Application of empirical models to adsorption of contaminants on natural heterogeneous sorbents is often challenging due to the uncertainty associated with fitting experimental data and determining adjustable parameters. Sediment samples from contaminated and uncontaminated portions of a study site in Maine, USA were collected and investigated for adsorption of arsenate [As(V)]. Two kinetic models were used to describe the results of single solute batch adsorption experiments. Piecewise linear regression of data linearized to fit pseudo-first order kinetic model resulted in two distinct rates and a cutoff time point of 14–19 h delineating the biphasic behavior of solute adsorption. During the initial rapid adsorption stage, an average of 60–80% of the total adsorption took place. Pseudo-second order kinetic models provided the best fit to the experimental data (R2 > 0.99) and were capable of describing the adsorption over the entire range of experiments. Both Langmuir and Freundlich isotherms provided reasonable fits to the adsorption data at equilibrium. Langmuir-derived maximum adsorption capacity (St) of the studied sediments ranged between 29 and 97 mg/kg increasing from contaminated to uncontaminated sites. Solid phase As content of the sediments ranged from 3.8 to 10 mg/kg and the As/Fe ratios were highest in the amorphous phase. High-pH desorption experiments resulted in a greater percentage of solid phase As released into solution from experimentally-loaded sediments than from the unaltered samples suggesting that As(V) adsorption takes place on different reversible and irreversible surface sites.

Arsenic is a non-threshold carcinogenic metalloid. Thus, human exposure should be minimised, e.g. by chemically stabilizing As in soil. Since iron is a potential As immobiliser, it was investigated whether root iron plaque, formed under aerobic conditions, affects As uptake, metabolism and distribution in Lupinus albus plants. White lupin plants were cultivated in a continuously aerated hydroponic culture containing Fe/EDDHA or FeSO4 and exposed to arsenate (5 or 20 μM). Only FeSO4 induced surficial iron plaque in roots. LA-ICP-MS analysis accomplished on root sections corroborated the association of As to this surficial Fe. Additionally, As(V) was the predominant species in FeSO4-treated roots, suggesting less efficient As uptake in the presence of iron plaque. Fe/EDDHA-exposed roots neither showed such surficial FeAs co-localisation nor As(V) accumulation; in contrast As(III) was the predominant species in root tissue. Furthermore, FeSO4-treated plants showed reduced shoot-to-root As ratios, which were >10-fold lower compared to Fe/EDDHA treatment. Our results highlight the role of an iron plaque formed in roots of white lupin under aerobic conditions on As immobilisation. These findings, to our knowledge, have not been addressed before for this plant and have potential implications on soil remediation (phytostabilisation) and food security (minimising As in crops).

This study analyzed 405 surface sediment samples, obtained from across the Bohai Sea, for concentrations of five potentially harmful elements (Ag, As, Hg, Sb, and Se) and several ancillary parameters (Al, Fe, Mn, total organic carbon (TOC), and grain size). Statistically, the spatial distributions of these elements were correlated positively with Al, Fe, TOC, and grain size, indicating natural sources for these elements or common accumulation mechanisms. The assessment of potential environmental risk with empirical sediment quality guidelines showed that a significant proportion of the samples had As and Sb concentrations that exceeded the effects range low (ERL) or T20 values in the Bohai Sea, indicating the potential for adverse biological effects. However, the assessment results differed when using evaluation methods that considered background values. Based on the geoaccumulation index (Igeo), Hg and Ag were found to have the highest percentages (35% and 60%, respectively) in samples that were moderately contaminated. The estimated contamination degree (Cd) suggested higher contamination levels for the entire area, with 69% of the samples being moderately contaminated. Generally, except for some local hotspots, such as Jinzhou Bay, the contamination levels of these elements in the Bohai Sea were established as slight to moderate. Samples from the Jinzhou Bay area had concentrations that were 10–100 times higher than in the rest of the Bohai Sea, indicating severe contamination.

