Pollution characteristics and source apportionment of heavy metal(loid)s in soil and groundwater of a retired industrial park.

Heavy metal(loid)s (HMs) pollution has become a common and complex problem in industrial parks due to rapid industrialization and urbanization. Here, soil and groundwater were sampled from a retired industrial park to investigate the pollution characteristics of HMs. Results show that Ni, Pb, Cr, Zn, Cd, and Cu were the typical HMs in the soil. Source analysis with the positive matrix factorization model indicates that HMs in the topsoil stemmed from industrial activities, traffic emission, and natural source, and the groundwater HMs originated from industrial activities, groundwater-soil interaction, groundwater-rock interaction, and atmosphere deposition. The sequential extraction of soil HMs reveals that As and Hg were mainly distributed in the residue fraction, while Ni, Pb, Cr, Zn, Cd, and Cu mainly existed in the mobile fraction. Most HMs either in the total concentration or in the bioavailable fraction preferred to retain in soil as indicated by their high soil-water partitioning coefficients (Kd), and the Kd values were correlated with soil pH, groundwater redox potential, and dissolved oxygen. The relative stable soil-groundwater circumstance and the low active fraction contents limited the vertical migration of soil HMs and their release to groundwater. These findings increase our knowledge about HMs pollution characteristics of traditional industrial parks and provide a protocol for HMs pollution scrutinizing in large zones.

[Fraction Characteristic and Risk Assessment of Heavy Metals in Surface Sediments of the Yellow River Mainstream].

Heavy metals(HMs) are highly toxic and do not easily degrade in the environment. They can accumulate in the human body through the food chain, with serious impacts on the ecological environment and human health. In this study, 14 sampling sites along the mainstream of the Yellow River were investigated, and the total content and chemical fractions of six heavy metals(As, Cd, Cr, Cu, Pb, and Zn) in sediments were analyzed. The geo-accumulation index, potential ecological risk index, and risk assessment coding were used to assess the contamination level and bioavailability of HMs in sediment. Principal component analysis and redundancy analysis were used to identify the main sources of HMs. The results showed that the average content of heavy metals was in the order of Cr>Zn>Cu>Pb>As>Cd. Cd had the highest excess rate relative to the background value of each reach, reaching 85.7%. In the sediments, As, Zn, Pb, and Cu were predominantly in the oxidizable fraction(F3:sulfide and organic matter-bound), Cd was mainly occupied by the acid-soluble(F1:exchangeable and carbonate-bound) and a residual fraction(F4:mineral matrix-bound), and Cr was predominantly in the residual fraction. As, Cr, Cu, Pb, and Zn showed the lowest bioavailability in the upstream, increased in the midstream, and finally decreased in the downstream. The risk assessment showed that Cd, the element with the highest pollution risk level in the Yellow River, was prone to pose a serious threat to the ecological environment and should be prevented and controlled first. The PCA and RDA analyses revealed that fine sediment and total organic matter controlled HMs contamination. Therefore, the prevention and control of soil erosion and sediment migration should be emphasized to control HMs pollution in the Yellow River Basin.

Spatial-temporal evolution patterns and drivers of PM2.5 chemical fraction concentrations in China over the past 20 years.

The quantitative assessment of the spatial and temporal variability and drivers of fine particulate matter (PM2.5) fraction concentrations are important for pollution control and public health preservation in China. In this study, we investigated the spatial temporal variation of PM2.5 chemical component based on the PM2.5 chemical component datasets from 2000 to 2019 and revealed the driving forces of the differences in the spatial distribution using geodetector model (GD), multi-scale geographically weighted regression model (MGWR), and a two-step clustering approach. The results show that: the PM2.5 chemical fraction concentrations show a trend of first increasing (2000-2007) and then decreasing (2007-2019). From 2000 to 2019, the change rates of PM2.5, organic matter (OM), black carbon (BC), sulfates (SO2- 4), ammonium (NH+ 4), and nitrates (NO- 3) were -0.59, -0.23, -0.07, -0.15, -0.02, and 0.04µg/m3/yr in the entirety of China. The secondary aerosol (i.e., SO2- 4, NO- 3, and NH+ 4; SNA) had the highest fraction in PM2.5 concentrations (55.6-68.1% in different provinces), followed by OM and BC. Spatially, North, Central, and East China are the regions with the highest PM2.5 chemical component concentrations in China; meanwhile, they are also the regions with the most significant decrease in PM2.5 chemical fraction concentrations. The GD and MGWR model shows that among all variables, the number of enterprises, disposable income, private car ownership, and the share of secondary industry non-linearly enhance the differences in the spatial distribution of PM2.5 component concentrations. Electricity consumption has the strongest influence on NH+ 4 emissions in Northwest China and BC and OM emissions in Northeast China.

