Fractionation of trace metals (Mn,Zn, Cu,Pb) in Red Sea sediments,Gulf of Aden,Yemen

A sequential extraction technique was applied to estimate the chemical association of Mn, Zn, Cu and Pb in five chemical phases (exchangeable, carbonate, Fe–Mn oxides, organic matter and residual) in sediments of the Gulf of Aden, Yemen. The results indicated that a higher level of Mn was associated with the residual fraction (natural sources) than the non-residual fraction (anthropogenic sources). Zn fractionations revealed that it was associated more with Fe–Mn oxides and organic fractions than exchangeable and carbonate fractions. Most of the Cu was present in the residual form (60–72%) except for in the main port area (zone III), where it was associated with the organic phase (77% of the total Cu content, the organic matter content was 5%). Similarly, most Pb was bound in the residual fraction (56–71%) except the main port area where ～ 62% of the total Pb was bound in non-residual fractions. It was also found that the Pb concentration in the exchangeable fraction was very high compared with other metals. The risk assessment code for the metals showed a low risk for Zn and Cu, but low to medium risk for Mn. Fractionation of Pb showed medium risk at most of the regions except at the eastern area, which revealed a high risk for the aquatic environment.     

Geographical distribution and risk assessment of heavy metals: a case study of mine tailings pond

ABSTRACT

In China, a large number of tailings deposited on natural surfaces, the potential risk of tailings attracts people’s attention. In this study, heavy metals distribution, geo-accumulation index, ecological risk index, microbial diversity and community were examined to evaluate the risks of a tailings pond. Results indicated the tailings pH is about 8.17, and the redox potential was lower than zero. Heavy metals could be leached and migrate from the tailings. The tailings pond had more influence on the distribution of Pb, Zn, As, Cu, and S. The influence distance of Pb, Zn, and Cu was less than 10?m, and the influence distance of As and S was less than 50?m. S and As had stronger migration capability than other elements in the soil. The biggest potential ecological risk resulted from Pb, and the distances more than 100?m had low ecological risk. The tailings decreased microbial richness and diversity of the surrounding environment. Oxidising bacteria and reducing bacteria existed in both the tailings and the surrounding soils; however, there were more oxidising and reducing microbes in the tailings than in the surrounding soils. The tailings pond currently has little impact on the environment, but the potential risk still exists.     

重金属Cu,Pb,Zn,Cr,Cd在水稻植株中的富集和分布

研究了外源可溶性重金属进入水稻土环境后，在水稻植株中的迁移、在水稻植株不同部位的分布及其分布随时间的变化。在水稻生长季节，重金属在水稻植株中迁移能力的大小依次为：Cd,Cr＞Zn,Cu＞Pb。重金属在水稻植株不同部位的积累分布是：根部＞根基茎＞主茎＞穗＞籽实＞叶部。水稻分蘖期重金属在根部、茎干部和叶片的积累量达到最大，随着时间的延长，在根部积累的重金属愈来愈少；在茎干部积累的重金属在拔节期降至最小，随后含量又稍微上升；叶片上的重金属含量在拔节期迅速下降，随后趋于稳定。     

Heavy metal accumulation and phytostabilization potential of dominant plant species growing on manganese mine tailings

Screening plants that are hypertolerant to and excluders of certain heavy metals plays a fundamental role in a remediation strategy for metalliferous mine tailings. A field survey of terrestrial higher plants growing on Mn mine tailings at Huayuan, Hunan Province, China was conducted to identify candidate species for application in phytostabilization of the tailings in this region. In total, 51 species belonging to 21 families were recorded and the 12 dominant plants were investigated for their potential in phytostabilization of heavy metals. Eight plant species, Alternanthera philoxeroides, Artemisia princeps, Bidens frondosa, Bidens pilosa, Cynodon dactylon, Digitaria sanguinalis, Erigeron canadensis, and Setaria plicata accumulated much lower concentrations of heavy metals in shoots and roots than the associated soils and bioconcen- tration factors （BFs） for Cd, Mn, Pb and Zn were all 〈 1, demonstrating a high tolerance to heavy metals and poor metals translocation ability. The field investigation also found that these species grew fast, accumulated biomass rapidly and developed a vegetation cover in a relatively short time. Therefore, they are good candidates for phytostabilization purposes and could be used as pioneer species in phytoremediation of Mn mine tailings in this region of South China.     

