Challenges in understanding the sources of bioaccumulated metals in biota inhabiting turbid river systems

Bioaccumulation of As, Cd, Cu, Pb and Zn by Macrobrachium prawns was observed to occur in the Strickland River downstream of a gold mine at Porgera, Papua New Guinea. This was despite the total metal concentrations of waters and sediments indicating no difference from reference sites within tributaries. To provide information on potential sources and bioavailability of metals to prawns, an extensive range of analyses were made on waters, suspended solids, deposited sediments and plant materials within the river system. Dissolved metal concentrations were mostly sub-micrograms per liter and no major differences existed in concentrations or speciation between sites within the Strickland River or its tributaries. Similarly, no differences were detected between sites for total or dilute acid-extractable metal concentrations in bed sediments and plant materials, which may be ingested by the prawns. However, the rivers in this region are highly turbid and the dilute acid-extractable cadmium and zinc concentrations in suspended solids were greater at sites in the Strickland River than at sites in tributaries. The results indicated that mine-derived inputs increased the proportion of these forms of metals or metalloids in the Strickland River. These less strongly bound metals and metalloids would be more bioavailable to the prawns via the dietary pathway. The results highlighted many of the difficulties in using routine monitoring data without information on metal speciation to describe metal uptake and predict potential effects when concentrations are low and similar to background. The study indicated that the monitoring of contaminant concentrations in organisms that integrate the exposure from multiple exposure routes and durations may often be more effective for detecting impacts than intermittent monitoring of contaminants in waters and sediments.     

Metal behaviour in an estuary polluted by acid mine drainage: the role of particulate matter

The concentrations of dissolved and suspended particulate Cd, Cu and Zn have been determined in water samples obtained during two axial transects of the Rio Tinto-Huelva Ria system in south-west Spain, which is severely impacted by acid mine drainage. Although the metal concentrations in both phases were elevated, dissolved metals were dominant and, in the upper estuary, constituted > 99% of total metal in the water column. Dissolved metals behaved non-conservatively on each transect, with maximum concentrations in the low salinity region. There was no evidence of metal adsorption within the turbidity maximum zone, despite the high specific surface areas of resuspending particles. Measurements of electrophoretic mobility showed that the suspended particulate matter (SPM) had a positive surface charge in the salinity range 0-4, where the waters had a pH < 3. Desorption experiments were carried out in which SPM from the turbidity maximum zone was resuspended in coastal seawater. The desorption of the metals was monitored for 24 h, using anodic stripping voltammetry (ASV) to detect the variation in total dissolved Cd, Cu and Zn and the species of Cu and Zn. Total dissolved Cd concentrations doubled during the incubation period, whereas the concentration of total dissolved Cu declined and that of Zn remained rather constant. The ASV-labile fraction of dissolved Cu and Zn showed an initial sharp release followed by a slower uptake. However, desorption was shown to be a minor source of dissolved metals and made little contribution to the non-conservative behaviour in the low salinity zone. The results are used to predict the effects of acid mine drainage on estuarine ecology.     

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.     

The asiatic clam, Corbicula fluminea: An indicator of trace metal pollution in the Shatt al-Arab River, Iraq

The potential of Corbicula fluminea (Müller) as an indicator for trace metal pollution was investigated. Laboratory experiments show that Corbicula has the capability to accumulate and eliminate trace metals in relation to their concentrations in ambient water. However, an effect of individual size was observed. Seasonal variations in the concentrations of Cd, Co, Cu, Fe, Mn, Ni, Pb, V and Zn in Corbicula, water and particulate matter from the upper section of the Shatt al-Arab River were studied. Sediment samples were also analysed. Metal concentrations were determined by means of flameless AAS. It was found that Corbicula is a suitable bio-indicator for monitoring of trace metal pollution. Metal concentrations in Corbicula tissues correlated better with their corresponding concentrations in particulate matter than with the dissolved form. Temporal variations in metal concentrations were attributed to several factors, including fluctuations in metal inputs, and in geochemical and hydrological characteristics of the water. The obtained levels of trace metals were comparable to those reported for control sites, with the exception of Cd, Cu and Zn whose concentrations were higher in both Corbicula and particulate matter.     

Trace metal speciation and bioavailability in urban soils

Urban soils often contain concentrations of trace metals that exceed regulatory levels. However, the threat posed by trace metals to human health and the environment is thought to be dependent on their speciation in the soil solution rather than the total concentration. Three inactive railway yards in Montréal, Québec, were sampled to investigate the speciation and bioavailability of Cd, Cu, Ni, Pb and Zn. Soil solutions were obtained by centrifuging saturated soil pastes. In the soil solutions, up to 59% of the dissolved Cd was in its free ionic form. For Cu, Pb and Zn, organic complexes were the predominant species. Over 40% of Ni was present as inorganic complexes if the solution pH exceeded 8.1. Multiple regression analyses showed that pH and total metals in soil were significantly correlated with the activities of free metal ions, except for Cd(2+), which only had a weak correlation with soil pH. Free, dissolved and total soil metals were tested for their ability to predict metal uptake by plants in the field. However, none of these metal pools were satisfactory predictors. The results indicated that in these urban soils, trace metals were mainly in stable forms and bioavailability was extremely low.     