Cadmium tolerance in Elodea canadensis Michx: Subcellular distribution and metabolomic analysis.

The aquatic plant Elodea canadensis is considered a good candidate for ecotoxicological investigations. Cadmium (Cd) is a widespread contaminant in aquatic systems. In this study, to better elucidate the underlying tolerance mechanism and molecular impact of environmentally relevant Cd concentration in aquatic plants, subcellular distribution, chemical forms, and gas chromatography-mass spectrometry-based non-targeted metabolomics profiles were comprehensively analyzed in E. canadensis subjected to 0 and 10 µM Cd treatment for 5 d. Subcellular fractionation analysis of Cd-containing leaves showed that 67% of Cd was compartmentalized in cell wall followed by the soluble fraction (24 %) and organelles (9 %). The majority of Cd (90 %) was found in the extraction using 1 M NaCl. Metabolomic analysis using unsupervised principal component analyses and a supervised partial least squares discriminant analysis revealed clear differences in metabolic profiles between the two groups, demonstrating the metabolic effects of Cd. The 155 identified compounds altered by Cd were mainly from primary metabolism, including sugars, amino acids, organic acids, and their derivatives. Secondary metabolites such as polyphenols and phenolamides were also detected. The massive up-regulation of metabolites, including trehalose, proline, sarcosine, nicotianamine, putrescine, α-ketoglutaric acid, citric acid, and phytol might represent a detoxification mechanism. These findings highlighted the mechanistic strategies that E. canadensis employs to defend against Cd toxicity.

Release characteristics of heavy metals from electrolytic manganese residue under varying environmental factors.

High levels of manganese (Mn) and other heavy metals from electrolytic manganese residue (EMR) stockpiled would be released into the environment under natural conditions. A batch-leaching test was carried out to investigate the release characteristics of heavy metals from EMR with different storage times under simulated environmental conditions such as acid rain with different pH (3.0, 4.5, 5.6, and 7.0) at contact times of 1, 2, 4, 6, and 12 h; liquid to solid ratio (L/S) (5:1, 10:1, 20:1, and 30:1); and temperature (15, 25, 35, and 45 °C). The results showed that low pH (3.0 and 4.5) and high temperature (35 and 45 °C) could significantly promote heavy metal leaching from EMRs and increasing the L/S ratio above 20:1 mL/g significantly decreased heavy metal leachate concentrations due to dilution effect. Cr, Mn, and Pb concentrations in leachate increased almost continuously throughout the leaching process, while Zn decreased slightly at the 12th hour. Meanwhile, heavy metal concentrations in EMR1 (fresh EMR) were higher than in EMR2 (out stockpiled for more than 3 months). The concentrations of Mn, Pb, and Zn in leachates from EMRs at pH 3.0 and 4.5 leaching far exceeded the allowable maximum discharge concentrations for pollutants of the integrated wastewater discharge standard in China (GB8978-1996) by 57.5-59.0, 1.3-4.3, and 1.1-1.8 and 53.5-56.0, 3.04-7.25, and 1.0-1.91 times, respectively. Additionally, the Mn concentrations from both EMR leachates at pH 7.0 were above the national safe emission threshold. The morphological structure of EMRs changed after leaching, and XRD analysis showed the disappearance of MnO2, SiO2, FeS2, and CaSO4. The XPS revealed that Cr, Mn, Pb, and Zn existed as Cr3+, MnO, PbSO4, and ZnSiO3, respectively, after leaching. The study concluded that Mn, Pb, and Zn from EMRS leached by acid rain might pose a high potential environmental risk. Therefore, developing appropriate disposal techniques for EMR is necessary to prevent heavy metal pollution.

