Agricultural soil is one of the main sink for both heavy metals and nanomaterials (NMs). Whether NMs can impact heavy metals uptake or bioaccumulation in plants is unknown. Here, cucumber plants were cultivated in a multi-heavy metals contaminated soil amended with four types of NMs (SiO2, TiO2, ZnS and MoS2) separately for four weeks. Physiological and biochemical parameters were determined to investigate the impact of NMs on plant growth. Inductively coupled plasma mass spectrometry was employed to determine the metal content in plants. Results showed that none of the tested NMs impacted plants biomass, but all the NMs showed different degrees of reduction in heavy metals bioaccumulation in plant roots, stems and leaves. However, four NMs showed different degrees of reduction in macro and micro nutrients uptake. MoS2 decreased the bioaccumulation of heavy metals (As, Cd, Cr, Cu, Ni, Al, Ti and Pb) for 36.4–60.6% and nutrients (Mg, Fe, K, Si and Mn) for 40.1%–50.1% in roots. Exposure to MoS2 NMs also significantly increased 23.4% of Si in leaves, 205.6% and 83.9% of Mo in roots and stems, respectively. In general, the results of this study showed promising potential for NMs to reduce uptake of heavy metals in crop plants, especially MoS2 NMs. However, the negative impacts of perturbing nutrients uptake should be paid attention as well.

Aryl phosphorus-containing flame retardants (aryl-PFRs) have been frequently detected with increasingly used worldwide as one of alternatives for brominated flame retardants. However, information on their adverse effects on human health and ecosystem is insufficient, with limited study on their molecular mode of action in vitro. In this study, the cytotoxicity, DNA damage, mitochondrial impairment and the involved molecular mechanisms of certain frequently detectable aryl-PFRs, including 2-ethylhexyldiphenyl phosphate (EHDPP), methyl diphenyl phosphate (MDPP), bisphenol-A bis (diphenyl phosphate) (BDP), isodecyl diphenyl phosphate (IDPP), cresyl diphenyl phosphate (CDP) and the structurally similar and widely used organophosphorus pesticide chlorpyrifos (CPF), were evaluated in A549 cells using high-content screening (HCS) system. Aryl-PFRs showed different lethal concentration 50 (LC50) values ranging from 97.94 to 546.85 μM in A549 cells using CCK-8 assay. EHDPP, IDPP, CDP, MDPP and CPF demonstrated an ability to induce DNA damage, evidenced by increased DNA content and S phase-reducing cell cycle arrest effect using fluorophore dye cocktail assay. Additionally, the selected aryl-PFRs induced mitochondrial impairment by the increasing mitochondrial mass and decreasing mitochondrial membrane potential. Moreover, BDP, MDPP, and CDP, which contain short alkyl chains showed their potential oxidative stress with intracellular ROS and mitochondrial superoxide overproduction from an initially relatively low concentration. Additionally, based on the promotion of firefly luminescence in p53-transfected A549 cells, p53 activation was found to be involved in aryl-PFRs-induced DNA damage. Further real-time PCR results showed that all selected aryl-PFRs triggered p53/p21/gadd45β-, and p53/p21/mdm2-mediated cell cycle pathways, and the p53/bax mediated apoptosis pathway to induce DNA damage and cytotoxic effects. These results suggest that aryl-PFRs (e.g., BDP, MDPP, CDP) cause oxidative stress-mediated DNA damage and mitochondrial impairment, and p53-dependent pathway was involved in the aryl-PFRs-induced DNA damage and cell cycle arrest. In conclusion, this study improves the understanding of PFRs-induced adverse outcomes and the involved molecular mechanism.