Trace metal speciation and fluxes within a major French wastewater treatment plant: impact of the successive treatments stages

Seven metals (Cd, Co, Cr, Cu, Fe, Ni and Pb) were monitored at the Seine-Aval wastewater treatment plant during 6 sampling campaigns in April 2004. Particulate and dissolved metals have been measured in 24 h composite samples at each treatment stage (primary settling, secondary activated sludge and tertiary flocculation by FeCl₃). In addition, the diffusive gradient in thin film technique (DGT) was used to determine the dissolved inert and labile metal fraction. Although all treatment stages were able to decrease particulate metals concentrations in wastewater, most dissolved metals concentrations were mainly affected during primary settling. This unexpected result was attributed to tertiary sludge filtrate recirculation. Metals added via the FeCl₃ reagent at the tertiary treatment were shown to lower the overall Cr removal from wastewater and to enrich Ni in effluents. The plant operating conditions (recirculation and reagent addition) appear therefore as important as treatment processes for the metals removal. Total metal fluxes were highly decreased by the whole treatment plant for Cd, Cr, Cu and Pb and to a lesser extend for Co and Ni. However, the labile metal fluxes were poorly decreased for Cu (18%), not significantly decreased for Ni and increased for Fe. The labile fraction of Cd, Co and Cr was not detectable at any stage of the plant. Discharged labile fluxes, at least for Ni, were potentially significant compared to the labile metal fluxes in the river measured downstream the plant. Treated urban wastewater discharges should be carefully considered as a possible source of bioavailable trace metals.     

Removal of Cu, Zn, and Cd from aqueous solutions by the dairy manure-derived biochar

Purpose

Biochar derived from waste biomass is now gaining much attention for its function as a biosorbent for environmental remediation. The objective of this study was to determine the effectiveness of biochar as a sorbent in removing Cd, Cu, and Zn from aqueous solutions.

Methods

Biochar was produced from dairy manure (DM) at two temperatures: 200°C and 350°C, referred to as DM200 and DM350, respectively. The obtained biochars were then equilibrated with 0–5 mM Cu, Zn or Cd in 0.01 M NaNO₃ solution for 10 h. The changes in solution metal concentrations after sorption were evaluated for sorption capacity using isotherm modeling and chemical speciation Visual MINTEQ modeling, while the solid was collected for species characterization using infrared spectroscopy and X-ray elemental dot mapping techniques.

Results

The isotherms of Cu, Zn, and Cd sorption by DM200 were better fitted to Langmuir model, whereas Freundlich model well described the sorption of the three metals by DM350. The DM350 were more effective in sorbing all three metals than DM200 with both biochars had the highest affinity for Cu, followed by Zn and Cd. The maximum sorption capacities of Cu, Zn, and Cd by DM200 were 48.4, 31.6, and 31.9 mg g^?1, respectively, and those of Cu, Zn, and Cd by DM350 were 54.4, 32.8, and 51.4 mg g^?1, respectively. Sorption of the metals by the biochar was mainly attributed to their precipitation with PO ₄ ^3? or CO ₃ ^2? originating in biochar, with less to the surface complexation through –OH groups or delocalized π electrons. At the initial metal concentration of 5 mM, 80–100 % of Cu, Zn, and Cd retention by DM200 resulted from the precipitation, with less than 20 % from surface adsorption through phenonic –OH complexation. Among the precipitation, 20–30 % of the precipitation occurred as metal phosphate and 70–80 % as metal carbonate. For DM350, 75–100 % of Cu, Zn, and Cd retention were due to the precipitation, with less than 25 % to surface adsorption through complexation of heavy metal by phenonic –OH site or delocalized π electrons. Among the precipitation, only less than 10 % of the precipitation was present as metal phosphate and more than 90 % as metal carbonate.

Conclusions

Results indicated that dairy manure waste can be converted into value-added biochar as a sorbent for sorption of heavy metals, and the mineral components originated in the biochar play an important role in the biochar's high sorption capacity.     

