the bidentate complex. The isolation of phosphate by the shrinking effect explains the low phosphate bioavailability in the soil environment, while the colloidal properties of the bidentate complex on maghaemite are the reason for colloidal mobilization. To the best of our knowledge, this study not only addresses the shrinking and swelling properties of iron (hydr)oxide nanoparticles but also demonstrates preferential adsorption on binary sorbents using in situ ATR-FTIR for the first time.

The structural configuration of arsenate on iron (hydr)oxide determines its leachability and bioavailability in the soil environment. It is important to understand how the stability of iron hydroxide and the structural configuration of arsenate complexes vary in response to changes in environmental conditions. Therefore, we investigated the effects of drying, pH and surface loadings on the stability of goethite and the structural configuration of arsenate through batch experiments and TEM and XAS measurements with DFT calculation. As a result, we observed no significant transformation of goethite under most conditions, but TEM confirmed the partial formation of bernalite in the presence of arsenate at a pH of 10, and the bernalite showed 2.18 times higher arsenate sorption than the goethite. The linear combination fitting of the EXAFS spectra with DFT calculations revealed that tridentate and bidentate complexes were dominant under low surface loading and pH conditions in the sedimented samples, while monodentate complexes were abundant under high surface loading and pH conditions. Based on our results, we conclude that the formation of arsenic-rich colloids could account for mobilization in the soil environment, and the density of available sorption sites combined with the concentration of solute could cause the change in structural configuration.

The effect of bentonite and sand, as natural capping agents, on the fluxes of nutrients and trace metals across the sediment-water interface was studied through sediment incubation, and the ecotoxicological impact was assessed by using Daphnia magna. Bentonite and sand were layered on the sediment at 15, 75, and 225 mg cm(-2), and the concentration of cations, nutrients, and trace metals was measured. Sediment incubation showed that bentonite reduced the N flux but increased the P flux as a result of dissolution of non-crystalline P from bentonite, while sand slightly decreased the N fluxes but not the P flux. The concentration of Na increased in the overlying water with increasing application rates of bentonite, while that of Ca decreased. However, regardless of the rate of sand application, concentrations of all cation species remained unchanged. The concentration of As and Cr increased with bentonite application rate but decreased with sand. Both capping materials suppressed fluxes of Cd, Cu, Ni, and Zn compared to control, and the extent of suppression was different depending on the trace metal species and capping agents used. During sediment incubation, the survival rate of D. magna significantly decreased in bentonite suspension but began to decrease at the end in sand suspension. Sediment capping of mildly polluted sediments by using bentonite and sand lowered the level of nutrients and trace metals. However, unexpected or undesirable side effects, such as influxes of P and As from bentonite to the overlying water and a possibility of toxic impacts to aquatic ecosystems, were observed, suggesting that capping agents with an adequate assessment of their side effects and toxicity should be predetermined for site-specific sediment management strategies.

The short-term effects of low-level contamination by heavy metals (As, Cd, Cu, and Pb) on the soil health were examined by analyzing soil nematode community in soils planted with tomatoes. For this, the soils were irrigated with five metal concentrations ([1, 1/4, 1/4(2), 1/4(3), and 0] × maximum concentrations [MC] detected in irrigation waters near abandoned mine sites) for 18 weeks. Heavy metal concentrations were significantly increased in soils irrigated with MC of heavy metals, among which As and Cu exceeded the maximum heavy metal residue contents of soil approved in Korea. In no heavy metal treatment controls, nematode abundances for all trophic groups (except omnivorous-predatory nematodes [OP]) and colonizer-persister (cp) values (except cp-4-5) were significantly increased, and all maturity indices (except maturity index [MI] of plant-parasitic nematodes) and structure index (SI) were significantly decreased, suggesting the soil environments might have been disturbed during 18 weeks of tomato growth. There were no concentration-dependent significant decreases in richness, abundance, or MI for most heavy metals; however, their significant decreases occurred in abundance and richness of OP and cp-4, MI2-5 (excluding cp-1) and SI, indicating disturbed soil ecosystems, at the higher concentrations (MC and MC/4) of Pb that had the most significant negative correlation coefficients for heavy metal concentrations and nematode community among the heavy metals. Therefore, the short-term effects of low-level heavy metal contamination on soil health can be analyzed by nematode community structures before the appearance of plant damages caused by the abiotic agents, heavy metals.

Bioavailability and bioaccessibility determine the level of metal toxicity in the soils. Inorganic soil amendments may decrease metal bioavailability and enhance soil quality. This study used mussel shell, cow bone, and biochar to reduce lead (Pb) toxicity in the highly contaminated military shooting range soil in Korea. Water-soluble and 1-M ammonium nitrate extractions, and a modified physiologically based extraction test (PBET) were performed to determine Pb bioavailability and bioaccessibility in the soil, respectively. Active C in the soil was also measured to evaluate the effects of the amendments on biological soil quality. The Pb contaminated soil was diluted in serial with uncontaminated soil for the bioassays. Seed germination and root elongation tests using lettuce (Lactuca sativa) showed increases in germination percentage and root length in soil treated with the amendments. Biochar was most effective and increased seed germination by 360% and root length by 189% compared to the unamended soil. Up to 20% soil dilution resulted in more than 50% seed germination. Bioavailability and bioaccessibility of Pb in the soils were decreased by 92.5% and 48.5% with mussel shell, by 84.8% and 34.5% with cow bone, and by 75.8% and 12.5% with biochar, respectively, compared to the unamended soil. We found that the Pb availability in the military shooting range soil can be reduced effectively by the tested amendments or soil dilution alternately, thereby decreasing the risk of ecotoxicity. Furthermore, the increasing active C from the amendments revitalized the soil contaminated with Pb., (Copyright © 2012 Elsevier Inc. All rights reserved.)