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.     

Concentrations of Potentially Toxic Metals in Urban Soils of Seville: Relationship with Different Land Uses

Fifty-two samples of surface soils were taken in the urban area of Seville, to assess the possible influence of different land uses on their metal contents and their relationship with several soil properties. The samples corresponded to five categories or land uses: agricultural, parks, ornamental gardens, riverbanks, and roadsides. Sequential extraction of metal according to the procedure proposed by the former Community Bureau of Reference (BCR) was carried out, and pseudo-total (aqua regia soluble) metal contents were determined. Lower organic C, total N and available P and K contents were found in riverbank samples, probably due to the lack of manuring of those sites, left in a natural status. In contrast, significantly higher electrical conductivity was found in those sites, due to the tidal influence of the nearby Atlantic Ocean. Other land uses did not show significant differences in the general properties. Concentrations of Cu, Pb and Zn, both aqua-regia soluble and sequentially extracted, were clearly higher in soils from ornamental gardens, whereas the concentrations in the riverbank samples were slightly lower than the other categories. In contrast, other metals (Cd, Cr, Fe, Mn, Ni) were uniformly distributed throughout all land uses. A strong statistical association is found among the concentrations of Cu, Pb, Zn and organic C, suggesting that the larger contents of these metals in ornamental gardens are partly due to organic amendments added to those sites more frequently than to other kinds of sites. Considering the conclusions of previous studies, heavy traffic can also contribute to those `urban’ metals in urban soils. Periodic monitoring of the concentrations of urban metals in busy city centres and of the quality of amendments added to soils of recreational areas are recommended.     

An Investigation Into the Mechanism by Which Synthetic Zeolites Reduce Labile Metal Concentrations in Soils

The addition of synthetic zeolites and similar materials to metal contaminated soils has been shown to reduce soil phytotoxicity and to improve the quality of plant growth on such amended soils. To gain an understanding of the mechanism by which the phytotoxicity of contaminated soils is reduced when treated with synthetic zeolites, sequential extraction procedures and soil solution techniques have been used to identify changes associated with metal speciation in amended soils. Sequential extraction data and changes in soil solution composition are presented for three different contaminated soils, amended with three synthetic zeolites (P, 4A and Y) at concentrations of 0.5%, 1% and 5% w/w, or lime at 1%. The soils were collected from the site of a metal refinery, an old lead zinc mine spoil tip and from a field which had been treated with sewage sludge. After incubation of the zeolite treated soils for between one and three months, results showed a reduction in the metal content of the ammonium acetate fraction between 42% and 70%, depending on soil, zeolite and rate of addition, compared with the unamended soils. In addition, soil solution experiments indicated that synthetic zeolite amendments were more efficient at reducing metal content than comparable lime treatment. The mechanism by which synthetic zeolites reduce metal bioavailability in contaminated soils is discussed and compared to other amendments.     

中国东部花岗岩、玄武岩及石灰岩上土壤微量元素含量的纬向分异

在中国东部花岗岩、玄武岩和石灰岩地区布设91个采样点,采集土壤剖面和母岩样品,测试13种微量元素的含量,研究其纬向分异规律及影响因素。结果表时：（1）土壤微量元素含量顺序为：玄武岩土壤＞石灰岩土壤＞花岗岩土壤;（2）花岗岩和玄武岩上土壤微量元素含量与母岩接近,石灰岩上土壤微量元素含量远高于母岩;（3）花岗岩上土壤微量元素的含量由北向南呈降低趋势,而玄武岩和石灰岩上土壤微量元素含量由北向南均呈增高趋势,且与游离氧化铁含量的增高同步;（4）微量元素含量与氧化铁含量在玄武岩土壤中的相关性大于这两者在花岗岩土壤中的相关性。     

