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This study investigated the influence of various plasticizers commonly used in the manufacture of polymer inclusion membranes (PIMs), such as 2-nitrophenyl octyl ether (NPOE), phthalates, adipates, and sebacates on the mechanical, thermal, and transport properties of membranes. Additionally, butyl stearate (BTS), chosen for its non-toxic nature compared to phthalates and its cost-effectiveness relative to adipates and sebacates, was evaluated as a plasticizer in PIMs for the first time. All plasticizers were incorporated in PIMs made of either cellulose triacetate (CTA) or poly(vinyl chloride) (PVC) as the base polymers and the task-specific ionic liquid trioctylmethylammonium thiosalicylate (TOMATS) as the carrier. The plasticizers were found to significantly affect the characteristics of membrane hydrophilicity, mechanical flexibility, and thermal stability. Transport experiments using Hg(II) as a model target ion revealed that, for CTA-based PIMs, the plasticizer did not significantly affect transport efficiency. However, for PVC-based PIMs, BTS exhibited better efficiency when compared to NPOE. These findings highlight the potential of BTS as an attractive alternative to currently used plasticizers in PVC-based PIM formulations., This work was supported by the Ministerio de Ciencia, Innovación y Universidades (MCIU) through project PID2019-107033GB-C22/AEI/10.13039/501100011033, Ministerio de Ciencia e Innovación, through project PID2022-140312NB-C22/MCIN/AEI/10.13039/501100011033/FEDER, UE, and European Union’s NextGenerationEU, through the National Recovery and Resilience Plan of the Republic of Bulgaria (Project No. BG-RRP-2.004-0008)., Peer Reviewed, Postprint (published version)

During the last few decades, inputs of mercury (Hg) to the environment from anthropogenic sources have increased. The Ebro Delta is an important area of rice production in the Iberian Peninsula. Given the industrial activity and its legacy pollution along the Ebro river, residues containing Hg have been transported throughout the Ebro Delta ecosystems. Rice paddies are regarded as propitious environments for Hg methylation and its subsequent incorporation to plants and rice paddies' food webs. We have analyzed how Hg dynamics change throughout the rice cultivation season in different compartments from the paddies' ecosystems: soil, water, rice plants and fauna. Furthermore, we assessed the effect of different agricultural practices (ecological vs. conventional) associated to various flooding patterns (wet vs. mild alternating wet and dry) to the Hg levels in rice fields. Finally, we have estimated the proportion of methylmercury (MeHg) to total mercury in a subset of samples, as MeHg is the most bioaccumulable toxic form for humans and wildlife. Overall, we observed varying degrees of mercury concentration over the rice cultivation season in the different compartments. We found that different agricultural practices and flooding patterns did not influence the THg levels observed in water, soil or plants. However, Hg concentrations in fauna samples seemed to be affected by hydroperiod and we also observed evidence of Hg biomagnification along the rice fields' aquatic food webs.

This study investigated the influence of various plasticizers commonly used in the manufacture of polymer inclusion membranes (PIMs), such as 2-nitrophenyl octyl ether (NPOE), phthalates, adipates, and sebacates on the mechanical, thermal, and transport properties of membranes. Additionally, butyl stearate (BTS), chosen for its non-toxic nature compared to phthalates and its cost-effectiveness relative to adipates and sebacates, was evaluated as a plasticizer in PIMs for the first time. All plasticizers were incorporated in PIMs made of either cellulose triacetate (CTA) or poly(vinyl chloride) (PVC) as the base polymers and the task-specific ionic liquid trioctylmethylammonium thiosalicylate (TOMATS) as the carrier. The plasticizers were found to significantly affect the characteristics of membrane hydrophilicity, mechanical flexibility, and thermal stability. Transport experiments using Hg(II) as a model target ion revealed that, for CTA-based PIMs, the plasticizer did not significantly affect transport efficiency. However, for PVC-based PIMs, BTS exhibited better efficiency when compared to NPOE. These findings highlight the potential of BTS as an attractive alternative to currently used plasticizers in PVC-based PIM formulations.

