Heavy metal (Cu, Zn, Cd and Pb) contamination of vegetables in urban India: a case study in Varanasi

The contributions of heavy metals in selected vegetables through atmospheric deposition were quantified in an urban area of India. Deposition rate of Zn was recorded maximum followed by Cu, Cd and Pb. The concentrations of Zn and Cu were highest in Brassica oleracea, Cd in Abelmoschus esculentus and B. oleracea, while Pb was highest in Beta vulgaris. Heavy metal pollution index showed that B. oleracea was maximally contaminated with heavy metals followed by A. esculentus and then B. vulgaris. The results of washing showed that atmospheric deposition has contributed to the increased levels of heavy metals in vegetables. Both Cu and Cd posed health risk to local population via test vegetables consumption, whereas Pb posed the same only through B. oleracea. The study concludes that atmospheric depositions can elevate the levels of heavy metals in vegetables during marketing having potential health hazards to consumers.     

Dynamic modelling of atmospherically-deposited Ni, Cu, Zn, Cd and Pb in Pennine catchments (northern England)

Simulation modelling with CHUM-AM was carried out to investigate the accumulation and release of atmospherically-deposited heavy metals (Ni, Cu, Zn, Cd and Pb) in six moorland catchments, five with organic-rich soils, one with calcareous brown earths, in the Pennine chain of northern England. The model considers two soil layers and a third layer of weathering mineral matter, and operates on a yearly timestep, driven by deposition scenarios covering the period 1400-2010. The principal processes controlling heavy metals are competitive solid-solution partitioning of solutes, chemical interactions in solution, and chemical weathering. Agreement between observed and simulated soil metal pools and surface water concentrations for recent years was generally satisfactory, the results confirming that most contemporary soil metal is from atmospheric pollution. Metals in catchments with organic-rich soils show some mobility, especially under more acid conditions, but the calcareous mineral soils have retained nearly all anthropogenic metal inputs. Complexation by dissolved organic matter and co-transport accounts for up to 80% of the Cu in surface waters.     

Evaluation of the effectiveness of phosphate treatment for the remediation of mine waste soils contaminated with Cd, Cu, Pb, and Zn

The effectiveness of phosphate treatment for Cd, Cu, Pb, and Zn immobilization in mine waste soils was examined using batch conditions. Application of synthetic hydroxyapatite (HA) and natural phosphate rock (FAP) effectively reduced the heavy metal water solubility generally by about 84-99%. The results showed that HA was slightly superior to FAP for immobilizing heavy metals. The possible mechanisms for heavy metal immobilization in the soil involve both surface complexation of the metal ions on the phosphate grains and partial dissolution of the phosphate amendments and precipitation of heavy metal-containing phosphates. HA and FAP could significantly reduce Cd, Cu, Pb, and Zn availability in terms of water solubility in contaminated soils while minimizing soil acidification and potential risk of eutrophication associated with the application of highly soluble phosphate sources.     

Biosorption of divalent Pb, Cd and Zn on aragonite and calcite mollusk shells

The potential of using mollusk shell powder in aragonite (razor clam shells, RCS) and calcite phase (oyster shells, OS) to remove Pb²⁺, Cd²⁺ and Zn²⁺ from contaminated water was investigated. Both biogenic sorbents displayed very high sorption capacities for the three metals except for Cd on OS. XRD, SEM and XPS results demonstrated that surface precipitation leading to crystal growth took place during sorption. Calcite OS displayed a remarkably higher sorption capacity to Pb than aragonite RCS, while the opposite was observed for Cd. However, both sorbents displayed similar sorption capacities to Zn. These could be due to the different extent of matching in crystal lattice between the metal bearing precipitate and the substrates. The initial pH of the solution, sorbent’s dosage and grain size affected the removal efficiency of the heavy meals significantly, while the organic matter in mollusk shells affected the removal efficiency to a lesser extent.     

Kinetic extractions to assess mobilization of Zn, Pb, Cu, and Cd in a metal-contaminated soil: EDTA vs. citrate

Kinetic EDTA and citrate extractions were used to mimic metal mobilization in a soil contaminated by metallurgical fallout. Modeling of metal removal rates vs. time distinguished two metal pools: readily labile (QM1) and less labile (QM2). In citrate extractions, total extractability (QM1+QM2) of Zn and Cd was proportionally higher than for Pb and Cu. Proportions of Pb and Cu extracted with EDTA were three times higher than when using citrate. We observed similar QM1/QM2 ratios for Zn and Cu regardless of the extractant, suggesting comparable binding energies to soil constituents. However, for Pb and Cd, more heterogeneous binding energies were hypothesized to explain different kinetic extraction behaviors. Proportions of citrate-labile metals were found consistent with their short-term, in-situ mobility assessed in the studied soil, i.e., metal amount released in the soil solution or extracted by cultivated plants. Kinetic EDTA extractions were hypothesized to be more predictive for long-term metal migration with depth.     