Geochemical anomalies in two sulfide-bearing waste disposal areas: Fe,Cu, Zn,Cd, Pb,and As in contaminated waters and snow,Kemerovo and Chelyabinsk regions,Russia

Sulfide-bearing mill wastes are sources of high concentrations of acid, soluble metals, Sb, and As. Contents of Cu, Zn, Fe, Pb, Cd, As, and Sb in wastes of the Belovo Zn-processing and the Karabash mineral-processing plants (Russia) exceed the average content in the upper continental crust and background soils. High-dissolved metal and As concentrations are found in acid drainages, which form as a result of interaction between sulfide wastes and water. Monitoring research using geochemical and geophysical methods was performed to evaluate the contamination of the surrounding area (water and bottom sediments in the contaminated rivers and snow cover). Zones of geochemical anomalies were identified where the concentrations of Fe, Cu, Zn, Cd, Pb, and As are 2–3 orders of magnitude higher than in drinking water standards (for rivers) and background levels (for snow). The use of geophysical methods allowed us to prove penetration of drainage solutions into the groundwaters. The total environmental damage caused by the pollution of water and land resources in the Belovo Zn-processing plant waste disposal area amounted to $156 million at the time of 2011, and could reach $480 million by 2030, if steps are not taken in recycling and remediation of disturbed areas.     

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.     

The gastropod Osilinus atrata as a bioindicator of Cd,Cu, Pb and Zn contamination in the coastal waters of the Canary Islands

The aim of this study was to assess the use of Osilinus atrata (Gastropoda, Mollusca) as a biomonitor of heavy metals (Cd, Cu, Pb and Zn) within the coastal zone of the Canary Islands. In general, this top-shell snail showed high intraspecific variability in its tissue metal concentrations, which decreased according to the following sequence: Cu≥Zn>Cd≥Pb. In particular, Cd and Zn concentrations were higher in males than in females, whereas Cu concentrations increased slightly with weight, and Pb concentrations decreased. Cd and Cu concentrations showed notable spatial variability; Cd concentrations were higher in the eastern islands (Alegranza, La Graciosa, Lanzarote and Fuerteventura) and La Palma, whereas Cu levels were highest in some western islands (Gran Canaria, La Gomera and El Hierro). The arrival of waters from the African coastal upwelling, the pollution of coastal waters with agricultural fertilisers and the competition for uptake between metals appear to be the likely causes within these patterns of accumulation. In conclusion, O. atrata presents a great potential as a biomonitor of heavy metals, however, more information and further studies are necessary.     

A homogeneous and low-cost biosorbent for Cd,Pb and Cu removal from aqueous effluents

Heavy metal pollution of aqueous effluents is a matter of widespread concern. The use of low-cost materials for the adsorption of heavy metals seems to be a suitable choice for waste water treatment. Polyporus tenuiculus, easily cultivated on lignocellulosic waste, was assayed for Cu, Pb and Cd removal from aqueous solutions. Pb was removed more efficiently. Kinetics studies suggested a pseudo-second-order reaction and equilibrium was reached in ～ 30 min in all cases. The metal-sorption data were analysed according to several two-parameter isotherms. Data better fitted the Langmuir model for the three metals. A great dependence of metal adsorption with pH was observed. Characterisation of both the biomass and the complex metal-biomass was performed by FT-IR and SEM-EDX. Results suggest an ion exchange mechanism.     

Tissue distribution of Cd,Cu, Zn,Ni, Cr,Pb and Hg in striated heron,Butorides striatus (Aves: Ardeidae), in a fluvial ecosystem

In this study, the striated heron (Butorides striatus), a species that reproduces in the Middle Paraná River floodplain, was examined for lead, cadmium, chromium, zinc, nickel, mercury and copper concentrations, using liver, kidney, muscle, vertebra and feathers. The results showed low exposure to chromium because all tissue samples had concentrations below the limit of detection. Similar results were obtained for nickel and lead, with the exception of vertebra. This might be associated with either long-term exposure to these metals, or it may be that both nesting and wintering areas are non-polluted. Zinc and copper, both essential metals, were found in all tissues and their concentrations were within the ranges reported in the literature. Mercury was also found in all tissues, but at very low concentrations and even at concentrations below those that produce negative effects in several species of birds (e.g. reproductive success, food intake). Studies of this type are needed to interpret the role of organisms within environments impacted by different human activities.     