Cadmium,copper, and zinc in carrots in Japan

Cadmium (Cd), copper (Cu), and zinc (Zn) in carrots obtained from different regions throughout Japan were assessed in a baseline study on the contents of trace metals in foods. These three metals were measured by flameless atomic absorption spectrophotometry. The geometric mean contents (with one geometric standard deviation indicated in parentheses) of Cd, Cu, and Zn were 0.02 (2.2), 0.7 (2.1), and 2.4 (1.6) mg?kg^?1 wet weight in carrots obtained in Japan. While there was a close relationship among the contents of the three metals in the carrots grown in Cambisols and Gleysols, a significant relationship was recognized only between the contents of Cd and Zn in those grown in Andosols and Fluvic Gleysols. Cd and Zn are classified as 2B metals in the periodic table of elements, and the authors speculate that the similarity of the metal characteristics between Cd and Zn may be responsible for the close relationship in the contents of the two metals, with no relation to the soil type.     

Heavy metals,occurrence and toxicity for plants: a review

Metal contamination issues are becoming increasingly common in India and elsewhere, with many documented cases of metal toxicity in mining industries, foundries, smelters, coal-burning power plants and agriculture. Heavy metals, such as cadmium, copper, lead, chromium and mercury are major environmental pollutants, particularly in areas with high anthropogenic pressure. Heavy metal accumulation in soils is of concern in agricultural production due to the adverse effects on food safety and marketability, crop growth due to phytotoxicity, and environmental health of soil organisms. The influence of plants and their metabolic activities affects the geological and biological redistribution of heavy metals through pollution of the air, water and soil. This article details the range of heavy metals, their occurrence and toxicity for plants. Metal toxicity has high impact and relevance to plants and consequently it affects the ecosystem, where the plants form an integral component. Plants growing in metal-polluted sites exhibit altered metabolism, growth reduction, lower biomass production and metal accumulation. Various physiological and biochemical processes in plants are affected by metals. The contemporary investigations into toxicity and tolerance in metal-stressed plants are prompted by the growing metal pollution in the environment. A few metals, including copper, manganese, cobalt, zinc and chromium are, however, essential to plant metabolism in trace amounts. It is only when metals are present in bioavailable forms and at excessive levels, they have the potential to become toxic to plants. This review focuses mainly on zinc, cadmium, copper, mercury, chromium, lead, arsenic, cobalt, nickel, manganese and iron.     

Natural and anthropogenic metal inputs to soils in urban Uppsala, Sweden

Urban soils are complex systems due to human activities that disturb the natural development of the soil horizons and add hazardous elements. Remediation projects are common in urban areas and guideline values are set to represent a desired level of elements. However, the natural content of trace elements may not always equal the desired levels. In this study, an attempt is made to distinguish between metals that are present in the soil due to natural origins and to anthropogenic origins. Seventy-five soil samples of the 0–5, 5–10 and 10–20 cm layers were collected from 25 sites in urban areas of Uppsala City and analysed for aluminium (Al), arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe), mercury (Hg), manganese (Mn), nickel (Ni), lead (Pb), tungsten (W) and zinc (Zn) using aqua regia for digestion. In order to highlight elements of geological origin, the results were compared to a similar study carried out in Gothenburg City, which has about three times as many inhabitants as Uppsala and has a more industrial history. A cluster analysis was also performed to distinguish between elements of natural and anthropogenic origin. Contents of As, Al, Fe, Cr, Ni, Mn and W in Uppsala were concluded to be of mainly geological origin, while contents of Cd, Cu, Zn, Pb and Hg seemed to have been impacted upon by mainly urban activities.     

