Seasonal and time variability of heavy metal content and of its chemical forms in sewage sludges from different wastewater treatment plants

Sewage sludges obtained from seven wastewater treatment plants from the province of Salamanca, Spain, were periodically sampled to determine seasonal and time variation of their elemental composition over 2000 to 2002. The aim of this paper was to provide additional insight to evaluate the potential environmental impact following soil incorporation of these materials as amendments. Aqua regia extractable metals (pseudo total content) of Cd, Cr, Cu, Ni, Pb and Zn were determined and furthermore, the main chemical forms of metals within the sludge were evaluated using a five-step fractionation procedure. All the studied sludges displayed high fertility properties due to their richness of OC, P and K. Total mean concentrations of Cd, Cr, Cu, Ni, Pb and Zn in the sludges were within the regulation of the Spanish legislation. Using an multifactor analysis of variance, significant differences between Cr, Cu, Ni, Pb and Zn pseudo total contents (p<0.01) of sludges at different sites were found while the Cd content was statistically similar. Also significant differences were found between these pseudo total contents of heavy metals in samples collected along the time after three years (0.001相似文献   

Concentrations of heavy metals and plant nutrients in water, sediments and aquatic macrophytes of anthropogenic lakes (former open cut brown coal mines) differing in stage of acidification.

Concentration of heavy metals (Al, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, V and Zn) as well as macronutrients (N, P, K, Ca, Mg, S) were measured in water, bottom sediments and plants from anthropogenic lakes in West Poland. The collected plants were: Phragmites australis, Potamogeton natans, Iris pseudoacorus, Juncus effusus, Drepanocladus aduncus, Juncus bulbosus, Phalaris arundinacea, Carex remota and Calamagrostis epigeios. Two reference lakes were sampled for Nymphaea alba, Phragmites australis, Schoenoplectus lacustris, Typha angustifolia and Polygonum hydropiper. These plants contained elevated levels of Cd, Co, Cr, Cu and Mn, and part of the plants contained in addition elevated levels of Mn, Fe, Pb, Ni and Zn. Analyses of water indicated pollution with sulfates, Cd, Co, Ni. Zn, Pb and Cu, and bottom sediments indicated that some of the examined lakes were polluted with Cd, Co and Cr. Strong positive correlations were found between concentrations of Co in water and in plants and between Zn in sediments and plants, indicating the potential of plants for pollution monitoring for this metal. Heavy metal accumulation seemed to be directly associated with the exclusion of Ca and Mg.     

Quantities and associations of lead, zinc, cadmium, manganese, chromium, nickel, vanadium, and copper in fresh Mississippi delta alluvium and New Orleans alluvial soils

The topic of this study is the effect of anthropogenic metals on the geochemical quality of urban soils. This is accomplished by comparing the metal contents and associations between two alluvial soils of the lower Mississippi River Delta, freshly deposited alluvial parent materials and alluvial soils collected from a nearby urban environment. Fresh alluvium samples (n = 97) were collected from the Bonnet Carré Spillway. The urban alluvial soil samples (n = 4026) were collected from New Orleans and stratified by census tracts (n = 286). The Spillway samples tend to have less Pb and Zn than generally noted for the baseline of natural soils. Except for Mn and V, Spillway alluvium contains significantly less metal than urban soils. For Spillway samples, the median metal content (in microg g(-1)) is 4.7 Pb, 11.1 Zn, 0.7 Cd, 164 Mn, 0.8 Cr, 3.9 Ni, 3.2 V, and 3.9 Cu. For urban soils, the median metal content (in microg g(-1)) is 120 Pb, 130 Zn, 3.2 Cd, 138 Mn, 2.1 Cr, 9.8 Ni, 3.8 V, and 12.7 Cu. Metal associations also differ between Spillway alluvium and urban alluvial soils. Fresh alluvium correlation coefficients between individual metals vary from 0.87 to 0.99 (P < 10(-13)) except for Cr which ranges from 0.57 to 0.68 (P < 10(-7)). The urban soil correlation coefficients for metals and the index value are 0.40-0.98. In urban soils, Pb, Zn, Cr, and Cu are dominant metals and highly associated, with a correlation coefficient ranging from 0.83 to 0.98 (P < 10(-25)). Their strong association justifies the use of GIS to map the integrated soil metal index (sum of the medians of metals by census tract) of New Orleans. Although also positively correlated (0.40-0.68, P < 10(-10)), Cd, Mn, Ni and V differ in their distribution in the city compared to Pb, Zn, Cr and Cu. Overall, significantly higher metal values occur in the inner city and lower values occur in outlying areas. The human health impact of the mixture of metals is not well understood. This study provides empirical data about the mixture and distribution of metals in New Orleans alluvial soils. Given common technical development, especially of traffic flows in cities, similar patterns of soil metals are expected for all US cities and probably international cities as well. Primary prevention of urban metal accumulations is necessary to enhance and sustain the development of urban culture.     