Ninety-eight soil samples were collected from farmland soils from Beijing-Tianjin-Hebei core area, Northern China, where agricultural lands were subjected to contamination from intense urban and industrial activities. Twelve organophosphates flame retardants (OPFRs) were analyzed with total soil concentrations ranging from 0.543 μg/kg to 54.9 μg/kg. Chlorinated OPFRs were dominating at mean level of 3.64 μg/kg and Tris(2-chloroisopropyl) phosphate contributed the most (mean 3.36 ± 5.61 μg/kg, 98.0%). Tris(2-ethylhexyl) phosphate was fully detected at levels of 0.041–1.95 μg/kg. Generally, tris(2-butoxyethyl) phosphate and triphenyl phosphate contributed the most to alkyl- (53.6%) and aryl-OPFRs (54.3%), respectively. The levels of ∑OPFRs close to the core urban areas were significantly higher than those from background sites. The occurrence and fate of OPFRs in soil were significantly associated with total organic carbon content and mostly with fine soil particles (<0.005 mm), and a transfer potential from the atmosphere was predicted with logKSA values. Comparable soil levels with poly brominated diphenyl ethers s in other studies suggested that the contamination of OPFRs occurred in farmland soil with an increasing trend but currently showed no significant environmental risk based on risk quotient estimation (<1). This investigation warrants further study on behaviors of OPFRs in a soil system and a continual monitoring for their risk assessment.

As a new type of emerging pollutant in the ocean, microplastics have received global attention in recent years. Considering the increasing amount of human activities around the South China Sea, it is important to determine the current status of microplastic pollution in this region. In this study, we analyzed the abundance and distribution of microplastics at Zhubi Reef in the South China Sea. Microplastic abundance ranged from 1,400 to 8,100 items/m3 of surface water, which was much higher than the values reported from other ocean areas. About 80% of the microplastics were smaller than 0.5 mm in size. Fibers and pellets comprised the most common microplastic types. The dominant microplastics were transparent or blue in color. The main polymer types were polypropylene (25%) and polyamide (18%). In general, our results revealed Zhubi Reef was contaminated with microplastics, which were likely derived from the intensive fisheries in the area and emissions from coastal cities. This study also provides baseline data that are useful for additional studies of microplastics in the South China Sea.

There is an increasing awareness of the threats posed by the worldwide presence of microplastics (MPs) in the environment. Due to their high persistence, MPs will accumulate in the environment and their quantities tend to increase with time. MPs end up in environments where often also chemical contaminants are present. Since the early 2000s, the number of studies on the sorption of chemicals to plastic particles has exponentially increased. The objective of this study was to critically review the literature to identify the most important factors affecting the sorption of chemical contaminants to MPs. These factors include the physicochemical properties of both the MPs and the chemical contaminants as well as environmental characteristics. A limited number of studies on soil together with an increased notion of the importance of this compartment as a final sink for MPs was observed. Therefore, we assessed the distribution of model chemicals (two PCBs and phenanthrene) in the soil compartment in the presence of MPs using a mass balance model. The results showed a high variation among chemicals and microplastic types. Overall, a higher partitioning to MPs of chemical contaminants in soil is expected in comparison to aquatic environments. As sorption to a large extent determines bioavailability, the effects of combined exposure to chemicals and MPs on the toxicity and bioaccumulation in biota are discussed. Finally, some considerations regarding sorption and toxicity studies using MPs are given.

This study aimed to evaluate and qualify field-based potential risks of seven neonicotinoid and phenylpyrazole (fipronil) insecticides on aquatic invertebrates, including estuary-resident marine crustaceans. One hundred and ninety-three estuarine water samples, with salinity ranging from 0.5 to 32.7, were collected from four estuarine sites in the Seto Inland Sea of Japan, in 2015–2018 and the insecticide levels were measured. Five neonicotinoid and fipronil insecticides were successfully identified, and their occurrence varied temporally. Marine crustaceans were simultaneously harvested every month from one of the estuarine water sampling sites in 2015–2017. Three predominant crustacean species, kuruma prawn (Penaeus japonicus), sand shrimp (Crangon uritai), and mysid (Neomysis awatschensis), were captured and their seasonal presence was species independent. A 96-h laboratory toxicity study with the insecticides using kuruma prawn, sand shrimp, and a surrogate mysid species (Americamysis bahia) indicated that fipronil exerted the highest toxicity to the three crustaceans. Using both toxicity data and insecticide occurrence in estuarine water (salinity ≥10, n = 169), the potential risks on the three marine crustaceans were quantified by calculating the proportion of mixture toxicity effects (Pₘᵢₓ). The Pₘᵢₓ of seven neonicotinoids on the crustaceans was less than 0.8%, which is likely to be too low to indicate adverse effects caused by the insecticides. However, short temporal detection of fipronil (exclusively in June and July) significantly affected the Pₘᵢₓ, which presented the maximal Pₘᵢₓ values of 21%, 3.4%, and 72% for kuruma prawn, sand shrimp, and mysid, respectively, indicating a significant effect on the organisms. As for estuarine water (salinity <10), some water samples contained imidacloprid and fipronil exceeding the freshwater benchmarks for aquatic invertebrates. The present study provides novel insights into the seasonally varying risks of insecticides to estuarine crustaceans and highlights the importance of considering whether ecological risk periods coincide with crustacean presence.

