Inhalation exposure to fine particulate matter (PM₂.₅) represents a global concern due to the adverse effects in human health. In the last years, scientific community has been adopted the assessment of the PM₂.₅-bound pollutant fraction that could be released (bioaccessible fraction) in simulated lung fluids (SLFs) to achieve a better understanding of PM risk assessment and toxicological studies. Thus, bioaccessibility of 49 organic pollutants, including 18 polycyclic aromatic hydrocarbons (PAHs), 12 phthalate esters (PAEs), 11 organophosphorus flame retardants (OPFRs), 6 synthetic musk compounds (SMCs) and 2 bisphenols in PM₂.₅ samples was evaluated. The proposed method consists of a physiologically based extraction test (PBET) by using artificial lysosomal fluid (ALF) to obtain bioaccessible fractions, followed by a vortex-assisted liquid-liquid microextraction (VALLME) and a final analysis by programmed temperature vaporization-gas chromatography-tandem mass spectrometry (PTV-GC-MS/MS). The highest inhalation bioaccessibility ratio was found for bisphenol A (BPA) with an average of 83%, followed by OPFRs, PAEs and PAHs (with average bioaccessibilities of 68%, 41% and 34%, respectively). Correlations between PM₂.₅ composition (major ions, trace metals, equivalent black carbon (eBC) and UV-absorbing particulate matter (UVPM)) and bioaccessibility ratios were also assessed. Principal Component Analysis (PCA) suggested that PAHs, PAES and OPFRs bioaccessibility ratios could be positively correlated with PM₂.₅ carbonaceous content. Furthermore, both inverse and positive correlations on PAHs, PAEs and OPFRs bioaccessibilites could be accounted for some major ions and metal (oid)s associated to PM₂.₅, whereas no correlations comprising considered PM₂.₅ major ions and metal (oid)s contents and BPA bioaccessibility was observed. In addition, health risk assessment of target PM₂.₅-associated PAHs via inhalation was assessed in the study area considering both total and bioaccessible concentrations, being averaged human health risks within the safe carcinogenic and non-carcinogenic levels.

The increasing use of rare earth elements (REEs) in various industries has led to a rise in discharge points, thus increasing discharge rates, circulation, and human exposure. Therefore, REEs have received widespread attention as important emerging pollutants. This article thus summarizes and discusses the distribution and occurrence of REEs in the world's soil and water, and briefly introduces current REEs content analysis technology for the examination of different types of samples. Specifically, this review focuses on the impact of REEs on plants, including the distribution and fractionation of REEs in plants and their bioavailability, the effect of REEs on seed germination and growth, the role of REEs in plant resistance, the physiological and biochemical responses of plants in the presence of REEs, including mineral absorption and photosynthesis, as well as a description of the substitution mechanism of REEs competing for Ca in plant cells. Additionally, this article summarizes the potential mechanisms of REEs to activate endocytosis in plants and provides some insights into the mechanisms by which REEs affect endocytosis from a cell and molecular biology perspective. Finally, this article discusses future research prospects and summarizes current scientific findings that could serve as a basis for the development of more sustainable rare earth resource utilization strategies and the assessment of REEs in the environment.

Both inorganic and organic fertilizers are widely used to increase rice yield. However, these fertilizers are also found to aggravate mercury methylation and methylmercury (MeHg) accumulation in paddy fields. The aim of this study was to reveal the mechanisms of inorganic and organic fertilizers on MeHg accumulation in rice grains, which are not yet well understood. Potting cultures were conducted in which different fertilizers were applied to a paddy soil. The results showed that both inorganic and organic fertilizers increased MeHg concentrations rather than biological accumulation factors (BAFs) of MeHg in mature rice grains. Inorganic fertilizers, especially nitrogen fertilizer, enhanced the bioavailability of mercury and the relative amount Hg-methylating microbes and therefore intensified mercury methylation in paddy soil and MeHg accumulation in rice grains. Unlike inorganic fertilizers, organic matter (OM) in organic fertilizers was the main reason for the increase of MeHg concentrations in rice grains, and it also could immobilize Hg in soil when it was deeply degraded. The enhancement of MeHg concentrations in rice grains induced by inorganic fertilizers (5.18–41.69%) was significantly (p < 0.05) lower than that induced by organic fertilizers (80.49–106.86%). Inorganic fertilizers led to a larger increase (50.39–99.28%) in thousand-kernel weight than MeHg concentrations (5.18–41.69%), resulting in a dilution of MeHg concentrations in mature rice grains. Given the improvement of soil properties by organic fertilizer, increasing the proportion of inorganic fertilizer application may be a better option to alleviate MeHg accumulation in rice grains and guarantee the rice yield in the agricultural production.

