Natural attenuation of arsenic in the wetland system around abandoned mining area

Mechanisms of natural attenuation of arsenic (As) by wetland plants may be classified by plant uptake and adsorption and/or co-precipitation by iron (oxy)hydroxide formed on the root surface of plants or in rhizosediment. A natural Cattail (Typha spp.) wetland impacted by tailings containing high levels of As from the Myungbong abandoned Au Mine, South Korea was selected, and the practical capability of this wetland to attenuate As was evaluated. The As concentrations in the plant tissues from the study wetland were several-fold higher than those from control wetland. SEM-EDX analyses demonstrated that iron plaques exist on the rhizome surface. Moreover, relatively high As contents bonded with hydrous iron oxides were found in the rhizosediments rather than in the bulk sediments. It was revealed through the leaching and sequential extraction analyses that As existed as more stable forms in the wetland sediment compared with adjacent paddy soil, which is also contaminated with As due to input of mine tailings. The As concentration ratios of extracted solution to sediment/soil represented that the wetland sediment showed significant lower values (10-fold) rather than the paddy soil with indicating high As stability. Also, As in the wetland sediment was predominantly bonded with residual phases on the basis of results from sequential extraction analysis. From these results, it is concluded that transformation of As contaminated agricultural field to wetland environment may be helpful for natural attenuation until active remediation action.     

矿区周围土壤中重金属危害性评估研究

分别用总量法和连续萃取法对广东大宝山矿周围土壤、植物和沉积物中重金属的总量和化学形态进行了详细分析。结果发现，矿山废水流入的横石河沉积物中Pb、Zn、Cu和Cd的质量分数分别为1841．02、2326．28、1522．61和10.33mg／kg；经此河水灌溉的稻田中重金属(Cu、Cd、Pb和Zn)的质量分数也远远超出了土壤环境二级标准值，其中Cu、Cd超标倍数分别为14．01和4．17倍。结果还表明，生长在矿区周围的植物也受到不同程度重金属的污染且不同植物吸收和积累重金属的能力相差很大。用Tessier连续法对土壤中重金属进行萃取发现，虽然重金属主要存在于残余态中，但在Fe-Mn氧化态、有机结合态中的质量分数也很高．说明这些土壤确实受到了有毒有害重金属元素的严重污染。     

土壤重金属化学形态的生物可利用性评价

重金属化学形态是近年来土壤化学、植物营养和环境科学研究领域的一个热点和难点,利用重金属的化学形态分布和含量变化来评价重金属的生物可利用性,有利于全面研究重金属的危害性和治理重金属污染土壤。结果表明,水溶态和交换态的重金属易被生物吸收利用,而残留态重金属一般不被生物利用,其它形态如碳酸盐结合态、铁锰氧化物结合态和有机物结合态的生物可利用性主要取决于外界环境的变化。     

Contamination and vertical distribution of As,Cd, Cr,Cu, Pb,Tl, and Zn in paddy soil irrigated with untreated leachate from tailings retention ponds

The contamination and vertical distribution of As, Cd, Cr, Cu, Pb, Tl, and Zn in paddy soil irrigated with untreated leachate from the tailings retention pond were investigated. As, Cr, Cu, and Zn were slightly contaminated in the surface soil and hence their vertical distribution was not obvious. However, Cd and Pb were highly contaminated in the surface soil, while their concentrations decreased with depth, being negatively correlated with pH and positively with total organic matter. Tl was considerably contaminated in the surface soil and a V-shaped vertical distribution was observed where the concentration increased to a maximum at about 30 cm depth and decreased thereafter. The findings revealed that the regular irrigation with untreated leachate from the tailings retention ponds could cause considerable contamination of Cd, Pb, and Tl, and thus tailings should be stringently treated before disposal to minimize their potential environmental impacts on the surroundings.     