Insight into the Speciation of Heavy Metals in the Contaminated Soil Incubated with Corn Cob-Derived Biochar and Apatite.

Soil heavy metal contamination is a severe issue. The detrimental impact of contaminated heavy metals on the ecosystem depends on the chemical form of heavy metals. Biochar produced at 400 °C (CB400) and 600 °C (CB600) from corn cob was applied to remediate Pb and Zn in contaminated soil. After a one month amendment with biochar (CB400 and CB600) and apatite (AP) with the ratio of 3%, 5%, 10%, and 3:3% and 5:5% of the weight of biochar and apatite, the untreated and treated soil were extracted using Tessier's sequence extraction procedure. The five chemical fractions of the Tessier procedure were the exchangeable fraction (F1), carbonate fraction (F2), Fe/Mn oxide fraction (F3), organic matter (F4), and residual fraction (F5). The concentration of heavy metals in the five chemical fractions was analyzed using inductively coupled plasma mass spectroscopy (ICP-MS). The results showed that the total concentration of Pb and Zn in the soil was 3023.70 ± 98.60 mg kg-1 and 2034.33 ± 35.41 mg kg-1, respectively. These figures were 15.12 and 6.78 times higher than the limit standard set by the United States Environmental Protection Agency (U.S. EPA 2010), indicating the high level of contamination of Pb and Zn in the studied soil. The treated soil's pH, OC, and EC increased significantly compared to the untreated soil (p > 0.05). The chemical fraction of Pb and Zn was in the descending sequence of F2 (67%) > F5 (13%) > F1 (10%) > F3 (9%) > F4 (1%) and F2~F3 (28%) > F5 (27%) > F1 (16%) > F4 (0.4%), respectively. The amendment of BC400, BC600, and apatite significantly reduced the exchangeable fraction of Pb and Zn and increased the other stable fractions including F3, F4, and F5, especially at the rate of 10% of biochar and a combination of 5:5% of biochar and apatite. The effects of CB400 and CB600 on the reduction in the exchangeable fraction of Pb and Zn were almost the same (p > 0.05). The results showed that CB400, CB600, and the mixture of these biochars with apatite applied at 5% or 10% (w/w) could immobilize lead and zinc in soil and reduce the threat to the surrounding environment. Therefore, biochar derived from corn cob and apatite could be promising materials for immobilizing heavy metals in multiple-contaminated soil.

Temporal distribution and accumulation pattern of cadmium and arsenic in the actual field calcareous soil-maize system, northwest China.

The contrasting chemical behaviors of two toxic elements, arsenic (As) and cadmium (Cd) in co-contamination calcareous soil and its absorption by crops have not been thoroughly explored, especially in the implementation of the measure of prohibiting the use of wastewater to irrigate farmland. We propose that the present environmental characteristics of ecologically fragile areas and appropriate restoration measures are critical determinant of soil remediation. In this study, the typical field farmland irrigated by industrial and domestic wastewater in the Chinese Loess Plateau for >50 years was selected. The results showed that after the sewage irrigation was stopped, the mean contents of Cd (7.09 mg/kg) and As (13.47 mg/kg) in the soil were still rising, which might be a potential input source. The average values of soil risk indices such as the potential ecological risk (PERI = 2394), pollution load index (PLI > 4 for 60 % of studied samples), and degree of contamination (Dc = 86.6) showed severe soil pollution in the study area. The decrease of soil pH, the loss of soil texture and calcium carbonate were found to be the reasons for the high chemical activity of Cd. The bioconcentration factors (< 0.2) and translocation factor (> 1.0) of Cd indicate that corn is an excluder plant and an ideal phytoremediation method. Thus, 20 % of studied samples were higher than maximum permitted levels of Cd in grain, indicating potential related health hazards. On the contrary, As was mainly adsorbed in calcareous soil, and its bioavailability was lower compared with Cd. The difference between DTPA extraction and sequential extraction may be due to the transformation of chemical forms, resulting in unstable fractions increased the bioavailability of toxic elements. Overall, the findings provide new insights for solutions to manage and repair farmlands under the post-wastewater irrigation period.

