Accumulation of potentially toxic elements (PTEs) in agricultural soils has become an increasingly global issue driven by industrialization. A credible knowledge of their distribution and diverse sources in soils is essential to developing effective measures of identifying accumulation of PTEs in rural and periurban environments. However, the assessment of PTE pollution levels and discrimination of anthropogenic and natural sources remain a serious challenge. In China, most studies are focused on highly industrialized and/or urbanized regions, while limited attention has been given to agricultural areas where diffuse source contamination prevails. Therefore, a large dataset of 5207 surface soil samples (1 × 1 km) and 1311 subsoil samples (2 × 2 km) were collected from an agriculturally dominated region in eastern China. Soil total concentrations of As, Cd, Cr, Cu, Hg, Ni, Pb and Zn were analyzed along with additional edaphic variables relevant to PTE accumulation in soils (e.g., pH, SOC). Concentrations of Cr, Ni, Pb and Zn for all sites were lower than those of the risk-screening values. However, elevated concentrations of Cd and Hg observed in surface soils were associated with anthropogenic activities. Land use pattern had a significant impact on the spatial variation of PTEs. Elevated levels of Cd were uniquely associated with high phosphorus and soil organic matter (SOM) contents, and elevated Hg was associated with coal-fired power plants and historical application of fertilizer and Hg-containing pesticides. The data presented herein indicated that geogenic process likely caused a net depletion of As, Cr, Cu, Ni, Pb and Zn in topsoil, despite surface deposition from anthropogenic sources. The result of this study revealed that using subsoil concentrations of PTEs to establish background or reference concentrations might lead to an erroneous assessment of pollution levels in surface soils.

Southwestern China contains the largest and most well-developed karst region in the world, and the potentially toxic elements (PTEs) content in the soils of the region is remarkably high. To explore the internal and external control factors and sources of soil PTEs enrichment in this area and to provide a basis for the treatment of PTE pollution, 113 soil samples were collected from Hengxian County, a karst region in Guangxi Province, southwestern China. The importance of eighteen influencing factors including parent material, weathering, physicochemical properties, topography and human activities were quantitatively analyzed by (partial) redundancy analysis. The sources of PTEs were identified using the Pb isotope ratio and absolute principal component score/multiple linear regression (APCS-MLR) model. The contents of all soil PTEs were higher than the corresponding background values of Guangxi soils. The contents in Cu, Zn, Cd, Hg and Pb were the highest in the soil from carbonate rock. The factor group of geological background and weathering explained 26.5% for the accumulation and distribution of soil PTEs and the influence of physicochemical properties was less than 2% but increased to 25.6% through interaction with weathering. Fe (47.1%), Al (42.1%), Mn (22%), chemical index of alteration (12.8%) and clay (11.9%) were the key factors affecting the soil PTEs, while the influence of human activities was weak. Pb isotope ratio and APCS-MLR classified 62.8–74% of soil PTEs as derived from natural sources, whereas 18.23% and 18.95% were derived from industrial activities and agricultural practice/traffic emissions, respectively. The Pb isotope ratio showed that the natural sources account for up to 90% of the Pb in the soil from carbonate rock, the highest contribution among the studied soils. The results of the study can provide background information on the soil PTEs contamination in the karst areas of China and other areas worldwide.

The aim of the research was to study short-term variations in concentrations of 17 elements in two widely distributed natural plant species (couch grass and plantain) and in the rhizosphere soil of the plants. The plant and soil samples were collected in a field from a small site over a daytime. In the course of the day, the variations of the total amounts of C, N, and H in the rhizosphere soil were rather marked and different for the soils taken from roots of plantain and couch grass. The concentrations of some other elements in the rhizosphere soil of the plants varied in a similar way. The short-term variations of element concentrations in roots and leaves of the plants were also rather large. In many cases, a decrease of element concentration in roots correlated with an increase of its concentration in leaves. Although couch grass and plantain were collected simultaneously and from the same site, mean concentrations of many elements in the two plant species were statistically significantly different. This may be result of the fact that the plants belong to different clades. The differences between concentrations of most part of elements in roots and leaves of the plants were also statistically significant. The concentrations of many trace elements were higher in roots than in leaves, while the concentrations of essential plant nutrients were often higher in leaves compared to roots. The distribution of elements between different plant parts were not the same in couch grass and plantain.

