For further understanding leaching characteristics of heavy metals in tailings and better immobilization on heavy metals against acid rain, batch experiments were conducted. The leaching results of Cu(II), Zn(II), Cd(II) and Mn(II) can be well fit by second-order kinetics equation, and Pb(II) can be well fit by two-constant equation. The leaching intensity of heavy metals in tailings was ranged as: Mn(II)> Cu(II)> Cd(II)> Zn(II)> Pb(II). Triethylenetetramine functioned montmorillonite (TETA-Mt) was successfully synthesized and can obtain simultaneous immobilization effect compared with Mt and TETA, and immobilization rates on Cu(II), Cd(II), Mn(II) and Zn(II) can reach above 90%, the immobilization rate on Pb(II) can reach more than 75%. The mechanisms for efficient immobilization of heavy metals on TETA-Mt included buffering and adsorption abilities. The mechanism for TETA-Mt adsorption of heavy metals included physical absorption, chelation and chemical sedimentation. The results showed that TETA-Mt can be applied to effective immobilization of heavy metals in tailings and efficient remediation of acid mine drainage (AMD) in acid rain area.

For decades, a vast array of innovative biosorbents have been found out and used in the removal of heavy metals, including bacteria, algae and fungi, etc. Although extensive biological species have been tried as a biosorbent for heavy metals removal, for removal efficiency or economy efficiency limited, it has failed to make a substantial breakthrough in practical application. Thus, many improved methods based on biosorbents emerged. In this review, based on the literature and our research results, we highlight three types of novel methods for biosorbents removal of heavy metals: chemical modification of biosorbents; biomass and chemical materials combination; multiple biomass complex systems. We mainly focus on their configuration, biosorption performance, their creation method, regeneration/reuse, their application and development in the future. Through the comparative analysis of various methods, we think that intracellular autogenous nanomaterials may open up another window in biosorption of heavy metals area. At the same time, the combination of various treatment methods will be the development tendency of heavy metal pollution treatment in the future.

China is the largest rice producer and consumer in the world, and mercury (Hg) levels, particularly methylmercury (MeHg), in rice and health exposure risks are public concerns. Total Hg (THg) and MeHg levels in 767 (domestic = 709 and abroad = 58) Chinese commercial rice were investigated to evaluate Hg pollution level, dietary exposures and risks of IHg and MeHg. The mean rice THg and MeHg levels were 3.97 ± 2.33 μg/kg and 1.37 ± 1.18 μg/kg, respectively. The highest daily intake of MeHg and IHg were obtained in younger groups, accounted for 6% of the reference dose-0.1 μg/kg bw/day for MeHg, 0.3% of the provisional tolerance week intake-0.571 μg/kg bw/day for IHg. Residents in Central China and Southern China meet the highest rice Hg exposure, which were more than 7 times of those in Northwest China. Lower concentrations than earlier studies were observed along the implementations of strict policies since 2007. This may indicate that a declining temporal trend of Hg in Chinese grown rice and associated exposures could be obtained with the implementations of strict policies. Though there exist Hg pollution in commercial rice, Hg levels in Chinese commercial rice is generally safe compared with Hg polluted sites. Populations dwelling in China have relatively a quite low and safe MeHg and IHg exposure via the intake of commercial rice. Strict policies contributed to the decrease in THg and MeHg levels in Chinese-grown rice. More attention should be paid to younger groups.

