Microplastics are hardly biodegradable and thus accumulate rather than decompose in the environment. Due to sedimentation processes, meiobenthic fauna is exposed to microplastics. Within the meiofauna, nematodes are a very abundant taxon and occupy an important position in benthic food webs by connecting lower and higher trophic levels. However, the key determinants of the uptake of microplastics by freshwater nematodes are still unknown. To investigate the bioaccessibility of microplastics for nematodes, we performed single- and multi-species ingestion experiments in which the ability of seven nematode species (six bacterial and one fungal feeder), diverse in their buccal cavity morphology (1.3–10.5 μm), to ingest fluorescence-labelled polystyrene (PS) beads along with their natural diet was examined. Applied beads sizes (0.5, 1.0, 3.0 and 6.0 μm), exposure time (4, 24 and 72 h) and concentration (3 × 10⁶ PS beads ml⁻¹ and 10⁷ PS beads ml⁻¹) were varied. Ingested beads were localized and quantified via fluorescence microscopy in the nematodes. In contrast to fungal-feeding nematode species with a stylet, bacterial-feeding species ingested 0.5- and 1.0-μm PS beads with up to 249 and 255 beads after 24 h, respectively. Microplastics ≥0.5 μm could only be ingested and transported into the gastrointestinal tract, if the buccal cavities were considerably (>1.3 times) larger than the beads. At concentrations of 10⁷ PS beads ml⁻¹ ingestion rates were influenced by exposure time and PS bead concentration. In case of a known microplastic size distribution in the environment, predictions on the potential ingestion for nematode communities can be made based on the feeding type composition and the size of their buccal cavities.

Mercury (Hg) and methylmercury (CH3Hg) bind strongly to micro and nano (NP) particles and this partitioning impacts their fate and bioaccumulation into food webs, and, as a result, potential human exposure. This partitioning has been shown to influence the bioavailability of inorganic Hg to methylating bacteria, with NP-bound Hg being more bioavailable than particulate HgS, or organic particulate-bound Hg. In this study we set out to investigate whether the potential interactions between dissolved ionic Hg (HgII) and CH3Hg and NPs was due to incorporation of Hg into the core of the cadmium selenide and sulfide (CdSe; CdS) nanoparticles (metal exchange or surface precipitation), or due purely to surface interactions. The interaction was assessed based on the quenching of the fluorescence intensity and lifetime observed during HgII or CH3Hg titration experiments of these NP solutions. Additional analysis using inductively coupled plasma mass spectrometry of CdSe NPs and the separated solution, obtained after HgII additions, showed that there was no metal exchange, and X-ray photoelectron spectroscopy confirmed this and further indicated that the Hg was bound to cysteine, the NP capping agent. Our study suggests that Hg and CH3Hg adsorbed to the surfaces of NPs would have different bioavailability for release into water or to (de)methylating organisms or for bioaccumulation, and provides insights into the behavior of Hg in the environment in the presence of natural or manufactured NPs.

An evaluation of the concentrations, bioavailability and sources of polycyclic aromatic hydrocarbons (PAHs) and persistent organic pollutants (POPs) was performed in the industrialized estuary of Santos-São Vicente and in the Cananéia-Iguape estuarine lagoon system, considered an Atlantic forest biosphere reserve, using different approaches. Semipermeable membrane devices (SPMDs) and bivalves (Crassostrea brasiliana) were deployed in both estuarine systems. Samples of water, suspended particulate material (PM), and sediments were also collected in these regions. The concentrations of PAHs in the water and in the PM from both estuarine systems were similar. In the sediment, the concentrations of PAHs and POPs were higher in the estuary of Santos-São Vicente than in the Cananéia-Iguape estuarine lagoon system. The accumulation of PAHs and POPs by the SPMD and C. brasiliana revealed that in both regions the bioavailability of contaminants was similar. Because of the hydrophobicity of the organic compounds, each matrix responded in a different manner to the source of the contaminants; C. brasiliana and sediment were primarily associated with 4–5 ring-PAHs that represent pyrolytic sources of hydrocarbons, whereas water and the SPMDs were correlated with the 2–3 ring-PAHs, which represent petrogenic sources. The PM produced an intermediated concentration among these compartments and was related to the concentration of POPs. Because no significant differences between the mean concentrations of contaminants in both studied regions were observed, anthropogenic effects currently impact the Cananéia-Iguape lagoon system, which was initially considered a pristine area.