Polycyclic aromatic hydrocarbons containing at least 24 carbon atoms (≥C₂₄-PAH) are often associated with pyrogenic processes such as combustion of fuel, wood or coal, and occur in the environment in diesel particulate matter, black carbon and coal tar. Some of the ≥C₂₄-PAH, particularly the group of dibenzopyrenes (five isomers, six aromatic rings) are known to show high mutagenic and carcinogenic activita.Gas chromatography – mass spectrometry is a well-established method for the analysis of lower molecular weight PAH but is not optimally suited for the analysis of ≥C₂₄-PAH due to their low vapor pressures. Also, hundreds of ≥C₂₄-PAH isomers are possible but only a few compounds are commercially available as reference standards. Therefore, in this study, a combination of multidimensional liquid chromatography, UV–Vis diode array detection, PAH selective and highly sensitive atmospheric pressure laser ionization – mass spectrometry is used to detect and unequivocally identify PAH. For identification of PAH in two bituminous coals and one petrol coke sample, unique and compound specific UV–Vis spectra were acquired. It was possible to identify ten compounds (naphtho[1,2,3,4-ghi]perylene, dibenzo[b,ghi]perylene, dibenzo[e,ghi]perylene, dibenzo[cd,lm]perylene, benzo[a]coronene, phenanthrol[5,4,3,2-abcde]perylene, benzo[ghi]naphtho[8,1,2-bcd]perylene, benzo[pqr]naphtho[8,1,2-bcd]perylene, naphtho[8,1,2-abc]coronene and tribenzo[e,ghi,k]perylene) by comparison of acquired spectra with spectra from literature. Additionally, it was possible to detect similar distribution patterns in different samples and signals related to alkylated naphthopyrenes, naphthofluoranthenes or dibenzopyrenes. Subsequent effect-directed analysis of a bituminous coal sample using the microEROD (ethoxyresorufin-O-deethylase) bioassay showed high suitability and revealed lower EROD induction for the ≥C₂₄-PAH (TEQ range 0.67–10.07 ng/g) than for the allover < C₂₄-PAH containing fraction (TEQ 84.00 ng/g). Nevertheless, the toxicity of ≥C₂₄-PAH has a significant impact compared with <C₂₄-PAH and must be considered for risk assessment. The LC-DAD-APLI-MS method, presented in this study, is a powerful tool for the unequivocal identification of these ≥ C₂₄-PAH.

The intensive use of antibiotics results in the continuous release of antibiotics into wastewater treatment systems, leading to the spread of antibiotic resistance. Nitrifying system is reported to be capable of degrading antibiotics, yet few studies have systematically investigated the inherent correlation among ammonium oxidation rate, antibiotic degradation and genetic expression of nitrifying bacteria along the process. This study selected a widely used sulfonamide antibiotic, sulfadiazine (SDZ), to investigate its biodegradation potential by an enriched nitrifying culture and the response of nitrifying bacteria against antibiotic exposure. Our results demonstrated that SDZ degradation was mainly contributed by cometabolism of ammonia-oxidizing bacteria (AOB), rather than biomass adsorption. The quantitative reverse transcription PCR (RT-qPCR) analysis revealed that the expression level of amoA gene was down-regulated due to the SDZ exposure. In addition, the degradation products of SDZ did not exhibit inhibitory effect on Escherichia coli K12, indicating the biotoxicity of SDZ could be mitigated after biodegradation. The findings offer insights regarding the biodegradation process of sulfonamide antibiotics via cometabolism by AOB.