Trace elements (TEs) from various natural and anthropogenic activities contaminate the agricultural water and soil environments. The use of nanoparticles (NPs) as nano-fertilizers or nano-pesticides is gaining popularity worldwide. The NPs-mediated fertilizers encourage the balanced availability of essential nutrients to plants compared to traditional fertilizers, especially in the presence of excessive amounts of TEs. Moreover, NPs could reduce and/or restrict the bioavailability of TEs to plants due to their high sorption ability. In this review, we summarize the potential influence of NPs on plant physiological attributes, mineral absorption, and TEs sorption, accumulation, and translocation. It also unveils the NPs-mediated TE scavenging-mechanisms at plant and soil interface. NPs immobilized TEs in soil solution effectively by altering the speciation of TEs and modifying the physiological, biochemical, and biological properties of soil. In plants, NPs inhibit the transfer of TEs from roots to shoots by inducing structural modifications, altering gene transcription, and strengthening antioxidant defense mechanisms. On the other hand, the mechanisms underpinning NPs-mediated TEs absorption and cytotoxicity mitigation differ depending on the NPs type, distribution strategy, duration of NP exposure, and plants (e.g., types, varieties, and growth rate). The review highlights that NPs may bring new possibilities for resolving the issue of TE cytotoxicity in crops, which may also assist in reducing the threats to the human dietary system. Although the potential ability of NPs in decontaminating soils is just beginning to be understood, further research is needed to uncover the sub-cellular-based mechanisms of NPs-induced TE scavenging in soils and absorption in plants.

Size segregated samples (<0.49, 0.49–0.95, 0.95–1.5, 1.5–3.0, 3.0–7.2 and > 7.2 μm) of atmospheric particulate matter (APM) were collected at a traffic site in the urban agglomeration of Thessaloniki, northern Greece, during the cold and the warm period of 2020. The solvent-extractable organic matter was analyzed for selected organic contaminants including polycyclic aromatic hydrocarbons (PAHs), and their nitro- and oxy-derivarives (NPAHs and OPAHs, respectively). Mean concentrations of ∑₁₆PAHs, ∑₆NPAHs and ∑₁₀OPAHs associated to total suspended particles (TSP) were 18 ng m⁻³, 0.2 ng m⁻³ and 0.9 ng m⁻³, respectively, in the cold period exhibiting significant decrease (6.4, 0.2 and 0.09 ng m⁻³, respectively) in the warm period. The major amount of all compounds was found to be associated with the alveolar particle size fraction <0.49 μm. The inhalation bioaccessibility of PAHs and O/N PAHs was measured in vitro using two simulated lung fluids (SLFs), the Gamble's solution (GS) and the artificial lysosomal fluid (ALF). With both SLFs, the derived bioaccessible fractions (BAFs) followed the order PAHs > OPAHs > NPAHs. Although no clear dependence of bioaccessibility on particle size was obtained, increased bioaccessibility of PAHs and PAH derivatives in coarse particles (>7.2 μm) was evident. Bioaccessibility was found to be strongly related to the logKOW and the water solubility of individual compounds hindering limited mobilization of the most hydrophobic and less water-soluble compounds from APM to SLFs. The lifetime cancer risk due to inhalation exposure to bioaccessible PAHs, NPAHs and OPAHs was estimated and compared to those calculated from the particulate concentrations of organic contaminants.