Pollution status and risk assessment of heavy metals in the sediment of a historically contaminated lake treated by oxidation pond in China.

Sediment plays an important role in controlling biogeochemical cycling of heavy metals in aquatic environment. The Ya-Er Lake is a typical lake which was historically contaminated by heavy metals in Hubei province, China. After industries surrounding the Ya-Er Lake being shut down, oxidation pond treatment and dredging program were conducted for pollution management since 1970s. To date, the Ya-Er Lake has been used for aquaculture for several decades. However, the status of heavy metal levels and ecological risks in this lake remains unclear. Herein, concentrations, chemical fractions, and risk assessment of heavy metals were investigated in the Ya-Er Lake sediment. Results showed that concentrations of heavy metals in the Ya-Er Lake sediment were higher than other reported lake systems, suggesting that heavy metal pollution in the Ya-Er Lake is still serious. Relatively higher proportions of carbonates bound form of Cd and Ni indicated high-risk potential of these two heavy metals, and Cd and Ni should be listed as the primary heavy metal pollutants in the Ya-Er Lake according to the results of potential ecological risk index (PERI) and sediment quality guidelines (SQGs). The risk assessment code (RAC) analysis showed that Ni and Cd poses higher bioavailability and mitigation potential, and may affect the Ya-Er Lake ecosystem and downstream aquatic environment. These findings reflected that oxidation pond treatment and dredging sediment to near place are not effective to control heavy metal pollution, and a long-term ecological risk is still posed to surrounding aquatic environment. Our study provides scientific basis on pollution control and management in aquatic system contaminated by heavy metals.

[Speciation Characteristics and Risk Assessment of Soil Heavy Metals from Puding Karst Critical Zone, Guizhou Province].

The Community Bureau of Reference (BCR) sequential extraction method was used to analyze the distribution and chemical fractions of soil heavy metals (i.e., Cd, Cr, Zn, Fe, Ni, and Mn) under different land uses from the Puding karst critical zone, and the bioavailability and potential ecological risk of these heavy metals were evaluated. The results showed that the Fe, Zn, Cr, and Ni mainly were mainly concentrated in residual fractions and not likely to be absorbed by organisms, whereas the available fractions of Cd and Mn were in higher concentration, which retained strong potential migration and bioavailability. The richer organic matter in Puding soil might have promoted the transformation of oxidizable speciation of Fe, Ni, Cr, and Cd. The oxidizable forms of Fe, Mn, and Ni tended to accumulate in macro-aggregate soil. The risk assessment of RAC and RSP showed that the Puding karst soil was at slight ecological risk, and most heavy metals (except Cd) were at low risk to the ecological environment. Among the five land use types, the environmental risk of Cd in cropland and abandoned farmland was higher, which was mainly related to the input of Cd caused by fertilization, spraying pesticides, and other agricultural activities.

Partitioning behavior and ecological risk of arsenic and antimony in the sediment-porewater profile system in the Three Gorges Reservoir, China.