Mass balance and distribution of sludge-borne trace elements in a silt loam soil following long-term applications of sewage sludge

Soil samples were collected at 15-cm increments to a depth of 75 cm from plots on a silt loam soil where until several years earlier and for 14 years, anaerobically digested sewage sludge had been annually applied by furrow irrigation. The study protocol consisted of four replications of 6.1 x 12.2-m plots with 0 (T0), 1/4-maximum (T1), 1/2-maximum (T2) and maximum (T3) sludge application rates randomized within blocks. When sludge applications were terminated, maximum sludge-treated plots had received 765 Mg ha-1 (dry weight equivalent) of sludge solids. Total soil concentrations of Cd, Cr, Cu, Ni, Pb and Zn had been significantly enhanced by all sludge application rates to a soil depth of 30 cm. Below the 30-cm depth, total soil Cd was increased to 75 cm, total Zn to 45 cm (T2 and T3 only), total Cr to 60 cm (T2 and T3 only), but total Cu, Pb, and Ni were not increased at depth. Despite the lack of significant increases in subsoil concentrations for some metals, mass balance calculations showed a relatively high proportion of all the above sludge-borne heavy metals to be unaccounted for in the soil profile for each application rate. Mass balance calculations of losses ranged from a high of 60% for Ni to a low of 36% for Cu and Pb. Similar losses were calculated from metal concentrations measured in soil samples taken at the time the sludge was applied. In soil surface samples (0-15 cm) from maximum sludge-treated plots, percentages of total metal concentration extracted with 4.0 M HNO3 ranged from a low of 31 for Zn to a high of 75 for Cu. Efficiency of metal extraction by HNO3 was inconsistent, depending on the soil horizon and sludge treatment, so that evaluation of HNO3-extractable metals is not a reliable method of estimating total metal retention in the profiles. In soil surface samples from maximum sludge-treated plots, the percentage of total metal contents extracted with DTPA ranged from a low of 0.03 for Cr to a high of 59 for Cd. The DTPA extractable levels of Cu, Ni, and Pb were higher in the subsoils of the sludge-treated soils, indicating that these metals had been redistributed from the surface layer to deeper zones in the profile of sludge-amended soil, despite the absence of elevated total concentrations of these three metals in the deeper subsoil.     

Assessment of river Po sediment quality by micropollutant analysis

Trace metals, PCB congeners and DDT homologues were determined in composite sediment samples collected from 10 representative sites along the river Po in two separate seasons. The aim was to identify the most anthropogenically impacted areas for future monitoring programmes and to aid development of Italian sediment quality criteria. The surface samples were collected during low flow conditions. Trace metal concentrations were assayed by electrothermal (Cd, Co, Cr, Cu, Ni, Pb), flame (Fe, Mn, Zn) or hydride generation (As) atomic absorption spectrometry after microwave assisted acid digestion. Hg was determined on solid samples by automated analyser. Organic microcontaminants were determined by gas-chromatography with 63Ni electron capture detector after Soxhlet extraction. Concentrations of trace metals, total PCB and DDT homologues showed two distinct peaks at the sites immediately downstream of Turin and Milan, respectively, and in each case decreased progressively further downstream. Principal component analysis identified three major factors (from a multi-dimensional space of 35 variables) which explained 85-90% of the total observed variance. The first and second factors corresponded to anthropogenic inputs and geological factors on sediment quality; the third included seasonal processes of minor importance. Sediment quality assessment identified Cd, Cu, Hg, Pb, Zn and organic microcontaminants as posing the most serious threats to river sediment quality. A reference site within the Po basin provided useful background values. Moderate pollution by organochlorine compounds was ascribed both to local sources and to atmospheric deposition.     