Occurrence, behavior, and fate of 11 OPEs in multiple environmental matrices, which include air, rainwater, dustfall, paddy soil, irrigation water, and rice plants from nine subtropical paddy fields of South China, were investigated. The total concentrations of 11 OPEs (∑₁₁OPEs) in all matrices are generally higher in the urban areas than in rural areas, and they are higher in summer than in fall. However, both urban and rural areas showed a similar composition profile of OPEs, indicating that the OPEs come from similar sources in the two areas. Except for irrigation water, significant positive correlations of ∑₁₁OPEs were observed between air and the other five matrices. The exchange and partition of OPEs among air, soil, and water demonstrate that most of OPEs were transferred from air into water and soil, and from water into soil. Thus, the air may be an important source of OPEs in the paddy fields, and the soil may act as a principal environmental reservoir of OPEs. The contribution of air-soil exchange, atmospheric deposition (rainwater plus dustfall), and irrigation water to the total input fluxes of OPEs (2100 ± 980 ng/m²/day) reached an average of 19%, 38% (37% + 1%), and 43%, respectively. The water (rainwater plus irrigation water) is the primary medium transferring the OPEs into the paddy fields and contributed to the input flux by 80%. Output flux of OPEs via mature rice plants was about 220 μg/m², 2% of which were presented in rice, and the remaining 98% may be re-released into the environment through the pathway of straw turnover or burning. Dietary exposure via rice was much higher than inhalation exposure, dust ingestion, and dermal absorption via dust. However, no data shows that all of the intakes via the four exposure pathways could cause the risks to human health at present.

Plastic polymers such as polyvinyl chloride (PVC) may contain chemical additives, such as lead (Pb), that are leachable in aqueous solution. The fragmentation into microplastics (MPs) of plastics such as PVC may facilitate desorption of chemical additives and increase exposure of aquatic animals. In this study, the role of chemical additives in the aqueous toxicity of PVC, high-density polyethylene (HDPE) and polyethylene terephthalate (PET) MPs were investigated in early-life stage zebrafish (Danio rerio) by assessment of changes in expression of biomarkers. Exposure of zebrafish larvae to PVC for 24 h increased expression of metallothionein 2 (mt2), a metal-binding protein, but no changes in expression of biomarkers of estrogenic (vtg1) or organic (cyp1a) contaminants were observed. HDPE and PET caused no changes in expression of any biomarkers. A filtered leachate of the PVC also caused a significant increase in expression of mt2 and indicated that a desorbed metal additive likely elicited the response in zebrafish. Metal release was confirmed by acid-washing the MPs which mitigated the response in mt2. Metal analysis showed Pb leached from PVC into water during exposures; at 500 mg PVC L⁻¹ in water, 84.3 ± 8.7 μg Pb L⁻¹ was measured after 24 h. Exposure to a Pb-salt at this concentration caused a comparable mt2 increase in zebrafish as observed in exposures to PVC. These data indicated that PVC MPs elicited a response in zebrafish but the effect was indirect and mediated through desorption of Pb from PVC into the exposure water. Data also indicated that PVC MPs may act as longer-term environmental reservoirs of Pb for exposure of aquatic animals; the Pb leached from PVC in 24 h in freshwater equated to 2.52% of total Pb in MPs leachable by the acid-wash. Studies of MPs should consider the potential role of chemical additives in toxicity observed.

A self-assembly method was adopted to synthesize loading architecture of ZnO/g-C₃N₄ heterojunction composites by hybridization of g-C₃N₄ nanosheets and ZnO nanoparticles utilizing a refluxing method at a low temperature. More importantly, we provided a novel route to regulate the π-π restacking thickness of the g-C₃N₄ nanosheets among ZnO/g-C₃N₄ composites by the controlling the refluxing time in the ethanol solution, which can optimize the surface hybrid structure, optical response and photocatalytic activity. Among all of samples, ZnO/g-C₃N₄ composites with a refluxing 12 h showed the enhancement of photocatalytic activity. The enhanced visible light photocatalytic activity of ZCN-12 composites can be ascribed to the synergistic effects of the construction of hybrid structures, reduction of structural defects of g-C₃N₄ nanosheets and suitable π-π restacking g-C₃N₄ nanosheets loading thickness.

Among the seafood used globally, shellfish consumption is in great demand. The utilization of these shellfish such as prawn/shrimp has opened a new market for the utilization of the shellfish wastes. Considering the trends on the production of wealth from wastes, shrimp shell wastes seem an important resource for the generation of high value products when processed on the principles of a biorefinery. In recent years, various chemical strategies have been tried to valorize the shrimp shell wastes, which required harsh chemicals such as HCl and NaOH for demineralization (DM) and deproteination (DP) of the shrimp wastes. Disposal of chemicals by the chitin and chitosan industries into the aquatic bodies pose harm to the aquatic flora and fauna. Thus, there has been intensive efforts to develop safe and sustainable technologies for the management of shrimp shell wastes. This review provides an insight about environmentally-friendly methods along with biological methods to valorize the shrimp waste compared to the strategies employing concentrated chemicals. The main objective of this review article is to explain the utilization shrimp shell wastes in a productive manner such that it would be offer environment and economic sustainability. The application of valorized by-products developed from the shrimp shell wastes and physical methods to improve the pretreatment process of shellfish wastes for valorization are also highlighted in this paper.