Arsenic and antimony are widely distributed toxic metalloids in aquatic environments. However, their partitioning behaviors in the sediment profile remain not well understood. Here, partitioning behaviors, diffusive fluxes, as well as the ecological risks of As and Sb in the sediment-porewater profile system in the tributaries of the Three Gorges Reservoir (TGR) were investigated. As and Sb showed markedly different spatial variations in the longitudinal profiles of both porewater and sediment samples. Specifically, the concentration of As showed an accumulation trend with depth, while that of Sb showed a relatively complicated trend. Further, As showed lower sediment-porewater partitioning coefficient (Kd) values, suggesting that it had a relatively lower sediment affinity and a higher mobility than Sb. Its residual fraction (30%-60%) was also lower than that of Sb. This phenomenon could be attributed to the chemical fractions of the trace metals and the pH value of the sediments. Furthermore, the Kd values corresponding to As were influenced by both the residual fraction (r = 0.338, p < 0.05) and the exchangeable fraction (r = -0.643, p < 0.01), while those corresponding to Sb were only influenced by pH. Additionally, even though these two trace metals showed low ecological and mobility risks, the diffusive fluxes at the sediment-water interface suggested that the sediment acted as a source of As and a sink for Sb relative to the overlying water. This study indicated that As and Sb had different partitioning behaviors and release risks in the sediment-porewater profile system, enhanced the understanding the transport and fate of As and Sb in the aquatic environment.

Effects of a barium-based additive on gaseous and particulate emissions of a diesel engine.

The addition of barium-based additives is one of the main methods used to suppress smoke emissions in non-road diesel engines. Herein, a commercial barium-based additive was added to diesel fuel at the manufacturer's recommended concentration and used in a non-road four-cylinder supercharged diesel engine, without an after-treatment system, in bench experiments. Regulated emissions of the diesel engine were measured, volatile organic compounds (VOCs) and particulate matter (PM) were sampled. The carbonaceous fraction, water-soluble ions and inorganic elements in the PM were analyzed. Results indicated that the additive effectively reduced carbon monoxide (CO), hydrocarbon (HC) and smoke emissions from the engine. A 71% reduction in smoke was observed at the rated working condition, which was the maximum reduction of the three tested conditions. The additive produced a 36% reduction of VOCs at the rated working condition. The proportion of high carbon number hydrocarbons in the VOCs increased while the atmospheric reactivity of the VOCs decreased. The additive suppressed the concentration of organic carbon (OC) and elemental carbon (EC) emissions with a maximum reduction (40%) of total carbon achieved under the rated working condition. After the application of the additive, the concentration of water-soluble ions (Cl-, SO42-, NO3-, Na+, K+, Ca2+, NH4+) and elements (Fe, Mn, S, Ca, Ba) in the PM increased. A trend of increasing Barium content in the PM matched a similar trend of decreasing smoke.

Heavy metals in a typical city-river-reservoir system of East China: Multi-phase distribution, microbial response and ecological risk.

The rapid construction of artificial reservoirs in metropolises has promoted the emergence of city-river-reservoir systems worldwide. This study investigated the environmental behaviors and risks of heavy metals in the aquatic environment of a typical system composed of main watersheds in Suzhou and Jinze Reservoir in Shanghai. Results shown that Mn, Zn and Cu were the dominant metals detected in multiple phases. Cd, Mn and Zn were mainly presented in exchangeable fraction and exhibited high bioavailability. Great proportion and high mobility of metals were found in suspended particulate matter (SPM), suggesting that SPM can greatly affect metal multi-phase distribution process. Spatially, city system (CiS) exhibited more serious metal pollution and higher ecological risk than river system (RiS) and reservoir system (ReS) owing to the diverse emission sources. CiS and ReS were regarded as critical pollution source and sink, respectively, while RiS was a vital transportation aisle. Microbial community in sediments exhibited evident spatial variation and obviously modified by exchangeable metals and nutrients. In particular, Bacteroidetes and Firmicutes presented significant positive correlations with most exchangeable metals. Risk assessment implied that As, Sb and Ni in water may pose potential carcinogenic risk to human health. Nevertheless, ReS was in a fairly safe state. Hg was the main risk contributor in SPM, while Cu, Zn, Ni and Sb showed moderate risk in sediments. Overall, Hg, Sb and CiS were screened out as priority metals and system, respectively. More attention should be paid to these priority issues to promote the sustainable development of the watershed.

Functional soil organic matter fraction in response to short-term tillage management under the double-cropping rice paddy field in southern of China.