This study critically evaluated the native pygmy mussel (Xenostrobus securis) as a biomonitor of the key metal contaminants in the highly urbanised Sydney Estuary, south-eastern Australia. Five metals (Cd, Cr, Cu, Pb and Zn) were identified as key contaminants, based on their enrichment factors (EFs) in the whole soft tissue of X. securis at 24 sampling sites, relative to baseline values from near-pristine reference sites in the adjacent Hawkesbury Estuary. Inverse relationships established between mussel size (dry tissue weight) and tissue concentrations of each metal were used to reduce variance (by 4-fold) among individuals; gender and reproductive status had no significant (p > 0.05) effect on tissue metal concentrations in X. securis. Metal concentrations in three environmental matrices – filtered (<0.2 μm) surface water (operationally defined as the dissolved/colloidal phase), suspended particulate matter (SPM; >0.2 μm) and surface sediment (<2 mm particle size), which are most relevant to a suspension-feeding estuarine bivalve, were also determined at each sampling site. For each of the five metals, highly significant (p < 0.01) positive linear regressions were established between metal EFs for mussel tissue and each environmental matrix. Metals in surface sediment and SPM explained 80–91% and 81–90%, respectively, of the variability in metal concentrations in mussel tissue, with filtered surface water explaining 74–86%. Cumulative mussel tissue EFs of all five metals, when regressed against each environmental matrix, showed that surface sediment concentrations explained 93% of their variability between sites, SPM 94% and filtered surface water 87–90%. Hence, X. securis very closely reflects the metal concentrations in its aquatic environment. The study provides a quality-assured benchmark of key metal contamination in the Sydney Estuary, and an appropriate methodology that may be used to discern any changes in metal contaminant status using X. securis.

Incineration has overtaken landfilling as the most important option for disposal of the increasing volumes of municipal solid waste (MSW) generated in China. Accordingly, disposal of the incineration fly ash, which is enriched with a range of heavy metals, has become a key challenge for the industry. This review analyzes the temporal and spatial trends in the distributions of As, Cd, Cr, Cu, Ni, Pb, Zn, and Hg in MSW incineration fly ash between 2003 and 2017, and estimates the inventories of heavy metals associated with the fly ash and the average levels of heavy metals in Chinese MSW based on their mass flow during MSW incineration. It was estimated that MSW incinerators in China released approximately 1.12 × 10², 2.96 × 10³, 1.82 × 10², 3.64 × 10⁴, 1.00 × 10², 7.32 × 10³, 2.42 × 10², and 1.47 × 10¹ tonnes of Cd, Pb, Cr, Zn, Ni, Cu, As, and Hg, respectively, with the fly ash in 2016. Due to the much greater fly ash generation rate, the incinerators based on circulating fluidized bed combustor (CFBC) technology released more heavy metals during incineration of MSW compared to those based on grate furnace combustor (GFC) technology. Results of mass-flow modeling indicate that the geometric mean contents of Cd, Pb, Cr, Zn, Ni, Cu, As, and Hg in Chinese MSW were 3.0, 109, 101, 877, 34, 241, 21, and 1.7 mg/kg, respectively, which are comparable to those in the MSW from other countries. To protect the environment from the significant potential ecological risk posed by heavy metals in the mismanaged fly ash, strict regulation enforcement and compliance monitoring are necessary to reduce the heavy metal pollution brought by improper disposal of MSW incineration fly ash, and more research and development efforts on advanced technologies for stabilization of heavy metals in fly ash and its environmentally sound reuse can help mitigate its environmental risk.