Concentrations of selected metals in honey consumed in Nigeria

The concentration of metals, cadmium (Cd), lead (Pb), nickel (Ni), chromium (Cr), copper (Cu), cobalt (Co), iron (Fe), manganese (Mn), and zinc (Zn) was measured in selected samples of honey in Nigeria with a view to providing information on the regional concentration profile of metals in these honeys. The honey samples were digested with a mixture of acids and analysed for metal concentrations using atomic absorption spectrophotometry. The concentrations of metals (mg kg^?1) in these honeys ranged from < 0.3 for Cd,<0.50–39.75 for Pb,<0.25–6.98 for Ni,<0.25–55.25 for Cr,<0.25–71.25 for Cu,<0.25–3.50 for Co,<5.0–163.15 for Fe,<11.0–31.75 for Mn and 1.0–31.0 for Zn. The concentrations of metals were relatively high but lower than their respective permissible limits in food except for Pb and Cu in some samples. The regional distribution patterns of metals indicated that honey samples from the Niger Delta region of Nigeria had higher mean concentrations of Ni, Cr, Co, Fe and Zn than honey samples from other regions. The honey samples from the northern region had higher mean concentrations of Pb and Cu.     

Relationships among total recoverable and reactive metals and metalloid in St. Lawrence River sediment: bioaccumulation by chironomids and implications for ecological risk assessment

The availability and bioaccumulation of metals and metalloids, and the geochemical interactions among them, are essential to developing an ecological risk assessment (ERA) framework and determining threshold concentrations for these elements. The purpose of this study was to explore the relationships among total recoverable and reactive metals and metalloid in sediment and their bioaccumulation by chironomids. In the fall of 2004 and 2005, 58 stations located in the three fluvial lakes of the St. Lawrence River and its largest harbour area in Montreal, Canada, were sampled. Nine total recoverable and reactive metals (Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) and one metalloid (As) were measured in whole sediment using two extraction methods: HCl/HNO(3) and HCl 1N, respectively. The bioaccumulation of six metals (Cd, Cr, Cu, Ni, Pb and Zn) and As by chironomids was evaluated in a subset of 22 stations. Strong collinearities were observed between some total recoverable or reactive metal concentrations in sediment; two principal clusters, including collinear metals, were obtained. The first one included metals of mainly geological origin (Al, Cr, Fe, Mn, Ni), while the second one included As, Cd, Cu, Pb and Zn, which likely derive mainly from point sources of anthropogenic contamination. Each element also showed strong collinearity between their total recoverable and reactive forms (0.65< or =r < or =0.97). We can conclude that both chemical forms are equivalent for use in statistical models needed to explain biological responses and also in screening risk assessment. However, these relationships are not always proportional. Lower availability percentages were observed for Cd, Cu and Zn in the highly mixed-contaminated area of the Montreal Harbour, even though concentrations in sediment were higher. We observed a significant correlation (0.50< or =r < or =0.56) between concentrations in chironomids and concentrations of both total recoverable and reactive Cr and Pb in sediment. Arsenic was an exception, with accumulation by chironomids being highly related to reactive sediment concentrations. Finally, we observed variable influences of explanatory factors (e.g. sediment grain size, Al, Fe, Mn, S, TOC), depending on which metal or metalloid was being predicted in chironomids. In this context, it is difficult to choose a universal predictive method to explain the bioaccumulation of specific metals, and more research is still needed into normalization procedures that consider a combination of explanatory factors.     

The relation between heavy metals and particle size fractions within the severn estuary (U.K.) inter-tidal sediments

Samples of Severn Estuary (U.K.) inter-tidal sediments were fractionated into a range of particle sizes. The heavy metal concentrations in the non-residual portion (acid leach) of the sediment increased with decreasing particle size. However, the general trend was upset by a large proportion of coal particles from the adjacent S. Wales coalfield, within one specific fraction causing an enhanced heavy metal concentration. There were significant (99% confidence level) correlations between the amount of less than 20 μm material in the sediment and the concentration of Fe, Pb, Cu and Mn; lower, but still significant correlations (95% confidence level) were found for Zn, Cd, Ni and Cr. No significant correlation was found for Co. The ratio of heavy metal associated with the less than 20-μm fraction of the sediment to the metal associated with the unfractionated sediment increased for Cu, Pb, Cd and Zn in the lower part of the estuary.     