Soil organic matter (SOM) and its fraction play an important role in maintaining and improving soil fertility of paddy field. However, there is still limited information about how SOM fraction response to carbon (C) sequestration with different short-term tillage practices under the double-cropping rice paddy field in southern of China. Therefore, the effects of 5-year short-term tillage treatments on different SOM fractions (physically protected, physico-chemically protected, physico-biochemically protected, chemically protected, biochemically protected, and unprotected) under the double-cropping rice paddy field in southern of China were studied in this paper. The field experiment included four different tillage treatments: rotary tillage with crop residue removed as a control (RTO), conventional tillage with crop residue incorporation (CT), rotary tillage with crop residue incorporation (RT), and no-tillage with crop residue retention (NT). The results showed that soil unprotected (cPOM), biochemically (NH-dSilt), physically-biochemically (NH-µSilt), and chemically protected (H-dSilt) fractions with different tillage treatments were the mainly C storage fraction in paddy field. The soil organic carbon (SOC) content in unprotected (cPOM and fPOM), physically protected (iPOM), and physico-chemically protected (H-µClay) fractions with CT treatment was increased by 1.45, 2.13, 1.91, and 1.42 times higher than that of RTO treatment, respectively. The results showed that largest proportion of fraction to SOC content was biochemically protected, followed by unprotected and physically-biochemically protected, and physically protected was the lowest. These results indicated that soil physically protected, physically-chemically protected, and physically-biochemically protected fractions with CT and RT treatments were higher than that of NT and RTO treatments. In summary, it was a benefit practice for increasing SOM fraction under the double-cropping rice paddy field in southern of China by combined application of conventional tillage and rotary tillage with crop residue incorporation management.

Cadmium subcellular distribution and chemical form in Festuca arundinacea in different intercropping systems during phytoremediation.

Intercropping with Cicer arietinum L has been suggested to improve the Cd decontamination capacity of Festuca arundinacea. However, the mechanisms stimulating this effect have not been revealed. The current study was designed to evaluate the changes in the subcellular distribution and chemical forms of Cd in different leaf types of F. arundinacea intercropped with C. arietinum L under different schemes. The results indicated that more than half of the Cd was bound in the cell wall in plant organs under all planting schemes, showing that cell wall deposition is an important detoxication pathway for the metal. Relative to the monoculture scheme, coordinate and malposed intercropping schemes increased the Cd concentration deposited in the cytoplasm of below-ground tissues from 37.6% to 45.2% and 45.1%, respectively. Additionally, the proportion of inorganic and water-soluble Cd in the below-ground parts of F. arundinacea increased from 73.6% in the monoculture scheme to 80.6% and 84.7%, in the coordinate and malposed intercropping schemes, respectively. The results exhibited that intercropping schemes can activate the metal in below-ground tissues and move it to aerial parts. The present study revealed the promoting mechanism of intercropping schemes on the phytoremediation efficiency of F. arundinacea for Cd at a subcellular level.

Chemical fractionation and risk assessment of surface sediments in Luhun Reservoir, Luoyang city, China.

To understand the potential risks of heavy metals, including their bioavailability and toxicity, 15 surface sediment samples were collected from Luhun Reservoir in Luoyang city, China. Total concentrations and chemical fractions of Cd, Cr, Cu, Ni, Pb, and Zn were analyzed. Various rating methods were used to evaluate the degree, risk, and toxicity of the heavy metal pollution. Results showed that Cd and Pb were preferentially associated with exchangeable (55.77-69.76%) and reducible (53.54-69.43%) fractions, respectively, and therefore exhibited high potential availability. Cr (57.14-86.56%) and Ni (32.21-72.77%) occurred primarily in the residual fraction. Metal concentrations in the effective fraction of the sediment decreased in the order: Cd (96.32%) > Pb (91.61%) > Cu (64.54%) > Zn (57.23%) > Ni (41.51%) > Cr (21.68%). Risk assessment indicated that the risk for Cd is extremely high (62.96%); Cu, Pb, and Zn are ranked as medium risk. Based on the potential ecological risk index, these metals (especially Cd) showed higher potential risk near the dam region. Toxic unit values (2.89-6.05) in more than 60% of sediment sites exceeded a value of 4, and Pb had a relatively higher contribution (1.06-2.65). Cd and Pb are the main contaminants in sediments of Luhun Reservoir and should be paid more attention in the future.