浮游球衣菌对Pb2+、Cu2+、Zn2+、Cd2+的吸附性能研究

研究了浮游球衣菌（Sphaerotilus natans）在不同吸附条件下对溶液中Pb^2＋、Cu^2＋、Zn^2＋、Cd^2＋的吸附规律。结果表明,Sphaerotilus natans对这4种重金属离子均有一定的吸附作用,并在20min内达到吸附平衡,pH对吸附过程影响较大,pH为5.5时Sphaerotilus natans对这4种金属离子的吸附效果最好,Sphaerotilus natans对它们的吸附选择性为Pb^2＋〉Cu^2＋〉Zn^2＋〉Cd^2＋,Pb^2＋、Cu^2＋能部分置换出已被菌体吸附的Zn^2＋、Cd^2＋。HCI和EDTA溶液可有效地将金属离子从菌体上解吸下来,解吸后的菌体可重复使用。     

Three common metal contaminants of urban runoff (Zn, Cu & Pb) accumulate in freshwater biofilm and modify embedded bacterial communities

We investigated the absorption rates of zinc, copper and lead in freshwater biofilm and assessed whether biofilm bacterial populations are affected by exposure to environmentally relevant concentrations of these metals in flow chamber microcosms. Metals were rapidly accumulated by the biofilm and then retained for at least 14 days after transfer to uncontaminated water. Changes in bacterial populations were assessed by Automated Ribosomal Intergenic Spacer Analysis (ARISA) and 16S rRNA gene clone libraries. Significant differences in bacterial community structure occurred within only three days of exposure to metals and remained detectable at least 14 days after transfer to uncontaminated water. The rapid uptake of stormwater-associated metals and their retention in the biofilm highlight the potential role of biofilms in the transfer of metals to organisms at higher trophic levels. The sensitivity of stream biofilm bacterial populations to metal exposure supports their use as an indicator of stream ecological health.     

Effect of pore-water velocity on chemical nonequilibrium transport of Cd,Zn, and Pb in alluvial gravel columns

This paper investigates the effects of pore-water velocity on chemical nonequilibrium during transport of Cd, Zn, and Pb through alluvial gravel columns. Three pore-water velocities ranging from 3 to 60 m/day were applied to triplicate columns for each metal. Model results for the symmetric breakthrough curves (BTCs) of tritium (3H2O) data suggest that physical nonequilibrium components were absent in the uniformly packed columns used in these studies. As a result, values of pore-water velocity and dispersion coefficient were estimated from fitting 3H2O BTCs to an equilibrium model. The BTCs of metals display long tailing, indicating presence of chemical nonequilibrium in the system, which was further supported by the decreased metal concentrations during flow interruption. The BTCs of the metals were analysed using a two-site model, and transport parameters were derived using the CXTFIT curve-fitting program. The model results indicate that the partitioning coefficient (beta), forward rate (k1), and backward rate (k2) are positively correlated with pore-water velocity (V); while the retardation factor (R), mass transfer coefficient ((omega), and ratio of k1/k2 are inversely correlated with V. There is no apparent relationship between the fraction of exchange sites at equilibrium (f) and V. The influence of Von k2 is much greater than on R, beta, omega, and k1. A one-order-of-magnitude change in V would cause a two-order-of-magnitude change in k2 while resulting in only a one order-of-magnitude change in R, beta, omega, and k1. The forward rates for the metals are found to be two to three orders-of-magnitude greater than the corresponding backward rate. However, the difference between the two rates reduces with increasing pore-water velocity. Model results also suggest that Cd and Zn behave similarly, while Pb is much more strongly sorbed. At input concentrations of about 4 mg/l and pore-water velocities of 3-60 m/day in the groundwater within alluvial gravel, this study suggests retardation factors of 26-289 for Cd, 24-255 for Zn, and 322-6377 for Pb.     

