Influence of hydrology on heavy metal speciation and mobility in a Pb-Zn mine tailing

Among the inorganic toxicants of greatest concern in mine tailings, Pb, Zn, Cu, Cd and As figure prominently due to their abundance and potential toxicity. Here we report on their biolability and solid-phase speciation in two sediment cores subject to variable hydrological regimes at an abandoned pyritic mine tailing. The oxic conditions of well-drained sediments induced pyrite oxidation and the subsequent liberation of H+, SO4(2-) and considerable quantities of Fe(III), which precipitated as goethite. Solubility of Pb, Zn, Cu and Cd was closely coupled to pH and goethite presence. Metal lability was particularly low in zones of neutralization, formed by the accumulation of calcite, first carried then deposited by percolating waters in both saturated and unsaturated cores. We conclude that differential hydrology induces variable heavy metal speciation and biolability in Pb-Zn mine tailings, and suggest that site-specific risk assessments must account for past and present hydrological regimes.     

Speciation of metals in contaminated sediments from Oskarshamn Harbor,Oskarshamn, Sweden

Bottom sediments in coastal regions have been considered the ultimate sink for a number of contaminants, e.g., toxic metals. In this current study, speciation of metals in contaminated sediments of Oskarshamn harbor in the southeast of Sweden was performed in order to evaluate metal contents and their potential mobility and bioavailability. Sediment speciation was carried out by the sequential extraction BCR procedure for As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn and the exchangeable (F1), reducible (F2), oxidizable (F3), and residual (R) fractions were determined. The results have shown that Zn and Cd were highly associated with the exchangeable fraction (F1) with 42–58 % and 43–46 %, respectively, of their total concentrations in the mobile phase. The assessment of sediment contamination on the basis of quality guidelines established by the Swedish Environmental Protection Agency (SEPA) and the Italian Ministry of Environment (Venice protocol for dredged sediments) has shown that sediments from Oskarshamn harbor are highly contaminated with toxic metals, especially Cu, Cd, Pb, Hg, As, and Zn posing potential ecological risks. Therefore, it is of crucial importance the implementation of adequate strategies to tackle contaminated sediments in coastal regions all over the world.     

Accumulation of heavy metals in native Andean plants: potential tools for soil phytoremediation in Ancash (Peru)

Metal contamination is a recurring problem in Peru, caused mainly by mine tailings from a past active mining activity. The Ancash region has the largest number of environmental liabilities, which mobilizes high levels of metals and acid drainages into soils and freshwater sources, posing a standing risk on human and environmental health. Native plant species spontaneously growing on naturally acidified soils and acid mine tailings show a unique tolerance to high metal concentrations and are thus potential candidates for soil phytoremediation. However, little is known about their propagation capacity and metal accumulation under controlled conditions. In this study, we aimed at characterizing nine native plant species, previously identified as potential hyperaccumulators, from areas impacted by mine tailings in the Ancash region. Plants were grown on mine soils under greenhouse conditions during 5 months, after which the concentration of Cd, Cu, Ni, Pb, and Zn was analyzed in roots, shoots, and soils. The bioaccumulation (BAF) and translocation factor (TF) were calculated to determine the amount of each metal accumulated in the roots and shoots and to identify which species could be better suited for phytoremediation purposes. Soil samples contained high Cd (6.50–49.80 mg/kg), Cu (159.50–1187.00 mg/kg), Ni (3.50–8.70 mg/kg), Pb (1707.00–4243.00 mg/kg), and Zn (909.00–7100.00 mg/kg) concentrations exceeding national environmental quality standards. After exposure to mine tailings, concentrations of metals in shoots were highest in Werneria nubigena (Cd, 16.68 mg/kg; Cu, 41.36 mg/kg; Ni, 26.85 mg/kg; Zn, 1691.03 mg/kg), Pennisetum clandestinum (Pb, 236.86 mg/kg), and Medicago lupulina (Zn, 1078.10 mg/kg). Metal concentrations in the roots were highest in Juncus bufonius (Cd, 34.34 mg/kg; Cu, 251.07 mg/kg; Ni, 6.60 mg/kg; Pb, 718.44 mg/kg) and M. lupulina (Zn, 2415.73 mg/kg). The greatest BAF was calculated for W. nubigena (Cd, 1.92; Cu, 1.20; Ni, 6.50; Zn, 3.50) and J. bufonius (Ni, 3.02; Zn, 1.30); BCF for Calamagrostis recta (Cd, 1.09; Cu, 1.80; Ni, 1.09), J. bufonius (Cd, 3.91; Cu, 1.79; Ni, 18.36), and Achyrocline alata (Ni, 137; Zn, 1.85); and TF for W. nubigena (Cd, 2.36; Cu, 1.70; Ni, 2.42; Pb, 1.17; Zn, 1.43), A. alata (Cd, 1.14; Pb, 1.94), J. bufonius (Ni, 2.72; Zn, 1.63), and P. clandestinum (Zn, 1.14). Our results suggest that these plant species have a great potential for soil phytoremediation, given their capability to accumulate and transfer metals and their tolerance to highly metal-polluted environments in the Andean region.     