Biomonitoring of heavy metal (Cd,Cu, Pb,and Zn) concentrations in the west intertidal area of Peninsular Malaysia by using Nerita lineata

Snails, Nerita lineata, were collected from 15 sites along the west intertidal area of Peninsular Malaysia from December 2005 until April 2006. The concentrations of heavy metals (Cd, Cu, Pb, and Zn) were determined in the total soft tissues, operculums, and shells of the snails. Different patterns of heavy metal distributions were found in the different tissues (shell, operculums, and soft tissues) as well as spatial variations of heavy metal concentrations in the snails. This shows that the distribution of metals in the shells and the total soft tissues of N. lineata were not similar which could be due to different rates of metal accumulation, excretion, and sequestration. Since N. lineata is abundant on the rocky shores, below jetties and mangrove trees along the west intertidal area of Peninsular Malaysia and accumulate heavy metals, the snails are therefore potential biomonitors of heavy metal contamination for the west intertidal area of Peninsular Malaysia.     

Levels of heavy metals (Zn,Cu, Cd,and Pb) in mudskippers (Periophthalmodon schlosseri) and sediments collected from intertidal areas at Morib and Remis,Peninsular Malaysia

The concentrations of Zn, Cu, Cd, and Pb were determined in different tissues of mudskipper fishes Periophthalmodon schlosseri caught at two selected locations (Morib and Remis) of the intertidal mudflat area of Selangor state, West Coast of Peninsular Malaysia and in surface sediment samples. Metal concentrations in the mudskipper tissue and in the sediment samples tended to vary significantly (p < 0.05) between the two locations. Higher metal concentrations (except for Zn) were mostly found in the tissues of mudskippers from Remis. For sediment samples, significantly (p < 0.05) higher metal concentrations of all metals were also found at Remis. Generally, metal distribution between different tissues of mudskipper varied with scales being highly accumulative of Zn, Cd, and Pb, while for Cu, the highest mean concentrations were found in the liver. The lowest mean concentrations of Zn, Cu, and Cd were found in the muscles except for Pb, which was lowest in the liver. This study suggests that mudskippers can be potential biomonitoring organisms for heavy metal bioavailability and contamination of intertidal coastal mudflats. The concentrations of Cd and Pb were slightly above the acceptable limits of Malaysian and European food safety guidelines.     

Adsorptive removal of mercury from acid mine drainage: a comparison of silica and maghemite nanoparticles

Mercury adsorption by silica and maghemite nanoparticles (NPs) was studied with the aim of comparing their performance in the remediation of acid mine drainage (AMD) contaminated water. Calculated distribution coefficients (K_d) showed that both NPs are exceptional adsorbents. However, adsorbate coverage per unit area was 30 times higher for maghemite than for silica NPs, despite the latter having a surface area ～15 times greater. Maghemite adsorbed 75% of available Hg compared to 56% by silica, making it a more efficient sorbent than silica under AMD conditions. Kinetics and isotherm data for both adsorbents were fitted by the pseudo-second-order (R² = 1) and the Freundlich (R² ≥ 0.98) models, implying that adsorption to both NP types was by chemisorption. Adsorption increased with NP concentrations and pH and was enhanced in the presence of manganese and sulfate ions although adsorption to silica was inhibited in 1:2 Hg-to-Mn systems. Importantly, trends in simulated wastewater were replicated in actual AMD-contaminated water samples. This study highlights the fact that properties besides surface area and charge of adsorbents determine adsorbent performance, and superior attributes may not always lead to higher adsorption efficiencies.     

Effect of Pb,Cd and Cu on survival and development of Culex quinquefasciatus (Diptera: Culicidae)

ABSTRACT

The present research aimed to determine the lowest levels of three heavy metals (Pb, Cd and Cu) to which the larvae of Southern House Mosquito, Culex quinquefasciatus are susceptible in water. The study also aimed to investigate the effects of these heavy metals on the development of Cx. quinquefasciatus at concentrations set by Pakistan Environmental Protection Agency (Pak-EPA) as permissible levels for liquid industrial effluents. The 2nd instar larvae of Cx. quinquefasciatus were exposed to different concentrations of Pb, Cd and Cu and their effects on oviposition preference, egg hatching rate and larval development were studied. The LC₅₀ values of Pb, Cd and Cu were 12.6, 6.3 and 2.6?ppm, respectively. Gravid female mosquito adults deposited a significantly lower number of egg rafts in containers containing 0.50?ppm Pb or 1.0?ppm Cu in water. Each of the heavy metals in water resulted in significantly (p?<?0.05) lower egg hatching rate, prolonged time to pupation, lower pupation rate, prolonged time to adult emergence, lower adult emergence rate and higher female to male ratio. It is concluded that the 2nd instar larvae of Cx. quinquefasciatus are susceptible to Pak-EPA permissible levels of Pb, Cd and Cu in municipal and liquid industrial effluents.     