Mercury's extreme toxicity and persistence in the environment justifies a thorough evaluation of its dynamics in ecosystems. Aveiro Lagoon (Portugal) was for decades subject to mercury effluent discharges. A Nature-based Solution (NbS) involving Zostera noltei re-colonization is being tested as an active ecosystem restoration measure. To study the effect of Zostera noltei on the sediment contaminant biogeochemistry, seasonal (summer/winter) sediment, interstitial water and labile mercury vertical profiles were made in vegetated (Transplanted and Natural seagrass meadows) and non-vegetated sites (Bare-bottom area). While no significant differences (p > 0.05) were observed in the sedimentary phase, Zostera noltei presence reduced the reactive/labile mercury concentrations in the top sediment layers by up to 40% when compared to non-vegetated sediment, regardless of season. No differences were found between vegetated meadows, highlighting the fast recovery of the contaminant regulation ecosystem function provided by the plants after re-colonization and its potential for the rehabilitation of historically contaminated ecosystems.

Mercury is a global contaminant found in the Amazon; it can be biomagnified in the aquatic trophic chain. The use of piscivorous birds for biomonitoring of mercury contamination is increasing, mainly due to the non-mobility of mercury in bird feathers. We examined the concentrations of total mercury and methylmercury in different tissues of the green kingfisher, Chloroceryle americana collected from the Teles Pires and Juruena Rivers in the southern Brazilian Amazon. We also evaluated total mercury in small Characidae fish (potential C. americana food) in the same areas. The results indicate contamination of the birds with high concentrations, on average two-times higher in the green kingfishers from the Teles Pires River compared to the Juruena River; the same results were found for the fish specimens. Fifty-eight per cent of the feather samples from the Juruena River and 90% from the Teles Pires River had total mercury concentrations above 5 µg/g, a level previously associated with adverse effects related to bird breeding. The methylmercury concentration was lowest in the liver, followed by feathers and highest in muscle. Although Juruena River bird feathers had a lower total mercury concentration, > 96% of the total mercury was methylmercury, the highest amount for specimens from both rivers. Although the concentration of Hg in the muscle of the green kingfisher is higher when compared to the feather and liver, the non-invasive monitoring through analysis of samples of feathers is an efficient biomonitoring tool for evaluation of mercury contamination in tropical birds.

Despite being one of the most important tropical biomes in the world, the Atrato River basin has experienced a critical ecological deterioration due to gold mining, posing a significant threat to wildlife and human health. In this study, we measured the concentrations of mercury (Hg) and arsenic (As) in sediments at various swamps within the basin. Classical indices were employed to assess the associated ecological and human health risks linked to exposure to these elements. The concentrations of Hg and As in the sediments ranged between 0.09 and 0.23 mg/kg and 0.59-2.68 mg/kg, respectively. The highest Hg values were found at upstream stations impacted by gold mining activities. For As, the highest levels were found near river mouth (except for station B), where agricultural practices are taken place. The contamination factor (CF) indicated that most of the sediments exhibited moderate contamination levels of Hg and As, depending on the specific sampling area. Conversely, the pollution load index (PLI) suggested a contamination level ranging from basic to moderate, with the exception of station B, which showed a progressive deterioration of the site. The geoaccumulation index (Igeo) indicated that the sediments were moderately contaminated with Hg, while showing signs of increasing contamination for As. According to the criteria for limiting effect concentrations (TEC), Hg concentrations exceeded the TEC at stations B and C, indicating a potential toxic risk to aquatic biota. A moderate potential ecological risk (PERI) was detected at downstream stations (D and E), and a high risk was detected at upstream stations (A, B and C). The hazard index (HI), used for non-carcinogenic risk assessment, suggested a risk of adverse effects on the population, particularly in children, with HI values exceeding 1. However, all lifetime cancer risk (TLCR) values fell within the acceptable range (1 × 10-6 to 1 × 10-4), indicating a negligible risk. Oral ingestion and inhalation wer