A high-resolution soil sampling has been applied to two forest podzols (ACB-I and ACB-II) from SW Europe in order to investigate the soil components and processes influencing the content, accumulation and vertical distribution of Hg. Total Hg contents (THg) were 28.0 and 23.6 μg kg⁻¹ in A horizons of ACB-I and ACB-II, then they strongly decreased in the E horizons and peaked in the Bhs horizons of both soils (55.3 and 63.0 μg kg⁻¹). THg decreased again in BwC horizons to 17.0 and 39.8 μg kg⁻¹. The Bhs horizons accounted for 46 and 38% of the total Hg stored (ACB-I and ACB-II, respectively). Principal component analysis (PCA) and principal components regression (PCR), i.e. using the extracted components as predictors, allowed to distinguish the soil components that accounted for Hg accumulation in each horizon. The obtained model accurately predicted accumulated Hg (R² = 0.845) through four principal components (PCs). In A horizons, Hg distribution was controlled by fresh soil organic matter (PC4), whereas in E horizons the negative values of all PCs were consistent with the absence of components able to retain Hg and the corresponding very low THg concentrations. Maximum THg contents in Bhs horizons coincided with the highest peaks of reactive Fe and Al compounds (PC1 and PC2) and secondary crystalline minerals (PC3) in both soils. The THg distribution in the deepest horizons (Bw and BwC) seemed to be influenced by other pedogenetic processes than those operating in the upper part of the profile (A, E and Bhs horizons). Our findings confirm the importance of soils in the global Hg cycling, as they exhibit significant Hg pools in horizons below the uppermost O and A horizons, preventing its mobilization to other environmental compartments.

The levels of eight organophosphate esters (OPEs) were analyzed in air and soil samples collected at Ny-Ålesund and London Island, Svalbard during the Chinese Scientific Research Expedition to the Arctic during 2014–2015. The concentrations of total OPEs (∑OPEs) ranged from 357 pg/m³ to 852 pg/m³ in the air and from 1.33 ng/g to 17.5 ng/g dry weight (dw) in the soils. Non-Cl OPEs accounted for 56 ± 13% and 62 ± 16% of ∑OPEs for the air and soil, respectively. Tris(2-chloroethyl) phosphate (TCEP) was the dominant compound in the air, with an average concentration of 180 ± 122 pg/m³. Triphenyl phosphate, tri(1-chloro-2-propyl) phosphate, and TCEP were the most abundant OPEs in the soils, with mean values of 1.77, 2.13, and 1.02 ng/g dw, respectively. Compared with the levels of polybrominated diphenyl ethers found in Arctic regions in previous studies, OPEs showed significantly higher concentrations, thereby indicating the large production and wide usage of OPEs globally. In addition, the fugacity fraction results indicated that net deposition from air to soil was dominated in the area. Overall, the occurrence and distribution of OPEs in the air and soils in the Arctic region indicated that OPEs can undergo long-range atmospheric transport and accumulate in remote regions.

Dairy manure often has elevated concentrations of copper (Cu) that when applied to soil may create toxicity risks to seedlings and soil microbes. Manure application also increases dissolved organic matter (DOM) in soil solution. We hypothesize that high rates of dairy manure amendment over several years will cause increased DOM in the soil that complexes Cu, increasing its mobility. To test this hypothesis, this study investigated water soluble Cu concentrations and dissolved organic carbon (DOC) in soil samples from 3 years of manure-amended soils. Samples were collected at two depths over the first 3 years of a long-term manure-amendment field trial. DOC, Cu, Fe, and P concentrations were measured in water extracts from the samples. Ultraviolet/visible (UV/Vis) spectra were used to assess the DOC characteristics. After 3 years of manure application, extractable Cu concentration was approximately four times greater in the surface and two times greater in subsurface samples of manure-amended soils as compared to non-amended control soils and traditional mineral fertilizer-amended soils. The extractable Cu concentration was greatest in plots that had the highest manure amendment rates (35 t ha⁻¹ and 52 t ha⁻¹, dry weight). The UV/Vis parameters SUVA₂₅₄ and E₂/E₃ correlated with Cu concentration in the extracts (p < 0.05), suggesting that DOC characteristics are important in Cu-binding. The molecular characteristics of the DOC in the subsurface after 3 years of manure amendment were distinct from the DOC in the control plot, suggesting that manure amendment creates mobile DOC that may facilitate Cu mobilization through soil. The 10-fold increase in extractable Cu concentration after only 3 years of manure application indicates that repeated applications of the dairy manure sources used in this study at rates of 35 t/ha or greater may create risks for Cu toxicity and leaching of Cu into ground and surface waters.

Usage of neonicotinoids is common in all agricultural regions of the world but data on environmental contamination in tropical regions is scarce. We conducted a survey of five neonicotinoids in soil, water and sediment samples along gradients from crops fields to protected lowland tropical forest, mangroves and wetlands in northern Belize, a region of high biodiversity value. Neonicotinoid frequency of detection and concentrations were highest in soil (68%) and lowest in water (12%). Imidacloprid was the most common residue reaching a maximum of 17.1 ng/g in soil samples. Concentrations in soils differed among crop types, being highest in melon fields and lowest in banana and sugarcane fields. Residues in soil declined with distance to the planted fields, with clothianidin being detected at 100 m and imidacloprid at more than 10 km from the nearest applied field. About half (47%) of the sediments collected contained residues of at least one compound up to 10 km from the source. Total neonicotinoid concentrations in sediments (range 0.014–0.348 ng/g d. w.) were about 10 times lower than in soils from the fields, with imidacloprid being the highest (0.175 ng/g). A probabilistic risk assessment of the residues in the aquatic environment indicates that 31% of sediment samples pose a risk to invertebrate aquatic and benthic organisms by chronic exposure, whereas less than 5% of sediment samples may incur a risk by acute exposure. Current residue levels in water samples do not appear to pose risks to the aquatic fauna. Fugacity modeling of the four main compounds detected suggest that most of the dissipation from the agricultural fields occurs via runoff and leaching through the porous soils of this region. We call for better monitoring of pesticide contamination and invertebrate inventories and finding alternatives to the use of neonicotinoids in agriculture.

