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.

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 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.

Little information is available about effect of particle size and crystal structure of nTiO₂ on their trophic transfer. In this study, 5 nm anatase, 10 nm anatase, 100 nm anatase, 20 nm P25 (80% anatase and 20% rutile), and 25 nm rutile nTiO₂ were selected to investigate the effects of size and crystal structure on the toxicity, bioconcentration, and trophic transfer of nTiO₂ to algae and daphnia. In the exposed daphnids, metabolic pathways affected by nTiO₂ and nTiO₂-exposed algae (nTiO₂-algae) were also explored. The 96 h IC₅₀ values of algae and the 48 h LC₅₀ values of daphnia were 10.3, 18.9, 43.9, 33.6, 65.4 mg/L and 10.5, 13.2, 37.0, 28.4, 60.7 mg/L, respectively, after exposed to nTiO₂-5A, nTiO₂-10A, nTiO₂-100A, nTiO₂-P25, and nTiO₂-25R, respectively. The bioconcentration factors (BCFs) for 0.1, 1, and 10 mg/L nTiO₂ in daphnia ranged from 21,220 L/kg to 145,350 L/kg. The nTiO₂ biomagnification factors (BMFs) of daphnia fed with 1 and 10 mg/L nTiO₂-exposed algae were consistently greater than 1.0 (5.7–122). The results show that the acute toxicity, BCF, and BMF all decreased with increasing size or rutile content of nTiO₂. All types of nTiO₂ were largely accumulated in the daphnia gut and were not completely depurated within 24 h. At the molecular level, 22 Kyoto Encyclopedia of Genes and Genomes (KEGG) metabolic pathways of daphnia were impacted by the nTiO₂ and nTiO₂-algae treatments, including glutathione metabolism, aminoacyl-tRNA biosynthesis, among others. Six and four KEGG metabolic pathways were significantly disturbed in daphnids exposed to nTiO₂ and nTiO₂-algae, respectively, indicating the presence of algae partially alleviated the negative impact of nTiO₂ on metabolism. These findings increase understanding of the impacts of physicochemical properties of nTiO₂ on the food chain from molecular scale to that of the whole organism, and provide new insight into the ecological effect of nanomaterials.

Perfluorooctanoic acid (PFOA) toxicity is of considerable concern due to its wide application, environmental persistence, and bioaccumulation. In the current study, we used a scaffold-free three-dimensional (3D) spheroid model of mouse liver cells (AML12) to explore the toxicity of PFOA and emerging alternatives (HFPO-DA and PFO4DA). Comparing the short-term (24 and 72 h treatment) toxicity of PFOA between conventional 2D monolayer cells and 3D spheroids, we found that spheroids had higher EC₅₀ values and lower ROS levels after treatment, indicating their greater resistance to PFOA. Cell viability (i.e., adenosine triphosphate (ATP) content and lactate dehydrogenase (LDH) leakage) and liver-specific function (i.e., albumin secretion) were stable in spheroids through 28 day of culture. However, under 100 and 200 μM-PFOA treatment for 28 day, ROS levels, LDH leakage, and caspase3/7 activity all increased significantly. As a sensitive parameter, ROS showed a significant increase at 21 day, even in the 50 μM-PFOA group. Consistent with the elevation of ROS and caspase3/7, the expressions of oxidative stress- and apoptosis-related genes, including Gsta2, Nqo1, Ho-1, caspase3, p53, and p21, were induced in dose- and time-dependent manners after PFOA exposure. The peroxisome proliferator-activated receptor alpha (PPARα) pathway was also activated after treatment, with significant induction of its target genes, Fabp4 and Scd1. Similar to PFOA, both HFPO-DA and PFO4DA activated the PPARα pathway, induced ROS levels, and initiated cell damage, though at a relatively lower extent than that of PFOA. Our results imply that the 3D spheroid model is a valuable tool in chronic toxicological studies.

The trophic balance of freshwater aquaculture activities has traditionally been monitored by chemical analysis of water; however, the parameters measured are usually characterized by high temporal variability. Aquatic mosses can be used as biomonitors as they integrate both continuous and episodic contamination events. Here we report, for the first time, a method for monitoring N enrichment in the surroundings of fish farms by measuring the N content and isotopic signal (δ15N) of transplanted living and devitalized specimens of the aquatic moss Fontinalis antipyretica. For this purpose, moss samples (“moss bags”) were exposed at increasing distances (10, 100, 300 and 1000 m) up- and downstream of the effluent discharge points of four trout farms, for 10 and 30 days. The low natural (background) variability in δ15N in upstream samples enabled detection of outlier values, caused by aquaculture discharges, at distances of 10 and 100 m downstream, especially in devitalized moss and after 10 days of exposure. However, the unexpectedly low N contents of moss samples exposed close to the discharge points complicates interpretation of the high levels of N forms detected by conventional physicochemical analysis of water. Although the mechanisms that modify N parameters in moss tissues were not clear, measurement of the isotopic signal δ15N in devitalized moss exposed for 10 days proved useful for monitoring the N pollution associated with intensive freshwater aquaculture.

Hexabromocyclododecanes (HBCDDs) are common chemical additives in expanded polystyrene foam (EPS). To evaluate the bioaccumulation potential of endogenous HBCDDs in EPS microparticles by earthworms, two ecologically different species of earthworms (Eisenia fetida and Metaphire guillelmi) were exposed to soil added with EPS microparticles of different particle sizes (EPS2000, 830–2000 μm and EPS830, <830 μm). To clarify the accumulation mechanisms, leaching experiments using EPS microparticles in different solutions were conducted. After exposure to EPS microparticles-amended soils (S-EPS) for 28 d, the total concentrations of HBCDDs reached 307–371 ng g−1 dw in E. fetida and 90–133 ng g−1 dw in M. guillelmi, which were higher than those in earthworms exposed to the soil that was artificially contaminated with a similar level of HBCDDs directly (ACS). The accumulation of HBCDDs in earthworms was significantly influenced by EPS microparticles' size and earthworms' species. The total concentrations of HBCDDs in earthworms' cast were significantly higher than the theoretical concentration of HBCDDs in S-EPS, which suggested that EPS microparticles can be ingested by earthworms. The release rate of HBCDDs from EPS5000 (2000–5000 μm) into water-based solutions (<1%) after a 3.5-h incubation was far lower than that into earthworm digestive fluid (7%). These results illustrated that the ingestion of EPS microparticles and consequent solubilization of HBCDDs by digestive fluid play an important role in the accumulation of HBCDDs contained in EPS microparticles in earthworms. After a 28-d incubation with the soil solution, 4.9% of the HBCDDs was accumulatively leached from the EPS5000, which indicated that HBCDDs can be released from EPS microparticles to soil environment, and then accumulated by earthworms. Moreover, similar to those exposed to ACS, the diastereoisomer- and enantiomer-specific accumulation of HBCDDs in earthworms occurred when exposed to S-EPS. This study provides more evidence for the risk of microplastics to the soil ecosystem.