Source apportionment can be an effective tool in mitigating soil pollution but its efficacy is often limited by a lack of information on the factors that influence the accumulation of pollutants at a site. In response to this limitation and focusing on a suite of heavy metals identified as priorities for pollution control, the study established a comprehensive pollution control framework using factor identification coupled with spatial agglomeration for agricultural soils in an industrialized part of Zhejiang Province, China. In addition to elucidating the key role of industrial and traffic activities on heavy metal accumulation through implementing a receptor model, specific influencing factors were identified using a random forest model. The distance from the soil sample location to the nearest likely industrial source was the most important factor in determining cadmium and copper concentrations, while distance to the nearest road was more important for lead and zinc pollution. Soil parent materials, pH, organic matter, and clay particle size were the key factors influencing accumulation of arsenic, chromium, and nickel. Spatial auto-correlation between levels of soil metal pollution and industrial agglomeration can enable a more targeted approach to pollution control measures. Overall, the approach and results provide a basis for improved accuracy in source apportionment, and thus improved soil pollution control, at the regional scale.

Aging is a leading cause of mortality for the elderly and DNA methylation age is reported to be predictive of biological aging. However, few studies have investigated the associations between multiple metals exposure and accelerated aging in the elderly. We performed a pilot study of 288 elderly participants aged 50–115 years and measured genome-wide DNA methylation and 22 blood metals concentrations. Measures of DNA methylation age were estimated using CpGs from Illumina HumanMethylation EPIC BeadChip. Linear mixed regression and Bayesian kernel machine regression (BKMR) models were used to estimate the individual and overall associations between multiple metals and accelerated methylation aging. Single metal models revealed that each 1-standard deviance (SD) increase in log-transformed vanadium, cobalt, nickel, zinc, arsenic, and barium was associated with a −2.256, −1.318, 1.004, −1.926, 1.910 and −1.356 changes in ΔAge, respectively; meanwhile, for aging rate, the change was −0.019, −0.013, 0.010, −0.018, 0.023, and −0.012, respectively (all P < 0.05). The BKMR models showed reverse U-shaped associations of the overall metals mixture with ΔAge and aging rate. Downward trends of ΔAge and aging rate were observed for increasing quantiles of essential metals mixture, but upward trends were observed for non-essential metals mixture. Further individual analysis of the BKMR revealed that the 95% confidence interval of ΔAge and aging rate associated with vanadium, zinc, and arsenic did not cross 0, when other metals concentrations set at 25th, 50th, and 75th percentile. Our findings suggest reverse U-shaped associations of the overall metals mixture with accelerated methylation aging for the first time, and vanadium, zinc, and arsenic may be major contributors driving the associations.

In this report, we investigated the accumulation of heavy metals in the lizard Microlophus atacamensis, in three coastal areas of the Atacama Desert, northern Chile. We captured reptiles in a non-intervened area (Parque Nacional Pan de Azúcar, PAZ), an area of mining impact (Caleta Palitos, PAL) and an active industrial zone (Puerto de Caldera, CAL). Our methods included a non-lethal sampling of reptiles’ tails obtained by autotomy and a few sacrificed animals to perform a stomach contents analysis. The concentrations of lead, copper, nickel, zinc and cadmium were measured by atomic absorption spectrophotometry in both soil and prey and compared to those recorded in the lizards’ tails. Data obtained from lizard tails captured in PAL showed significantly high concentrations of Pb, Cu, Ni, and Zn compared to the other two sites PAZ and CAL. We did not find statistically significant differences among PAZ, PAL and CAL soils, probably due to the similar geological composition of the sites. However, the regional background values for Pb indicate contamination or at least metal enrichment in soils of the three sites, for Cu the global background values indicate contamination for the three sites, and for Cd both the regional and global backgroud values show high values. The analysis of the stomach content showed differences in the food sources of the lizards among the sites studied. The concentration of heavy metal in lizard tissues versus prey delivered values of the Trophic Transfer Factor higher than one (1), suggesting that food may be a primary source of metals in the tissues of M. atacamensis. Calculations of the Bioaccumulation Factor (BAF) and the Ecological Risk (IR) resulted in values higher than one (1) indicating the relevance of this process in the sites studied. In this article, we report relationships between environmental contaminants, mainly putative preys, and concentrations found in lizard tails, which is more substantial in areas with historical heavy metal contamination such as PAL where the non-lethal technique developed in this research suggests a process of metal bioaccumulation in M. atacamensis.