Integration of subcellular partitioning and chemical forms to understand silver nanoparticles toxicity to lettuce (Lactuca sativa L.) under different exposure pathways.

The current understanding of the biological impacts of silver nanoparticles (AgNPs) is restricted to the direct interactions of the particles with biota. Very little is known about their intracellular fate and subsequent toxic consequences. In this research we investigated the uptake, internal fate (i,e., Ag subcellular partitioning and chemical forms), and phytotoxicity of AgNPs in lettuce following foliar versus root exposure. At the same AgNP exposure concentrations, root exposure led to more deleterious effects than foliar exposure as evidenced by a larger extent of reduced plant biomass, elevated oxidative damage, as well as a higher amount of ultrastructural injuries, despite foliar exposure leading to 2.6-7.6 times more Ag bioaccumulation. Both Ag subcellular partitioning and chemical forms present within the plant appeared to elucidate this difference in toxicity. Following foliar exposure, high Ag in biologically detoxified metals pool (29.2-53.0% by foliar exposure vs. 12.8-45.4% by root exposure) and low Ag proportion in inorganic form (6.1-11.9% vs. 14.1-19.8%) potentially associated with AgNPs tolerance. Silver-containing NPs (24.8-38.6 nm, 1.5-2.3 times larger than the initial size) were detected in lettuce plants exposed to NPs and to dissolved Ag+, suggesting possible transformation and/or aggregation of AgNPs in the plants. Our observations show that the exposure pathway significantly affects the uptake and internal fate of AgNPs, and thus the associated phytotoxicity. The results are an important contribution to improve risk assessment of NPs, and will be critical to ensure food security.

Soil accumulation and chemical fractions of Cu in a large and long-term coastal apple orchard, North China.

PURPOSE: Coastal orchards, with greater humidity and precipitation, are favorable for fruit production, as well as mildew fungi development, thus becoming hot spots of Cu concentrations in soils due to the use of copper-based fungicides. However, little is known on the variation tendencies of Cu availability and mobility from these soils. This study aims to investigate the accumulation, spatial-temporal distribution, and chemical fractions of soil Cu in one of the largest coastal apple-producing area with over 40-year intensive cultivation in China. MATERIALS AND METHODS: A total of 104 orchard and 31 farmland topsoil samples were collected from Jiaodong Peninsula, Shandong Province. The total Cu concentration (T-Cu) and major element components (MnO, TiO2, SiO2, Fe2O3, and Al2O3) in the soil were determined by X-ray fluorescence spectroscopy. Available Cu concentration (A-Cu) was extracted with HCl or DTPA. Chemical fractionations of Cu were determined via sequential extraction method. The variation tendencies of T-Cu, A-Cu, Cu available ratio (AR), and chemical fractions with planting duration in the orchards were explored while a cokriging method was selected to predict their spatial distributions. Moreover, Pearson's correlation and multiple linear stepwise regressions were constructed to distinguish the vital factors in controlling Cu availability and mobility from these soils. RESULTS AND DISCUSSION: The results showed that long-term application of Cu-containing fungicides had increased Cu concentrations in orchard soils (85.77 mg kg-1) 3.5 times higher than the background value (24.0 mg kg-1) of local agricultural soils, in which 23.8% existed in the available form. Cu in the weak acid-soluble fraction (F1, 5.0 ± 3.5 %), reducible fraction (F2, 24.7 ± 6.6%), and oxidizable fraction (F3, 18.5 ± 7.8%) in orchard soils increased significantly with increasing planting durations whereas the residual fraction (F4, 51.7 ± 15.4%) exhibited a reverse trend. Total content, available content, and chemical fractions of Cu showed strong spatial heterogeneity. The availability and mobility of Cu in orchard soils were mainly controlled by total Cu content, pH, and soil organic carbon. CONCLUSIONS: Coastal orchards under warm and humid climate condition in China exhibited higher Cu input, along with acidification and rapid organic carbon turnover in the soils, eventually leading to large accumulation and high mobility of Cu in the soils.

