Impacts of polypropylene microplastics on the distribution of cadmium, enzyme activities, and bacterial community in black soil at the aggregate level.

Microplastics (MPs) can co-occur widely with heavy metals in soil. This study intended to investigate the influences of the co-exposure of polyethylene MPs (0.5 %, w/w) and cadmium (Cd) in black soil on the Cd distribution, enzyme activities, and bacterial communities in both bulk soil and different sized soil aggregates (> 1, 0.50-1, 0.25-0.50, and < 0.25 mm aggregates) after a 90-day incubation. Our results showed that the existence of MPs increased the distributions of Cd in >1 mm and < 0.25 mm soil aggregates and decreased its distributions in 0.50-1 mm and 0.25-0.50 mm soil aggregates. About 12.15 %-17.65 % and 9.03 %-11.13 % of Cd were distributed in the exchangeable and oxidizable forms in bulk soil and various sized soil aggregates after the addition of MPs which were higher than those in the only Cd-treated soil (11.17 %-14.72 % and 8.66 %-10.43 %, respectively), while opposite tendency was found for Cd in the reducible form. Urease and ß-glucosidase activities in the Cd-treated soils were 1.14-1.18 and 1.07-1.31 times higher than those in the Cd-MPs treated soils. MPs disturbed soil bacterial community at phylum level and increased the bacteria richness in bulk soil. The levels of predicted functional genes which are linked to the biodegradation and metabolism of exogenous substances and soil C and N cycles were altered by the co-exposure of Cd and MPs. The findings of this study could help deepen our knowledge about the responses of soil properties, especially microbial community, to the co-occurrence of MPs and heavy metals in soil.

Levels of heavy metal in soil and vegetable and associated health risk in peri-urban areas across China.

Peri-urban vegetable field plays an essential role in providing vegetables for local residents. Because of its particularity, it is affected by both industrial and agricultural activities which have led to the accumulations of heavy metal in soil. So far, information on heavy metal pollution status, spatial features, and human health risks in peri-urban vegetable areas across China is still scarce. To fill this gap, we systematically compiled soil and vegetable data collected from 123 articles published between 2010 and 2022 at a national level. The pollution status of heavy metals (i.e., cadmium (Cd), mercury (Hg), arsenic (As), lead (Pb), chromium (Cr), copper (Cu), nickel (Ni), and zinc (Zn)) in peri-urban vegetable soils and vegetables were investigated. To evaluate the levels of heavy metal pollution in soil and human health risks, the geoaccumulation index (Igeo) and target hazard quotient (HQ) were calculated. The results showed that mean concentrations of Cd, Hg, As, Pb, Cr, Cu, Ni, and Zn in peri-urban vegetable soils were 0.50, 0.53, 12.03, 41.97, 55.56, 37.69, 28.55, and 75.38 mg kg-1, respectively. The main pollutants in peri-urban vegetable soil were Cd and Hg, and 85.25% and 92.86% of the soil samples had Igeo > 1, respectively. The mean Igeo values of this regions followed the order of northwest > central > south > north > east > southwest > northeast for Cd and northeast > northwest > north > southwest > east > central > south for Hg. The mean Cd, Hg, As, Pb, Cr, Cu, Ni, and Zn concentrations in vegetables were 0.30, 0.26, 0.37, 0.54, 1.17, 6.17, 1.96, and 18.56 mg kg-1, respectively. Approximately 87.01% (Cd), 71.43% (Hg), 20% (As), 65.15% (Pb), 27.08% (Cr) of the vegetable samples exceeded the safety requirement values. The vegetables grown in central, northwest, and northern China accumulated much more heavy metals than those grown in other regions. As the HQ values for adults, 53.25% (Cd), 71.43% (Hg), 84.00% (As), and 58.33% (Cr) of the sampled vegetables were higher than 1. For children, the HQ values were higher than 1 for 66.23% (Cd), 73.81% (Hg), 86.00% (As), and 87.50% (Cr) of the sampled vegetables. The findings of this study demonstrate that the situation of heavy metal pollution in peri-urban vegetable areas across China are not optimistic and residents who consume the vegetables are at high risk of health issues. To ensure soil quality and human health, strategies should be taken to guide vegetable production and remedy soil pollution in peri-urban areas with the rapidly urbanizing China.

Assessing the ecological loss of mining areas in Taiwan.

