Multi-scale spatial heterogeneity of heavy metals in paddy soils: Source-driver coupling identification using Geodetector and positive matrix factorization integration

BACKGROUND: Most of the tailings have been left without any management in abandoned meta lliferous mines and have become the main source of heavy metal contamination for agricultural soils and crops in the these areas. METHODS AND RESULTS: This experiment was carried out to investigate the assessment of the heavy metal contamination in paddy soils located on downstream of the closed metalliferous mine. The average total concentrations of cadmium (Cd), copper (Cu), lead (Pb), zinc (Zn), and arsenic (As) in paddy soils were 8.88, 56.7, 809, 754, and 37.9 mg/kg, respectively. Specially, the average concentrations of Cd, Pb and Zn were higher than those of warning criteria for soil contamination(4 mg/kg for Cd, 200 mg/kg for Pb, and 300 mg/kg for Zn) in agricultural soil established by Soil Environmental Conservation Act in Korea. The proportions of 0.1 M HCl extractable Cd, Cu, Pb, Zn, and As concentration to total concentration of these heavy metals in paddy soils were 27.7, 21.3, 35.1, 13.8 and 10.5%, respectively. The pollution index of these five metals in paddy soils ranged from 0.42 to 11.92. Also, the enrichment factor (EFc) of heavy metals in paddy soils were in the order as Cd>Pb>Zn>Cu>As, and the enrichment factor in paddy soil varied considerably among the sampling sites. The geoaccumulation index (Igeo) of heavy metals in soils were in the order as Cd>Pb>Zn>Cu>As, specially, the average geoaccumulation index of Cd, Pb, and Zn (Igeo 2.49 ～3.10) were relatively higher than that of other metals in paddy soils.

BACKGROUND: For the heavy metal cotamination sites, it is very important to estimate the human bioavailability quotients for heavy metals in paddy soils released from mine tailings, which is a major source of contamination in Korea, and to assess the human health risks of heavy metals. METHODS AND RESULTS: This experiment was carried out to investigate the human bioavailability quotient of the heavy metals in paddy soils below part of the closed metalliferous mine. For estimating the human bioavailability quotients for heavy metals, 30 paddy soils below part of the closed mine were collected, and analyzed for Cd, Cu, Pb, Zn, and As using simple bioavailability extraction test(SBET). The quantities of Cd, Cu, Pb, Zn and As extracted from paddy soils below part of the mine by using the SBET analysis were 28.1, 17.3, 34.1, 14.6 and 2.3% respectively. Specially, the maximum values of Cd, Pb and Zn were 73.3, 81.5 and 58.1% of human bioavailability quotient, respectively, and varied considerably among the sampling sites. The human bioavailability quotient of Cd, Cu, Pb and Zn in soils near the closed mine showed significant positive correlation among soil pH value, O.M. and Ex. Ca. contents, while it correlated negatively between soil Ex. K and Ex. Mg contents in paddy soils. Also, its of Cd, Cu, Pb and Zn in paddy soils showed significant positive correlation with 0.1M HCl extractable and total contents, while in soils, it correlated negatively with As content in soil near the closed mine. CONCLUSION: The results of the simple bioavailability extraction test (SBET) indicate that regular ingestion of soils by the local population could be closed a potential health threat due to long-term heavy metals exposure in these mine areas.

Accumulation, ecological-health risks assessment, and source apportionment of heavy metals in paddy soils: A case study in Hanzhong, Shaanxi, China

This study was carried out with the intention of evaluating heavy metal contamination in cultivated paddy areas. The speciation of heavy metals in paddy soils was determined in order to gain insight regarding their origin and distribution in soils. Five sampling sites were randomly selected from Kedah (Yan, Kota Setar, Kubang Pasu district) and Penang (Bumbung Lima district), where the soils constituted marine alluvial deposits. A site in Langkawi, where organic paddy farming is practised was used as the control. The sequential extraction method was adopted in order to obtain the four heavy metal fractions namely the easily leachable and ion exchange (ELFE), acid reducible (AR), oxidizable organic (OO) and resistant (RR) fractions. This study shows that the soil samples were clayey (82 to 96% of grain size Mn>Cr>Cd>Pb>Zn>Cu. Heavy metals such as Pb, Cu, Cr and Zn predominantly occurred in the insoluble form (RR fraction), with the oxides of Fe and Mn incorporated into the clay minerals. Although, the fertilizers and pesticides studied contained low amounts of heavy metals, the elevated amount of amount of Mn and Cd in the soils (ELFE fraction) could possibly be attributed to the longterm and repeated application of these materials to the cultivated paddy areas.