Concentration of trace elements in feathers of three Antarctic penguins: Geographical and interspecific differences

Antarctica is often considered as one of the last pristine regions, but it could be affected by pollution at global and local scale. Concentrations of Al, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Cd and Pb were determinated by ICP-MS in feathers (n = 207 individuals) of gentoo, chinstrap and Adélie penguin collected in 8 locations throughout the Antarctic Peninsula (2006-2007). The highest levels of several elements were found in samples from King George Island (8.08, 20.29 and 1.76 μg g⁻¹ dw for Cr, Cu and Pb, respectively) and Deception Island (203.13, 3.26 and 164.26 μg g⁻¹ dw for Al, Mn and Fe, respectively), where probably human activities and large-scale transport of pollutants contribute to increase metal levels. Concentrations of Cr, Mn, Cu, Se or Pb, which are similar to others found in different regions of the world, show that some areas in Antarctica are not utterly pristine.     

Eighty-year sedimentary record of heavy metal inputs in the intertidal sediments from the Nanliu River estuary, Beibu Gulf of South China Sea

²¹⁰Pb analysis in the sediment core C11 was used to reconstruct the historical fluxes of Hg, Cu, Pb, Zn, Cd, Cr and As in the Nanliu River estuary during the last ∼81 year. The ²¹⁰Pb_xs-derived sedimentation rates, molar C/N ratios, enrichment factors and excess fluxes indicated that the natural inputs prevailed till the early 1990s. When the erosion related to land-use modifications enhanced, it promoted higher accumulation rates of the sedimentary material. In the recent sediments they were found a moderate enrichment of Cd and Hg (maximum 3.5- and 2.8-fold corresponding to the local background levels, respectively) and a slight enrichment of Cr, Zn, As and Pb (maximum 1.3-, 1.3-, 1.3- and 1.2-fold, respectively). The excess metal fluxes also showed a consistently increasing tread since the early 1990s, which could be associated with the intensive use of phosphate fertilizers and the combustion of fossil fuels derived from human activities.     

Content, distribution and fate of 33 elements in sediments of rivers receiving wastewater in Hanoi, Vietnam

Untreated industrial and domestic wastewater from Hanoi city is discharged into rivers that supply water for various agricultural and aqua-cultural food production systems. The aim of this study was to assess the content, distribution and fate of 33 elements in the sediment and pore water of the main wastewater receiving rivers. The sediment was polluted with potentially toxic elements (PTEs) with maximum concentrations of 73 As, 427 Cd, 281 Cr, 240 Cu, 218 Ni, 363 Pb, 12.5 Sb and 1240 Zn mg kg(-1) d.w. Observed distribution coefficients (log(10) K(d,obs)) were calculated as the ratio between sediment (mg kg(-1) d.w.) and pore water (mg L(-1)) concentrations. Maxima log(10) K(d,obs) were >4.26 Cd, >6.60 Cu, 4.78 Ni, 7.01 Pb and 6.62 Zn. The high values show a strong PTE retention and indicate the importance of both sorption and precipitation as retention mechanisms. Sulphide precipitation was a likely mechanism due to highly reduced conditions.     

Using stable lead isotopes to trace heavy metal contamination sources in sediments of Xiangjiang and Lishui Rivers in China

Lead isotopes and heavy metal concentrations were measured in two sediment cores sampled in estuaries of Xiangjiang and Lishui Rivers in Hunan province, China. The presence of anthropogenic contribution was observed in both sediments, especially in Xiangjiang sediment. In the Xiangjiang sediment, the lower ²⁰⁶Pb/²⁰⁷Pb and higher ²⁰⁸Pb/²⁰⁶Pb ratio, than natural Pb isotope signature (1.198 and 2.075 for ²⁰⁶Pb/²⁰⁷Pb and ²⁰⁸Pb/²⁰⁶Pb, respectively), indicated a significant input of non-indigenous Pb with low ²⁰⁶Pb/²⁰⁷Pb and high ²⁰⁸Pb/²⁰⁶Pb. The corresponding concentrations of heavy metals (As, Cd, Zn, Mn and Pb) were much higher than natural values, suggesting the contaminations of heavy metals from extensive ore-mining activities in the region.     