In this work, several binding gels were successfully prepared in Diffusive Gradient in Thin-film (DGT) that targeted the inclusion of novel biomass-derived materials for the determination of the labile fraction of mercury (Hg) in water. First, five biomass-derived materials were tested and the descending order as a function of the average percentage of Hg removal in solution was feathers > biochar > cork > canola meal > rice husk. The best two materials were treated and pulverized into powder to be embedded in a hydrogel; and so, feathers were pyrolyzed preserving the sulfur contained in their keratin structure (FBC), and biochar (BC) was modified and pyrolyzed with sublimated sulfur (SBC) to increase the Hg sorption sites in its structure. Analysis by Energy Dispersive X-ray fluorescence (EDXRF) spectrometry confirmed that the different pyrolysis procedures increased sulfur absorption successfully. The efficiency of the new gels (BC, SBC and FBC) in agarose was evaluated by comparative Hg uptake tests, showing a larger efficacy in the following order: SBC > BC > FBC. To assess the suitability of their application in freshwater environments, novel DGT devices were also evaluated to determine their diffusion coefficients (D). This test was conducted under controlled laboratory conditions, with particular focus on the potential competence of trace elements (Mn, Cu, Zn, Ni, Pb, Cd and As), which are commonly present in natural waters affected by mining. A stronger linear relationship between the Hg uptake by binding layers and the deployment time were obtained for the DGT devices with SBC (R2 = 0.948) vs. BC (R2 = 0.885). Therefore, the D obtained for Hg were 8.94 × 10-6 cm2 s-1 for DGT-SBC and 5.12 × 10-6 cm2 s-1 for DGT-BC devices at 25 °C, both within the same order of magnitude reported by previous studies. The good performance obtained by DGT-SBC devices is a promising result and indicates the potential for valorization of waste materials in the DGT technique.

Residual municipal solid waste (RMSW) is a rapidly expanding problem worldwide and a good waste management system could reduce concerns about its correct treatment. The purpose of this study was to characterize RMSW from urban and rural areas with the ultimate goal of estimating the recycling potential of the identified fractions and implementing waste collection and recovery methods according to the type of area that generates them. A direct sampling campaign of RMSW was performed. The results showed that the highest organic waste rate was found in the rural area (11.9%); urban-area-produced RMSW mainly constituted recyclable fractions such as plastic (26.3%), paper (21.8%), glass (3.5%) and metals (3.3%). The physical-chemical characteristics of RMSW showed levels of heavy metals below the detection threshold. The conditions necessary for composting could be met only for the organic fraction coming from rural areas as demonstrated by a pH value of 6.9 and a moisture content of 46.5%. These data will be extended to all the urban and rural areas to design appropriate disposal and/or recovery plants with profitable economic interventions that will lead to a reduction in costs in the planning of the integrated solid waste management.

Biomagnification of trace elements is increasingly evident in aquatic ecosystems. In this review we investigate the drivers of biomagnification of mercury (Hg), arsenic (As) and selenium (Se) in aquatic food webs. Despite Hg, As and Se biomagnify in food webs, the biomagnification potential of Hg is much higher than that of As and Se. The slope of trophic increase of Hg is consistent between temperate (0.20), tropical (0.22) and Arctic (0.22) ecosystems. Se exerts a mitigating role against Hg toxicity but desired maximum and minimum concentrations are unknown. Environmental (e.g. latitude, temperature and physicochemical characteristics) and ecological factors (e.g. trophic structure composition and food zone) can substantially influence the biomagnification process these metal (oids). Besides the level of bioaccumulated concentration, biomagnification depends on the biology, ecology and physiology of the organisms that play a key role in this process. However, it may be necessary to determine strictly biological, physiological and environmental factors that could modulate the concentrations of As and Se in particular. The information presented here should provide clues for research that include under-researched variables. Finally, we suggest that biomagnification be incorporated into environmental management policies, mainly in risk assessment, monitoring and environmental protection methods.

The determination of the concentration of an environmental pollutant is not sufficient to assess the related health risk because this pollutant may not be bioavailable. Therefore, methods to determine pollutant bioavailability are more relevant to assess toxicity than measuring the total concentration. For instance, the diffusive gradient in thin films (DGT) is an in situ dynamic technique used to measure the concentration of labile compounds in the environment. Here we review the latest developments achieved in speciation and bioavailability of metals and metalloids using this technique. We detail the technique, common binding agents and diffusive gels. We give laboratory procedures to prepare the gels, and we explain calculations using the DGT-induced fluxes in soils (DIFS) modeling. DIFS models can predict the resupply capacities from soils to porewater, and the uptake of trace elements by plants. Procedures for in situ field deployments, including issues of biofilm growth, are also discussed.