The source apportionment of pollutants is the key to preventing and controlling the pollution caused by heavy metals in soils. The aim of this study was to investigate the main sources of heavy metals in the soils of black shale areas in western Zhejiang, China. Based on geostatistical spatial analysis, this research employed positive matrix factorization (PMF) for the source apportionment of heavy metals in paddy soil. The results showed that contaminated arable soils were concentrated in the western and southern study areas. At least five major sources of heavy metals were screened in this study: natural sources (39.66%), traffic emissions (32.85%), industrial emissions (9.23%), agricultural activities (9.17%), and mining (9.10%). To be specific, Cd was mainly from mining; As originated from agricultural inputs such as fertilizers and pesticides; and Hg, as an industrial pollutant, was transported by atmospheric deposition in the study area. The accumulation of Pb, Zn, and Cu was mainly influenced by natural sources and anthropogenic sources, i.e., traffic emissions, while that of Cr and Ni was controlled by natural sources.

Pollution assessment, ecological risk and source identification of heavy metals in paddy soils and rice grains from Salem, South India

Contamination of soils with heavy metals is widespread and poses a long-term risk to ecosystem health. Abandoned and active mining sites contain residues from ore-processing operations that are characterised by high concentrations of heavy metals. The distribution and mobility characteristics of heavy metals (As, Cd, Cu, Pb, and Zn) in paddy soil samples from Kočani Field (Macedonia) using ICP-EAS and a sequential extraction procedure was evaluated. The results indicate that highly elevated concentrations of As, Cd, Cu, Pb, and Zn were detected in the paddy soil sample from location VII-2 in the vicinity of Zletovo mine and Zletovska river in the western part of Kočani Field, which drains the untreated acid mine waters and mine wastes from the active Zletovo mine. The degree of contamination based on index of geoaccumulation (I geo) from strong to weak in the paddy soils samples is Pb > As > Cd > Zn > Cu. The mobility potential of heavy metals in all paddy soil samples increases in the order As < Cu < Pb < Zn < Cd. According to the results of the anthropogenic impact on the paddy soils, a further study on the heavy metal concentrations in rice and other edible crops, the remediation process of the paddy soils and a dietary study of the local population are needed.

Biochar is a stabilised, carbon-rich material created when biomass is heated to temperatures usually between 450 and 550 °C, under low-oxygen concentrations. This study evaluated the effectiveness of sawdust, cocoa pod ash and rice husk biochars in remediating metal-contaminated paddy soil in Nobewam, Ghana. Biochar was applied 21 days before cultivating the rice for 120 days, followed by soil sampling and rice harvesting for metals and physicochemical analyses. Compared to the untreated soils, biochar treatments exhibited an enhancement in soil quality, characterised by an increase in pH of 1.01–1.20 units, an increase in available phosphorus (P) concentration of 6.76–13.05 mg/kg soil and an increase in soil total nitrogen (N), and organic carbon (OC) concentration, ranging from 0.02% to 0.12%. Variabilities in electrical conductivity and effective cation exchange capacity were observed among the treated soils. Concentrations of potentially toxic metals (arsenic, cadmium, copper, mercury, lead and zinc) in paddy soils and rice analysed by atomic absorption spectroscopy showed significant differences (p &lt; 0.05) among the sampled soils. The concentrations of arsenic and lead in all soil samples exceeded the Canadian Council of Ministers of the Environment soil quality guideline for agricultural soils, with untreated soils having the highest levels among all the soils. Cadmium had a potential ecological risk index &gt; 2000 and a geoaccumulation index above 5, indicating pollution in all samples. In contrast, arsenic and mercury contamination were only found in the untreated soils. Among the tested treatments, rice husk and its combinations, particularly with cocoa pod ash, showed significant efficacy in reducing metal concentrations in the soils. The potential non-carcinogenic human health risks associated with the consumption of rice grown in biochar-treated soils were lower for all the metals compared to the control samples. Future research should focus on long-term field studies to validate these findings and explore the underlying mechanisms governing metal immobilization in paddy fields.