Quantitative–spatial assessment of soil contamination in S. Francisco de Assis due to mining activity of the Panasqueira mine (Portugal)

Through the years, mining and beneficiation processes produces large amounts of As-rich mine wastes laid up in huge tailings and open-air impoundments (Barroca Grande and Rio tailings) that are the main source of pollution in the surrounding area once they are exposed to the weathering conditions leading to the formation of AMD and consequently to the contamination of the surrounding environments, in particularly soils. In order to investigate the environmental contamination impact on S. Francisco de Assis (village located between the two major impoundments and tailings) agricultural soils, a geochemical survey was undertaken to assess toxic metals associations, related levels and their spatial distribution, and to identify the possible contamination sources. According to the calculated contamination factor, As and Zn have a very high contamination factor giving rise to 65.4 % of samples with a moderate to high pollution degree; 34.6 % have been classified as nil to very low pollution degree. The contamination factor spatial distribution put in evidence the fact that As, Cd, Cu, Pb, and Zn soils contents, downstream Barroca Grande tailing, are increased when compared with the local Bk soils. The mechanical dispersion, due to erosion, is the main contamination source. The chemical extraction demonstrates that the trace metals distribution and accumulation in S. Francisco de Assis soils is related to sulfides, but also to amorphous or poorly crystalline iron oxide phases. The partitioning study allowed understanding the local chemical elements mobility and precipitation processes, giving rise to the contamination dispersion model of the study area. The wind and hydrological factors are responsible for the chemical elements transport mechanisms, the water being the main transporter medium and soils as one of the possible retention media.     

Metal contamination and solid phase partitioning of metals in urban roadside sediments

This study was undertaken to assess the anthropogenic impact on metal concentrations of urban roadside sediments (N = 633) in Seoul city, Korea and to estimate the potential mobility of selected metals (Zn, Cu, Pb, Cr, Ni, and Cd) using sequential extraction. Comparison of metal concentrations in roadside sediments with mean background values in sediments collected from first- or second-order streams in Korea shows that Zn, Cu and Pb are most affected by anthropogenic inputs. The 206Pb/207Pb ratios of roadside sediments (range = 1.1419-1.1681; mean 1.1576 +/- 0.0068) suggest that Pb is mainly derived from industrial sources rather than from leaded gasoline. A five-step sequential extraction of roadside sediments showed that Zn, Cd and to a lesser degree Ni occur predominantly in the carbonate bound fraction, while Pb is highest in the reducible fraction, Cu in the organic fraction, and Cr in the residual fraction. It was found that the concentrations in the readily available exchangeable fraction were generally low for most metals examined, except for Ni whose exchangeable fraction was appreciable (average 15.2%). Considering the proportion of metals bound to the exchangeable and carbonate fractions, the comparative mobility of metals probably decreases in the order of Zn > Ni > Cd > Pb > Cu > Cr. As potential changes of redox state and pH may remobilize the metals bound to carbonates, reducible, and/or organic matter, and may release and flush them through drain networks into streams, careful monitoring of environmental conditions appears to be very important. With respect to ecotoxicity, it is apparent the Zn and Cu pollution is of particular concern in Seoul city.     