Optimization of anaerobic processes by speciation and bioavailability of trace metals

The deficiency trials of some trace metals (copper, nickel, zinc) were made in laboratory Upflow Anaerobic Sludge Blanket (UASB) reactors containing the inoculum of an industrial anaerobic sludge, a basal medium with the rest of nutrients and vitamins in comparison with a control reactor with the optimal doses of trace elements. From the main control parameters (alkalinity, acidity, DQO), no inactivation by deficit of essential elements was detected, but the control reactor showed greater mineralization and solid content, being necessary to make purge to avoid bulking. The inoculum has high metallic element contents, so the additional contribution produces high bacterial growth, also purge being necessary to avoid bulking. The purge, made after 120 days in continuous operation, eliminates a great quantity of solids and increases the volatile solids (VS)/total solids (TS) ratio. The comparison of the initial content of metallic elements in the solid and liquid phases with the contents after 120 days showed a progressive depletion of metals in all reactors without a clear appreciation of the lack of the studied metals. Finally, in 210 days, the reactors without addition of a metallic element accumulated greater quantity of major (Ca, Fe, Mg) and trace (Co, Ni, Cu) elements in the solid phase with respect to the control.     

Heavy metals in soils and crops in Southeast Asia 2. Thailand

A reconnaissance soil geochemical and concomitant plant survey based on 318 soil (0-15 cm) and 122 plant samples was used for the assessment of heavy metal pollution of agricultural soils and crops of Thailand. Arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), mercury (Hg), nickel (Ni), lead (Pb) and zinc (Zn) were determined in soils using aqua regia digestion, and in plants using nitric acid digestion. Organic carbon (C), pH, electrical conductivity (EC) and available phosphorus (P) were determined on the soil samples using appropriate procedures. Results indicated that concentrations of heavy metals varied widely among the different regions of Thailand. Regression analysis between the concentrations of metals in soil (aqua regia extractable) and edible plant parts indicated a small but positive relationship for Cd in all the plants sampled in the survey (R2 = 0.081, p < 0.001). There was also a positive relationship between soil and plant Cd concentrations in rice (R2 = 0.242, p < 0.010), and negative relationships for Zn in rice (R2 = 0.385, p < 0.001), and Cu (R2 = 0.355, p < 0.001) and Zn (R2 = 0.122, p < 0.026) in glutinous rice. Principal component analysis of the soil data suggested that concentrations of As, Co, Cr, Cu, Hg, Ni and Pb were strongly correlated with concentrations of Al and Fe, which is suggestive of evidence of background variations due to changes in soil mineralogy. Thus, the evidence for widespread contamination of soils by these elements through agricultural activities is not strong. On the other hand, Cd and Zn were strongly correlated with organic matter and concentrations of available and aqua regia extractable P. This is attributed to input of contaminants in agricultural fertilisers and soil amendments (e.g. manures, composts).     

开阳磷矿10种木本植物叶片重金属富集特征

植物对重金属具有一定的吸附能力,植物修复是生态修复不可或缺的一部分,利用植物减缓和治理重金属污染具有重要意义.选取开阳磷矿马路坪矿区生命周期较长的木本植物及其土壤作为研究对象,探究木本植物受Cu、Zn、Pb、Cd、As等5种重金属污染土壤的效应,对植物重金属含量及其富集特性进行研究分析,筛选出累积重金属的植物,作为矿区...     

Assessment of metal contamination in soil banks of the Rhumel wadi (Northeast Algeria)

Levels of six trace metals were assessed in bank soils of the Rhumel wadi (Northeast Algeria) and their association with soil properties was investigated. Samples were collected at 10 sites. The soils are neutral to moderately alkaline, have high contents of carbonate, and are low in organic carbon and clay. Mean metal concentrations are 1.1 (Cd), 63 (Cr), 20 (Cu), 26 (Ni), 31 (Pb), and 98 (Zn) mg kg^?1. The Cd, Cu, Pb, and Zn contents in soil from sites closest to Constantine City were higher than in uncontaminated soils worldwide, indicating accumulation due to human activities (residential, industrial, and agricultural). Statistical analyses (correlation and principal component analysis) demonstrated that Cd, Pb, and Zn are of anthropogenic origin in the urban areas, whereas Cr and Cu enrichment in some situations is caused by industrial activities, while Ni was geogenic.     