[Contaminant Characteristics and Ecological Risk Assessments of Heavy Metals from River Networks in the Western Area of the Wangyu River].

To study the pollution characteristics and ecological risks of heavy metals in the western area of the Wangyu River, water and surface sediment samples of five rivers were investigated. The concentration and chemical fractions of eight heavy metals (Ni, Cu, Cr, Zn, As, Cd, Pb, and Hg) were analyzed, the pollution sources of heavy metals were studied using multivariate statistical analysis, and various ecological risk assessments were applied to identify the level of heavy metal contaminants. The results showed that the concentration of heavy metals in water was low, except for Hg, which was lower than the Class I standard of Surface Water Environmental Quality Standard. The content of heavy metals in surface sediments was high, except for Hg, which was significantly higher than the environmental background values. The partition coefficient of heavy metals in water-sediments showed that Cd, As, and Hg had strong re-emission potential. The Igeo indicated that Cu, Zn, and Cd were in a high pollution state as a whole. The RI showed that Cd was the main ecological risk factor in the study area. The RRSP indicated that the degree of pollution by Ni, Zn, and As was low because of its high residual fraction ratio, which was difficult to release under natural conditions. However, the degree of pollution by Cd was high because it had the highest content of weak acid extractable fraction among all the heavy metals. Therefore, it is necessary to pay more attention to Cd contamination. The source analysis of heavy metals showed that the western area of the Wangyu River was mainly affected by the pollution emissions from the surrounding machinery factories.

Arsenic concentration, speciation, and risk assessment in sediments of the Xijiang River basin, China.

In order to acquire the spatial distribution, speciation, and risk assessment of arsenic (As), 18 sediment samples were collected in the middle and upper reaches (Nanpan River, Beipan River, Hongshui River, Diaojiang River, and Duliu River) of the Xijiang River basin, China. The chemical fractions of As in the collected sediments were mainly dominated by the residual fraction and the Fe (Mn, Al) oxide/oxyhydroxides fractions. The correlation analysis results showed that the chemical fraction of As in sediments had close correlations with Mn, good correlations with Fe and organic matter (OM), while weak correlations with Al and carbonate. In addition, it also showed that Diaojiang River basin was found to have an extremely high As pollution status and suffered from high ecological risk. Duliu River and Nanpan River had moderately polluted levels of As and showed a low ecological risk. The other sample sites of Xijiang River basin were uncontaminated of As. The assessment results from this study indicated that the different types of species present based on the chemical fractionation of As from the Xijiang River basin showed different risks. Graphical abstract.

Cd, Cu, and Zn Accumulations Caused by Long-Term Fertilization in Greenhouse Soils and Their Potential Risk Assessment.

The intense management practices in greenhouse production may lead to heavy metal (HM) accumulations in soils. To determine the accumulation characteristics of HM and to evaluate possible HM sources in greenhouse soils, thirty typical greenhouse soil samples were collected in Shouguang District, Shandong Province, China. The results indicate that the Cd, Cu, and Zn concentrations are, respectively, 164.8%, 78.6%, and 123.9% higher than their background values. In the study area, Cd exhibits certain characteristics, such as wide variations in the proportion of its exchangeable form and the highest mobility factor and geo-accumulation index, which are indicative of its high bioavailability and environmental risk. In addition, there is a significant positive correlation between pairs of Cd, P, soil organic carbon, and cultivation age. Combined with principal component analysis, the results indicate the clear effects that agricultural activities have on Cd, Cu, and Zn accumulation. However, Cr, Ni, and Pb have a significant correlation with soil Fe and Al (hydr)-oxides, which indicates that these metals mainly originate from parent materials. This research indicated that long-term intensive fertilization (especially the application of chemical fertilizers and livestock manure) leads to Cd, Cu, and Zn accumulation in greenhouse soils in Shouguang. And the time required to reach the maximum permeable limit in agricultural soils for Cd, Cu, and Zn is 23, 51, and 42 years, respectively, based on their current increasing rates.