Environmental and health risk assessment of Pb,Zn, As and Sb in soccer field soils and sediments from mine tailings: solid speciation and bioaccessibility

Areas polluted by the persistent presence of metal(loid)s induce health problems, especially when recreational activities (on land or water) promote human exposure to the pollutants. This study focuses on one of the most encountered worldwide mining waste, i.e. those from the extraction of Pb–Zn–Ag. The representative Pb–Zn-rich tailing (about 64,100 m³) sampled is located near a soccer field and a famous river for fishing. The scientific interests is relative to: (1) mobility and bioaccessibility of metal(oid)s, (2) human risk assessments and (3) relationship between human risks and solid-bearing phases in the environment. Soccer field soils, tailings and sediments from the nearby river were sampled; moreover, metal(loid) speciation (from BCR experiments) and bioaccessibility were measured and solid speciation performed by X-ray diffraction and electron microscopy in order to highlight metal(loid) dispersion and impact. Results demonstrate that the soccer field is highly contaminated by Pb, Zn, As and Sb due primarily to waste runoff. In terms of risk assessment, Pb and As human bioaccessibility highlights the major health risk (48 and 22.5 % of human bioaccessibility, respectively). Since local populations are regularly in close contact with metal(loid)s, the health risk due to pollutant exposure needs to be reduced through sustainable waste disposal and the rehabilitation of polluted sites.     

Geochemical and mineralogical characterization of a neutral, low-sulfide/high-carbonate tailings impoundment, Markušovce, eastern Slovakia

Tailings deposits generated from mining activities represent a potential risk for the aquatic environment through the release of potentially toxic metals and metalloids occurring in a variety of minerals present in the tailings. Physicochemical and mineralogical characteristics of tailings such as total concentrations of chemical elements, pH, ratio of acid-producing to acid-neutralizing minerals, and primary and secondary mineral phases are very important factors that control the actual release of potentially toxic metals and metalloids from the tailings to the environment. The aims of this study are the determination of geochemical and mineralogical characteristics of tailings deposited in voluminous impoundment situated near the village of Marku?ovce (eastern Slovakia) and identification of the processes controlling the mobility of selected toxic metals (Cu, Hg) and metalloids (As, Sb). The studied tailings have unique features in comparison with the other tailings investigated previously because of the specific mineral assemblage primarily consisting of barite, siderite, quartz, and minor sulfides. To meet the aims, samples of the tailings were collected from 3 boreholes and 15 excavated pits and subjected to bulk geochemical analyses (i.e., determination of chemical composition, pH, Eh, acid generation, and neutralization potentials) combined with detailed mineralogical characterization using optical microscopy, X-ray diffraction (XRD), electron microprobe analysis (EMPA), and micro-X-ray diffraction (μ-XRD). Additionally, the geochemical and mineralogical factors controlling the transfer of potentially toxic elements from tailings to waters were also determined using short-term batch test (European norm EN 12457), sampling of drainage waters and speciation–equilibrium calculations performed with PHREEQC. The tailings mineral assemblage consists of siderite, barite, quartz, and dolomite. Sulfide minerals constitute only a minor proportion of the tailings mineral assemblage and their occurrence follows the order: chalcopyrite?>?pyrite?>?tetrahedrite?>?arsenopyrite. The mineralogical composition of the tailings corresponds well to the primary mineralization mined. The neutralization capacity of the tailings is high, as confirmed by the values of neutralization potential to acid generation potential ratio, ranging from 6.7 to 63.9, and neutral to slightly alkaline pH of the tailings (paste pH 7.16–8.12) and the waters (pH 7.00–8.52). This is explained by abundant occurrence of carbonate minerals in the tailings, which readily neutralize the acidity generated by sulfide oxidation. The total solid-phase concentrations of metal(loid)s decrease as Cu?>?Sb?>?Hg?>?As and reflect the proportions of sulfides present in the tailings. Sulfide oxidation generally extends to a depth of 2 m. μ-XRD and EMPA were used to study secondary products developed on the surface of sulfide minerals and within the tailings. The main secondary minerals identified are goethite and X-ray amorphous Fe oxyhydroxides and their occurrence decreases with increasing tailings depth. Secondary Fe phases are found as mineral coatings or individual grains and retain relatively high amounts of metal(loid)s (up to 57.6 wt% Cu, 1.60 wt% Hg, 23.8 wt% As, and 2.37 wt% Sb). Based on batch leaching tests and lysimeter results, the mobility of potentially toxic elements in the tailings is low. The limited mobility of metals and metalloids is due to their retention by Fe oxyhydroxides and low solubilities of metal(loid)-bearing sulfides. The observations are consistent with PHREEQC calculations, which predict the precipitation of Fe oxyhydroxides as the main solubility-controlling mineral phases for As, Cu, Hg, and Sb. Waters discharging from tailings impoundment are characterized by a neutral to slightly alkaline pH (7.52–7.96) and low concentrations of dissolved metal(loid)s (<5–7.0 μg/L Cu, <0.1–0.3 μg/L Hg, 5.0–16 μg/L As, and 5.0–43 μg/L Sb). Primary factors influencing aqueous chemistry at the site are mutual processes of sulfide oxidation and carbonate dissolution as well as precipitation reactions and sorption onto hydrous ferric oxides abundantly present at the discharge of the impoundment waters. The results of the study show that, presently, there are no threats of acid mine drainage formation at the site and significant contamination of natural aquatic ecosystem in the close vicinity of the tailings impoundment.     