Comparison of three sequential extraction procedures for trace element partitioning in three contaminated Mediterranean soils

The sequential extraction procedures described by Tessier et al., McGrath and Cegarra, and Gimeno-García et al. were compared to investigate trace element (As, Cr, Cu, Pb, and Zn) partitioning patterns and extraction efficiency in three contaminated soils from Mediterranean regions of Spain. Soils were selected from Onda (Castellón) (S1), Aznalcóllar (Sevilla) (S2), and Silla (Valencia) (S3). S1 was a soil contaminated with Pb and Zn after dumping of wastes from the manufacture of ceramic tiles, S2 was polluted accidentally with a highly acid and As-concentrated sludge from mining activities, and S3 was a soil with a high Cr content from tannery sludge disposal. Trace element distribution in the soils—soluble, exchangeable, organically bound, precipitated with carbonates, bound to iron and manganese oxides, and precipitated with sulfides fractions—varied significantly according to the extraction procedure used. In addition, different extraction efficiencies were found for the three sequential extraction procedures compared. Finally, the trace elements studied showed different and specific distribution patterns between the various soil fractions examined.     

Arsenic mobility in the amended mine tailings and its impact on soil enzyme activity

The objectives of this study were to elucidate the effects of soil amendments [Ferrous sulfate (Fe^II), red mud, Fe^II with calcium carbonate (Fe^II/L) or red mud (RM/F), zero-valent iron (ZVI), furnace slag, spent mushroom waste and by-product fertilizer] on arsenic (As) stabilization and to establish relationships between soil properties, As fractions and soil enzyme activities in amended As-rich gold mine tailings (Kangwon and Keumkey). Following the application of amendments, a sequential extraction test and evaluation of the soil enzyme activities (dehydrogenase and β-glucosidase) were conducted. Weak and negative relationships were observed between water-soluble As fractions (As_WS) and oxalate extractable iron, while As_WS was mainly affected by dissolved organic carbon in alkaline tailings sample (Kangwon) and by soil pH in acidic tailings sample (Keumkey). The soil enzyme activities in both tailings were mainly associated with As_WS. Principal component and multiple regression analyses confirmed that As_WS was the most important factor to soil enzyme activities. However, with some of the treatments in Keumkey, contrary results were observed due to increased water-soluble heavy metals and carbon sources. In conclusion, our results suggest that to simultaneously achieve decreased As_WS and increased soil enzyme activities, Kangwon tailings should be amended with Fe^II, Fe^II/L or ZVI, while only ZVI or RM/F would be suitable for Keumkey tailings. Despite the limitations of specific soil samples, this result can be expected to provide useful information on developing a successful remediation strategy of As-contaminated soils.     

Cu2＋胁迫下湿地微生物热代谢活性及Cu2＋的固定/转化率

应用微量热法结合常规分析方法,研究了桂林会仙湿地沼泽底泥和水稻田微生物在800 - 4 000 μg·g-1 Cu2＋胁迫下的热代谢活性及Cu2＋的固定/转化率。结果表明,在w（Cu2＋）为800 μg·g-1条件下,水稻田和沼泽底泥土壤微生物对Cu2＋的固定/转化率分别为44.93%和34.59%,但在w（Cu2＋）为4 000 μg·g-1 时则分别是93.16%和85.13%;Cu2＋对水稻田和沼泽底泥土壤微生物代谢活性的半抑制浓度分别为2 043和2 325 μg·g-1;水稻田土壤微生物代谢活性低于沼泽底泥,在土壤及其微生物共同作用下Cu2＋的固定/转化率随Cu2＋浓度递增而升高;在相同条件下,水稻田和沼泽底泥土壤微生物的代谢速率在α = 0.05或α = 0.01水平上显著相关。湿地土壤用途发生改变后,土壤微生物在固定/转化Cu2＋的作用上发生了明显变化。     

Investigation and risk assessment modeling of As and other heavy metals contamination around five abandoned metal mines in Korea

