The unified bioaccessibility method (UBM) was harnessed to assess in vitro oral bioaccessibility pools of dialkyl phthalate congeners (with methyl, –ethyl, –butylbenzyl, –n-butyl, –2-ethylhexyl, and –n-octyl moieties) and bisphenol A at the 17 μg g⁻¹ level in beach sand contaminated with polyethylene microplastics. A variety of sample preparation approaches prior to the analysis of the UBM gastrointestinal extracts, including traditional methods (protein precipitation, liquid-liquid extraction, and solid-phase extraction) and dispersive liquid-liquid microextraction (DLLME) were comprehensively evaluated for clean-up and analyte enrichment. DLLME was chosen among all tested approaches on account of the high extraction efficiency (73–95%, excluding bis(2-ethylhexyl)phthalate and di-n-octyl phthalate), high sample throughput (∼7 min per set of samples), and environmental friendliness as demonstrated by the analytical eco-scale score of 83, and the green analytical procedure index pictogram with green/yellow labeling. The release of the less hydrophobic plastic-laden compounds (dimethyl phthalate, diethyl phthalate and bisphenol A) from the contaminated sample into the body fluids was significant, with bioaccessibility values ranging from 30 to 70%, and from 43 to 74% in gastric and gastrointestinal fluids, respectively, and with relative standard deviation < 17% in all cases. The majority of the compounds were leached during gastric digestion, likely as the combined action of the low pH and the gastric enzymes. The risk exposure analysis revealed that accumulation/concentration in the body fluids is potentially relevant for dimethyl phthalate, diethyl phthalate and bisphenol A, with relative accumulation ratios ranging from 1.1 ± 0.1 to 2.6 ± 0.4. The average daily intake values for the suite of compounds, corrected with the bioaccessibility fraction, ranged from 60 to 430 ng kg of body weight⁻¹·day⁻¹, in all cases, far below the tolerable daily intakes, thus indicating the lack of children health risk by ingestion of microplastic-laden sand with elevated concentrations of plasticizers.

Passive biomonitoring was applied in four Atlantic forest plots in southeast Brazil, affected by different levels of trace metal pollution (OP site located in Minas Gerais State and PEFI, PP and STG located in São Paulo State). Native tree species were selected as biomonitors according to their abundance in each plot and successional classification. Current trace metal concentrations in total suspended particles, leaves of non-pioneer (NPi) and pioneer (Pi) species, topsoil (0–20 cm) and litter and concentration ratios at the plant/soil interface were analyzed to verify the atmosphere-plant-soil interactions, basal concentrations, spatial variations and metal accumulation at the ecosystem level. Redundant analysis helped to identify similar characteristics of metal concentrations in PP and PEFI, which can be influenced by the high concentrations of elements related to anthropogenic inputs. Analysis of variance and multivariate statistics indicated that the trees of OP presented higher concentrations of Cr, Fe, Mn and Ni than those in the other sites. High enrichment of Cd, Fe, Ni in non-pioneer plants indicated that the PP forest (initially considered as the least polluted) has still been affected by metal pollution. Soil collected in STG was enriched by all elements, however these elements were low available for plant uptake. Metal deposited in leaves and litter was an important sink for soil cycling, nevertheless, these metals are not bioavailable in most cases. Non-pioneer tree species revealed to be more appropriate than pioneer species to indicate the current panorama of the contamination and bioavailability levels of trace metals in the tree community-litter-soil interface of the Atlantic forest remnants included in this study.

Titanium dioxide nanoparticles (TiO₂NPs) application in variety of commercial products would likely release these NPs into the environment. The interaction of TiO₂NPs with terrestrial plants upon uptake can disturb plants functional traits and can also transfer to the food chain members. In this study, we investigated the impact of TiO₂NPs on wheat (Triticum aestivum L.) plants functional traits, primary macronutrients assimilation, and change in the profile of bio-macromolecule. Moreover, the mechanism of biochar-TiO₂NPs interaction, immobilization, and tissue accumulation to cell translocation of NPs in plants was also explored. The results indicated that the contents of Ti in wheat tissues was reduced about 3-fold and the Ti transfer rate (per day) was reduced about 2 fold at the 1000 mg L⁻¹ exposure level of TiO₂NPs in biochar amended exposure medium. Transmission electron microscopy (TEM) with elemental mapping confirmed that Ti concentrated in plant tissues in nano-form. The interactive effect of TiO₂NPs + biochar amendment on photosynthesis related and gas exchange traits was observed at relatively low TiO₂NPs exposure level (200 mg L⁻¹), which induced the positive impact on wheat plants proliferation. TiO₂NPs alone exposure to wheat also modified the plant’s bio-macromolecules profile with the reduction in the assimilation of primary macronutrients, which could affect the food crop nutritional value and quality. X-ray photoelectron spectroscopy (XPS) chemical analysis of biochar + TiO₂NPs showed an additional peak, which indicated the binding interaction of NPs with biochar. Moreover, Fourier-transform infrared (FTIR) spectroscopy confirmed that the biochar carboxyl group is the main functionality involved in the bonding process with TiO₂NPs. These findings will help for a mechanistic understanding of the role of biochar in the reduction of NPs bioavailability to primary producers of the terrestrial environment.