Heavy metal content and speciation in groundwater of the Guadiamar river basin

This work presents the conclusions of a speciation study concerning Zn, Cd, Pb and Cu in groundwater from ten wells in the alluvial aquifers of the Guadiamar river, affected by Aznalcollar mine tailing spill (April 1998). The sampling campaign took place in January 2000, almost two years after the mining accident. Four metal fractions were determined: labile metal forms, H+ exchangeable metal forms, strongly inert forms (associated with organic and inorganic matter in solution), and forms associated with suspended matter. Total metal concentration in groundwater followed the trend Cd < Pb < Cu < Zn. The speciation study showed that Zn and Cd were present to a great extent in available forms (labile and H+ exchangeable), while Pb and Cu were found mostly in the less available forms (strongly inert). These results can illustrate the potential value of the speciation tool for the follow-up of spill-induced pollution in the area.     

Distribution of potentially toxic elements (PTEs) in tailings,soils, and plants around Gol-E-Gohar iron mine,a case study in Iran

This study investigated the concentration of potentially toxic elements (PTEs) including Al, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Sb, V, and Zn in 102 soils (in the Near and Far areas of the mine), 7 tailings, and 60 plant samples (shoots and roots of Artemisia sieberi and Zygophylum species) collected at the Gol-E-Gohar iron ore mine in Iran. The elemental concentrations in tailings and soil samples (in Near and Far areas) varied between 7.4 and 35.8 mg kg^?1 for As (with a mean of 25.39 mg kg^?1 for tailings), 7.9 and 261.5 mg kg^?1 (mean 189.83 mg kg^?1 for tailings) for Co, 17.7 and 885.03 mg kg^?1 (mean 472.77 mg kg^?1 for tailings) for Cu, 12,500 and 400,000 mg kg^?1 (mean 120,642.86 mg kg^?1 for tailings) for Fe, and 28.1 and 278.1 mg kg^?1 (mean 150.29 mg kg^?1 for tailings) for Ni. A number of physicochemical parameters and pollution index for soils were determined around the mine. Sequential extractions of tailings and soil samples indicated that Fe, Cr, and Co were the least mobile and that Mn, Zn, Cu, and As were potentially available for plants uptake. Similar to soil, the concentration of Al, As, Co, Cr, Cu, Fe, Mn, Mo, Ni, and Zn in plant samples decreased with the distance from the mining/processing areas. Data on plants showed that metal concentrations in shoots usually exceeded those in roots and varied significantly between the two investigated species (Artemisia sieberi > Zygophylum). All the reported results suggest that the soil and plants near the iron ore mine are contaminated with PTEs and that they can be potentially dispersed in the environment via aerosol transport and deposition.     

Environmental and socioeconomic assessment of impacts by mining activities—a case study in the Certej River catchment,Western Carpathians,Romania

Background, aim and scope

In the region of the Apuseni Mountains, part of the Western Carpathians in Romania, metal mining activities have a long-standing tradition. These mining industries created a clearly beneficial economic development in the region. But their activities also caused impairments to the environment, such as acid mine drainage (AMD) resulting in long-lasting heavy metal pollution of waters and sediments. The study, established in the context of the ESTROM programme, investigated the impact of metal mining activities both from environmental and socioeconomic perspectives and tried to incorporate the results of the two approaches into an integrated proposition for mitigation of mining-related issues.

Study site

The small Certej catchment, situated in the Southern Apuseni Mountains, covers an area of 78 km². About 4,500 inhabitants are living in the basin, in which metal mining was the main economic sector. An open pit and several abandoned underground mines are producing heavy metal-loaded acidic water that is discharged untreated into the main river. The solid wastes of mineral processing plants were deposited in several dumps and tailings impoundment embodying the acidic water-producing mineral pyrite.

Methods

The natural science team collected samples from surface waters, drinking water from dug wells and from groundwater. Filtered and total heavy metals, both after enrichment, and major cations were analysed by inductively coupled plasma optical emission spectroscopy (ICP-OES). Major anions in waters, measured by ion chromatography, alkalinity and acidity were determined by titration. Solid samples were taken from river sediments and from the largest tailings dam. The latter were characterised by X-ray fluorescence and X-ray diffraction. Heavy metals in sediments were analysed after digestion. Simultaneously, the socioeconomic team performed a household survey to evaluate the perception of people related to the river and drinking water pollution by way of a logistic regression analysis.

