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Diffusive gradients in thin films technique (DGT) is recognized as a more reliable method for determining labile heavy metal (HM) concentration in soil than traditional destructive methods. However, the current DGT measurement index, C DGT , theoretically underestimates the true labile concentration (C labile ) of HMs in soil and lacks direct comparability with the conventional soil HM content indices due to unit differences. Here, we proposed C DGT-W , a new simple index which is defined as the HM accumulation in the binding layer, normalized to the weight of soil (optimized water content = 100% of the maximum water holding capacity) filled in the open cavity-type DGT device over a specified deployment time (optimized time = 24 h). The procedure for measuring C DGT-W is analogous to that of C DGT but includes precise determination of water content (water/dry soil) and the mass of soil filled in the cavity. We conducted measurements of Cu, Pb, Cr(Ⅵ) and As(V) as C DGT-W , C DGT , solution concentration (C soln ), and CaCl 2 extractable concentration (C CaCl2 ) on three soils with a diverse range of HM concentrations. C DGT-W showed significant linear correlations with all other tested indexes. The ratios of C DGT-W to C CaCl2 varied between 0.30 and 0.98 for all HM-soil combinations with only one exception, a range much greater than C DGT /C soln (typically <0.1) but lower than 1. This suggested that C DGT-W may more accurately reflect C labile than C DGT (theoretically underestimates C liable ) and C CaCl2 (likely overestimates C liable ). Additionally, C DGT-W measurements for these four HMs exhibited a broad measure concentration range and a low detection limit (mg/kg level). Consequently, C DGT-W may offer a more reliable alternative to C DGT for characterizing C labile in unsaturated soils., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The rapid increase in soil acidity coupled with the deleterious effects of cadmium (Cd) toxicity had led to a decline in worldwide agricultural production. Rice absorbs and accumulates Cd(II) from polluted paddy soils, increasing human health risks throughout the food chain. A 35-day hydroponic experiment with four japonica and four indica (two each of them tolerant and sensitive cultivars) was conducted in this study to investigate the adsorption and absorption of Cd(II) by rice roots as related with surface chemical properties of the roots. The results showed that the three chemical forms of exchangeable, complexed, and precipitated Cd(II) increased with the increase in Cd(II) concentration for all rice cultivars. The roots of indica rice cultivars carried more negative charges and had greater functional groups and thus adsorbed more exchangeable and complexed Cd(II) than those of japonica rice cultivars. This led to more absorption of Cd(II) by the roots and greater toxicity of Cd(II) to the roots of indica rice cultivars and more inhibition of Cd(II) stress on the growth of the roots and whole plants of indica rice cultivars compared with japonica rice cultivars, which was one of the main reasons for more declines in the biomass and length of indica rice roots and shoots than japonica rice cultivars. Cd(II) stress showed more toxicity to the sensitive rice cultivars and thus greater inhibition on the growth of the cultivars due to more exchangeable and complexed Cd(II) adsorbed by their roots induced by more negative charges and functional groups on the roots compared with tolerant rice cultivar for both indica and japonica, which resulted in greater decreases in the biomass and length of roots and shoots as well as chlorophyll contents of the sensitive cultivars than the tolerant cultivars. The roots of sensitive rice cultivars also absorbed more Cd(II) than tolerant rice cultivars due to the same reasons as above. These findings will provide useful references for the safe utilization and health risk prevention of Cd-contaminated paddy fields., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Hexavalent chromium (Cr(VI)) is a toxic heavy metal and its mobility and bioaccessibility in soils are influenced by soil properties. In this study, the soil pH and organic carbon contents of Ultisol, Alfisol, and Inceptisol were adjusted before they were polluted with 230 mg kg -1 Cr(VI). Alkaline digestion, sequential extraction, and an in vitro experiment were conducted to study the valence state, species, and bioaccessibility of Cr in the soils. The results showed that a high soil pH was not favorable for reduction of Cr(VI); therefore the Cr(VI) and exchangeable Cr contents were positively related to soil pH. Soil organic carbon promoted the reduction of Cr(VI). Almost all Cr(VI) was reduced to Cr(III) when the soil organic carbon content reached 10 g kg -1 . Chromium bioaccessibility in simulated gastric and intestinal phase solutions was influenced by Cr(VI) and Cr(III) adsorption/desorption, dissolution/precipitation, and redox reactions. Chromium bioaccessibility differences between the gastric and intestinal phases were associated with the Cr(VI)/Cr(III) ratio. Acidic conditions and a high organic carbon content promoted the conversion of Cr(VI) to Cr(III). When soil pH was increased from 4.01 to 5.85, Cr(VI) in Alfisol without the addition of humic acid increased from 96.38 to 174.78 mg kg -1 , the exchangeable Cr proportion increased from 9.7% to 22.6%, and Cr bioaccessibility increased from 41.29% to 49.14% in the gastric phase and from 41.32% to 48.24% in the intestinal phase. When the organic carbon content increased from 3.95 to 9.28 g kg -1 in