Mines are mostly located in the mountains and national forestlands in Taiwan. The development and use of mines have severely damaged the environment. Despite the long history of mining, the value of forest ecological services lost during mining operations have not yet been incorporated into the expenses borne by miners, and miners are not liable for compensation for ecological damage. This study evaluated the forest ecosystem service benefits lost since mining began, with the aim of providing future reference for calculating ecological damage related to mining. We investigated Mount Taibai mines in Yilan (northeast Taiwan) and Mount Yongshi mines in Hualian (east Taiwan), which are richly forested areas. According to Article 13 of the Mining Act in Taiwan, mining rights have a limitation of 20 years, and the two mines in this study have been in operation for 20 years. By using four ecological services-forest production, carbon sequestration, water resource replenishment, and forest recreation-we estimated the loss of ecological values in both mining regions. The result indicated that the loss of total forest production benefits over 20 years was 7,498.6 k New Taiwanese dollars (NTD) in Mount Taibai mines and 6,543.1 k NTD for Mount Yongshi mines, while the loss for the total carbon sequestration benefits over 20 years was 19,950 k NTD in Mount Taibai mines and 17,400 k NTD in Mount Yongshi mines. The loss of value for the total water conservation benefits over 20 years was 11,160 k NTD in Mount Taibai mines and 5,070 k NTD in Mount Yongshi mines. The loss value of forest recreation over 20 years was 1,443,855 k NTD for the two mines.

Colloid-facilitated mobilization of cadmium: Comparison of spring freeze-thaw event and autumn freeze-thaw event.

Freeze-thaw action has the potential to facilitate the mobilization of colloid-associated contaminants in soil. However, the differences in colloid-associated contaminants following autumn freeze-thaw (AFT) events and spring freeze-thaw (SFT) events remain unclear. In this study, the potential influence mechanisms of AFT and SFT on both the generation and migration of colloids and colloid-associated cadmium (Cd) in soil were explored. Higher aggregate stabilities were found in soils after AFT compared with after SFT. After SFT, lower Cd concentrations were found in soil aggregates of 0.25-0.50 mm and <0.106 mm and higher concentrations were found in 0.106-0.25 mm aggregates. Moreover, SFT generated higher amounts of colloidal Cd than AFT, while AFT increased the total Cd concentration in leachates. Additionally, compared with SFT, AFT led to higher Cd concentrations in dissolved and colloid-associated forms in leachates. These findings demonstrate that higher amounts of colloid and fewer loadings of Cd in colloids in Cd contaminated soil can be found after SFT events. Thus, to better understand the environmental risk of contaminants in areas subject to seasonal freeze-thaw cycles, the differences between freeze-thaw processes in spring and autumn should be considered.

Effects of soil aging conditions on distributions of cadmium distribution and phosphatase activity in different soil aggregates.

Aging behaviors of metals in the field differ from those in a controlled laboratory environment. Whether aging conditions influence the fates of metals in soil remains unclear. In this study, distributions of cadmium (Cd) and phosphatase activity were compared in soil aggregates (i.e., >2, 1-2, 0.25-1, and <0.25 mm) along a profile (0-5, 5-10, and 10-15 cm) at the end of 500-day aging experiments under both controlled laboratory and field conditions. Cd concentration in the 0-5 cm layer was lower and Cd concentration in the 5-10 cm layer was higher in field-aged soil compared to laboratory-aged soil. 25.26-35.62% of soil Cd was loaded in >2 mm aggregates of field-aged soils, and 58.41-66.95% was in laboratory-aged soils. Higher loadings of Cd in 0.25-1 and <0.25 mm aggregates were found in field-aged soil. A higher proportion of exchangeable Cd fraction (20.93% of total soil Cd) was found in the 0-5 cm layer of field-aged soil than in laboratory-aged soil (17.63%), while the opposite tendency was found in deeper soil layers. Soil phosphatase activities in field-aged soils were 1.13-1.26 times higher than in laboratory-aged soils. Phosphatase loadings in the >2 mm aggregates were lower and loadings in both the 1-2 and 0.25-1 mm aggregates were higher in field-aged soils than in laboratory-aged soils. Furthermore, correlation analysis and principal component analysis indicated that available Cd fractions accounted for most of the variations in phosphatase activities. In summary, the fates of the exogenous metal Cd differed between field and controlled laboratory conditions. To better understand the behaviors of heavy metals in soil, especially in a seasonal freeze-thaw area, further field studies are needed.

Do freeze-thaw cycles affect the cadmium accumulation, subcellular distribution, and chemical forms in spinach (Spinacia oleracea L.)?

To date, although there are many studies investigating the toxicity of heavy metal to plant, little research exists in the seasonal freeze-thaw (FT) regions where FT cycles often happen during the plant growing process. To reveal the adaptive mechanisms of plants to the combination stresses of cadmium (Cd) and FT, the Cd accumulation, subcellular distribution, chemical forms, and antioxidant enzyme activity (peroxidase (POD)) were investigated in spinach (Spinacia oleracea L.) growing under different soil Cd levels (i.e., 0.10 mg Cd kg-1 soil (low), 1.21 mg Cd kg-1 soil (medium), and 2.57 mg Cd kg-1 soil (high)). Compared to the non-freeze-thaw (NFT) treatments, higher Cd concentrations in the root and lower translocation factors from root to leaf were found for the plants experiencing FT cycles. FT significantly decreased the Cd concentrations in the leaves under the low- and medium-Cd treatments, while similar values were found for the high-Cd treatments. Generally, FT could decrease the concentrations and proportions of Cd stored in the cell wall and soluble fractions and increase them in the organelle fractions for the medium- and high-Cd treatments, while opposite tendency was found for the low-Cd treatments. Moreover, larger Cd amounts in the inorganic and water-soluble forms were found for the low- and medium-Cd treated plants under FT, while lower values were found for the high-Cd treatments. Additionally, POD, which presented higher activities at the low- and medium-Cd treatments and lower activities at the high-Cd treatments under FT, were also significantly influenced by the Cd × FT interaction. This study indicated that FT could significantly change the accumulations of Cd in plant, and it provided a new insight into the Cd accumulation by plants in the seasonal FT region.