To trace the sources and evaluate the health risks of heavy metals in paddy soils of Jiulong River Basin, seventy-one samples of paddy soils were collected in July 2017. The heavy metals contents were determined using inductively coupled plasma mass spectrometry (ICP-MS) and atomic fluorescence spectrophotometry (AFS). The geo-accumulation index (Igeo) and potential ecological risk index (RI) methods were applied to evaluate the contamination of heavy metals, principal component analysis (PCA) and absolute principal component scores-multiple linear regression (APCS-MLR) were applied to trace the sources, and dose–response model was applied to assess the health risks to the human body. The results indicated that the paddy soils were moderately to heavily polluted by Cd and slightly polluted by Hg, Pb, As and Zn. Heavy metals in paddy soils presented considerable to high potential ecological risk, mostly contributed by Cd and Hg with contribution rates of 59.4% and 26.2%, respectively. The heavy metals contaminating paddy soils were derived from natural sources, agricultural activities, industrial discharge, coal combustion and unidentified sources, with source contribution rates of 31.37%, 24.87%, 19.65%, 18.05% and 6.06%, respectively. The heavy metals in paddy soils presented carcinogenic risks which humans can tolerate and no non-carcinogenic risks. The total non-carcinogenic risks mainly derived from agricultural activities and coal combustion, with contribution rates of 62.16% and 20.21%, respectively, while the total carcinogenic risks mainly derived from natural sources and industrial discharge, with contribution rates of 51.17% and 18.98%, respectively.

The interaction between particulate organic matter and copper, zinc in paddy soil

A modified critical load assessment method of heavy metals in paddy soil at large scale

Effect of moisture regime on the redistribution of heavy metals in paddy soil

There is an increasing concern for potentially hazardous metals pollution, which can threaten crops production and human health. In this study, the spatial distribution and environmental risks of eight heavy metals in surface soil samples collected from the paddy fields in Yongshuyu irrigation area, Northeast China were investigated. The mean concentrations of Pb, Cr, Cu, Ni, Zn, Cd, Hg and As were 34.6 ± 4.67, 82.8 ± 9.51, 17.3 ± 4.09, 21.2 ± 12.0, 88.6 ± 17.9, 0.18 ± 0.15, 0.22 ± 0.07 and 8.77 ± 2.47 mg/kg, respectively, which were slightly higher than their corresponding background values of Jilin Province, indicating enrichment of these metals in the paddy soils, especially for Ni, Cd and Hg. The spatial distribution of heavy metals was closely correlated with local anthropogenic activities, such as agricultural production, mining and transportation. The hot-spot areas of As and Cd were mainly concentrated in the up-midstream where were associated with agricultural activities. Cr and Cu showed similar spatial distributions with hot-spot areas distributed the whole irrigation area uniformly. Ni was mainly distributed in the downstream where Ni quarries concentrated, while the spatial distribution patterns of Hg was mainly located in the upstream and downstream where the soil was significantly influenced by irrigation and coal mining emission. The spatial distributions of Pb and Zn were mainly concentrated along the highway side. The pollution levels of Yongshuyu irrigation area were estimated through index of geo-accumulation (Igeo), Nemerow integrated pollution index (NIPI) and potential ecological risk index (PERI). The results showed that Cd and Hg were the main pollutants in the study area. Health risk assessment results indicated that children were in higher non-carcinogenic and carcinogenic risks than adults with the carcinogenic metal of As. Ingestion was the main exposure pathway to non-carcinogenic and carcinogenic risk for both adults and children. Principal component analysis (PCA) indicated that Cr and Cu were mainly from parent materials, while Cd and As were mainly affected by agricultural activities. Pb and Zn were controlled by traffic activities, and the accumulations of Ni and Hg were associated with mining activities. This study would be valuable for preventing heavy metals inputs and safety in rice production of the Songhua river basin.