Heavy Metals in Sediments and Oysters From Bluefields Bay, Nicaragua

The distribution of trace metals (Co, Cu, Fe, Mn, Ni, Pb and Zn) was investigated during a year (1994-95) in surface and core sediment samples and in the oyster (Crassotrea rhizophorae) from Bluefields Bay, Nicaragua. the aim was to assess the arthropogenic impact of potential pollutant sources, mainly Bluefields City, since domestic waste waters are discharged directly or by infiltration to the bay. Lyophilised samples were submitted to different acid digestion methods and analysed by flame atomic absorption spectrophotometry. the results showed highest contents for copper, lead and zinc near Bluefields City, with an increase in the affected area in the rainy season that is generated by greater city run off. Metal contents in oysters do not show the same distribution pattern than in sediments and were similar to those from other areas without reflecting pollution levels.     

土壤调理剂对稻米中镉含量及其品质的影响

近年来土壤调理剂被大量投入到重金属污染农田治理修复中,大部分产品使用后可以达到农产品质量安全的效果,但对农产品品质影响方面关注较少。选取市面上销量较大的4种(A、B、C、D)土壤调理剂,通过早、晚两造水稻大田验证试验结果来评价调理剂对水稻生长的影响,对指导实际安全生产具有重要的意义。结果表明,施用土壤调理剂可以增加水稻产量,增幅在2%—6%之间;使稻米的镉含量降低18%—48%,调理剂的增产控Cd效果表现为早稻均优于晚稻。稻米中直链淀粉含量有不同程度的增加,晚稻效果更加明显,含量均处于国家优质米直链淀粉含量(14%—20%)之间。各处理稻米蛋白质含量均有提高,晚稻稻米中蛋白质含量整体高于早稻。施用调理剂可以增加稻米矿物质元素Ca、Mg、Cu、Zn、Fe、Mn在稻米中的积累,其中调理剂C对提高早稻稻米Ca、Cu、Zn含量效果最好;调理剂B对提高早稻稻米Mg、Fe、Mn含量效果最好,且也有利于提高晚稻稻米Fe含量;调理剂A对提高晚稻Ca、Mg、Zn、Mn效果最好;调理剂D对提高晚稻稻米铜元素含量效果最好。相关性分析结果表明,稻米中6种矿物质元素Ca、Mg、Cu、Zn、Fe、Mn均与稻米中Cd含量呈现负相关关系,并达到显著或极显著水平,说明提高稻米中矿物质元素含量能有效抑制镉向稻米中转移。     

干旱区绿洲灌漠土Cu、Zn和Pb的吸附解吸特征

土壤重金属吸附解吸是影响土壤系统中重金属移动性和归宿的主要过程,影响重金属的生物有效性以及重金属在食物链中的传递等.配制一系列不同浓度的重金属,灌漠土对重金属溶液进行吸附实验24 h以达到平衡,再用硝酸铵和乙酸铵进行解吸实验24 h以达到平衡.利用热力学吸附平衡法,对西北干旱区绿洲灌漠土重金属Cu、Ni和Pb的吸附解吸行为进行序批实验研究.实验结果表明:(1)灰漠土在常温下对铜、锌和铅重金属离子的吸附等温线符合Freundlich型吸附模式,灰漠土对重金属铜、锌和铅的吸附能力由强到弱的顺序为:铅,铜,锌.(2)硝酸铵和乙酸铵解吸重金属的量与灰漠土吸附重金属量呈现出线性正相关,乙酸铵解吸重金属的量比硝酸铵解吸重金属的量大,两种解吸剂对铜、锌和铅重金属离子的解吸能力由大到小的顺序都为:铜,锌,铅,说明了一般外源的铜、锌和铅进入土壤以后,铜和锌可能比铅容易向四周转移.(3)硝酸铵和乙酸铵的解吸率呈谷形曲线,开始时硝酸铵和乙酸铵解吸重金属量的百分比随灰漠土吸附重金属量的增加而减小,在吸附量达到某一特定值时,解吸率随吸附量的增加而增加.灰漠土对铜、锌和铅的吸附作用以专性吸附为主,被灰漠土吸附的铜、锌和铅重金属离子较难解吸.     