Patterns of metal bioaccumulation in two filter-feeding macroinvertebrates: Exposure distribution, inter-species differences and variability across developmental stages

This study focused on the metal bioaccumulation of two aquatic insects (Ephoron virgo and Hydropsyche spp.) in order to evaluate the spatial distribution of metals, the interspecific differences between both filter-feeders and the bioaccumulation dynamics during E. virgo development stages. Hg, Cd, Ni, Cr, As, Pb, Cu, Ti, Zn and Mn were quantified in insects and in suspended particulate matter (SPM) sampled downstream and upstream of a chemical plant, where more than 300,000 t of polluted sediments are deposited. Hg concentrations were one order of magnitude higher downstream of the sediment dump, which showed that the Hg pollution originated in the chemical plant. Cd, Ni, Cr, Pb, Ti, Zn and Mn in invertebrates revealed that metal pollution was present upstream in other parts of the river. Interspecific differences were observed for all metals but Mn; significantly higher concentrations were observed in E. virgo over Hydropsyche exocellata, except for Cd, which showed 10-fold higher values. Hg and Cd increased until E. virgo nymphs reached 11 mm and decreased afterwards in late instars when nymphs were about to emerge. Cr, Pb, Ti and Mn decreased along early instars followed by a steady state in late instars. Similar values were obtained for Cu, As and Zn along all instars. Sexual differences between males and females of E. virgo were observed for Cd, Cu and Mn. Hg and Cd persistence was strong across developmental stages since high concentrations were found in eggs and emerging adults. Because the behavior of different metals varied for the two species and during the developmental stages of E. virgo, care should be taken in the interpretation of insect metal concentrations when analyzing the food chain transfer of metals in river ecosystems.     

Metal contamination in water and bioaccumulation of metals in the planktons,molluscs and fishes in Jamshedpur stretch of Subarnarekha River of Chotanagpur plateau,India

Subarnarekha River is a rain‐fed peninsular river passing through industrial city Jamshedpur, an important industrial centre of Jharkhand, India. Heavy metal concentrations like Zn, Pb, Cr, Cd, Ni and Cu in water, sediment and in different food webs were determined using inductively coupled plasma‐mass spectrophotometer for two sampling sites that are found stressed with high contamination due to urbanization and anthropogenic activities. Present study mainly focuses on the metal concentration in water, sediment, plankton with bioaccumulation factor (BAF) in body parts of molluscs and fishes. The study revealed that Zn and Pb were found in highest concentration in plankton (Zn: 20.6 g/kg, Pb: 6.0 g/kg), molluscs (Zn: 4.6 g/kg, Pb: 0.6 g/kg) and in fish (Zn: 6.1 g/kg, Pb: 3.0 g/kg) as biomagnification. Calculated BAF indicated that in fish species Zn has highest BAF value followed by Pb, which may be harmful for human consumption.     

Heavy metal behaviour during the activated sludge process I. Extent of soluble and insoluble metal removal

The extent of removal of Ag, Bi, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Tl and Zn and their distribution between the soluble and insoluble phases in the influent, and effluent of the activated sludge process has been studied using a pilot-scale plant operated at sludge ages of 3, 6, 9 and 12 days. Molybdenum, Tl, Co, Mn and Ni were >50% soluble in the influent settled sewage. The mean removals of the former two metals were <3% and the latter three were 35 and 50%. Silver, Bi, Cd, Cr, Cu, Pb and Zn were all <35% soluble in the influent and had substantial removals of >75%. Solubilities were greater in the effluent than the influent with the exception of Mn. The observed overall removals of Ag, Bi, Co, Ni, Pb, Tl and Zn were almost entirely due to insoluble metal removal; Cd, Cr and Cu removals had a significant contribution from soluble metal removal. Overall Mn removal appeared to be solely due to soluble metal removal.     