底泥生长基质中重金属的迁移特征及生物有效性

河道底泥中重金属含量较高,重金属的迁移性及生物有效性是限制疏浚底泥土地施用或用作废弃场地修复基质资源化利用途径的主要因素。以沈阳细河待疏浚底泥为材料,通过盆栽实验的方法研究了河道底泥与碱性粉煤灰、炉渣和锯木屑配比基质中重金属在紫花苜蓿体内累积、迁移及生物有效性的变化。结果发现,配比底泥基质上紫花苜蓿生物量、株高及株径均好于纯底泥处理,其中底泥、粉煤灰、炉渣、锯木屑以2：0．5：0．5：0．5配比的s2处理中紫花苜蓿生物量是纯底泥处理的11．7倍。与底泥对照相比,配比底泥基质上植株体内重金属含量极显著降低,而且地上部重金属含量显著低于根部含量;底泥基质中紫花苜蓿地上部和根部对Cd、Cu、Pb、Zn的富集系数（BCF）显著低于底泥处理,但转移系数（TF）无显著变化,富集系数（BCF）和转移系数（TF）均小于1．0。紫花苜蓿种植后底泥基质中重金属含量显著低于农用污泥重金属控制标准,除Cd含量略高外,Cu、Pb和Zn含量低于土壤环境质量三级标准。这些结果表明,城市重污染河道底泥经过合理处置后,重金属浓度、活性及生物有效性降低,在其土地施用或废弃地修复中可以用作一些耐性植物的生长基质。     

Influence of synthetic surfactants on the uptake of Pd, Cd and Pb by the marine macroalga, Ulva lactuca

Uptake of Pd, Cd and Pb by the marine macroalga, Ulva lactuca, has been studied in the presence of an anionic (sodium dodecyl sulphate, SDS), cationic (hexadecyltrimethylammonium bromide; HDTMA) and non-ionic (Triton X-100; TX) surfactant. Compared with the surfactant-free system, metal sorption was reduced in the presence of SDS or TX. Neither surfactant, however, had any measurable impact on cell membrane permeability, determined by leakage of dissolved free amino acids (DFAA), or on metal internalisation. We attribute these observations to the stabilisation of aqueous Cd and Pb by SDS and the shielding of otherwise amenable sorption sites by TX. Presence of HDTMA resulted in a reduction in the extent of both sorption and internalisation of all metals and a significant increase in the leakage of DFAA. Thus, by enhancing membrane permeability, HDTMA exerts the greatest influence on metal behaviour in the presence of U. lactuca.     

矿区土壤中重金属元素含量异常的调查

对某金矿区下游土壤重金属元素含量异常区进行了调查,研究了异常元素的空间分布和相态组成.通过对土壤、水、农产品、大气沉降物等的采样分析表明,土壤中重金属元素含量异常是由于矿山开采,废水排放,下游引水灌溉造成的.对异常元素的环境影响进行了分析评价,并提出了土壤治理建议.     

Estimation of atmospheric trace metal emissions in Vilnius City, Lithuania, using vertical concentration gradient and road tunnel measurement data

A new approach for the estimation of trace metal emissions in Vilnius city was implemented, using vertical concentration profiles in the urban boundary layer and road tunnel measurement data. Heavy metal concentrations were examined in fine and coarse particle fractions using a virtual impactor (cut-off size diameter 2.5 μm). Negative vertical concentration gradients were obtained for all metals (Ba, Pb, V, Sb, Zn) and both fractions. It was estimated that the vertical concentration gradient was formed due to emissions from an area of about 12 km². Road tunnel measurements indicated that trace metal concentrations on fine particles were lower than those on coarse particles, which suggested that re-emitted road dust was highly enriched in trace metal due to historic emissions within the tunnel. Emission rates of different pollutants in the road tunnel were calculated using pollutant concentration differences at the tunnel entrance and exit and traffic flow data. Heavy metal emission rates from the area of Vilnius city were estimated using the vertical gradient of heavy metal concentrations and the coefficient of turbulent mixing, as derived from meteorological measurement data. The emission values calculated by the two different methods coincided reasonably well, which indicated that the main source of airborne trace metals in Vilnius city is traffic. The potential of the vertical concentration gradient method for the direct estimation of urban heavy metal emissions was demonstrated.     

Factors affecting distribution and mobility of trace elements (Cu, Pb, Zn) in a perennial grapevine (Vitis vinifera L.) in the Champagne region of France

Soil and Vitis vinifera L. (coarse and fine roots, leaves, berries) concentration and geochemical partitioning of Cu, Pb and Zn were determined in a contaminated calcareous Champagne plot to assess their mobility and transfer. Accumulation ratios in roots remained low (0.1-0.4 for Cu and Zn, <0.05 for Pb). Differences between elements resulted from vegetation uptake strategy and soil partitioning. Copper, significantly associated with the oxidisable fraction (27.8%), and Zn with the acid soluble fraction (33.3%), could be mobilised by rhizosphere acidification and oxidisation, unlike Pb, essentially contained in the reducible fraction (72.4%). Roots should not be considered as a whole since the more reactive fine roots showed higher accumulation ratios than coarse ones. More sensitive response of fine roots, lack of correlation between chemical extraction results and vegetation concentrations, and very limited translocation to aerial parts showed that fine root concentrations should be used when assessing bioavailability.     