Iron oxides and microorganisms are important soil components that profoundly affect the transformation and bioavailability of heavy metals in soils. Here, batch and pot experiments were conducted to investigate the immobilization mechanisms of Cd by Cd-loving Bacillus sp. N3 and ferrihydrite (Fh) as well as their impacts on Cd uptake by wheat and bacterial community composition in wheat rhizospheric soil. The results showed that the combination of strain N3 with Fh could immobilize more Cd compared to strain N3 and Fh, respectively. Furthermore, strain N3 facilitated Cd retention on Fh, which synergistically reduced the concentration of DTPA extracted Cd in the soil and decreased Cd content (57.1%) in wheat grains. Moreover, inoculation with strain N3 increased the complexity of the co-occurrence network of the bacterial community in rhizospheric soil, and the abundance of beneficial bacteria with multipel functions including heavy metal immobilization, dissimilatory iron reduction, and plant growth promotion. Overall, this study demonstrated the enrichment of strain N3 and iron oxides, together with increased soil pH, synergistically immobilized soil Cd, which strongly suggested inoculation with Cd-loving strains could be a promising approach to immobilize Cd and reduce wheat uptake of Cd, particular for soils rich in iron oxides.

Copper (Cu), as an essential element, is added to animal feed to stimulate growth and prevent disease. The forage crop alfalfa (Medicago sativa L.) produced during Cu phytoextraction may be considered a biofortified crop to substitute the Cu feed additives for livestock production, beneficially alleviating Cu contamination in soils and reducing its input into agriculture systems. To assess this, alfalfa was grown in three similar soils with different Cu levels, i.e., 11, 439 and 779 mg kg⁻¹ for uncontaminated soil (A), moderately Cu-contaminated soil (B) and highly Cu-contaminated soil (C), respectively. EDDS (Ethylenediamine-N,N′-disuccinic acid) was applied to the soils seven days before the first cutting at four rates (0, 0.5, 2 and 5 mmol kg⁻¹) to enhance bioavailable Cu uptake. Alfalfa grew well in soils A and B but not in the highly Cu-contaminated soil. After applying EDDS, a significant biomass reduction of the first cutting shoot was only observed with 5 mmol kg⁻¹ EDDS in the highly Cu-contaminated soil, with a 45% (P < 0.05) decrease when compared to the control. Alfalfa grown in the three soils gradually wilted after the first cutting with 5 mmol kg⁻¹ EDDS, and Cu concentrations in the first cutting shoot were augmented strongly, by 250% (P < 0.05), 3500% (P < 0.05) and 6700% (P < 0.05) compared to the controls, respectively. Cu concentrations in alfalfa shoots were found to be higher in this study than in some fodder plants and further augmented in soils with higher Cu levels and with EDDS application. These findings suggest that alfalfa grown on clean soils or soils with up to 450 mg Cu kg⁻¹ (with appropriate EDDS dosages) has the potential to be considered as a partial Cu supplementation for livestock. This research laid the foundation for the integration between Cu-phytoextraction and Cu-biofortification for livestock.

Rice consumption is the major pathway for human methylmercury (MeHg) exposure in inland China, especially in mercury (Hg) contaminated regions. MeHg production, a microbially driven process, depends on both the chemical speciation of inorganic divalent mercury, Hg(II), that determines Hg bioavailability for methylation. Studies have shown that Hg(II) speciation in contaminated paddy soils is mostly controlled by natural organic matter and sulfide levels, which are typically thought to limit Hg mobility and bioavailability. Yet, high levels of MeHg are found in rice, calling for reconsideration of the nature of Hg species bioavailable to methylators in paddy soils. Here, we conducted incubation experiments using a multi-isotope tracer technique including ¹⁹⁸Hg(NO₃)₂, natural organic matter bond Hg(II) (NOM-¹⁹⁹Hg(II)), ferrous sulfide sorbed Hg(II) (≡FeS-²⁰⁰Hg(II)), and nanoparticulate mercuric sulfide (nano-²⁰²HgS), to investigate the relative importance of geochemically diverse yet relevant Hg(II) species on Hg methylation in paddy soils across a Hg concentration gradient. We show that methylation rates for all Hg(II) species tested decreased with increasing Hg concentrations, and that methylation rates using NOM-¹⁹⁹Hg(II) and nano-²⁰²HgS as substrates were similar or greater than rates obtained using the labile ¹⁹⁸Hg(NO₃)₂ substrate. ≡FeS-²⁰⁰Hg(II) yielded the lowest methylation rate in all sites, and thus the formation of FeS is likely a sink for labile ¹⁹⁸Hg(NO₃)₂ in sulfide-rich paddy soils. Moreover, the variability in the methylation data for a given site (1 to 5-fold variation depending on the Hg species) was smaller than what was observed across the Hg concentration gradient (10³–10⁴ fold variation between sites). These findings emphasize that at broad spatial scales, site-specific characteristics, such as microbial community structure, need to be taken into consideration, alongside the nature of the Hg substrate available for methylation, to determine net MeHg production. This study highlights the importance of developing site-specific strategies for remediating Hg pollution.