This work reports the level and ecotoxicity impact of metals in the sediments of the Mallorquín swamp, a protected coastal lagoon in the Caribbean coast of Colombia. The distribution of metals was in the following decreasing order: Zn > Cu > Pb > Cd > Hg, showing statistically significant differences among sites. The average Pb and Cd concentrations in sediments were about 17 and 5 times higher, respectively, compared to those in background values. Several contamination indices suggested moderate contamination of Hg, Cu, and Zn, and strong pollution due to Cd and Pb. Multivariate analysis revealed spatial variations for metals and its anthropogenic origin, such as municipal and industrial wastewater discharges (Pb, Zn, and Hg) and agricultural activities (Cd and Cu). These findings showed the negative impact of human activities and the need to apply protective management strategies.

In order to investigate concentrations, variability, sources, and human health risk of trace elements, 38 atmospheric dust samples were collected around Arak industrial area. The average concentrations of Cd~Zn, As, and Pb were 3.3, 2.5, and 2.4 times higher than the corresponding geochemical background, respectively, while concentrations of Co, Cu, Ni, and Hg were lower. Based on geo-accumulation index (Igeo), trace elements were classified between practically uncontaminated to moderate contaminated levels. The potential risk (RI) map showed that about 86% of the study area for all trace elements was in the moderate risk class. According to the results of positive matrix factorization (PMF) model, four factors were extracted for trace elements, including industrial sources, natural sources, mining, and transportation, that contributed about 30, 27, 26, and 17% to pollution of the area, respectively. The carcinogenic risks for inhalation exposure to Cd, As, Ni, and Co were lower than the permissible risk limit than the EPA recommend (10−6), indicating an acceptable level of risk. Results of the health risk evaluation indicated that the non-carcinogenic health risk (i.e., hazard quotient, HQ) for children and adults decrease following: As > Pb > Ni > Zn > Cd > Cu > Co > Hg. When excluding As, the hazard index (HI) was lower than the safe level (HI < 1) for all the trace elements, whereas HQ values of As for children and adults were 17.1 and 1.6, respectively, indicating a potential risk for children. In sum, several remedial actions to eliminate or to reduce the dust pollution are urgently required in the industrial area of Arak.

With the aim of protecting human life and the environment, the Minamata Convention seeks to reduce and monitor mercury (Hg) concentrations in the environment. Artisanal and Small-scale Gold Mining (ASGM) has been identified as the most important anthropogenic source of Hg at a global scale and an important route of human exposure to Hg. In this context, this study assessed total Hg (THg) in blood, urine and hair, and methylmercury (MeHg) in human hair samples from 238 participants with occupational exposure to Hg in the most relevant ASGM communities of Colombia. Mercury concentrations in different biological matrices were related to several variables of interest such as age, gender, body mass index, fish consumption, exposure time, and specific occupational activities, such as amalgamation and amalgam burning. The median values of THg in blood (3.70 µg/L), urine (4.00 µg/L) and hair (1.37 mg/kg), and hair MeHg (1.47 mg/kg) for all participants were below permissible concentrations set by WHO. However, about 40% of the miners showed Hg concentrations in blood, urine and/or hair above the WHO thresholds. In all the biological matrices studied, miners burning amalgams showed significantly higher concentrations than miners who did not burn amalgams, with values 7-, 7-, and 8-fold higher in blood, urine and hair, respectively. A multiple linear regression model revealed that burning amalgam and fish consumption were significant predictors of Hg exposure in miners. Miners from Guainía had the highest concentrations in urine and hair, most likely due to the high manipulation and burning of amalgam, and a high fish consumption. In contrast, miners from Caldas showed the lowest Hg concentrations in all the biomarkers because they do not manipulate or burn amalgam, as well as reporting the lowest fish consumption. Our study also highlighted that gold miners exposure to Hg depends on their work practices. Therefore, the implementation of a health education programme on gold m