Effects of an iron-silicon material,a synthetic zeolite and an alkaline clay on vegetable uptake of As and Cd from a polluted agricultural soil and proposed remediation mechanisms

Economic and highly effective methods of in situ remediation of Cd and As polluted farmland in mining areas are urgently needed. Pot experiments with Brassica chinensis L. were carried out to determine the effects of three soil amendments [a novel iron-silicon material (ISM), a synthetic zeolite (SZ) and an alkaline clay (AC)] on vegetable uptake of As and Cd. SEM–EDS and XRD analyses were used to investigate the remediation mechanisms involved. Amendment with ISM significantly reduced the concentrations of As and Cd in edible parts of B. chinensis (by 84–94 % and 38–87 %, respectively), to levels that met food safety regulations and was much lower than those achieved by SZ and AC. ISM also significantly increased fresh biomass by 169–1412 % and 436–731 % in two consecutive growing seasons, while SZ and AC did not significantly affect vegetable growth. Correlation analysis suggested that it was the mitigating effects of ISM on soil acidity and on As and Cd toxicity, rather than nutrient amelioration, that contributed to the improvement in plant growth. SEM–EDS analysis showed that ISM contained far more Ca, Fe and Mn than did SZ or AC, and XRD analysis showed that in the ISM these elements were primarily in the form of silicates, oxides and phosphates that had high capacities for chemisorption of metal(loid)s. After incubation with solutions containing 800 mg L^?1 AsO₄ ^2? or Cd²⁺, ISM bound distinctly higher levels of As (6.18 % in relative mass percent by EDS analysis) and Cd (7.21 % in relative mass percent by EDS analysis) compared to SZ and AC. XRD analysis also showed that ISM facilitated the precipitation of Cd²⁺ as silicates, phosphates and hydroxides, and that arsenate combined with Fe, Al, Ca and Mg to form insoluble arsenate compounds. These precipitation mechanisms were much more active in ISM than in SZ or AC. Due to the greater pH elevation caused by the abundant calcium silicate, chemisorption and precipitation mechanisms in ISM treatments could be further enhanced. That heavy metal(loid)s fixation mechanisms of ISM ensure the remediation more irreversible and more resilient to environmental changes. With appropriate application rate and proper nutrients supplement, the readily available and economic ISM is a very promising amendment for safe crop production on multi-metal(loids) polluted soils.     

Comparative study between using natural and synthetic zeolites for the improvement of soil salinity and crop yield

The effects of natural zeolite (clinoptilolite, NZ) and synthetic zeolite (Y, SZ) on salinity and the presence of the harmful salts in the soil were compared on Raphanus sativus L. Nine soil treatments were studied: 1 (control), 2 (NaCl), 3 (Na₂SO₄), 4 (NZ), 5 (SZ), 6 (NZ?+?NaCl), 7 (SZ?+?NaCl), 8 (NZ?+?Na₂SO₄), and 9 (SZ?+?Na₂SO₄). Five radish seeds were planted in each pot. Each treatment was repeated 10 times. After 50 days under equal conditions some parameters consisting of the number of leaves (NL), total leaf area (TLA), total fresh weight (TFW), total dry weight (TDW), root fresh weight (RFW), air fresh weight (AFW), root dry weight (RDW) and air dry weight (ADW) were determined. Results showed that adding either NZ or SZ to salinic soil (treatments NZNaCl, NZNa₂SO₄, SZNaCl and SZNa₂SO₄) increased AFW, TFW and TDW. Using both NZ and SZ in normal soil increased the weight of plants by developing AFW. Further NZ was more effective on soil with NaCl than SZ.     