Temporal variability of bioavailable Cd,Hg, Zn,Mn and Al in an upwelling regime

Monthly variability of Cd, Hg, Zn, Mn and Al concentrations in mussels (Mytilus californianus) soft tissue and brown seaweed (Macrocystis pyrifera) was studied at a pristine rocky shore off San Quintin Bay, Baja California, México. The results were related to climatic and hydrographic conditions and to the physiological state of the mussels (condition index) by correlation analysis and principal component analysis (PCA). A "normalization" to account for the variability induced by the physiological state of the mussel was performed. The PCA was performed in two ways to relate the environmental variables and the condition index to: (1) the metal concentrations in mussels, and (2) the "normalized" mussel concentrations. The association of the variability of Cd with the upwelling season was revealed in both PCAs. The temporal variability of this metal in mussels was highly correlated to that in seaweed, suggesting that the dissolved phase determined the variability of Cd in mussels. However, for Hg, Zn, Mn and Al the results from both PCAs were different. The first PCA showed the relationship of these metals to pluvial precipitation and to the condition index. The PCA for the normalized mussel concentrations showed that, after eliminating the effect of the condition index, only Al was related to pluvial precipitation. Manganese, and to a less degree Zn, were related to these metals in seaweed. Because zinc is an essential element in mussels, some regulation of their internal concentrations is likely. Mercury was not detected in seaweed, but because of its reactive nature, it is not expected that the dissolved fraction could be a significant pathway; therefore, it can be concluded that its temporal variability was determined by the variability in the condition index only.     

Fifty-year sedimentary record of heavy metal pollution (Cd, Zn, Cu, Pb) in the Lot River reservoirs (France)

The Lot-Garonne fluvial system is known for its historic heavy metal pollution resulting from mining and smelting activities since the late 19th century. Here, we report 137Cs activities and heavy metal (Cd, Zn, Cu, Pb and V) concentration-depth profiles from sediment cores retrieved in 2001 from three reservoirs in the Lot River. High mean sedimentation rates of 2.4-2.8 cm a(-1) are indicated by 137Cs dating. The reservoir sediments have recorded the heavy metal deposition and thus allow establishing a connection between the temporal evolution of the heavy metal pollution and historical changes in smelting and waste-treatment proceedings. Based on heavy metal concentrations in sediments upstream of the anthropogenic inputs and bottom-sediments of the furthest downstream core (interpreted as old soil or riverbed), concentrations of approximately 17, approximately 82, approximately 0.33 and approximately 28 mg kg(-1) for Cu, Zn, Cd and Pb, respectively, are proposed as natural background values for the Lot fluvial system. The geoaccumulation index (Igeo [Müller, G., 1979. Schwermetalle in den Sedimenten des Rheins-Ver?nderungen seit. Umschav 79, 133-149.]) revealed that the Lot River sediments must be considered as "severely polluted" in Cd and Zn. Moreover, despite remediation efforts undertaken in the former smelting site, the Lot River is still "severely" (Igeo approximately 4) and "moderately to severely" (Igeo>2) impacted by Cd and Zn inputs, respectively.     

Influence of soil pH on the fractionation of Cr, Cu and Zn in solid phases from a landfill site

The spatial variability of soil pH for engineered Weathered Oxford Clay is described using 35 samples collected from the base of a new cell in an existing landfill. Soil pH variability influences the reactivity of Cr, Cu and Zn in the site. The reactivity of these metals as natural components was determined using a sequential extraction method. The total concentration of Cr, Cu and Zn and the mineralogical composition were also determined. The results showed that due to the presence of a layer rich in pyrite in the base, a natural acidification may occur which can produce a soil pH as low as 2.7. The spatial variability of soil pH in this area has been described with an anisotropical variogram model and the estimation of its values at unsampled locations was carried out using the ordinary kriging algorithm. From the spatial modelling of the soil pH, it was found that the metals in the soil solid phases follow a similar distribution.