矿区污染土壤Pb、Cd、Cu和Zn的形态分布及其生物活性的研究

调查湘南某铅锌矿区周围的菜园土和水稻土Pb、Cd、Cu和Zn的形态分布及其生物活性和迁移性。结果表明:两种土壤中Pb、Cd、Cu和Zn的总量分别超过国家土壤环境质量相应的标准。运用Tessier连续提取法研究发现,土壤中Pb、Cd、Cu和Zn的各形态含量之和与其总量非常的接近,其中菜园土Pb的提取率为96.3%,Cd的为94.1%,Cu的为93.4%和Zn的为91.7%;水稻土Pb的为97.6%,Cd的为92.0%,Cu的为92.1%和Zn的为91.7%,表明该形态分析方法的结果是合理的。土壤中Pb、Cd、Cu和Zn各形态的分布存在很大的差别,残渣态是主要形态,其中Pb的含量占60.7%~58.2%,Cd的是50.4%~59.2%,Cu的是37.3%~53.4%,Zn的是54.9%~46.9%,而交换态所占的比例最小。菜园土重金属的生物活性系数的大小是:Cd>Cu>Pb>Zn,迁移能力的顺序是Cd>Cu>Zn>Pb;水稻土重金属的活性大小和迁移能力的顺序都是:Cd>Pb>Zn>Cu。菜园土重金属的生物活性和迁移性较水稻土的大,其中Cd的生物活性和迁移性的最大。研究结果将为评估矿区污染土壤中重金属的危害提供科学依据。     

兰坪铅锌尾矿区豆科植物根瘤菌的多样性及抗性研究

对兰坪铅锌尾矿区自然发生的植物进行调查,共发现18种植物,分属于10科。对野豇豆（Vigna vexiauata（Linn.）Bench.）、长波叶山蚂蝗（Desmodium sequax Wall.）、三叶草（Trifolium pratense Linn.）、白刺花（Sophora davii（franch.）Skeels）、密花序黄芪（Astragalus forrestii Simpson.）、美丽胡枝子（Lespedeza Formosa（Vog.）Koehne.）6种8株豆科植物根瘤进行根瘤菌的分离纯化,共得到419株细菌,经镜检初步确定有94株为根瘤菌。对其中31株根瘤菌的淀粉水解、糖发酵等12项生理生化指标进行测定,并以平均连锁法进行聚类分析。结果表明,兰坪铅锌尾矿区31株根瘤菌在50%的相似水平上可分为6个类群,其表型特性存在明显差异,同一种植物中可能存在不同代谢类型的根瘤菌,同一种代谢类型的根瘤菌也可与不同植物共生。抗逆性测定结果表明,菌株（4G.7、5.4.3、7.4.3）对温度、（4A.12、4G.7、4G.10、5.4.3）对pH、（3.7.9、5.4.3）对盐、（3.7.19、4A.12、6.1.2、6.1.13）对抗生素有较强耐受性或抗性,大多数菌株能在较宽的温度、盐度和pH范围内生长。     

Use of different soft tissues of Perna viridis a s biomonitors of bioavailability and contamination by heavy metals (Cd,Cu, Fe,Pb, Ni,and Zn) in a semi-enclosed intertidal water,the Johore Straits

Green-lipped mussels, Perna viridis, were collected from the eastern and western parts of the Johore Straits in September 2004 and January 2005. Based on the heavy metal concentrations in the different soft tissues (gonad, foot, mantle, gills, muscle, and remaining soft tissues) of these mussel samples, the eastern part of the Johore Straits (which is divided into two portions by a causeway), recorded higher levels of bioavailability and contamination by Cd, Cu, Fe, Ni, and Zn when compared to the western part, while Kg. Pasir Puteh in the eastern part was found to record the highest bioavailability and contamination by heavy metals. The use of different soft tissues of P. viridis as biomonitors of bioavailability and contamination by Cd, Cu, Fe, Pb, Ni, and Zn in the semi-enclosed Johore Straits is proposed, since erroneous results due to spawning and the problem of defecation before dissection could be overcome. Hence, a more accurate interpretation of the bioavailability and contamination by heavy metals in coastal waters could be obtained. To our knowledge, this is the most detailed study on the bioavailability and contamination of heavy metals in the Johore Straits on the Malaysian side of the waterway carried out by using the different soft tissues and metal distribution based on the Mussel Watch approach.     