Rice is one of the major pathways of arsenic (As) exposure in human food chain, threatening over half of the global population. Greenhouse pot experiments were conducted to examine the effects of Si application on iron (Fe) plaque formation, As uptake and rice grain As speciation in indica and hybrid rice genotypes with different radial oxygen loss (ROL) ability. The results demonstrated that Si significantly increased root and grain biomass. Indica genotypes with higher ROL induced greater Fe plaque formation, compared to hybrid genotypes and sequestered more As in Fe plaque. Silicon applications significantly increased Fe concentrations in iron plaque of different genotypes, but it decreased As concentrations in the roots, straws and husks by 28–35%, 15–35% and 32–57% respectively. In addition, it significantly reduced DMA accumulation in rice grains but not inorganic As accumulation. Rice of indica genotypes with higher ROL accumulated lower concentrations of inorganic As in grains than hybrid genotypes with lower ROL.

Ethylbenzene and toluene degradation under nitrate-, Mn(IV)-, or Fe(III)-reducing conditions was investigated by compound specific stable isotope analysis (CSIA) using three model cultures (Aromatoleum aromaticum EbN1, Georgfuchsia toluolica G5G6, and a Azoarcus-dominated mixed culture). Systematically lower isotope enrichment factors for carbon and hydrogen were observed for particulate Mn(IV). The increasing diffusion distances of toluene or ethylbenzene to the solid Mn(IV) most likely caused limited bioavailability and hence resulted in the observed masking effect. The data suggests further ethylbenzene hydroxylation by ethylbenzene dehydrogenase (EBDH) and toluene activation by benzylsuccinate synthase (BSS) as initial activation steps. Notably, significantly different values in dual isotope analysis were detected for toluene degradation by G. toluolica under the three studied redox conditions, suggesting variations in the enzymatic transition state depending on the available TEA. The results indicate that two-dimensional CSIA has significant potential to assess anaerobic biodegradation of ethylbenzene and toluene at contaminated sites.

Wetland plants are considered as suitable biofilters for the removal of metal(loid)s and other contaminants from waters and wastewaters, due to their ability to accumulate and retain the contaminants in their roots. The iron plaque (IP) on the root surface influences the metal(loid)s retention processes. The stimulation of the IP development on roots of Phragmites australis by the external supply of a novel synthetic nanomaterial (nanomaghemite, nFe2O3) and FeSO4 (alone or in combination) was studied. An hydroponic experiment was carried out to evaluate the iron plaque formation after external iron addition, as well as their influence on arsenic immobilization capacity. Microscopic and spectroscopic techniques were utilized to assess the distribution of Fe and As in the roots. The addition of Fe stimulated the generation of the IP, especially when FeSO4 was involved. The nanoparticles alone were not efficient with regard to IP formation or As adsorption, even though they adhered to the root surface and did not enter into epithelial root cells. The combination of FeSO4 and nFe2O3 was the most effective treatment for improving the As removal capacity, and it seems to be an effective way to enhance the rhizofiltration potential of P. australis in As contaminated (waste)waters.

Information regarding chemical pollutant levels in farmed fish and shellfish, along with the risks associated with their consumption is still scarce. This study was designed to assess levels of exposure to 21 trace elements in fish (Dicentrarchus labrax), mussels (Mytilus galloprovincialis) and oysters (Crassostrea gigas) collected from aquaculture marine ecosystems of the northwestern Mediterranean Sea. Metal concentrations showed great variability in the three species; the highest values of the nonessential elements As and Cd were found in oysters while the highest levels of Al, Pb and V were found in mussels. The essential elements Cu, Mn and Zn were highest in oysters, but Fe, Cr, Ni, Se, Co and Mo levels were highest in mussels. Fish had the lowest concentrations for all trace elements, which were at least one order of magnitude lower than in bivalves. The rare earth elements cerium and lanthanum were found at higher levels in mussels than in oysters, but undetectable in fish. The maximum values set by European regulations for Hg, Cd and Pb were never exceeded in the examined samples. However, comparing the estimated human daily intakes (EHDIs) with the suggested tolerable copper and zinc intakes suggested a potential risk for frequent consumers of oysters. Similarly, people who consume high quantities of mussels could be exposed to concentrations of Al that exceed the proposed TWI (tolerable weekly intake).