Tailings, agricultural soils, vegetables and groundwater samples were collected from abandoned metal mines (Duckum, Dongil, Dongjung, Myoungbong and Songchun mines) in Korea. Total concentrations of arsenic (As) and heavy metals (Cd, Cu, Pb and Zn) were analyzed to investigate the contamination level. Several digestion methods (Toxicity characteristics leaching procedure (TCLP), synthetic precipitation leaching procedure (SPLP), 0.1 N/1 N HCl) and sequential extraction analysis for mine tailings were conducted to examine the potential leachability of As and heavy metals from the tailings. The order of urgent remediation for the studied mines based on the risk assessment and remedial goals was suggested. The Songchun mine tailings were most severely contaminated by As and heavy metals. Total concentrations of As and Pb in the tailings were 38,600–58,700 mg/kg (av. 47,400 mg/kg) and 11,800–16,800 mg/kg (av. 14,600 mg/kg), respectively. Agricultural soils having high As concentrations were found at the all mines. Average concentrations of Cd in the vegetables exceeded the normal value at all mines areas, while As only at the Dongjung, Myoungbong, and Songchun mine area. One groundwater sample each from the Dongil and Myoungbong mines, and 4 groundwater samples from the Songchun mine had values above 10 μg/L of As concentration. The TCLP method revealed that only Pb in the Songchun tailings, 6.49 mg/L, exceeded the regulatory level (5 mg/L). Employing the 1-N HCl digestion method, the concentration of As in the Songchun mine tailings, 4,250 mg/kg, was up to 3,000 times higher than its Korean countermeasure standard. Results from the sequential extraction of As in the tailings showed that the easily releasable fraction in the Myoungbong and Songchun mine tailings was more than 30% and the residual fraction was less than 40%. Based on results showing the exposure health risk employing the hazard quotient and cancer risk of As, Cd and Zn, the Dongil mine needs the most urgent remedial action. The concentration reduction factor (CRF) of As in both soil and groundwater follows the order: Songchun>Dongjung>Dongil>Myoungbong>Duckum mine.     

Arsenic (As), antimony (Sb), and lead (Pb) availability from Au-mine Technosols: a case study of transfer to natural vegetation cover in temperate climates

Soils from old Au-mine tailings (La Petite Faye, France) were investigated in relation to the natural vegetation cover to evaluate the risk of metals and metalloids (Pb, As, Sb) mobilizing and their potential transfer to native plants (Graminea, Betula pendula, Pteridium aquilinum, Equisetum telmateia). The soils are classified as Technosols with high contamination levels of As, Pb, and Sb. The single selective extractions tested to evaluate available fraction (CaCl₂, acetic acid, A-Rhizo, and DTPA) showed low labile fractions (<5 % of bulk soil contents), but still significant levels were observed (up to 342.6 and 391.9 mg/kg for As and Pb, respectively) due to the high contamination levels of soils. Even at high soil contaminations (considered as phytotoxic levels for plants), translocation factors for native plants studied are very low resulting in low concentrations of As, Sb, and Pb in their aerial part tissues. This study demonstrates the important role of (1) native plant cover in terms of “stabilization” of these contaminants, and (2) the poor effectiveness of extraction procedures used for this type of soil assemblages, i.e., rich in specific mineral phases.     

不同耕作制度对土壤中锰赋存形态及其有效性的影响

以花岗岩母质发育的旱地红壤和水稻土为研究对象，探讨了不同耕作制度下土壤中锰的赋存形态及其生物有效性。结果表明：在水旱轮作条件下，土壤中的锰更多地以代换态和晶形铁结合态存在；旱作土壤中的锰则较多地以有机态和无定形铁结合态存在．然而，单位有机质络合的锰量却是水稻土大于红壤。水旱轮作措施具有活化锰的作用，使得土壤中锰有效性更大并且主要以代换态存在。旱作土壤则不同，土壤活性锰除来自代换衣外，尚有大约４５％以有机态或无定形铁结合态存在。     