Steroid hormones are prevalent in the environment and have become emerging pollutants, but little is known about their effects on soil microbial community composition and function. In the present study, three representative soils in China were amended with environmentally relevant concentrations of testosterone and responses of soil bacterial community composition and soil function were assessed using high-throughput sequencing and nontargeted metabolomics. Our results showed that testosterone exposure significantly shifted bacterial community structure and metabolic profiles in soils at Ningbo (NB) and Kunming (KM), which may reflect high bioavailability of the hormone. Abundances of several bacterial taxa associated with nutrient cycling were reduced by testosterone and metabolites related to amino acid metabolism were downregulated. A close connection between bacterial taxa and specific metabolites was observed and confirmed by Procrustes tests and a co-occurrence network. These results provide an insight into the effects of steroid hormones on soil microbial community and highlight that nontargeted metabolomics is an effective tool for investigating the impacts of pollutants.

Knowledge of the concentration of the bioavailable forms of mercury in the soil is necessary, especially, if these soils contain above-limit total mercury concentrations. The bioavailability of mercury in soil samples collected from the vicinity of abandoned cinnabar mines was evaluated using diffusive gradients in the thin films technique (DGT) and mercury phytoaccumulation by vegetables (lettuce, spinach, radish, beetroot, carrot, and green peas). Mercury was accumulated primarily in roots of vegetables. The phytoaccumulation of mercury into edible plant parts was site-specific as well as vegetable species-specific. The mercury concentration in edible parts decreased in the order: spinach leaf ≥ lettuce leaf ≥ carrot storage root ≥ beetroot storage root > radish storage root > pea legume. The translocation index as well as the target hazard quotient indicate the possible usability of soils from the vicinity of abandoned cinnabar mines for planting pod vegetables (peas). A strong positive correlation (r = 0.75 to 0.92, n > 30, p < 0.05) was observed between mercury concentration in secondary roots, the storage roots, leaves of vegetables and the flux of mercury from soil to the DGT units, and the effective concentration of mercury in soil solutions.

Antarctic melt streams are important ecosystems that increasingly face contaminant pressures from anthropogenic sources. Metal contaminants are often reported in the limno-terrestrial environment but their speciation is not well characterised, making environmental risk assessments difficult. This paper characterises labile metal concentrations in five melt streams and three shallow lakes around the Casey and Wilkes research stations in East Antarctica using chemical extracts and field deployments of diffusive gradients in thin-film (DGT) samplers. An acute toxicity test with field-collected Ceratadon purpeus and taxonomic identification of diatoms in melt streams were used to infer environmental risk. Copper and zinc were the most labile metals in the melt streams. DGT-labile copper concentrations were up to 3 μg Cu L⁻¹ in melt-stream waters but not labile below the sediment-water interface. DGT-labile zinc concentrations were consistent above and below the sediment-water interface at concentrations up to 14 μg Zn L⁻¹ in four streams, but one stream showed evidence of zinc mineralisation in the sediment with a flux to overlying and pore waters attributed to the reductive dissolution of iron and manganese oxides. Other metals, such as chromium, nickel, and lead were acid-extractable from the sediments, but not labile in pore waters or overlying waters. All streams had unique compositions of freshwater diatoms, but one had particularly reduced diversity and richness, which correlated to metal contamination and sediment physico-chemical properties such as a finer particle size. In laboratory bioassays with field-collected samples of the Antarctic moss C. purpeus, there was no change in photosynthetic efficiency following 28-d exposure to 700, 900, 1060, or 530 μg L⁻¹ of cadmium, copper, nickel, and zinc, respectively. This study shows that microorganisms such as diatoms may be at greater risk from contaminants than mosses, and highlights the importance of geochemical factors controlling metal lability.

