Cropland contamination by toxic trace metal (loid)s (TTMs) has attracted increasing attention due to the serious consequential threat to crop quality and human health. Mitigation of plant TTM stress by silica amendment has been proposed recently. However, the relationship between the siliceous structure of phytoliths and TTMs in plants, and the environmental implications of phytolith-occluded trace metal (loid)s (PhytTMs) remain unclear. This study assessed the accumulation of five metal (loid)s, including lead (Pb), zinc (Zn), cadmium (Cd), copper (Cu) and arsenic (As), in the organic tissues and phytoliths of wheat grown in a mixed-TTM contaminated soil under both lightly and heavily contaminated conditions. The results show that the concentrations of plant TTMs and PhytTMs were significantly (p < 0.05) positively correlated, and higher in heavily contaminated wheats than those in lightly contaminated ones. The bio-enrichment factors between phytoliths and organic tissues were higher for As (1.83), Pb (0.27) and Zn (0.30) than for Cd (0.03) and Cu (0.14), implying that As, Pb and Zn were more readily co-precipitated with silicon (Si) in phytolith structures than Cd and Cu. Network analysis of the relationship between soil and plant elements with PhytTMs showed that severe contamination could impact the homeostasis of elements in plants by altering the translocation of TTMs between soils, plants, and phytoliths. The accumulation of TTMs in phytoliths was affected by the capacity of Si deposition in tissues and chelation of TTMs with silica, which could impact the role of PhytTMs in global biogeochemical TTM cycles.

The most prominent source of Cu contamination in soils is metal mining and processing, partly since the Middle Age. However, coal mining and combustion can also cause (some) Cu contamination. We studied the distribution of Cu concentrations and isotope ratios in soils of the Huaibei coal mining area. The contribution of the coal mining and combustion to total Cu concentrations in soil was determined with a two-end-member mixing model based on the distinct δ⁶⁵Cu values of the Cu emitted from coal mining and combustion and in native soil. The mean Cu concentration of 75 mg kg⁻¹ exceeded the local soil background value (round to 22.13 mg kg⁻¹). The similar δ⁶⁵Cu value of grass near the coal mining and combustion operation as in gangue and flying ash indicated a superficial Cu contamination. Mining input was the dominant source of Cu in the contaminated soils, contributing up to 95% and on average 72% of the total Cu in the topsoils. The mining-derived Cu was leached to a depth of 65 cm, where still 29% of the Cu could be attributed to the mining emissions. Grasses showed lower δ⁶⁵Cu values than the topsoils, because of the preferential uptake of light Cu isotopes. However, the Δ⁶⁵Cugᵣₐₛₛ₋ₛₒᵢₗ was lower in the contaminated than the uncontaminated area because of superficial adsorption of isotopically heavy Cu from the mining emissions. Overall, in this study the distinct δ⁶⁵Cu values of the mining-derived Cu emissions and the native soil allowed for the quantification of the mining-derived Cu and had already reached the subsoil and contaminated the grass by superficial adsorption in only 60 years of mining operation.

The properties and metal-binding abilities of dissolved organic matter (DOM) rely on its molecular weight (MW) structure. In this study, the spatial differences of DOM in compositions, MW structures, and binding mechanisms with copper (Cu²⁺) in Dongping Lake were investigated by applying excitation-emission matrix combining parallel factor analysis (EEM-PARAFAC), synchronous fluorescence (SF) spectra, two-dimensional correlation spectra (2D-COS), and Fourier transform infrared (FTIR) spectra. The EDOM for the entrance of the Dawen River and PDOM for the macrophyte-dominated region were divided from DOM of Dongping Lake based on hierarchical clustering analysis (HCA) and principal component analysis (PCA) and were size-fractioned into MW < 500 kDa and <100 kDa fractions. According to EEM-PARAFAC, Dongping Lake was dominated by tryptophan-like substances with MW < 500 kDa. The concentration of PDOM was higher than that of EDOM (p < 0.05). 2D-COS showed that protein-like components preceded humic-like components binding to Cu²⁺ regardless of sample type (215 nm > 285 nm > 310–360 nm). The Cu²⁺ binding capacity of DOM exhibited specific differences in space, components, and molecular weights. The humic-like component 1 (C1) and tryptophan-like component 4 (C4) of PDOM showed stronger binding abilities than those of EDOM. Endogenous tryptophan-like component 4 (C4) had a higher binding affinity for Cu²⁺ than humic-like components (logKₐ: C4 > C1 > C2) in PDOM irrespective of MW. Humic-like components with MW < 500 kDa displayed higher binding potentials for Cu²⁺. FTIR spectra showed that the main participants of DOM-Cu complexation included aromatic hydrocarbons, aliphatic groups, amide Ⅰ bands, and carboxyl functional groups. This study provides spatial-scale insights into the molecular weight structure of DOM in influencing the behavior, fate, and bioavailability of heavy metals in lakes.