Dietary arsenic (As) intake from food is of great concern, and developing a reliable model capable of predicting As concentrations in plant edible parts is desirable. In this study, pot experiments were performed with 16 Chinese upland soils spiked with arsenate [As(V)] to develop a predictive model for As concentrations in pepper fruits (Capsicum annum L.). Our results showed that after three months’ aging, concentrations of bioavailable As (extracted by 0.05 M NH₄H₂PO₄) in various soils varied widely, depending on soil total As concentrations and soil properties such as soil pH and amorphous iron (Fe) contents. Furthermore, both the bioconcentration factor (BCF, denoted as the ratio of fruit As to soil As) and total As concentrations in pepper fruits were largely determined by concentrations of bioavailable As, which explained 27% and 69% variations in the BCF and fruit As concentrations, respectively. Apart from bioavailable As, soil pH and Fe contents were another two important factors influencing As accumulation in pepper fruits. Taking the three factors into account, concentrations of fruit As can be well predicted using a stepwise multiple linear regression (SMLR) analysis (R² = 0.80, RMSE = 0.17). Arsenic species in soils and edible parts were also analyzed. Although As(V) predominated in soils (>96%), As in pepper fruits presented as As(V) (46%) and arsenite [As(III)] (39%) with small amount of methylated As (<15%). Aggregated boosted tree (ABT) analysis revealed that inorganic As concentrations in pepper fruits were determined by concentrations of bioavailable As, phosphorus (P) and Fe in soils. In contrast to inorganic As, methylated As concentrations were not correlated with those factors in soils. Taken together, this study established an empirical model for predicting As concentrations in pepper fruits. The predictive model can be used for establishing the As threshold in fruit vegetable farming soils.

Nitrogen (N) addition can change physicochemical properties and biogeochemical processes in soil, but whether or not these changes further affect the transport and transformation of heavy metal speciation is unknown. Here, a long-term (2004–2016) field experiment was conducted to assess the responses of different heavy metal speciation in three soil aggregate fractions to N additions in a temperate agroecosystem of North China. The organic matter turnover time was quantified based on changes in δ13C following the conversion from C3 (wheat) to C4 crop (corn). Averagely, N addition decreases and increases the heavy metal contents in bioavailable and organic bound fractions by 27.5% and 16.6%, respectively, suggesting N addition promotes the transformation of heavy metal speciation from bioavailable to organic bound, and such a promotion in a small aggregate fraction is more remarkable than that in a large aggregate fraction. The transformations of heavy metal speciation from bioavailable to organic bound in all soil aggregate fractions are largely dependent on the increments in the turnover time of organic matter. The increase in organic matter turnover time induced by N addition may inhibit the desorption of heavy metals from organic matter by prolonging the interaction time between heavy metals and organic matter and enhance the capacity of organic matter to adsorb heavy metals by increasing the humification degree and functional group. Our work can provide insights into the accumulation, migration, and transformation of heavy metals in soils in the context of increasing global soil N input from a microenvironmental perspective.

The aim of this study was to assess the effect of major cations (Ca²⁺, Mg²⁺, Na⁺, K⁺, and H⁺) on cadmium toxicity to the springtail Folsomia candida. Survival of the animals was determined after seven days exposure to different cadmium concentrations in an inert sand-solution medium, in different experimental setups with modification of the cation concentrations. Among the cations tested, Ca²⁺ and Mg²⁺ had protective effects on the toxicity of cadmium to the springtails while Na⁺, K⁺, and H⁺ showed less competition with free cadmium ions for binding to the uptake sites of the collembolans. Toxicity predicted with a biotic ligand model agreed well with the observed values. Calculated conditional binding constants and the fraction of biotic ligands occupied by cadmium to show 50% effects were similar to values reported in the literature. The results emphasize the important role of solution chemistry in determining metal toxicity to soil invertebrates.

Sorption studies of organic pollutants by microplastics (MPs) in single-solute systems are well established in the literature. However, actual aquatic environments always contain a mixture of contaminants. Prediction of the fate and biological effects of MPs-mediated chemical exposure requires a better understanding of sorption-desorption processes of multiple organic contaminants by MPs. In this study, the altered sorption and desorption behaviors of individual organic UV filters (BP-3 and 4-MBC) in the presence of cosolutes (BP-3, 4-MBC, EHMC and OC) on two types of MPs (LDPE and PS) were examined. In most cases, co-occurrence of other organic UV filters appeared to have an antagonistic effect on the sorption of primary solute, which was consistent with trends found in previous studies. Nevertheless, the sorption uptake of 4-MBC as primary solute on PS was enhanced in the presence of cosolute(s), arising presumably from solute multilayer formation caused by laterally attractive π-π interactions between adsorbed cosolute(s) and 4-MBC molecules. Such formation of multilayer sorption in multi-solute systems depends on the solute hydrophobicity and concentration as well as inherent sorptivity of MPs. Our further desorption experiments revealed that the bioaccessibility of primary solute was significantly elevated with cosolutes, even though competitive sorption was observed under the same experimental conditions. These findings supplement the current knowledge on sorption mechanisms and interactions of multiple organic contaminants on MPs, which are critical for a comprehensive environmental risk assessment of both MPs and hazardous anthropogenic contaminants in natural environments.