Trace element distribution and mobilization in Scottish soils with particular reference to cobalt,copper and molybdenum

Total and extractable trace element contents have been determined in about 1000 soil profiles representing the main soil series occurring throughout Scotland. The frequency distributions of a number of trace elements in these soils are described and some relationships between total and extractable contents discussed. The geological nature of the soil parent material, soil texture, organic matter content and environmental contamination are the principal factors controlling soil total contents. Soil drainage class, because of its effect on mineral weathering and soil oxidation-reduction conditions, has a major influence on soil extractable contents, availability to plants and crop uptake. Particular attention is paid to cobalt, copper and molybdenum because of their importance for animal health in Scotland.     

Geochemical and biological controls on trace metal transport in an acid mine impacted watershed

Water samples collected in an acid mine impacted watershed indicated that the concentrations of dissolved trace metals were diurnally influenced by mineral saturation, which is controlled primarily by pH and water temperature. Measurements taken suggested that these variations only occur at sample locations immediately downstream from the confluence of acidic and alkaline waters. It is at these locations where initial mineral precipitation occurred and where subtle changes in solubility were most affected, increasing trace metal removal when both the rate of photosynthesis (influencing pH in headwaters) and water temperature were at a maximum. The role of iron photoreduction (increased midday production of ferrous iron) on overall Cu, Mn, and Zn transport was also evaluated, but found to be inconclusive. Iron photoreduction may however influence adsorption and/or coprecipitation of trace metals through associated changes in oxidation state, solubility, and mineralogy of various iron colloids, which are produced upon the neutralization of acidic, metal enriched water. Furthermore, measured values of copper and zinc were compared to relative USEPA chronic criterion for exposure to continuous concentration (CCC) of metals by the calculation of a “toxicity unit” (TU). It was found that average values of both copper and zinc only exceeded the CCC (TU>1) in the acid mine-impacted Leona Creek. In general, zinc toxicity decreased while copper toxicity increased downstream of the confluence of the mine impacted Leona Creek and background Lion Creek (sampled at Lake Aliso), indicating a significant source of zinc in upstream, non mine-impacted samples.     

施用石灰对Pb、Cd、Zn在土壤中的形态及大白菜中累积的影响

重金属的不同形态对于作物吸收重金属及受害具有十分密切的关系,通过施用石灰改变重金属的形态、毒性以及对作物的影响具有重要的意义。以大白菜(Brassica pekinensis)为研究对象,通过盆栽试验,探讨了在铅、镉和锌污染土壤上,施用石灰对土壤中不同形态镉、铅和锌含量及在大白菜中累积的影响。结果表明,施用石灰后,土壤中碳酸盐结合态Pb、Cd和Zn含量明显减少,铁、锰氧化物结合态和有机物结合态Pb、Cd和Zn含量明显增加;对大白菜吸收Pb、Cd和Zn均起到较好的抑制作用,石灰用量为5g·kg-1土时,对大白菜吸收Pb、Cd和Zn的抑制效果最好。     

Study of trace elements in urine of some Nigerian medical patients

In this study, trace element concentrations were determined in urine samples of patients with kidney and liver conditions from the Obafemi Awolowo University Teaching Hospitals Complex, Ile-Ife Nigeria. Urine samples from 80 patients whose ages ranged from 15 to 79 were used for the trace metals analysis. Variation of the trace metals including lead (Pb), cadmium (Cd), mercury (Hg), zinc (Zn), copper (Cu), and manganese (Mn) in urine samples were correlated with respect to gender, age, professions, personal habits and patients’ conditions. The levels of Pb in the urine samples of both male and female patients were found to be generally higher than those of Cd, Hg, Zn, Cu, and Mn. Highest levels of Pb and Cd were found in patients who smoked and drank and those with various kidney and liver conditions. Most of the trace metals except Mn occurred at levels that are deleterious to human health as they are above the standard threshold values expected in normal human urine, and raised cause for concern.