Heavy metal pollution profiles of dated sediment cores from hebe haven, Hong Kong

Eight sediment cores from Hebe Haven were collected and studied for metals including Cd, Cr, Cu, Fe, Ni, Pb, Zn and Ca. ²¹⁰Pb and ¹³⁷Cs activities were determined to date the time of deposition of the sediment. Hebe Haven is a yacht area and is close to the urbanized coast with several dyeing factories. Except Cd, the greatest enrichment was found at locations closest to the Ho Chung Stream which carried domestic and industrial wastewater to Hebe Haven. Concentrations as high as 0.930, 120, 131, 42.3 and 50.9 mg/kg were found for Cd, Cr, Zn, Cu and Pb, respectively. The corresponding enrichment factors are 13(Cd), 7.0(Cr), 2.9(Zn), 5.2(Cu) and 2.4(Pb). The extent of pollution diminishes from the riverine source. Cr is a typical example because its enrichment was mostly attributed to the nearby dyeing operation. The distribution of Cd appears more complicated. A maximum concentration of 3.60 mg/kg was found at a location far from Ho Chung Stream and with no nearby municipal or industrial activity. No significant Fe and Ni enrichment was found in the area. Ca in all cores decreases towards the sediment-water interface. It is probable that the abundance of shellfish has decreased as a result of excessive exploitation as seafood and pollution. ²¹⁰Pb activity and heavy metal concentrations of surficial layers have been “diluted” by excessive deposition of Fe-deficient particles. This likely indicates the rapid deposition of coarser and sandy particles during the construction of a nearby large housing estate. Some ²¹⁰Pb activity profiles have periodic low values in deeper layers, which should correspond to events of rapid deposition of erosion during heavy typhoons and rainstorms. Overall, the sedimentation rates calculated were in the range of 0.351–0.561 cm/yr. In one site (Core S4) close to the riverine source and with the best available dating data, the recent anthropogenic fluxes of heavy metals in μg cm⁻² yr⁻¹ are estimated as: 0.081(Cd), 22(Cr), 20(Zn), 6.4(Cu) and 7.4(Pb).     

Partitioning of trace metals before and after biological removal of metals from sediments

Metal removal by biological solubilization in three strongly contaminated sediments was carried out in a two-liter stirred bioreactor. Biological treatment yielded metal removal efficiencies in the range of 11-30%, 43-57%, 60-79%, 61-90%, 18-21%, 0-10% for Pb, Cu, Zn, Cd, Ni and Cr, respectively. The treated sediments were then rinsed with a NaCl solution (0.5 M), resulting in an increase by nearly 47% in Pb removal for the three sediments, while for other metals (Cu, Zn, Cd, Ni, Cr), the NaCl rinse did not seem to allow any significant increase in metal solubilization. A standard procedure of sequential selective extraction (SSE) was applied to the sediments before and after each treatment. With regard to Pb, Zn and Cd, the carbonate bound fractions (2/3 sediments) represented 18-42% of metals prior to treatment, while the iron and manganese oxides bound fraction constituted 39-60% of metals for the three sediments. Between 90 and 100% of Pb, Zn and Cd removed by the process came from the fractions bound to carbonates and from those bound to Fe and Mn oxides. The organic matter and sulfide bound fractions contained 65-72% of total Cu present before treatment and the process removed, on average, 63% Cu present in this fraction. In contrast, Ni and Cr were found mainly in the residual fractions (50-80%). Finally, this biological treatment did not solubilize Cr appreciably, while removal of Ni mostly originated from the carbonate and Fe/Mn oxides fractions (70-80%).     

Variations in heavy metal concentrations in the moss species Abietinella abietina (Hedw.) Fleisch. according to sampling time,within site variability and increase in biomass

Concentrations of Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mo, Ni, Pb, V and Zn were analysed in the moss Abietinella abietina (Hedw.) Fleisch. to estimate atmospheric heavy metal depositions. Samples were taken at five comparable sites within a radius of 25 m four times during the year 2000 (July 3rd, August 3rd, September 7th, October 3rd). The samples were taken by means of a PVC-tube (r=10 cm) and could therefore be related to aboveground growth and aerial deposition. The investigation showed significant differences between the various sampling times for concentrations of all heavy metals in total but not between concentrations of a single metal. For Cu, Hg, Mo, Pb and Zn temporal variation (=variation between the four times of sampling) was larger than spatial variation (=variation of concentrations between sub-samples at a single sampling time). Growth rates of the mosses differed significantly between sampling times, which reflects the low precipitation at the beginning of the season. Biomass increase, dust and precipitation influenced the metal concentrations. The calculation of deposition rates, which takes growth rates into account, showed significant differences between the various sampling times for Al, Cd, Cr, Cu and Ni, which is controversial to the results obtained from concentrations of these elements. Additionally, the calculation of atmospheric deposition rates showed a constant increase of metal depositions throughout the investigated period, which can not be seen by considering the concentrations only.     