Oral bioaccessibility (BAc) is a surrogate for the bioavailability (BAv) of a broad range of substances, reflecting the value that the approach offers for assessing oral exposure and risk. BAc is generally considered to have been validated as a proxy for oral BAv for the important soil contaminants Pb, Cd, and As. Here, using literature data for Ni BAc and BAv, we confirmed that Ni BAc (gastric only, with HCl mimicking stomach conditions) is a conservative measure of BAv for the oral exposure pathway. Measured oral BAv of Ni in soil was shown to be 50–100 times less than the simplest oral BAc estimates (%BAv = 0.012(%BAc) - 0.023 (r = 0.701, 95%CI [0.456, 0.847], n = 30)) in rats, demonstrating a significant conservatism for exposure assessment. The relationship between the oral BAv and BAc of nickel sulfate hexahydrate (NSHH) was comparable to that of soil, with measured oral BAv of NSHH (1.94%) being a small fraction of NSHH gastric BAc (91.1%). BAc and BAv reflect the underlying Ni speciation of the sample, with the bioaccessible leaching limits being represented by the highly soluble Ni salts and the poorly soluble Ni monoxide, and the environmental (e.g. soil properties) or gastric (e.g. food present) conditions. BAc has potential utility for chemical classification purposes because pure Ni substances can be grouped by %BAc values(using standardized methodologies for the relevant exposure routes), these groupings reflecting the underlying chemistry and speciation of the samples of substances tested here, with 0.008% %BAc for alloys (SS304, SS316, Inconel, Monel), <1% in green NiO and Ni metal massives, 0.9–23.6% for Ni powders, 9.8–22.7% for Ni sulfides, 26.3–29.6% for black oxidic Ni, and 82–91% for the soluble Ni salts. Oral BAc provides realistic yet conservative estimates of BAv for the hazard classification and risk assessment of Ni substances.

Six ecotypes of Typha domingensis Pers. Jahlar (E₁), Sheikhupura (E₂), Sahianwala (E₃), Gatwala (E₄), Treemu (E₅) and Knotti (E₆) from different ecological regions were collected to evaluate the leaf anatomical and biochemical attributes under different levels of salinity and nickel stress viz; L₀ (control), L₁ (100 mM + 50 mg kg⁻¹), L₂ (200 mM + 100 mg kg⁻¹) and L₃ (300 mM + 150 mg kg⁻¹). Presence of salt and Ni in rooting medium consistently affected growth, anatomical and physio-biochemical attributes in all Typha ecotypes. Discrete anatomical modifications among ecotypes such as reduced leaf thickness, increased parenchyma area, metaxylem cell area, aerenchyma formation and improved metaxylem vessels were recorded with increasing dose of salt and Ni. The minimum anatomical damages were recorded in E₁ and E₆ ecotypes. In all ecotypes, progressive perturbations in ionic homeostasis (Na⁺, K⁺, Cl⁻, N) due to salt and metal toxicity were evident along with reduction in photosynthetic pigments. Maximum enhancement in Catalase (CAT), Superoxide dismutase (SOD), Peroxidase (POD) and modulated Malondialdehyde (MDA) activity was recorded in E₁ and E₆ as compared to other ecotypes. Accumulation of large amounts of metabolites such as total soluble sugars, total free amino acids content in Jahlar, Knotti, Treemu and Sahianawala ecotypes under different levels of salt and Ni prevented cellular damages in T. domingensis Pers. The correlation analysis exhibited a close relationship among different levels of salinity and Ni with various plant attributes. PCA-Biplot verified our correlational analysis among various attributes of Typha ecotypes. An obvious separation of Typha characters in response to different salinity and Ni levels was exhibited by PC1. We recommend that genetic potential of T. domingensis Pers. To grow under salt and Ni stresses must be investigated and used for phytoremediation and reclamation of contaminated soil.