刁江沿岸土壤重金属污染特征研究

受上游矿山开发的影响，刁江沿岸存在明显的As、Pb、Zn、Cd复合污染带，其污染区与洪水淹没区呈现高度的一致性；水田的犁底层对重金属具有明显的隔断作用，而旱地的淀积层中的重金属质量分数依然很高；上游地带土壤污染呈显性状态，土壤中尾砂沉积现象十分明显，而下游地带的土壤污染呈隐性状态，土壤中尾砂沉积现象不明显；蜈蚣蕨可以作为刁江沿岸土壤污染区的指示植物；土壤中Zn与Cd质量分数存在显著相关关系，表层土壤As与Pb质量分数呈现较好的相关性，而土壤垂直剖面中As与Pb质量分数除个别剖面外，相关关系不显著。     

Environmental contamination and risk assessment of mercury from a historic mercury mine located in southwestern China

A field survey of mercury pollution in environmental media and human hair samples obtained from residents living in the area surrounding the Chatian mercury mine (CMM) of southwestern China was conducted to evaluate the health risks of mercury to local residents. The results showed that mine waste, and tailings in particular, contained high levels of mercury and that the maximum mercury concentration was 88.50 μg g^?1. Elevated mercury levels were also found in local surface water, paddy soil, and paddy grain, which may cause severe health problems. The mercury concentration of hair samples from the inhabitants of the CMM exceeded 1.0 μg g^?1, which is the limit recommended by the US EPA. Mercury concentrations in paddy soil were positively correlated with mercury concentrations in paddy roots, stalks, and paddy grains, which suggested that paddy soil was the major source of mercury in paddy plant tissue. The average daily dose (ADD) of mercury for local adults and preschool children via oral exposure reached 0.241 and 0.624 μg kg^?1 body weight per day, respectively, which is approaching or exceeds the provisional tolerable daily intake. Among the three oral exposure routes, the greatest contributor to the ADD of mercury was the ingestion of rice grain. Open-stacked mine tailings have resulted in heavy mercury contamination in the surrounding soil, and the depth of appreciable soil mercury concentrations exceeded 100 cm.     

Mineralogical and geochemical characterization of arsenic in an abandoned mine tailings of Korea

The mineralogical and chemical characteristics of As solid phases in arsenic-rich mine tailings from the Nakdong As–Bi mine in Korea was investigated. The tailings generated from the ore roasting process contained 4.36% of As whereas the concentration was up to 20.2% in some tailings from the cyanidation process for the Au extraction. Thin indurated layers and other secondary precipitates had formed at the surfaces of the tailings piles and the As contents of the hardened layers varied from 2.87 to 16.0%. Scorodite and iron arsenate (Fe₃AsO₇) were the primary As-bearing crystalline minerals. Others such as arsenolamprite, bernardite and titanium oxide arsenate were also found. The amorphous As–Fe phases often showed framboidal aggregates and gel type textures with desiccation cracks. Sequential extraction results also showed that 55.7–91.1% of the As in tailings were NH₄-oxalate extractable As, further confirmed the predominance of amorphous As–Fe solid phases. When the tailings were equilibrated with de-ionized water, the solution exhibited extremely acidic conditions (pH 2.01–3.10) and high concentrations of dissolved As (up to 29.5 mg L⁻¹), indicating high potentials for As to be released during rainfall events. The downstream water was affected by drainage from tailings and contained 12.7–522 μg L⁻¹ of As. The amorphous As–Fe phases in tailings have not entirely been stabilized through the long term natural weathering processes. To remediate the environmental harms they had caused, anthropogenic interventions to stabilize or immobilize As in the tailings pile should be explored.     