Results and discussion

The inputs of acid mine waters drastically increased filtered heavy metal concentrations in the Certej River, e.g. Zn up to 130 mg L⁻¹, Fe 100 mg L⁻¹, Cu 2.9 mg L⁻¹, Cd 1.4 mgL⁻¹ as well as those of SO₄ up to 2.2 g L⁻¹. In addition, river water became acidic with pH values of pH 3. Concentrations of pollutant decreased slightly downstream due to dilution by waters from tributaries. Metal concentrations measured at headwater stations reflect background values. They fell in the range of the environmental quality standards proposed in the EU Water Framework Directive for dissolved heavy metals. The outflow of the large tailing impoundment and the groundwater downstream from two tailings dams exhibited the first sign of AMD, but they still had alkalinity.

Most dug wells analysed delivered a drinking water that exhibited no sign of AMD pollution, although these wells were a distance of 7 to 25 m from the contaminated river. It seems that the Certej River does not infiltrate significantly into the groundwater.

Pyrite was identified as the main sulphide mineral in the tailings dam that produces acidity and with calcite representing the AMD-neutralising mineral. The acid–base accounting proved that the potential acid-neutralising capacity in the solid phases would not be sufficient to prevent the production of acidic water in the future. Therefore, the open pits and mine waste deposits have to be seen as the sources for AMD at the present time, with a high long-term potential to produce even more AMD in the future.

The socioeconomic study showed that mining provided the major source of income. Over 45% of the households were partly or completely reliant on financial compensations as a result of mine closure. Unemployment was considered by the majority of the interviewed persons as the main cause of social problems in the area. The estimation of the explanatory factors by the logistic regression analysis revealed that education, household income, pollution conditions during the last years and familiarity with environmental problems were the main predictors influencing peoples’ opinion concerning whether the main river is strongly polluted. This model enabled one to predict correctly 77% of the observations reported. For the drinking water quality model, three predictors were relevant and they explained 66% of the observations.

Conclusions

Coupling the findings from the natural science and socioeconomic approaches, we may conclude that the impact of mining on the Certej River water is high, while drinking water in wells is not significantly affected. The perceptions of the respondents to pollution were to a large extent consistent with the measured results.

Recommendations and perspectives

The results of the study can be used by various stakeholders, mainly the mining company and local municipalities, in order to integrate them in their post-mining measures, thereby making them aware of the potential long-term impact of mining on the environment and on human health as well as on the local economy.

     

Lead and zinc in sediments and biota from Maarmorilik, West Greenland: an assessment of the environmental impact of mining wastes on an Arctic fjord system

Lead and zinc levels in sediments and biota from the fjord system surrounding the lead/zinc mine at Maarmorilik, West Greenland, were investigated to evaluate the impact of waste rock and marine-deposited tailings on the marine biota. Concentrations of metal in the sediment were up to 8,922 +/- 622 microg g(-1) (dry wt.) for lead and 19,351+/- 476 microg g(-1) (dry wt.) for zinc. Levels of lead and zinc were also elevated in a suite of monitor organisms. The feeding modes of the organisms were used to explain the sources of metals to the organisms. After closure of the mine, the concentrations of metals in the upper centimetres of the sediments decreased, and a decreased impact of metals on the brown alga Fucus distichus was observed. However, the metals in the sediments still affect the marine biota in the area.     

Heavy metal distribution in marine sediments from the southwest coast of Spain

The latest version (1999) of the BCR-sequential extraction technique was used to determine the distribution of metals (Cu, Zn, Cd, Pb, Fe, Ni, Cr, and Mn) with major sedimentary phases (acid-soluble, reducible, oxidisable and residual) in samples from the southwest coast of Spain. The total metal content was also determined. The results showed that an extensive area along the coast (35 km long), near the joint mouth of the Tinto and Odiel Rivers, contains sediments with high concentrations of metals, with maximums of 649 mg/kg of Zn, 336 mg/kg of Cu, 197 mg/kg of Pb and 2.5 mg/kg of Cd. The values found for Cr, Ni and Mn are comparable to those in unpolluted areas. Based on the chemical distribution of metals, we found that Zn is the most mobile (i.e., it can pass easily into the water under changing environmental conditions). This metal showed the highest percentages in the acid-soluble fraction (the most labile), especially in the central coastal area, where the samples contained over 50% of this element associated with this fraction. This area close to the Tinto and Odiel river mouths also shows a significant increase in the mobility of Cd and Cu. In both cases the amount present in the residual fraction is lower, and the acid-soluble fraction is increased for Cd and the oxidisable fraction for Cu. However, the highest percentages of Fe, Cr and Ni are found in the residual fraction (84%, 89% and 75%, respectively), which implies that these metals are strongly bound to the sediments.     