Copper has become one of the most important heavy metal pollutants in the environment because of its wide application and high toxicity, but research on water quality criteria (WQCs) on copper is limited, especially the derivation of seawater WQC. In addition, the toxicity of copper in the seawater system is affected by various environmental factors. Therefore, establishing a WQC that meets the characteristics of the regional environment is a top priority. The correlations between four factors of temperature, salinity, pH, dissolved organic carbon (DOC) and the toxic effect values of copper were analyzed in this study, and the temperature was determined as the most influential factor among the four factors in the Bohai Sea. A specific correlation between temperature and the toxic effects of copper was identified, and WQCs were derived based on the identified correlation and the variations of the Bohai Sea's temperature in different seasons by species sensitivity distribution (SSD) method. Under the condition of the winter, spring, autumn, and summer with an average water temperature of 0.09, 15.96, 17.83, and 24.87 °C, the obtained short-term water quality criteria (SWQCs) were 44.29, 4.70, 4.31, and 3.33 μg/L; the long-term water quality criteria (LWQCs) were 18.14, 1.93, 1.77 and 1.36 μg/L. The findings indicated the importance of introducing specific environmental conditions during the derivation process. This work could provide valuable information for pollution prevention and aquatic life protection in the Bohai Sea and provide a valuable reference for the derivation of criteria in other regions alike.

Zn and Cu are two of the essential trace elements and it is important to understand the regulation of their distribution on cellular functions. Herein, we for the first time investigated the subcellular fate and behavior of Zn and Cu in zebrafish cells through bioimaging, and demonstrated the completely different behaviors of Zn and Cu. The distribution of Zn²⁺ was concentration-dependent, and Zn²⁺ at low concentration was predominantly located in the lysosomes (76.5%). A further increase of cellular Zn²⁺ resulted in a spillover and more diffusive distribution, with partitioning to mitochondria and other regions. In contrast, the subcellular distribution of Cu⁺ was time-dependent. Upon entering the cells, Cu²⁺ was reduced to Cu⁺, which was first concentrated in the mitochondria (71.4%) followed by transportation to lysosomes (58.6%), and finally removal from the cell. With such differential transportation, Cu²⁺ instead of Zn²⁺ had a negative effect on the mitochondrial membrane potential and glutathione. Correspondingly, the pH of lysosomes was more sensitive to Zn²⁺ exposure and decreased with increasing internalized Zn²⁺, whereas it increased upon Cu²⁺ exposure. The responses of cellular pH showed an opposite pattern from the lysosomal pH. Lysosome was the most critical organelle in response to incoming Zn²⁺ by increasing its number and size, whereas Cu²⁺ reduced the lysosome size. Our study showed that Zn²⁺ and Cu²⁺ had completely different cellular handlings and fates with important implications for understanding of their toxicity.

The current study is the first attempt to prepare nanocomposites of Eleocharis dulcis biochar (EDB) with nano zero-valent Copper (nZVCu/EDB) and magnetite nanoparticles (MNPs/EDB) for batch and column scale sequestration of Congo Red dye (CR) from synthetic and natural water. The adsorbents were characterized with advanced analytical techniques. The impact of EDB, MNPs/EDB and nZVCu/EDB dosage (1–4 g/L), pH (4–10), initial concentration of CR (20–500 mg/L), interaction time (180 min) and material type to remove CR from water was examined at ambient temperature. The CR removal followed sequence of nZVCu/EDB > MNPs/EDB > EDB (84.9–98% > 77–95% > 69.5–93%) at dosage 2 g/L when CR concentration was increased from 20 to 500 mg/L. The MNPs/EDB and nZVCu/EDB showed 10.9% and 20.1% higher CR removal than EDB. The adsorption capacity of nZVCu/EDB, MNPs/EDB and EDB was 212, 193 and 174 mg/g, respectively. Freundlich model proved more suitable for sorption experiments while pseudo 2nd order kinetic model well explained the adsorption kinetics. Fixed bed column scale results revealed excellent retention of CR (99%) even at 500 mg/L till 2 h when packed column was filled with 3.0 g nZVCu/EDB, MNPs/EDB and EDB. These results revealed that nanocomposites with biochar can be applied efficiently for the decontamination of CR contaminated water.