Antarctic melt streams are important ecosystems that increasingly face contaminant pressures from anthropogenic sources. Metal contaminants are often reported in the limno-terrestrial environment but their speciation is not well characterised, making environmental risk assessments difficult. This paper characterises labile metal concentrations in five melt streams and three shallow lakes around the Casey and Wilkes research stations in East Antarctica using chemical extracts and field deployments of diffusive gradients in thin-film (DGT) samplers. An acute toxicity test with field-collected Ceratadon purpeus and taxonomic identification of diatoms in melt streams were used to infer environmental risk. Copper and zinc were the most labile metals in the melt streams. DGT-labile copper concentrations were up to 3 μg Cu L⁻¹ in melt-stream waters but not labile below the sediment-water interface. DGT-labile zinc concentrations were consistent above and below the sediment-water interface at concentrations up to 14 μg Zn L⁻¹ in four streams, but one stream showed evidence of zinc mineralisation in the sediment with a flux to overlying and pore waters attributed to the reductive dissolution of iron and manganese oxides. Other metals, such as chromium, nickel, and lead were acid-extractable from the sediments, but not labile in pore waters or overlying waters. All streams had unique compositions of freshwater diatoms, but one had particularly reduced diversity and richness, which correlated to metal contamination and sediment physico-chemical properties such as a finer particle size. In laboratory bioassays with field-collected samples of the Antarctic moss C. purpeus, there was no change in photosynthetic efficiency following 28-d exposure to 700, 900, 1060, or 530 μg L⁻¹ of cadmium, copper, nickel, and zinc, respectively. This study shows that microorganisms such as diatoms may be at greater risk from contaminants than mosses, and highlights the importance of geochemical factors controlling metal lability.

The Pearl River Estuary (PRE) is the largest estuary in southern China and under high metal stress. In the present study, we employed an integrated method of transcriptomics and proteomics to investigate the ecotoxicological effects of trace metals on the Hong Kong oyster Crassostrea hongkongensis. Three oyster populations with distinct spatial distributions of metals were sampled, including the Control (Station QA, the lowest metal levels), the High Cd (Station JZ, the highest Cd), and the High Zn–Cu–Cr–Ni (Station LFS, with the highest levels of zinc, copper, chromium, and nickel). Dominant metals in oysters were differentiated by principal component analysis (PCA), and theirgene and protein profiles were studied using RNA-seq and iTRAQ techniques. Of the 2250 proteins identified at both protein and RNA levels, 70 proteins exhibited differential expressions in response to metal stress in oysters from the two contaminated stations. There were 8 proteins altered at both stations, with the potential effects on mitochondria and endoplasmic reticulum by Ag. The genotoxicity, including impaired DNA replication and transcription, was specifically observed in the High Cd oysters with the dominating influence of Cd. The structural components (cytoskeleton and chromosome-associated proteins) were impaired by the over-accumulated Cu, Zn, Cr, and Ni at Station LFS. However, enhanced tRNA biogenesis and exosome activity might help the oysters to alleviate the toxicities resulting from their exposure to these metals. Our study provided comprehensive information on the molecular changes in oysters at both protein and RNA levels in responding to multi-levels of trace metal stress.