Comparative tolerance of Pinus radiata and microbial activity to copper and zinc in a soil treated with metal-amended biosolids

A study was conducted to evaluate the effects of elevated concentrations of copper (Cu) and zinc (Zn) in a soil treated with biosolids previously spiked with these metals on Pinus radiata during a 312-day glasshouse pot trial. The total soil metal concentrations in the treatments were 16, 48, 146 and 232 mg Cu/kg or 36, 141, 430 and 668 mg Zn/kg. Increased total soil Cu concentration increased the soil solution Cu concentration (0.03–0.54 mg/L) but had no effect on leaf and root dry matter production. Increased total soil Zn concentration also increased the soil solution Zn concentration (0.9–362 mg/L). Decreased leaf and root dry matter were recorded above the total soil Zn concentration of 141 mg/kg (soil solution Zn concentration, >4.4 mg/L). A lower percentage of Cu in the soil soluble?+?exchangeable fraction (5–12 %) and lower Cu²⁺ concentration in soil solution (0.001–0.06 μM) relative to Zn (soil soluble?+?exchangeable fraction, 12–66 %; soil solution Zn²⁺ concentration, 4.5–4,419 μM) indicated lower bioavailability of Cu. Soil dehydrogenase activity decreased with every successive level of Cu and Zn applied, but the reduction was higher for Zn than for Cu addition. Dehydrogenase activity was reduced by 40 % (EC₄₀) at the total solution-phase and solid-phase soluble?+?exchangeable Cu concentrations of 0.5 mg/L and 14.5 mg/kg, respectively. For Zn the corresponding EC₅₀ were 9 mg/L and 55 mg/kg, respectively. Based on our findings, we propose that current New Zealand soil guidelines values for Cu and Zn (100 mg/kg for Cu; 300 mg/kg for Zn) should be revised downwards based on apparent toxicity to soil biological activity (Cu and Zn) and radiata pine (Zn only) at the threshold concentration.     

Application of capillary electrophoresis combined with a modified BCR sequential extraction for estimating of distribution of selected trace metals in PM2.5 fractions of urban airborne particulate matter

The capillary electrophoresis (CE) method combined with a sequential extraction was applied to determine the distribution of Fe, Zn, Cu, Mn and Cd in urban ambient air PM2.5 samples. PM2.5 was collected on Teflon filters with dichotomous sampler, and the modified extraction procedure following the BCR leaching procedure was used to chemically fractionate metals into "easily exchangeable" with water, "acid extractable" with 0.11 mol/l acetic acid, "reducible" with 0.1 mol/l hydroxylamine hydrochloride acidified to pH 2.0 with nitric acid, and "oxidisable" with oxidation by 8.8 mol/l hydrogen peroxide (H2O2) followed by extraction with 1.0 mol/l ammonium acetate. Based on the obtained results it was concluded that the application of the studied methodology provides chemical fractionation data that reflect the general sources and potential health hazards of the studied metals.     

Heavy metal content in vegetables and fruits cultivated in Baia Mare mining area (Romania) and health risk assessment