Alfisol, Cr(VI) content decreased from 167.66 to 20.52 mg kg -1 , which led to a decrease in Cr bioaccessibility from 49.15% to 13.8% in the gastric phase and from 45.85% to 7.67% in the intestinal phase. Therefore, acidic conditions and increasing soil organic carbon levels can reduce the health risk posed by Cr in soils., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Phosphorus (P) availability in highly weathered soils is significantly influenced by the contents of iron (Fe)/aluminum (Al) oxides, clay minerals, and organic matter. With the increasing interest in biofertilizers (e.g. chitosan), it is important to understand how they affect P adsorption profiles on colloids of weathered soils rich in Fe/Al oxides. Thus, the effect of chitosan on the adsorption of P to colloids of hematite, gibbsite, Oxisol, and Ultisol was studied through electrokinetic measurements, spectroscopic analysis, and adsorption edge/isotherm profiles. The presence of chitosan significantly improved the surface positive charge and the decreasing trend of surface positive charge was slower for chitosan-treated colloids compared to the control with increasing pH. At pH 5.0, all the colloids were positively charged, with the oxides containing more positve charges than the soil colloids. At this pH value, the surface coverage capacity of P was 99.1, 61.6, 50.5, and 37.5 mmol kg⁻ 1 for Oxisol, Ultisol, hematite, and gibbsite, respectively. This suggests that clay minerals in soil colloids were vital in enhancing P adsorption. In the presence of chitosan, the surface coverage capacity of P was increased by 111%, 173%, 647%, and 488% for Oxisol, Ultisol, gibbsite, and hematite, respectively. Drawing inferences from spectroscopic analysis, citric acid desorption profile, and zeta potential analysis, we suggest that chitosan (CH) enhanced P adsorption by promoting the formation of (i) citric acid "undisplaceable" inner-sphere P complexes such as [Colloid-OP-O-CH] and [Colloid-OP-N-CH], (ii) citric acid "displaceable" outer-sphere P complexes such as {[Colloid-O-CH]-OP} and {[Colloid-N-CH]-OP}, and (iii) water "leachable or soluble" P complexes such as {[Colloid-CH] + PO 4 ³⁻} and {[Colloid-OP]⁻CH + }. Thus, applying chitosan as a biofertilizer (source of N) along with P in highly weathered soils could improve P availability while reducing P leaching., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

To explore the effects of the increases in pH and pH buffering capacity (pHBC) induced by crop residue biochars on the changes in soil available Cd content, six acidic paddy soils developed from different parents were amended with seeded sunflower plate biochar (SSPBC), peanut straw biochar (PSBC) and corn straw biochar (CSBC). The pH, pHBC, and available Cd of the soils were measured after laboratory incubation. The results showed that the incorporation of crop residue biochars led to the increases in soil pH and pHBC, but a decrease in soil available Cd content. The decreasing order of available Cd content was SSPBC > PSBC > CSBC and was consistent with the changes in soil pH induced by the biochars. During submerging and draining, soil pH increased first and then declined, however the content of available Cd decreased first and then increased significantly. Soil pH in the treatments with biochars showed little change during draining, which was different from the control without the biochars added. This was attributed to the enhancing effect of the biochars on soil pHBC. Also, there was a significant negative correlation between the change in available Cd content and soil pHBC during submerging/draining alternation and suggested that higher pHBC corresponded to smaller soil available Cd content. Consequently, the amount of Cd absorbed by rice was reduced, thereby reducing the potential risk of soil Cd to humans. These results can provide useful references for the remediation of Cd-contaminated paddy soils., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Soil-crop system is an important way that heavy metals harm the ecological environment and human health. To research and understand the process of heavy metal absorption, migration and accumulation in soil-crop system is important for the prevention and control of heavy metal pollution and the health of human beings. In this paper, we established a model for crop uptake of heavy metals to calculate the heavy metals contents of wheat roots, stems, leaves and grains, and we analyzed the accumulation process of heavy metals in roots, stems, leaves and grains in the growth cycle of wheat. The predicted values were compared with the measured values to test the accuracy of the model. The results demonstrated that different parts of wheat had different heavy metal absorption capacity, the absorption of the roots was the strongest, followed by leaves, and the absorption capacity of stems and grains was weak. In addition, the contents of different heavy metals in each part of wheat were also significantly different. The content of Cu was the highest, followed by Ni, while the contents of Pb and Cd were small. In the process of wheat growth, the heavy metal accumulation rate of stem, leaf and grain began to slow down at 90, 60 and 100 days respectively, and the concentration of heavy metals reached the maximum gradually, while the accumulation rate of heavy metals in roots showed a growing trend. We studied the process of absorption, migration and accumulation of heavy metals in soil-crop system by using numerical simulation technology, which can provide scientific basis for preventing the ecological and health risks of heavy metal pollution.