Detailed, high resolution time-series observations were performed to investigate sources, diel cycling, natural attenuation, and loadings of dissolved trace metals/metalloids in a subtropical headwater stream draining intensive horticulture in Australia. A transect of ∼3 km away from the source (farms) showed >75% reduction in concentration and loads of most trace elements. Mercury and arsenic had elevated loads downstream relative to other elements. Hourly time-series sampling revealed elevated creek discharge at night, accompanied by elevated nickel, selenium, copper, and mercury loads. Inputs from groundwater or treated sewage used for irrigation within the catchment are likely sources. Groundwater bore and treated sewage samples were highly contaminated with either zinc, copper, or mercury. Comparisons of daily and hourly samples indicated common sampling strategies can underestimate horticultural contaminant loadings. Load estimates for mercury and copper derived from hourly samples were 1.6- to 7- fold greater than loads from daily sample data collected over 79 days with varying rainfall. These high contaminant concentrations and loads are of concern to food products receiving irrigation and protected waterbodies downstream.

The present study aimed to show that nickel and fluoride exhibited synchronized co-inhibited uptake in the aromatic rice cultivar, Gobindobhog, since bioaccumulation of the two elements was lower than that during individual stress, so that overall growth under combined stress was similar to control seedlings. On the contrary, lead and fluoride stimulated their co-uptake which triggered oxidative damages, NADPH oxidase activity, methylglyoxal accumulation, photosynthetic inhibition, membrane-protein damages, necrosis and genomic template degradation. Accumulation of proline, anthocyanins, non-protein thiols and phytochelatins was stimulated for systemic protection against reactive oxygen species (ROS) and xenobiotic-mediated injuries during lead-fluoride toxicity. ROS accumulation during nickel-fluoride stress was insignificant due to which enhanced accumulation of most antioxidants was not required. Glutathione depletion during combined lead-fluoride toxicity was due to its utilization in the glyoxalase cycle and also inhibition of glutathione reductase. However, the nickel-fluoride-treated sets maintained glutathione reserves and glyoxalase activity similar to those in control. Presence of fluoride ‘safeguarded’ the glutathione-utilizing enzymes like glutathione reductase, glutathione peroxidase and glutathione-S-transferase during dual lead-fluoride stress. This was because these enzymes showed higher activity compared to that under lead toxicity alone. Enzymatic antioxidants like superoxide dismutase, ascorbate peroxidase and guaiacol peroxidase were activated during lead-fluoride toxicity due to altered iron and copper homeostasis. Catalase activity was strongly inhibited, resulting in the inability to scavenge H₂O₂ and suppression of the fluoride-adaptable phenotype. However, none of the enzymatic antioxidants were inhibited during nickel-fluoride stress, which cumulatively allowed the seedlings to maintain normal physiology. Overall our findings holistically reveal the physiological plasticity of Gobindobhog in response to two different heavy metals under the influence of fluoride.

The effectiveness of biochar as a sorptive material to remove contaminants, particularly heavy metals, from water is dependent on biomass type and pyrolysis condition. Biochars were produced from pulp mill sludge (PMS) and rice straw (RS) with nitrogen (N₂) or carbon dioxide (CO₂) as the purging gas. The sorptive capacity of the biochars for cadmium(II), copper(II), nickel(II) and lead(II) was studied. The heavy metal adsorption capacity was mainly affected by biomass type, with biochars adsorption capacities higher for lead(II) (109.9–256.4 mg g⁻¹) than for nickel(II) (40.2–64.1 mg g⁻¹), cadmium(II) (29.5–42.7 mg g⁻¹) and copper(II) (18.5–39.4 mg g⁻¹) based on the Langmuir adsorption model. The highest lead(II) adsorption capacities for PMS and RS biochars were 256.4 and 133.3 mg g⁻¹, respectively, when generated using N₂ as the purging gas. The corresponding lead(II) adsorption capacities were 250.0 and 109.9 mg g⁻¹, respectively, when generated using CO₂ as the purging gas. According to the intraparticle diffusion model, 30–62% of heavy metal adsorption was achieved in 1 h; film diffusion was the rate-dominating step, whereas pore diffusion was a rate-limiting step. Ion exchange and complexation between heavy metals and biochar surface functional groups such as carbonyl and hydroxyl groups were effective mechanisms for heavy metal sorption from the aqueous solution. We conclude that proper selection of both the feedstock type and the purging gas is important in designing biochars for the effective removal of potentially toxic metals from wastewater.