We sampled landlocked Arctic char (Salvelinus alpinus) from four lakes (Small, 9-Mile, North, Amituk) in the Canadian High Arctic that span a gradient of mercury contamination. Metals (Hg, Se, Tl, and Fe) were measured in char tissues to determine their relationships with health indices (relative condition factor and hepatosomatic index), stable nitrogen isotope ratios, and liver histology. A subcellular partitioning procedure was employed to determine how metals were distributed between potentially sensitive and detoxified compartments of Arctic char livers from a low- and high-mercury lake (Small Lake and Amituk Lake, respectively). Differences in health indices and metal concentrations among char populations were likely related to differences in feeding ecology. Concentrations of Hg, Se, and Tl were highest in the livers of Amituk char, whereas concentrations of Fe were highest in Small and 9-Mile char. At the subcellular level we found that although Amituk char had higher concentrations of Tl in whole liver than Small Lake char, they maintained a greater proportion of this metal in detoxified fractions, suggesting an attempt at detoxification. Mercury was found mainly in potentially sensitive fractions of both Small and Amituk Lake char, indicating that Arctic char are not effectively detoxifying this metal. Histological changes in char livers, mainly in the form of melano-macrophage aggregates and hepatic fibrosis, could be linked to the concentrations and subcellular distributions of essential or non-essential metals.

Rapid temperature rise in Arctic permafrost impacts not only the degradation of stored soil organic carbon (SOC) and climate feedback, but also the production and bioaccumulation of methylmercury (MeHg) toxin that can endanger humans, as well as wildlife in terrestrial and aquatic ecosystems. Currently little is known concerning the effects of rapid permafrost thaw on microbial methylation and how SOC degradation is coupled to MeHg biosynthesis. Here we describe the effects of warming on MeHg production in an Arctic soil during an 8-month anoxic incubation experiment. Net MeHg production increased >10 fold in both organic- and mineral-rich soil layers at warmer (8 °C) than colder (−2 °C) temperatures. The type and availability of labile SOC, such as reducing sugars and ethanol, were particularly important in fueling the rapid initial biosynthesis of MeHg. Freshly amended mercury was more readily methylated than preexisting mercury in the soil. Additionally, positive correlations between mercury methylation and methane and ferrous ion production indicate linkages between SOC degradation and MeHg production. These results show that climate warming and permafrost thaw could potentially enhance MeHg production by an order of magnitude, impacting Arctic terrestrial and aquatic ecosystems by increased exposure to mercury through bioaccumulation and biomagnification in the food web.

The sulfentrazone dechlorination using bimetallic nanoparticles of Fe/Ni was studied. Different variables that could influence the sulfentrazone conversion were investigated, such as nitrogen atmosphere, pH and dosage of the nanoparticles and initial concentration of sulfentrazone. The best results were obtained using controlled pH (pH 4.0) and 1.0 g L⁻¹ of nanomaterials, resulting in 100 % conversion in only 30 min. Kinetic studies were also conducted, evaluating the influence of different nanoparticle dosages (1.0 to 4.0 g L⁻¹), system temperatures (20 to 35 °C) and nickel levels in the composition of the nanomaterials (0.025 to 0.10 gNi/gFe). The mechanism of sulfentrazone conversion has changed due a direct reduction on the catalytic activity sites and indirect reduction by atomic hydrogen. Both mechanisms have followed pseudo-first order models. The conversion rate improved when the dosage of the nanomaterials, system temperature and nickel content in the composition of the nanocomposites were increased. Finally, the conversion products were elucidated by mass spectrometry and toxicity assays were performed using Daphnia Similis. The results showed that the dechlorination product is less toxic than sulfentrazone.