Freshwater ecosystems are the main source of water for sustaining life on earth, and the biodiversity they support is the main source of valuable goods and services for human populations. Despite growing recognition of the impairment of freshwater ecosystems by micropollutant contamination, different conceptual and methodological considerations can newly be addressed to improve our understanding of the ecological impact into these ecosystems. Here, we originally combined in situ ecotoxicology and community ecology concepts to unveil the mechanisms structuring macroinvertebrate communities along a regional contamination gradient. The novelty of our study lies in the use of an innovative biomonitoring approach (measurement of metal contents in caged crustaceans) allowing to quantify and compare on a regional scale the levels of bioavailable metal contamination to which stream communities are exposed. We were hence able to identify 23 streams presenting a significant gradient of bioavailable metal contamination within the same catchment area in the South West of France, from which we also obtained data on the composition of resident macroinvertebrate communities. Analyses of structural and functional integrity of communities revealed an unexpected decoupling between taxonomic and functional diversity of communities in response to bioavailable metal contamination. We show that despite the negative impact of bioavailable metal contamination exposure on taxonomic diversity (with an average species loss of 17% in contaminated streams), functional diversity is maintained through a process of non-random species replacement by functional redundant species at the regional scale. Such unanticipated findings call for a deeper characterization of metal-tolerant communities’ ability to cope with environmental variability in multi-stressed ecosystems.

Many organic materials have been used to decrease heavy-metal bioavailability in soil via in-situ remediation due to its high efficiency and easy operation; meanwhile, cheap materials have also been pursued to decrease the cost of remediation. Agricultural wastes exhibit their potential in remediation materials due to their low cost; however, raw agricultural wastes have a low ability to immobilize heavy metals in soil. Attempts have been made to modify agricultural wastes to improve the efficiency of heavy-metal passivation. In this study, novel agricultural waste-based materials, raw sugarcane bagasse (SB), citric acid modified (SSB) and citric-acid/Fe₃O₄ modified (MSB) sugarcane bagasse at 0.5% and 1% addition rates, were compared for their effectiveness in soil Cd passivation and Cd accumulations in pakchoi plants in a 30-day pot experiment. The addition of SB did not decrease soil bioavailable Cd effectively and slightly decreased Cd accumulation in plant roots and leaves. In comparison, SSB and MSB exhibited a great potential to decrease the transformation, translocation and accumulation of Cd with the decrease being greater at 1% than 0.5% rate in the soil-pakchoi system. For example, the addition of SSB and MSB at 0.5% decreased the concentration of Cd in leaves by 10%, and 16%, and at 1% decreased the concentration by 25% and 30%, respectively. High pH and abundant functional groups of three amendments played important roles in Cd immobilization. The enhanced microbial activities might also contribute to Cd passivation. However, plant growth was decreased in the amended treatments except SSB at 0.5% rate. The results suggest that citric-acid-modified sugarcane bagasse at addition rate of 0.5% has a potential to immobilize Cd in soil and decrease Cd accumulation in edible part of pakchoi effectively without decreasing vegetable growth.