Comparing the adsorption behaviors of Cd,Cu and Pb from water onto Fe-Mn binary oxide,MnO2 and FeOOH

The adsorption potential of FMBO, FeOOH, MnO₂ for the removal of Cd²⁺, Cu²⁺ and Pb²⁺ in aqueous systems was investigated in this study. Comparing to FMBO and FeOOH, MnO₂ offered a much higher removal capacity towards the three metal ions. The maximal adsorption capacity of MnO₂ for Cd²⁺, Cu²⁺ and Pb²⁺ were 1.23, 2.25 and 2.60 mmol·g^-1, respectively. And that for FMBO were 0.37, 1.13, and 1.18 mmol·g^-1 and for FeOOH were 0.11, 0.86 and 0.48 mmol·g^-1, respectively. The adsorption behaviors of the three metal ions on the three adsorbents were all significantly affected by pH values and heavy metal removal efficiency increased with pH increased. The Langmuir and Freundlich adsorption models were used to describe the adsorption equilibrium of the three metal ions onto the three adsorbents. Results showed that the adsorption equilibrium data fitted well to Langmuir isotherm and this indicated that adsorption of metal ions occurred on the three metal oxides adsorbents limited to the formation of a monolayer. More negative charged of MnO₂ surface than that of FMBO and FeOOH could be ascribed by lower pH_iep of MnO₂ than that of FMBO and FeOOH and this could contribute to more binding sites on MnO₂ surface than that of FMBO and FeOOH. The higher metal ions uptake by MnO₂ than FMBO and FeOOH could be well explained by the surface charge mechanism.     

Contamination by Cd, Cu, Pb, and Zn in mine wastes from abandoned metal mines classified as mineralization types in Korea

The objective of this study was to investigate heavy metal contamination and geochemical characteristics of mine wastes, including tailings, from 38 abandoned mines classified as five mineralization types. Mine waste materials including tailings and soils were sampled from the mines and the physical and chemical characteristics of the samples were analyzed. The particle size of tailings was in the range of 10–100 μm. The pH of the waste covered a wide range, from 1.73 to 8.11, and was influenced by associated minerals and elevated levels of Cd, Cu, Pb, and Zn, extracted by a Korean Standard Method (digestion with 0.1 mol L⁻¹ HCl), which were found in the wastes. Half of the samples contained heavy metals at levels above those stipulated by the Soil Environmental Conservation Act (SECA) in Korea. In addition, extremely high concentrations of the metals were also found in mine wastes extracted by aqua regia, especially those from mines associated with sulfide minerals. Thus, it can be expected that trace elements in mine wastes may be dispersed both downstream and downslope through water and wind. Eventually they may pose a potential health risk to residents in the vicinity of the mine. It is necessary to control mine wastes by using a proper method for their reclamation, such as neutralization of the mine wastes using a fine-grained limestone.     

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.     

4种草对铅锌尾矿污染土壤重金属的抗性与吸收特性

盆栽试验的结果表明,高羊毛、早熟禾、黑麦草、紫花苜蓿在纯尾矿污染土壤或经处理的尾矿污染土壤上都能生长,但在处理的土壤上生长的植物长势明显优于对照,其中紫花苜蓿的生物量所受影响比其他几种草坪草更大,说明其重金属抗性低于其他几种植物。单位面积上 4 种植物体内重金属质量分数高低均为 w(Zn)>w(Pb)>w(Cu)>w(Cd),但每种植物对 Cd、Pb、Zn 和 Cu 的吸收质量分数和分布均不相同,一般为根系质量分数大于茎叶。加入改良剂(CaCO3)和有机肥(菜枯)使生长在铅锌尾矿污染土壤上的 4 种草坪草生物量显著增加,植物体中的 Cd、Pb、Zn 质量分数下降,但 Cu 质量分数反而上升,结果单位面积上草坪草吸收各重金属元素的量均有所增加,可见利用改良措施与草坪草相结合的方法来修复重金属污染土壤具有可行性。