Microplastic ingestion has been documented in various aquatic species. This causes physical damage, and additionally contaminated microplastics transfer attached pollutants and microbial pathogens to ingesting organisms. Continued metal accumulation can lead to toxicity and adverse health effects; attached microbial pathogens can cause dysbiosis - which lowers host immunity and promotes infections. Catfish, Clarias gariepinus, are a major food source in Southeast Asia, a hotspot of plastic pollution. This study aimed to quantify the transfer of the trace metals copper (Cu) and lead (Pb) -at environmentally relevant concentrations-from microplastics (polyamide 12, PA12, and polylactic acid, PLA) to catfish. Fish were reared for three months and exposed to seven different combinations of feed, supplemented with plastics and metals. At monthly intervals, fish gills, intestines, liver, and edible muscles were analysed for Cu and Pb concentrations using ICP-OES, and the intestines content assessed for Vibrio sp.. Our results showed that biodegradable PLA transferred higher amounts of metals to catfish than expected and also led to increased Vibrio counts in the intestines compared to PA12. Trace metal accumulation was significantly different in varying tissues, with highest concentrations observed in the gills, followed by liver, intestines, and lastly edible muscles. The results of this study further support the existing evidence that microplastics act as efficient shuttles to concentrate and transfer metals. They also indicate that their uptake can cause dysbiosis (increased numbers of Vibrio sp.). Most importantly, however, our study highlights that biodegradable polymers, such as PLA, could actually pose a greater environmental threat when ingested compared to the more common polymers such as PA12.

The adverse health effects associated with the inhalation and ingestion of naturally occurring radon gas produced during the uranium decay chain mean that there is a need to identify high-risk areas. This study detected radon-prone areas using a geographic information system (GIS)-based probabilistic and machine learning methods, including the frequency ratio (FR) model and a convolutional neural network (CNN). Ten influencing factors, namely elevation, slope, the topographic wetness index (TWI), valley depth, fault density, lithology, and the average soil copper (Cu), calcium oxide (Cao), ferric oxide (Fe₂O₃), and lead (Pb) concentrations, were analyzed. In total, 27 rock samples with high activity concentration index values were divided randomly into training and validation datasets (70:30 ratio) to train the models. Areas were categorized as very high, high, moderate, low, and very low radon areas. According to the models, approximately 40% of the study area was classified as very high or high risk. Finally, the radon potential maps were validated using the area under the receiver operating characteristic curve (AUC) analysis. This showed that the CNN algorithm was superior to the FR method; for the former, AUC values of 0.844 and 0.840 were obtained using the training and validation datasets, respectively. However, both algorithms had high predictive power. Slope, lithology, and TWI were the best predictors of radon-affected areas. These results provide new information regarding the spatial distribution of radon, and could inform the development of new residential areas. Radon screening is important to reduce public exposure to high levels of naturally occurring radiation.

Improper application of copper-based fungicides has made copper stress critical in viticulture, necessitating the need to identify substances that can mitigate it. In this study, leaves of ‘Shine Muscat’ (‘SM’) grapevine seedlings were treated with CuSO₄ solution (10 mM/L), CuSO₄ + 5-aminolevulinic acid (ALA) (50 mg/L), and distilled water to explore the mitigation effect of ALA. Physiological assays demonstrated that ALA effectively reduced malondialdehyde accumulation and increased peroxidase and superoxide dismutase activities in grapevine leaves under copper stress. Copper ion absorption, transport pathways, chlorophyll metabolism pathways, photosynthetic system, and antioxidant pathways play key roles in ALA alleviated-copper stress. Moreover, expression changes in genes, such as CHLH, ALAD, RCA, and DHAR, play vital roles in these processes. Furthermore, abscisic acid reduction caused by NCED down-regulation and decreased naringenin, leucopelargonidin, and betaine contents confirmed the alleviating effect of ALA. Taken together, these results reveal how grapevine responds to copper stress and the alleviating effects of ALA, thus providing a novel means of alleviating copper stress in viticulture.

Hydroxyapatite (HAP) can effectively immobilize soil heavy metals, but excess phosphate would be released to aquatic ecosystem, resulting in eutrophication. This study investigated the effects of ferrihydrite (FH) on the HAP immobilization of copper (Cu) and cadmium (Cd) and their reduction of phosphorus release under flooding-drainage alternation conditions. Results showed that the incorporation of HAP and FH significantly increased soil solution pH and decreased Cu²⁺ and Cd²⁺ concentrations. Applications of FH, HAP, and FH-HAP (FH and HAP combination) can all enhance soil pH and reduce CaCl₂-extractable and exchangeable Cu and Cd, but HAP addition increased soluble phosphate by 6.60–7.77 times compared to control. However, FH-HAP application can significantly reduce phosphate release by 92.7–99.7% compared to HAP application. FH-HAP was the most effective to reduce exchangeable Cu and Cd by 49.8–93.4% and 50.9–88.8% and decreased labile and moderately labile phosphorus by 34.0–74.4% and 13.5–18.6%, respectively, while increased stable phosphorus by 22–45.1% than single HAP. All FH treatments significantly increased amorphous iron oxides by the factors of 4.66–20.8, but only 3% and 5% of FH applications slightly enhanced crystal iron oxides by the factors of 0.81–1.27. The major implication is that the combination of FH and HAP can not only immobilize of Cu and Cd, but also reduce the risk of phosphate release by HAP addition.