The predominance of natural organic matter (NOM) in nonlinear sorption of nonionic organic compounds (NOCs) is a fundamental behavior that controlling the fate, transfer and bioavailability of NOCs in natural environment. There is a debate, i.e., whether the nonlinear sorption is captured by nonlinear partition mechanism or adsorption mechanism. The debate has been going on for decades because characteristics of nonlinear partition are still unknown due to the lack of an adsorbent that can partition NOCs nonlinearly. We find a resin ADS-21, with specific surface area undetectable (<0.5 m² g⁻¹) but high sorption capacity for NOCs (up to 1000 mg g⁻¹ for phenol as an example), is an ideal adsorbent for examining characteristics of nonlinear partitioning. This resin has nonlinear isotherms for phenols and anilines but linear isotherms for polycyclic aromatic hydrocarbons and nitrobenzenes. The observed positively linear relationship of sorption capacities of NOCs with NOCs solubility in water or octanol, could be one of the characteristics of nonlinear partition. Moreover, competitive sorption and no desorption hysteresis could be observed for the nonlinear partition. Hydrogen-bonding of phenols and anilines with ADS-21 is responsible for nonlinear partition, competitive sorption and isotherm nonlinearity. These evidences would be supportive for understanding nonlinear partition and the nonlinear sorption of NOCs by NOM.

Enhancing metals phytoextraction using gentile mobilizing agents might be an appropriate approach to increase the phytoextraction efficiency and to shorten the phytoremediation duration. The effect of sulfur-impregnated organoclay (SIOC) on the redistribution of potentially toxic elements (PTEs) among their geochemical fractions in soils and their plant uptake has not yet been studied. Therefore, our aim is to investigate the role of different SIOC application doses (1%, 3% and 5%) on operationally defined geochemical fractions (soluble + exchangeable; bound to carbonate; manganese oxide; organic matter; sulfide; poorly- and well-crystalline Fe oxide; and residual fraction) of Cd, Cr, Cu, Ni, Pb, and Zn, and their accumulation by pea (Pisum sativum) and corn (Zea mays) in a greenhouse pot experiment using a polluted floodplain soil. The SIOC caused a significant decrease in soil pH, and an increase in organic carbon and total sulfur content in the soil. The addition of SIOC increased significantly the soluble + exchangeable fraction and bioavailability of the metals. The SIOC leads to a transformation of the residual, organic, and Fe-Mn oxide fractions of Cd, Cu, Ni, and Zn to the soluble + exchangeable fraction. The SIOC addition increased the potential mobile (non-residual) fraction of Cr and Pb. The SIOC increased the sulfide fraction of Cr, Ni, and Zn, while it decreased the same fraction for Cd, Cu, and Pb. The effect of SIOC on the redistribution of metal fractions increased with enhancing application dosages. Pea accumulated more metals than corn with greater accumulation in the roots than shoots. Application of the higher dose of SIOC promoted the metals accumulation by roots and their translocation to shoots of pea and corn. Our results suggest the potential suitability of SIOC for enhancing the phytomanagement of PTEs polluted soils and reducing the environmental risk of these pollutants.

Hydrophobic legacy contaminants like dichlorodiphenyltrichloroethane (DDT) and polychlorinated biphenyls (PCBs) were banned almost half a century ago. While their residues still remain in many environmental compartments, they have undergone extensive aging and likely have lower bioaccessibility (the available fraction) compared to fresh residues. However, risk assessment relies heavily on the use of total chemical concentration, rather than accounting for age-diminished bioaccessibility, likely leading to overestimated risks. In this study, we used 24 h Tenax desorption to measure the potential bioaccessibility of DDTs and PCBs in two sediment cores taken from the Palos Verdes Shelf Superfund site in the Pacific Ocean. The total concentrations of DDTs and PCBs from the core located at the sewage outfall (8C) were as high as 41,000–15,700 μg/kg (dry weight, dw) and 530-2600 μg/kg dw, respectively, while those from a location 7 km northeast of the outfall (3C) were 2–3 orders of magnitude lower. Bioaccessibility estimated by 24-h Tenax-aided desorption (F24h) decreased in the order of DDD > DDE > DDT for DDT derivatives, and PCB 52 > PCB 70 > PCB 153 for PCB congeners, showing a negative correlation with their log Kow. Due to the extensive aging, F24h values were <20% of the total chemical concentration for most contaminants and <5% for DDT, DDE and PCB 153, suggesting that aging greatly diminished their bioavailability. However, a quantitative relationship between F24h and sediment age along the vertical profile was not found, likely because the contaminant residues had undergone aging before their offsite transport and deposition onto the ocean floor. As the use of man-made chemicals such as DDT and PCBs was discontinued in the U.S. many decades ago, the reduction in their bioavailability due to aging may be universal and should be taken into consideration to avoid overly conservative risk predictions or unnecessary mitigation interventions.