Rare earth elements and yttrium (REY) are critical elements for a wide range of applications and consumer products. Their growing extraction and use can potentially lead to REY and anthropogenic-REY chemical complexes (ACC-REY) being released in the marine environment, causing concern regarding their potential effects on organisms and ecosystems. Here, we critically review the scientific knowledge on REY sources (geogenic and anthropogenic), factors affecting REY distribution and transfer in the marine environment, as well as accumulation in- and effects on marine biota. Further, we aim to draw the attention to research gaps that warrant further scientific attention to assess the potential risk posed by anthropogenic REY release. Geochemical processes affecting REY mobilisation from natural sources and factors affecting their distribution and transfer across marine compartments are well established, featuring a high variability dependent on local conditions. There is, however, a research gap with respect to evaluating the environmental distribution and fate of REY from anthropogenic sources, particularly regarding ACC-REY, which can have a high persistence in seawater. In addition, data on organismal uptake, accumulation, organ distribution and effects are scarce and at best fragmentary. Particularly, the effects of ACC-REY at organismal and community levels are, so far, not sufficiently studied. To assess the potential risks caused by anthropogenic REY release there is an urgent need to i) harmonise data reporting to promote comparability across studies and environmental matrices, ii) conduct research on transport, fate and behaviour of ACC-REY vs geogenic REY iii) deepen the knowledge on bioavailability, accumulation and effects of ACC-REY and REY mixtures at organismal and community level, which is essential for risk assessment of anthropogenic REY in marine ecosystems.

Microplastics (MPs) are widely found in coastal areas and oceans worldwide. The MPs are environmentally concerning due to their bioavailability and potential impacts on a wide range of marine biota, so assessing their impact on the biota has become an urgent research priority. In the present study, we exposed Crassostrea gigas oysters to irregular MPs of two polymer types (polyethylene (PE) and polyethylene terephthalate (PET)) at concentrations of 10 and 1000 μg L⁻¹ for 21 days. Accumulation of MPs, changes in metabolic enzyme activity, and histological damage were evaluated, and metabolomics analysis was conducted. Results demonstrated that PE and PET MPs were detected in the gills and digestive gland following exposure to both tested concentrations, confirming ingestion of MPs by the organisms. Moreover, both PE and PET MPs inhibited lipid metabolism, while energy metabolism enzyme activities were activated in the oysters. Histopathological damage of exposed oysters was also observed in this study. Integrated biomarker response (IBR) results showed that MPs toxicity increased with increasing MPs concentration, and the toxic effects of PET MPs on oysters was greater than PE MPs. In addition, metabolomics analysis suggested that MPs exposure induced alterations in metabolic profiles in oysters, with changes in energy metabolism and inflammatory responses. This study reports new insights into the consequences of MPs exposure in marine bivalves at environmentally relevant concentrations, providing valuable information for ecological risk assessment of MPs in a realistic conditions.

To identify the role of gut microbiota in human health risk assessment, the bioaccessibility of heavy metals in 14 soil samples were determined in simulated gastrointestinal fluids. Compared to the small intestinal phase, the bioaccessibility values of the colon phase varied, either increased by 3.5-fold for As, by 2.2-fold for Cr, and by 1.6-fold for Ni, or reduced by 4.4-fold for Cu, respectively. The colon incubation with adult gut microbiota yielded higher bioaccessibility value of As (1.3 times) and Fe (3.4 times) than that of the child in most soil samples. Colon bioaccessibility was about 60% greater of Cd for the adult and 30% higher of Cr for the child. Congruent data on the bioaccessibility of Cu and Ni was observed. In addition, correlation analysis indicated that in vitro bioaccessibility was primarily related to total concentrations of heavy metals in soils, followed by soil pH and active Fe/Mn oxide. Significantly, risk assessment calculated based on colon bioaccessibility indicated that the target hazard quotient (THQ > 1) of As was presented in 3 soil samples for the adult (1.05–3.35) and in 9 soil samples for the child (1.06–26.93). The hazard index (HI) of the child was 4.00 on average, greater than that of the adult (0.62), primarily due to the contribution of As and Cd. It suggested non-carcinogenic risks are likely to occur in children through typical hand-to-mouth behavior. The adjustment of colon bioaccessibility will result in more accurate risk assessment of human exposure to heavy metals from oral ingestion of contaminated soils.

Contaminated land burdens the economy of many countries and must be dealt with.Researchers have published thousands of documents studying and developing soil and sediment remediation treatments. Amongst the targeted pollutants are the polycyclic aromatic hydrocarbons (PAHs), described as a class of persistent organic compounds, potentially harmful to ecosystems and living organisms.The present paper reviews and discusses three scientific trends that are leading current PAH-contaminated soil/sediment remediation studies and management.First, the choice of compounds that are being studied and targeted in the scientific literature is discussed, and we suggest that the classical 16 US-EPA PAH compounds might no longer be sufficient to meet current environmental challenges.Second, we discuss the choice of experimental material in remediation studies. Using bibliometric measures, we show the lack of PAH remediation trials based on co-contaminated or aged-contaminated material.Finally, the systematic use of the recently validated bioavailability measurement protocol (ISO/TS 16751) in remediation trials is discussed, and we suggest it should be implemented as a tool to improve remediation processes and management strategies.