China's rapid development of industrialization and urbanization causes the growing problem of heavy metal pollution of soil, threatening environment and human health. Therefore, prevention and management of heavy metal pollution become particularly important. Critical loads of heavy metals are an important management tool that can be utilized to prevent the occurrence of heavy metal pollution. Our study was based on three cases: status balance, water environmental effects and health risks. We used the steady-state mass balance equation to calculate the critical loads of Cd, Cu, Pb, Zn at different effect levels and analyze the values and spatial variation of critical loads. In addition, we used the annual input fluxes of heavy metals of the agro-ecosystem in the Yangtze River delta and China to estimate the proportion of area with exceedance of critical loads. The results demonstrated that the critical load value of Cd was the minimum, and the values of Cu and Zn were lager. There were spatial differences among the critical loads of four elements in the study area, lower critical loads areas mainly occurred in woodland and high value areas distributed in the east and southwest of the study area, while median values and the medium high areas mainly occurred in farmland. Comparing the input fluxes of heavy metals, we found that Pb and Zn in more than 90% of the area exceeded the critical loads under different environmental effects in the study area. The critical load exceedance of Cd mainly occurred under the status balance and the water environmental effect, while Cu under the status balance and water environmental effect with a higher proportion of exceeded areas. Critical loads of heavy metals at different effect levels in this study could serve as a reference from effective control of the emissions of heavy metals and to prevent the occurrence of heavy metal pollution.

Surface soil (0-20 cm) and peanut kernel samples were collected in four main peanut producing areas of Shandong Province, and the contents of six PAEs chemicals that classified by the U. S. Environmental Protection Agency as priority pollutants were determined by gas chromatography (GC). The results indicated that the total concentration of six PAEs (sigma PAEs) ranged from 0.34 to 2.81 mg x kg(-1), and the mean was 1.22 mg x kg(-1). In four different areas, the order of sigmaPAEs concentration in soil was hilly area of middle southern Shandong > western plain of Shandong > Jiaodong Peninsula > northern plain of Shandong. The concentration of DBP in four main peanut producing areas of Shandong Province seriously exceeded the control limit in USA. The content of PAEs ranged from 0.17 to 0.66 mg x kg(-1) in peanut kernels, with the average value 0.34 mg x kg(-1) which was less than the suggested targets in USA and Europe and of low health risk. DEHP and DBP were the main components of PAEs both in soils and peanut kernels, with higher percentage content and detection rate. The sigma PAEs contents in soils or peanut kernels under plastic mulching were significantly higher than that of open field cultivation pattern. The PAEs concentrations in peanut kernels and soils had significant correlation, with the Pearson coefficient 0. 786 (sigma PAEs), 0.747 (DBP) and 0.511 (DEHP), respectively.

The environmental pollution and food safety problems caused by phthalic acid esters (PAEs) have been attracted 'extensive attention around the world. As a large PAEs producer and consumer, China is facing severe PAEs environmental pollution problems. This paper reviewed the present pollution status of six PAEs classified by the U.S. Environmental Protection Agency as the priority pollutants in China farmland soils, analyzed the sources of these six PAEs in this country, and discussed the absorption and accumulation characteristics of the PAEs in different crops as well as the bio-toxic effects of PAEs pollutants. The PAEs concentrations in China farmland soils are significantly higher those in the farmland soils of the United States and European countries. The main sources of PAEs in China farmland soils are atmospheric deposition, agricultural films, sewage sludge application, and wastewater irrigation. There exist significant differences in the characteristics of PAEs absorption, accumulation, and distribution among different crops. PAEs not only have negative effects on soil quality, crop growth, and crop physiological and biochemical properties, but also possess bio-accumulative characteristics. The weaknesses in current researches were pointed out, and the suggestions for the further researches were given, e. g., to expand the scope of PAEs pollution survey, to explore the toxic mechanisms of PAEs on crops, and to develop the techniques for in situ remediation of PAEs-polluted soils.