Information about heavy metal concentrations in food products and their dietary intake are essential for assessing the health risk of local inhabitants. The main purposes of the present study were (1) to investigate the concentrations of Zn, Cu, Pb, and Cd in several vegetables and fruits cultivated in Baia Mare mining area (Romania); (2) to assess the human health risk associated with the ingestion of contaminated vegetables and fruits by calculating the daily intake rate (DIR) and the target hazard quotient (THQ); and (3) to establish some recommendations on human diet in order to assure an improvement in food safety. The concentration order of heavy metals in the analyzed vegetable and fruit samples was Zn?>?Cu?>?Pb?>?Cd. The results showed the heavy metals are more likely to accumulate in vegetables (10.8–630.6 mg/kg dw for Zn, 1.4–196.6 mg/kg dw for Cu, 0.2–155.7 mg/kg dw for Pb, and 0.03–6.61 mg/kg dw for Cd) than in fruits (4.9–55.9 mg/kg dw for Zn, 1.9–24.7 mg/kg dw for Cu, 0.04–8.82 mg/kg dw for Pb, and 0.01–0.81 mg/kg dw for Cd). Parsley, kohlrabi, and lettuce proved to be high heavy metal accumulators. By calculating DIR and THQ, the data indicated that consumption of parsley, kohlrabi, and lettuce from the area on a regular basis may pose high potential health risks to local inhabitants, especially in the area located close to non-ferrous metallurgical plants (Romplumb SA and Cuprom SA) and close to T?u?ii de Sus tailings ponds. The DIR for Zn (85.3–231.6 μg/day kg body weight) and Cu (25.0–44.6 μg/day kg body weight) were higher in rural areas, while for Pb (0.6–3.1 μg/day kg body weight) and Cd (0.22–0.82 μg/day kg body weight), the DIR were higher in urban areas, close to the non-ferrous metallurgical plants SC Romplumb SA and SC Cuprom SA. The THQ for Zn, Cu, Pb, and Cd was higher than 5 for <1, <1, 12, and 6 % of samples which indicates that those consumers may experience major health risks.     

Effects of organic acids on the photosynthetic and antioxidant properties and accumulations of heavy metals of <Emphasis Type="Italic">Melilotus officinalis</Emphasis> grown in Cu tailing

The effect of citric acid (CA), acetic acid (Ac), and ethylene diamine tetraacetic acid (EDTA) on the photosynthetic and antioxidant properties and the accumulation of some heavy metals (HMs) of Melilotus officinalis seedling growing in Cu mine tailings for 25 days were studied. Results showed that the formation of photosynthesizing cells of M. officinalis was inhibited by EDTA at 2 mmol/kg. Photosynthetic pigment contents under EDTA of 2 mmol/kg were reduced by 26, 40, and 19 %, respectively, compared to the control. The proline contents in aboveground and underground parts increased as the level of EDTA was enhanced. CA and Ac enhanced the activities of superoxide dismutase (SOD) and peroxidase (POD) in the aboveground parts and EDTA inhibited the activity of POD in the underground parts. The addition of CA promoted significantly the growth of M. officinalis, while the biomass decreased significantly under 2 mmol/kg EDTA. Cu contents in the aboveground parts treated with 0.5 and 2.0 mmol/kg EDTA reached 175.50 and 265.17 μg/g dry weight, respectively. Ac and EDTA treatments promoted Cd to translocate from root to aboveground parts. The result indicated that M. officinalis was a tolerant species of Cu tailing and can be used to remediate Cu contaminated environment, and rationally utilization of organic acids, especially EDTA, in the phytoremediation can improve the growth and metals accumulation of M. officinalis.     

Arsenic, copper, and zinc contamination in soil and wheat during coal mining, with assessment of health risks for the inhabitants of Huaibei, China

Field studies were conducted to investigate arsenic (As), copper (Cu), and zinc (Zn) contamination in agricultural soils and wheat crops at two areas in Huaibei, China. Area A is in the proximity of Shuoli coal mine. In area B, three coal mines and a coal cleaning plant were distributed. The potential health risk of As, Cu, and Zn exposure to the local inhabitants through consumption of wheat grains was also estimated. The results showed that significantly higher (p?<?0.05) concentrations of As, Cu, and Zn were found in soils collected from area B than in those from area A. Arsenic concentrations in wheat sampled from area A were negatively correlated with the distance from the coal mine (p?<?0.001). Concentrations of Cu and Zn in wheat seedlings and grains collected from area B were significantly higher (p?<?0.05) than in those collected from area A, with the exception of Zn in wheat seedlings. Concentrations of Cu and Zn in most wheat grain samples were above the permissible limits of Cu and Zn in edible plants set by the Food and Agriculture Organization/World Health Organization. The hazard index of aggregate risk through consumption of wheat grains was 2.3–2.4 for rural inhabitants and 1.4–1.5 for urban inhabitants. The average intake of inorganic As for rural inhabitants in Huaibei was above 10 μg day^?1. These findings indicated that the inhabitants around the coal mine are experiencing a significant potential health risk due to the consumption of locally grown wheat.     