Laboratory versus field soil aging: Impacts on cadmium distribution, release, and bioavailability.

To date, most studies about the aging of metals in soil were based on the controlled laboratory experiments, and few works have attempted to investigate how aging process influences the distribution and bioavailability of metals in soil under the field condition. The purpose of this study was to compare the aging of cadmium (Cd) in soils under the controlled laboratory and the field by monitoring time-dependent soil Cd speciation changes, Cd release kinetics, and Cd bioavailability to plant through the 438-day aging experiments. During the aging process, the proportions of Cd associated with the most weakly bound fraction tended to decrease, with corresponding increases in the more stable binding fractions. After aging, a higher concentration of available Cd was found in the field aging soil (0.74 mg kg-1) than the laboratory aging soil (0.65 mg kg-1). The Elovich equation was the best model to describe the soil available Cd aging process. The constant b in the Elovich equation, which was defined as the transformation rate, was in the order of laboratory aging soil > field aging soil. Moreover, higher Cd release amounts were found for the field aging soil (2.74 mg kg-1) than the laboratory aging soil (2.57 mg kg-1) at the end of aging. Additionally, higher body Cd concentrations were found for the vegetables grown in the field aging soils (1.49 mg kg-1, fresh weight) than those grown in the laboratory aging soils (1.32 mg kg-1, fresh weight). Therefore, this study indicated that the metal distribution process and its bioavailability may be overestimated or underestimated if research data from the laboratory experiments are used to derive soil quality criteria or investigate soil metal bioavailability.

Integration of chemical and toxicological tools to assess the bioavailability of copper derived from different copper-based fungicides in soil.

Because the extensive use of Cu-based fungicides, the accumulation of Cu in agricultural soil has been widely reported. However, little information is known about the bioavailability of Cu deriving from different fungicides in soil. This paper investigated both the distribution behaviors of Cu from two commonly used fungicides (Bordeaux mixture and copper oxychloride) during the aging process and the toxicological effects of Cu on earthworms. Copper nitrate was selected as a comparison during the aging process. The distribution process of exogenous Cu into different soil fractions involved an initial rapid retention (the first 8 weeks) and a following slow continuous retention. Moreover, Cu mainly moved from exchangeable and carbonate fractions to Fe-Mn oxides-combined fraction during the aging process. The Elovich model fit well with the available Cu aging process, and the transformation rate was in the order of Cu(NO3)2 > Bordeaux mixture > copper oxychloride. On the other hand, the biological responses of earthworms showed that catalase activities and malondialdehyde contents of the copper oxychloride treated earthworms were significantly higher than those of Bordeaux mixture treated earthworms. Also, body Cu loads of earthworms from different Cu compounds spiked soils were in the following order: copper oxychloride > Bordeaux mixture. Thus, the bioavailability of Cu from copper oxychloride in soil was significantly higher than that of Bordeaux mixture, and different Cu compounds should be taken into consideration when studying the bioavailability of Cu-based fungicides in the soil.

Adsorption behaviors of fungicide-derived copper onto various size fractions of aggregates from orchard soil.

Although the gradual accumulations of Cu in orchard soils due to the application of Cu-based fungicides have been widely reported, limited information is available about the retention characteristics of fungicide-derived Cu in soil, especially in various size soil aggregates. This study described the adsorption characteristics of Cu from commonly used fungicide, Bordeaux mixture (CuSO4 + Ca(OH)2), onto various aggregate fractions (2000-1000, 1000-500, 500-250, 250-106, and <106 µm) of orchard soil. The Cu(NO3)2 was selected as a comparison. Two different types of adsorption experiments were conducted as follows: variable pH and variable Cu concentration experiments. The adsorption processes of Bordeaux mixture and Cu(NO3)2 onto the studied soil samples followed well with the Freundlich isotherm, and the adsorption isotherms were the S shaped. The adsorption amounts of Cu from different Cu compounds differed, and Bordeaux mixture can result in more Cu retention in soil than Cu(NO3)2. The adsorption ability of different size soil aggregates varied, and it was mainly governed by soil properties. The findings of this study suggested that both the chemical compositions of Cu compounds and the soil physical structure should be taken into account when performing soil Cu retention experiments with fungicide-derived Cu.