Effect of biogeochemical interactions on bioaccessibility of arsenic in soils of a former smelter site in Republic of Korea

The total concentration-based regulations for soil remediation do not consider the possible changes in bioaccessibility of remaining arsenic (As) in soils due to biogeochemical interactions after remediation. This study used As-contaminated soil and pore water samples that were collected from the rice paddy and forest/farmland located in the vicinity of a former smelter site in Republic of Korea to elucidate the changes in As bioaccessibility due to biogeochemical interactions. Bioaccessibility and chemical forms of As in soils were determined by using an in vitro method and sequential extraction, respectively, and soil microbial community was evaluated. Bioaccessibility of As in the rice paddy soil samples was higher than that in the forest/farmland soil samples. This could be attributed to relatively higher dependence of bioaccessible As in the rice paddy soils on the soil concentration of iron (Fe), aluminum, or manganese, which could lead to greater changes in bioaccessible As via reductive dissolution. The strong linear relationship (R ² = 0.90, p value ≤0.001) between the pore water As and Fe concentrations, and the greater portion of bacterial species related to reductive dissolution of Fe oxides in the rice paddies can support the higher As bioaccessibility promoted by reductive dissolution. Therefore, it is necessary to consider the potential changes in the bioaccessible As due to biogeochemical interactions in remediation of As-contaminated soils, particularly when soils are likely to be reused under reductive dissolution-promoting conditions (e.g., flooded conditions).     

氧化与还原条件下水稻土重金属形态特征的对比

还原状态下的水稻土被风干处理后氧化还原等性质发生明显变化,对重金属的形态特征产生影响,进而影响对作物有效性的评价.利用BCR连续萃取法研究了张家港市南部不同pH水稻土在还原和氧化条件下Cu、Pb、Ni和Cd的形态变化状况.结果显示,氧化还原对重金属形态分配具有显著影响,而pH对Ni在还原状态下的形态分配有显著影响,对Cu、Pb和Cd形态分布影响不显著.样品经风干氧化处理后,氧化物结合态重金属均表现为不同程度的降低;Cu残渣态比例增加25%,氧化物结合态和有机结合态比例有所降低;Pb有机结合态比例增加33%,残渣态减少33%,酸可提取态和氧化物结合态变化不大;Ni受氧化还原条件影响更为强烈,表现为酸可提取态所占比例降低超过25%,氧化物结合态亦明显降低,残渣态提高超过60%;对Cd的影响主要表现为有机结合态所占比例降低约15%,残渣态提高约35%,酸可提取态和氧化物结合态变化不明显.氧化状态下的重金属形态并不是重金属在田间的真实状况,可能高估了Pb,低估Cu、Ni和Cd重金属在土壤中的危害性.     

不同来源重金属污染的土壤对水稻的影响

采用人工污染土壤、尾矿砂、污泥等不同载体的污染源来模拟土壤污染 ,研究其对水稻生长、吸收养分和吸收重金属的影响。结果表明 ,不同污染载体对水稻生长的影响不同 ,其影响的大小顺序为人工污染土壤 >尾矿砂 >污泥 >尾矿砂 +污泥。不同污染载体对水稻吸收重金属的影响亦不同 ,以纯化学试剂的形式添加到土壤中的重金属最易被提取出来 ,植物从中吸收的Cu、Zn、Pb、Cd最多 ,而从以污泥为污染载体的土壤中吸收的Zn、Pb、Cd最少。研究表明 ,用添加纯化学试剂的方法来模拟污染土壤对生态与环境的影响是可行的 ,确定土壤负载容量是安全的 ,因为在实验条件下它对供试植物的影响最明显     

Mercury fractionation in the sediments of Vembanad wetland, west coast of India

Transformations among different mercury species associated with sediments can have a major effect on the metal's mobility and potential for methylation and hence bioaccumulation. In the present study, various fractions of mercury in the sediments of Vembanad wetland system analysed. Total mercury (THg) concentration in the surface sediment varied from 16.3 to 4,230?ng/g. The results of sequential extraction showed that the major portion of mercury in these sediments existed as elemental form followed by organo-chelated form. The least portion observed was the residual fraction (mercury of natural origin). Even though the percentage of mercury observed in the easily available fractions is relatively small, absolute values of these mobile Hg fractions are quite high due to the very high total mercury values. The fractionation of mercury in the sediment was controlled by the organic matter, sulphur complexes and concentration of THg. The results showed that the bioavailability of mercury is high as the amount of mercury found in the initial three fractions is high, which can also enhance the methylation potential of the Vembanad wetland sediments. The fractionation pattern of mercury also revealed the presence of anthropogenic mercury content in the Vembanad wetland sediments.     