Impact of dredged urban river sediment on a Saronikos Gulf dumping site (Eastern Mediterranean): sediment toxicity,contaminant levels,and biomarkers in caged mussels

Impacts of chemical contaminants associated with dumping of dredged urban river sediments at a coastal disposal area in Saronikos Gulf (Eastern Mediterranean) were investigated through a combined approach of sediment toxicity testing and active biomonitoring with caged mussels. Chemical analyses of aliphatic hydrocarbons (AHs), polycyclic aromatic hydrocarbons (PAHs), Cu, and Zn in combination with the solid phase Microtox® test were performed on sediments. Concentrations of PAHs, AHs, Cu, and Zn as well as multiple biomarkers of contaminant exposure and/or effects were measured in caged mussels. Sediments in the disposal and neighboring area showed elevated PAHs and AHs concentrations and were characterized as toxic by the solid-phase Microtox® test during and after dumping operations. Biomarker results in the caged mussels indicated sublethal effects mainly during dumping operations, concomitantly with high concentrations of PAHs and AHs in the caged mussel tissues. Cu and Zn concentrations in sediments and caged mussels were generally not elevated except for sediments at the site in the disposal area that received the major amount of dredges. High PAHs and AHs levels as well as sublethal effects in the caged mussels were not persistent after termination of operations. The combined bioassay–biomarker approach proved useful for detecting toxicological impacts of dredged river sediment disposal in sediments and the water column. Nevertheless, further research is needed to evaluate whether sediment toxicity will have long-term effects on benthic communities of the disposal area.     

Distribution,Sources, and Possible Adverse Biological Effects of Trace Metals in Surface Sediments of a Tropical Estuary

Metal (Cu, Zn, Pb, Cd, Ni, Co, and Fe) contamination in sediments from a tropical estuary (Ébrié Lagoon, Ivory Coast) was assessed using pollution indices, multivariate analyses and sediment quality guidelines (SQGs). The results demonstrate that increased input of the studied metals occurred over the past 6 years compared to that from 20 years ago, due to rapid population growth, along with the increase of industrial and agricultural activities in the vicinity of the estuary. Ébrié Lagoon was also found to be one of the most contaminated tropical coastal estuaries. Very high average total organic carbon (TOC) content was found (1.9–3.70%) with significant spatial variation as a result of the influence of anthropogenic activities. This study also found that TOC plays an important role in the distribution of Cu, Zn, Co, and Cd in the Ébrié Lagoon sediments. Moderate to high sediment contamination was observed for Cd and Cu, moderate contamination was observed for Zn and Pb, while low contamination was observed for Ni, Co, and Fe. Cluster analysis (CA) and principal component analysis (PCA) investigation revealed that Cu, Zn, Cd, and Co result mainly from anthropogenic sources while Pb, Ni, and Fe may be of natural origin. The pollution-loading index (PLI) indicated that all of the sites close to wastewater discharges were highly polluted. The sediments are likely to be an occasional threat to aquatic organisms due to Cu, Zn, Pb, Cd, and Ni contents, based on the SQGs approach.     

Preliminaries on pollution risk factors related to mining and ore processing in the Cu-rich pollymetallic belt of Eastern Carpathians, Romania

The present study focuses on the mineralogical and geochemical patterns of mining and ore-processing wastes from some occurrences in the Eastern Carpathians; its aim is to identify the main factors and processes that could lead to the pollution of the environment. In this respect, the following types of solid waste were investigated: efflorescent salts developed on the surface of rock blocks from a quarry, ore-processing waste from two tailings ponds, and salt crusts developed at the surface of a tailings pond. The potential risks emphasized by these preliminary investigations are the following: (1) the risk of wind-driven removal and transport of the waste from the surface of tailings ponds, given that fine grains prevail (up to 80 %); (2) the risk of tailings removal through mechanical transport by water, during heavy rainfall; (3) the appearance of hydrated sulfates on the rock fragments from the mining waste, sulfates which are highly susceptible to the generation of acid mine drainage (pH?<?4); (4) the high amount of toxic elements (Pb, Cd, Cu, Zn, As, etc.) that acid mine drainage leachates contain; and (5) the development of a salt crust on the flat, horizontal surfaces of the waste deposit, due to this very shape. Statistical data regarding the amount of both major and minor elements in the tailings have revealed two statistical populations for nearly all the toxic metals. This suggests that, beyond the effect that the tailings have upon the environment through their mere presence in a given area, there are alleged additional factors and processes which intensify the pollution: the location of the waste deposit relative to the topography of the area; the shape of the waste deposit; the development of low areas on the surface of the deposit, areas which favor the appearance of salt crusts; and the mineralogy of efflorescent aggregates.