Sources, nature, and fate of heavy metal-bearing particles in the sewer system

A preliminary insight into metal cycling within the urban sewer was obtained by determining both the heavy metal concentrations (Cu, Zn, Pb, Cd, Ni, Cr) in sewage and sediments, and the nature of metal-bearing particles using TEM–EDX, SEM–EDX and XRD. Particles collected from tap water, sump-pit deposits, and washbasin siphons, were also examined to trace back the origin of some mineral species. The results show that the total levels in Cu, Pb, Zn, Ni, and Cr in sewage are similar to that reported in the literature, thus suggesting that a time-averaged heavy metal fingerprint of domestic sewage can be defined for most developed cities at the urban catchment scale. Household activities represent the main source of Zn and Pb, the water supply system is a significant source of Cu, and in our case, groundwater infiltration in the sewer system provides a supplementary source of Ni and Cd. Concentrations in heavy metals were much higher in sewer sediments than in sewage suspended solids, the enrichment being due to the preferential settling of metal-bearing particles of high density and/or the precipitation of neoformed mineral phases. TEM and SEM–EDX analyses indicated that suspended solids, biofilms, and sewer sediments contained similar heavy metal-bearing particles including alloys and metal fragments, oxidized metals and sulfides. Copper fragments, metal carbonates (Cu, Zn, Pb), and oxidized soldering materials are released from the erosion of domestic plumbing, whereas the precipitation of sulfides and the sulfurization of metal phases occur primarily within the household connections to the sewer trunk. Close examination of sulfide phases also revealed in most cases a complex growth history recorded in the texture of particles, which likely reflects changes in physicochemical conditions associated with successive resuspension and settling of particles within the sewer system.     

Assessment of two-compartment models as predictive tools for the bioaccumulation of trace metals in the amphipod Gammarus oceanicus Segerstråle, 1947 from Grunnfjord (Northern Norway)

The objective of the present study is to evaluate the suitability of the eulittoral gammaridean amphipod Gammarus oceanicus Segerstr?le, 1947 from Grunnfjord (Northern Norway) as a biomonitor for trace metals Cd, Cr, Pb, Cu, Ni and Zn and to analyse whether the two-compartment model could be used as a predictive tool to assess environmental quality. The focus here is on the adjustment of this model to situations where a linear extrapolation of accumulated metals to increasing external metal exposures is not applicable. The amphipods tested accumulated metals upon exposure and it was possible to estimate significant model parameters of two-compartment models, with the sole exception of Zn. These could be used to predict accumulation of Cd, Cr and Pb in a concentration-dependent uptake study, for Cr directly and regarding simultaneous parameter estimation, for Cd and Pb after adjustment taking into account a non-linear relationship between bioconcentration factors (BCFs) and external metal exposures. The elements Cu and Ni need further evaluation, since linear predictions from the two-compartment models were not applicable, whilst a relationship between kinetic parameters and metal exposures could not be established. Kinetic BCFs at theoretical equilibrium were 80-202 for Cd, 80-112 for Cr, 306 for Cu, 251-520 for Pb and 23 for Ni. A tentative estimation showed the following sequence of sensitivity of G. oceanicus to an increase of soluble metal exposure: 0.6 microg Cdl(-1), 0.8 microg Pbl(-1), 2.5-2.9 microg Crl(-1), 8.5 microg Cul(-1) and 11 microg Nil(-1). Available information can be used to quantify a measure of agreement or disagreement between bioaccumulation in different amphipods. This can be regarded as an important step in the calibration of biomonitors, which is necessary to assess the potential for bioaccumulation on a large geographical scale.     

Heavy metal pollution associated with mining activity in the Kouh-e Zar region,NE Iran