The widespread use of neonicotinoid insecticides is controversial due to their persistence in the environment and concerns the long-term consequences of their use. We present a simple, low-cost method for the sensitive and efficient extraction of three important neonicotinoids from soil with a detection limit <1 ng g−1 wet soil. We have validated this method by applying it to uncontaminated soil samples spiked with thiamethoxam, clothianidin and imidacloprid at environmentally concentrations. Absolute recoveries were >80% for thiamethoxam, clothianidin and imidacloprid. We also applied the method to soil samples collected from maize fields in New Zealand's North Island and found imidacloprid in 43 out of 45 samples and clothianidin in every one. Mean imidacloprid concentrations varied from 0.5 to 9.4 ng g−1 (wet weight) and clothianidin from 2.1 to 26.7 ng g−1 (wet weight). Imidacloprid concentrations exceed the New Zealand Environmental Protection Agency's Environmental Exposure Limit of 1 ng g−1 (dry weight) at eight of the nine sites sampled. These results are also remarkable because we have detected multiple neonicotinoid residues at every site. Imidacloprid residues appear to persist at significant concentrations at five of our sites from an application at least two years previous. This is only the third study to report the presence of neonicotinoid residues in NZ's environment and the first to show that those residues are persistent in the environment at nominally hazardous concentrations.

Hexa-mix-chlorinated/brominated benzenes (HXBs), a group of newly found analogues of hexachlorobenzene (HCB) and hexabromobenzene (HBB), may exhibit similar environmental risks and toxicities as HCB and HBB, and therefore possess high interests in environmental and toxicological research. Yet information regarding HXBs in the environment remains scarce. In this study, we developed an isotope dilution method for quantitative and semiquantitative determination of five HXBs in fly ash, soil and air using gas chromatography high resolution mass spectrometry (GC-HRMS) in multiple ion detection mode. The samples were Soxhlet-extracted and purified with multilayer composite silica gel-alumina columns, followed by GC-HRMS detection. Identification of HXBs was conducted by the comparison between theoretical and detected mass spectra using paired-samples T test and cosine similarity analysis. Two HXBs (C₆BrCl₅ and C₆Br₄Cl₂) with reference standards were quantitatively determined while the rest three (C₆Br₂Cl₄, C₆Br₃Cl₃ and C₆Br₅Cl) without reference standards were semiquantitatively analyzed by sharing the calibration curves of C₆BrCl₅ and C₆Br₄Cl₂ in cooperation with isotopologue distribution computation. The accuracies for C₆BrCl₅ and C₆Br₄Cl₂ were 87.3–107.8% with relative standard deviations (RSD) of 2.8–5.0%. The method limits of quantification of the HXBs were 0.10 ng/g in fly ash and soil samples and 0.09 pg/m³ in ambient air samples. The recoveries ranged from 42.7% to 102.1% with RSD of 3.7–13.9%. This method has been successfully applied to the analysis of the HXBs in the environmental samples. The total concentrations of HXBs in the fly ash, soil and ambient air samples were 19.48 ng/g, 10.44 ng/g and 5.13 pg/m³, respectively, which accounted for 10.6%, 0.4% and 10.8% of the corresponding total concentrations of HCB and HBB. This study provides a reference method for quantitative and/or semiquantitative analyses of novel mix-halogenated organic compounds, and sheds light on the full picture of HXBs pollution in the environment.

Contamination of agricultural soil by heavy metals has become a global issue concerning food security and human health risk. In this study, a soil investigation was conducted to evaluate metals accumulation, potential ecological and health risks as well as to identify sources of metals in paddy soils in Hanzhong City, which is located in a sedimentary basin. Ninety-two (92) surface soil samples (bulk soil) and their corresponding rice samples, 21 irrigation water samples, and 18 fertilizer samples were collected from two typical counties and quantified for the heavy metals (i.e., As, Cd, Cu, Hg, Pb, and Zn) concentrations. The results showed that As, Cd, and Zn were the main contaminants in soils in the studied area. Additionally, elevated Hg content in soils might also pose risks to the local ecosystem. Cadmium and As demonstrated high mobility, and their average contents in rice grains were slightly higher than the permissible threshold (0.20 mg kg⁻¹). Moreover, Pb, As, and Cd intake via rice consumption might result in potential risks to local residents. Metal distribution revealed that pollution in the studied area is non-homogeneous, and agricultural activities (As, Cu, and Cd), transportation emission (Cu and Pb), coal combustion (Hg and As), and smelting activities (Zn, Pb, and Cu) were ascertained as the potential sources based on the Positive matrix factorization (PMF) analysis results.