Fraction distribution and migration of heavy metals in mangrove-sediment system under sulphur and phosphorus amendment

In this study, mangrove seedlings (Kandelia obovata (S. L.)) were cultivated in rhizo-boxes, which contain sediments collected from natural mangrove forest and modified with different rates of sulphate and phosphate. The fraction distributions of Zn, Cd, Cu, Ni and Pb in rhizosphere and non-rhizosphere sediments were studied by using a sequential extraction method. Metal concentrations in plant tissues and iron plaque on root surface were also determined to reveal migration variation of heavy metals in the plant-sediment system. The results showed that the activities of K. obovata roots enhance the reducible metals while reducing acid-extractable and oxidisable metals; sulphur amendment benefits the combination of metal ions with S^2– and therefore reduces the bioavailability of metal pollutants; addition of sulphur also improves the content of iron plaque on the root surface, which plays an important role in metal accumulation by K. obovata root tissue; the addition of sulphur markedly reduces the concentration of Cd in roots, but significantly enhanced the concentrations of Cu, Zn, Ni and Pb in roots. The results indicate that sulphur and phosphorus content in mangrove sediment, and the growth of mangrove plant can significantly influence the migration of heavy metals in the mangrove wetland ecosystem.     

Assessment of As and Heavy Metal Contamination in the Vicinity of Duckum Au-Ag Mine, Korea

In order to assess the potential of As and heavy metal contamination derived from past mining activity and to estimate the human bioavailability quotients for As and heavy metals. Tailings, soils and crop samples were collected and analysed for As, Cd, Cu, Pb and Zn. The mean concentrations of As, Cd, Cu, Pb and Zn in the tailings were 68.5, 7.8, 99, 3,754 and 733 µg g^–1, respectively. Maximum Pb concentration in tailings was up to 90 times higher than its tolerable level. The concentrations of these metals were highest in the soils from the dressing plant area, and decreased in the order: farmland soil to paddy soil. In particular, some of the soils from the dressing plant area contained more than 1% of Pb and Zn. The pollution index ranged from 0.19 to 1.93 in paddy soils, and from 1.47 to 3.60 in farmland soils. The average concentrations of heavy metals in crops collected from farmland were higher than those in rice stalks or rice grains, and higher than the internationally accepted limits for vegetables. Element concentrations extracted from farmland soils within the simulated human stomach for 1 h are 9.4 mg kg^–1 As, 3.8 mg kg^–1 Cd, 37 mg kg^–1 Cu, 250 mg kg^–1 Pb and 301 mg kg^–1 Zn. In particular, the extracted concentrations of Cd, Pb and Zn are in excess of the tolerable levels. The results of the simple bioavailability extraction test (SBET) indicate that regular ingestion (by inhalation and from dirty hands) of soils by the local population could pose a potential health threat due to long-term toxic element exposure.     

Soil remediation using in situ immobilisation techniques

The main objective of this study was to investigate the efficiency of different substrates to reduce the extraction of heavy metals concentration in a heavily contaminated soil. Two contaminated soils by Cu and Zn were used to evaluate the effectiveness of eight substrates (calcium carbonate, bentonite, kaolinite, charcoal, manganese oxide, iron oxide, zeolite, phosphate) to reduce metal availability and to study the change of metals speciation in different forms using sequential extraction technique (single step). Sequential extraction technique (single step, 0.11 M acetic acid, HONH₃Cl, H₂O₂+NH₄OAc, Aqua regia) was applied on contaminated soils after and before treatment to evaluate metals speciation. Results indicate that the most effective treatments in decreasing available metal concentrations were calcium carbonate, zeolite and manganese or iron oxide. Metal sequential fractionations indicate that the exchangeable fraction of Cu and Zn in contaminated soils can be transformed into unavailable forms after chemical remediation.