Invasive plants readily invade metal-contaminated areas. The hyperaccumulation of toxic heavy metals is not an uncommon feature among plant species. Although several hypotheses were proposed to explain this phenomenon, it is currently unclear how hyperaccumulation may benefit plants. The invasive Crofton weed (Ageratina adenophora) is a known hyperaccumulator of chromium and lead. We previously found that the species can also hyperaccumulate cadmium. The role of phytoaccumulation in defense to pathogen attack is unclear. We inoculated A. adenophora plants with a common generalist pathogen (Rhizoctonia solani) to test its resistance under cadmium treatment. We found evidence that cadmium hyperaccumulation reduced pathogen infection in A. adenophora. Our findings indicate elemental defense is highly cost efficient for hyperaccumulators inhabiting metal-contaminated sites, where plants were only modestly affected by cadmium. The reduction in pathogen damage conferred by cadmium was relatively high, particularly under lower cadmium levels. However, the benefits at higher levels may be capped. Elemental defense may be a key mechanism for plant invasion into polluted sites, especially in regions with widespread industrial activity. Our study highlights the importance of testing different metal concentrations when testing plant resistance and the importance of considering enemy attack when selecting plants for phytoremediation.

Bioaccessibility extractions are increasingly applied to measure the fraction of pollutants in soil, sediment and biochar, which can be released under environmentally or physiologically relevant conditions. However, the bioaccessibility of hydrophobic organic chemicals (HOCs) can be markedly underestimated when the sink capacity of the extraction medium is insufficient. Here, a novel method called “Membrane Enhanced Bioaccessibility Extraction” (MEBE) applies a semipermeable membrane to physically separate an aqueous desorption medium that sets the desorption conditions from an organic medium that serves as acceptor phase and infinite sink. The specific MEBE method combines HOC (1) desorption into a 2-hydroxypropyl-β-cyclodextrin solution, (2) transfer through a low-density polyethylene (LDPE) membrane and (3) release into ethanol, serving as analytical acceptor phase. The surface to volume ratio within the LDPE membrane is maximized for rapid depletion of desorbed molecules, and the capacity ratio between the acceptor phase and the environmental sample is maximized to achieve infinite sink conditions. Several experiments were conducted for developing, optimizing and pre-testing the method, which was then applied to four soils polluted with polycyclic aromatic hydrocarbons. MEBE minimized sample preparation and yielded a solvent extract readily analyzable by HPLC. This study focused on the proof-of-principle testing of the MEBE concept, which now can be extended and applied to other samples and desorption media.

Recently, environmental risk and toxicity of neonicotinoid insecticides to honey bees have attracted extensive attention. However, toxicological understanding of neonicotinoid insecticides on gut microbiota is limited. In the present study, honey bees (Apis mellifera L.) were exposed to a series of nitenpyram for 14 days. Results indicated that nitenpyram exposure decreased the survival and food consumption of honey bees. Furthermore, 16S rRNA gene sequencing revealed that nitenpyram caused significant alterations in the relative abundance of several key gut microbiotas, which contribute to metabolic homeostasis and immunity. Using high-throughput RNA-Seq transcriptomic analysis, we identified a total of 526 differentially expressed genes (DEGs) that were significantly altered between nitenpyram-treated and control honey bee gut, including several genes related to metabolic, detoxification and immunity. In addition, Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analysis showed nitenpyram affected several biological processes, of which most were related to metabolism. Collectively, our study demonstrates that the dysbiosis of gut microbiota in honey bee caused by nitenpyram may influence metabolic homeostasis and immunity of bees, and further decrease food consumption and survival of bees.