The Kouh-e Zar mining area is located in the central part of the “Khaf–Bardaskan” volcanic-plutonic zone, NE Iran. Mining activity has resulted in pollution of soil and water resources by potentially toxic elements including arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), antimony (Sb), nickel (Ni) and zinc (Zn). In this study, the major source of heavy metal pollution and elucidating the probable environmental risks associated with this area were determined by quantifying pollution in soils and water resources. Concentrations of Cd, Cr, Cu, Pb and Zn in the Kouh-e Zar mining area varied in the range of 5–470, 33–442, 25–5125, 81.15–12,096.27 and 55–4210 mg/kg, respectively. The geo-accumulation index for Cd in all samples was extremely high (I_geo > 5) and the enrichment factor also shows an extremely high amount (EF > 40), both representing evidence for highly polluted soil in the area. However, the coefficients of aqueous migration (K_x) of Cd, Cr, Cu, Pb and Zn were K_x < 0.1, so they are classified as “least mobile and inert” grade. Also, the heavy metals tend to remain in soil (solid environment). Cluster analysis (CA) determined the lithogenic origin for Zn, Cu, Cr and Cd, and the anthropogenic origin (mining activity) for Pb in the soils of the mining area. The concentrations of Cd, Cu, Pb and Zn in water are controlled by free Fe and Mn oxy-hydroxide content in the soils. Both water–rock interaction and mining activity have contributed to pollution in the area.

     

Metal concentrations in a shallow groundwater aquifer underneath petrochemical complex

Duplicate groundwater samples were collected from 104 monitoring wells (piezometers) from shallow aquifers underneath an industrial city in the Eastern Province of Saudi Arabia. Concentrations of Al, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Ti, V, Zn, Ca, Mg, K, Na, Cl, SO₄, alkalinity, salinity, total dissolved salts, and pH were determined in these samples. Analysis of variance showed significantly (p < 0.05) wide variations in the concentrations of the above parameters. The contour maps of metal concentrations indicated that these variations were related to important landmarks in the study area. The results of correlation analyses suggest that geographical as well as chemical factors may influence metal distribution in the groundwater samples. To investigate the geographical effects, the analytical data were normalized (element/Cl ratios were calculated) for chemical variability. As expected, contour mapping of the ratio data of element/Cl of Na, Ca, Mg, K, SO₄, alkalinity, salinity, total dissolved salts, and Sr vary in a relatively small range and did not show a particular geographical trend. The groundwater sample from the industrial-dust area contained higher ratios between concentrations of Cl and Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, and Zn. These observations clearly suggest an extraneous contamination source, probably industrial dust, in the area. Another geographical area where metal (As, Cd, Cu, Mo, Ni, Ti,and V)/Cl ratios were found to be large was in the vicinity of an oil-refinery. Groundwater samples collected from the vicinity of a fertilizer plant and green-belt area contained relatively higher ratios of Al, Cd, Cr, Co, and Ni. The results of this study suggest that leachate from the industrial dust, leakage from the oil refinery and fertilizer plant, and drainage of irrigation water are some of the important pollution sources in the industrial city.     

Assessment of daily intake of trace elements due to consumption of foodstuffs by adult inhabitants of Rio de Janeiro city

Concentrations of Al, Cd, Cr, Cu, Mn, Ni, Pb, U and Zn were determined in vegetables (leafy vegetables, fruit, root, grain and cereal), derived products (sugar, coffee, manioc flour, wheat flour, corn flour, and pasta) and animal products (meat, fish, milk) most frequently consumed by adult inhabitants of Rio de Janeiro city. A total of 90 samples were analyzed using inductively coupled plasma mass spectrometry (ICPMS) as the principal method following sample dissolution by dry and wet ashing. Generally, highest contributions for the intake of micronutrients (Cu, Mn, Ni and Zn) arise from bean, rice and wheat flour consumption. Meat, cow milk and the flours, wheat and manioc, are major sources of Al, Cd, Pb and U intake. The daily intake of nine elements via foodstuffs was estimated as: 3.4x10(-4) mg of U, 1.8x10(-3) mg of Cd, 2.8x10(-2) mg of Pb, 2.3x10(-2) mg of Cr, 8.9x10(-2) mg of Ni, 1.12 mg of Cu, 2.5 mg of Mn, 3.5 mg of Al and 4.8 mg of Zn. The intake of toxic elements ranged between 2.7% (Cd) and 30% (U) of the provisional tolerable daily intake and reference dose values indicating that food consumption is, at present, no critical factor for the uptake of these toxic metals, in the population studied here. Concerning micronutrients, the recommended values of daily intake of Cu and Mn are conveniently supplied by the diet; however, for Cr and Zn they are lower than the recommend daily allowance. Due to high metal concentrations and consumption rates, black bean is the foodstuff that provided the highest ingestion rates of Cu, Mn, Ni and Zn (36-60% of the reference dose), being therefore a very important source of micronutrient supply.