A combined amendment (CF) consisting of 90% calcium sulfate (CaSO4) and 10% ferric oxide (Fe2O3) was used to investigate the feasibility, active principles, and possible mechanisms of the immobilization of heavy metals in paddy soil. A soil incubation experiment, two consecutive pot trials, and a field experiment were conducted to evaluate the effectiveness and persistence of CF on metal(loid) immobilization. Soil incubation experiment results indicated that the application of CF significantly decreased the concentrations of cadmium (Cd), lead (Pb), and arsenic (As) in soil solution. CF treatments simultaneously reduced the accumulation of Cd, Pb, and As in two consecutive pot trials. The total Cd, Pb, and As concentrations in the rice grains were respectively 0.02, 2.08, and 0.62 mg kg-1 in the control treatment in the second year, which exceeded the safety limits of contaminants in food products in China. However, a high amount of CF amendment (CF-H, 0.3%) effectively decreased Cd, Pb, and As by 75.0%, 75.5%, and 46.8%, respectively. Further, with the CF amendment, the bioavailable Cd and Pb in the soil and the accumulation of Cd, Pb, and As in rice grain in the field experiment were also significantly decreased. The concentrations of Cd, Pb, and As in grains were respectively 0.02, 0.03, and 0.39 mg kg-1 in the control treatment in the field experiment, which decreased to 0.01, 0.01, and 0.22 mg kg-1 with CF addition, suggesting that grains produced in the field could pose less health risk. In conclusion, these results implied that CF was an effective and persistent combined amendment to immobilize heavy metals in soil and thereby can reduce the exposure risk of metal(loid)s associated with rice consumption.

공업단지 인근 중금속 복합오염 농경지에서 중금속 오염 특성과 재배작물인 미나리중에 흡수 축적된 중금속과의 관계를 구명하기 위해 토양내 중금속의 상대적인 오염평가지수, 미나리의 중금속 축적양상 및 식물흡수도 등을 분석 검토하였다. 토양의 화학성분은 일반 논토양보다 대체로 높았으며, 특히 토양 pH및 치환성 Ca 함량이 매우 높았다. 토양의 중금속 중 Cd 및 Cu 농도가 우리나라 토양환경기준을 초과하였고, 년차별 0.1N-HCl 추출 가용성함량은 감소하는 경향을 보였다. 토양의 중금속 오염지수(PI) 및 그 편차는 재배토양 보다 농수로 퇴적토양에서 높았고, 중금속별 지화학적농축계수(Igeo)는 Cu>Cd>Ni>Zn>Pb 순이었다. 토양의 전함량에 대한 0.1N-HCl 침출성 함량 비율은 Cd>Cu>Zn>Ni>Pb 순이었고, 그 관계에서 Cd 및 Ni 성분은 고도의 정의 상관을 나타내었다. 미나리 부위별 중금속은 대부분이 뿌리에 축적되었으며, 지상부로의 이행지수(TF)는 Zn 및 Cu가 높은 경향이었다. 식물 흡수도는 비나리 부위 및 성분별로 큰 차이를 보였고, 토양 및 부위별 농도간에는 Cd, Cu 및 Ni 성분이 상관성이 높게 나타났다. 이상의 결과에서 토양의 중금속 오염도는 매우 높았으나 재배작물인 미나리중의 중금속은 대부분 뿌리에서 축적되고, 가식부위인 지상부로의 이행성은 매우 낮은 것을 알 수 있었다. This experiment was conducted to investigate heavy metal transition and bioavailability from soil to the edible pare of water dropwort near industrial complex. The soils were collected from the paddies cultivating water dropwort stream sediments, and background soils near industrial complex. The pH values, organic matter, Av. <TEX>$P_2O_5$</TEX>, Ex. Ca content of paddy soils were higher than those measured for nor-contaminated paddy fields in 2003. The contents of Cd and Cu was higher than those of standard level for soil contamination by Soil Environmental Conservation Act in Korea. The pollution index in stream sediments were higher than those of paddies cultivating water dropwort. The geoaccumulation index of heavy metals in paddy soils and stream sediment were in the order Cu>Cd>Ni>Zn>Pb. The rates of 0.1N-HCl extractable heavy metals to total contents in soils were in the order Cd>Cu>Zn>Ni>Pb. In case of Cd and Ni in paddy soils near industrial complex, 0.1N-HCl extractable heavy metals and total content were highly correlated with each other. Heavy metal contents in mot parts were higher than those in top pare of water dropwort. The Zn and Cu transfer factor from soil to the top pare of water dropwort were higher than those of other heavy metals. The bioavailability of water dropwort varied considerably between the different parts and heavy metals. Cd, Cu and Ni contents in water dropwort were correlated with each elements in paddy soils.