Trace metals in flounder, Platichthys flesus (Linnaeus, 1758), and sediments from the Baltic Sea and the Portuguese Atlantic coast

Trace metals were examined in the muscle tissue of flatfish species of flounder, Platichthys flesus (Linnaeus, 1758), sediments from two southern Baltic Sea sites (Gdańsk Bay and Ustecko-?ebskie as a reference) and in two areas of the Portuguese Atlantic coast (Douro River estuary and Atlantic fishing ground as a reference) to evaluate spatial differences in trace metals. Additionally, the accumulation of trace metals in flounder of different length classes was assessed. Flounder from the Gdańsk Bay area contained twofold more cupper (Cu), lead (Pb) and mercury (Hg) than did flounder from the Douro River estuary, but zinc (Zn) and cadmium (Cd) were at similar concentrations. The sediments from Gdańsk Bay contained significantly more Zn and threefold more Cd, while concentrations of Cu and Pb were twofold lower. The concentrations of metals in the sediments did not correlate with those in the flounder. Spatial differences were noted in metal concentrations in flounder from the southern Baltic Sea and the Portuguese Atlantic coast as well as within these regions, with higher concentrations in the flounder from the Baltic Sea Gdańsk Bay. The flounder in length class 25–30 cm from Gdańsk Bay contained metal concentrations comparable to those of class 40–45 cm specimens from the Atlantic coast. The accumulation of metals in flounder length classes differed in the two regions.     

Mobility of heavy metals from polluted sediments of a semi-enclosed basin: in situ benthic chamber experiments in Taranto’s Mar Piccolo (Ionian Sea,Southern Italy)

In situ benthic flux experiments were conducted at two stations in the Mar Piccolo of Taranto (Italy), one of the most industrialised and contaminated coastal areas of the Mediterranean. Sediments of the two stations are notably different in their trace metal content, with a station closer to a Navy harbour showing higher mean concentrations of almost all investigated metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn). Conversely, both stations are characterised by significant Hg contamination, compared to the local baseline. Results of a sequential extraction scheme on surface sediments suggest a relatively scarce mobility of the examined metals (Zn > Ni > Cr > As > Cu > Pb). A Hg-specific extraction procedure showed that most of the element (93.1 %) occurs in a fraction comprising Hg bound to Fe/Mn oxi-hydroxides. Reduction of these oxides may affect Hg remobilisation and redistribution. Porewater profiles of dissolved trace metals were quite similar in the two sites, although significant differences could be observed for Al, Cu, Fe and Hg. The highest diffusive fluxes were observed for As, Fe and Mn. Mobility rates of several trace elements (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn) were directly measured at the sediment–water interface. Results from benthic in situ incubation experiments showed increasing dissolved metal concentrations with time, resulting in higher fluxes for Cu, Fe, Hg, V and Zn in the most contaminated site. Conversely, fluxes of Mn, Ni and Pb were comparable between the two stations. The estimated flux of Hg (97 μg m^?2 day^?1) was the highest observed among similar experiments conducted in other highly contaminated Mediterranean coastal environments. Benthic fluxes could be partially explained by considering rates of organic matter remineralisation, dissolution of Fe/Mn oxy-hydroxides and metal speciation in sediments. Seasonal and spatial variation of biogeochemical parameters can influence metal remobilisation in the Mar Piccolo area. In particular, metals could be promptly remobilised as a consequence of oxygen depletion, posing a serious concern for the widespread fishing and mussel farming activities in the area.     

Heavy metals in soils from a typical industrial area in Sichuan,China: spatial distribution,source identification,and ecological risk assessment

Anthropogenic activities could result in increasing concentrations of heavy metals in soil and deteriorating in soil environmental quality. Topsoil samples from a typical industrial area, Shiting River Valley, Sichuan, Southwest China, were collected and determined for the concentrations of Cu, Zn, Cr, Cd, As, and Hg. The mean concentrations of these metals were lower than the national threshold values, but were slightly higher than their corresponding background values, indicating enrichment of these metals in soils in the valley, especially for Cu, Zn, and Hg. The topsoils in this area demonstrated moderate pollution and low potential ecological risk. Principal component analysis coupled with cluster analysis was applied to analyze the data and identified possible sources of these heavy metals; the results showed that soil Cd, Hg, As, Cu, and Zn were predominantly controlled by human activities, whereas Cr was mainly from the parent material. The spatial distribution of the heavy metals varied distinctly and was closely correlated to local anthropogenic activities. Furthermore, the concentrations of heavy metals in the industrial land demonstrated relatively higher levels than those of other land use patterns. Soil metal concentrations decreased with the distance increase from the traffic highway (0–1.0 km) and water system (0–2.0 km). Additionally, soil properties, especially pH and soil organic matter, were found to be important factors in the distribution and composition of metals.     

Octanol-solubility of dissolved and particulate trace metals in contaminated rivers: implications for metal reactivity and availability

The lipid-like, amphiphilic solvent, n-octanol, has been used to determine a hydrophobic fraction of dissolved and particulate trace metals (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) in contaminated rivers. In a sample from the River Clyde, southwest Scotland, octanol-solubility was detected for all dissolved metals except Co, with conditional octanol-water partition coefficients, D(ow), ranging from about 0.2 (Al and Cu) to 1.25 (Pb). In a sample taken from the River Mersey, northwest England, octanol-solubility was detected for dissolved Al and Pb, but only after sample aliquots had been spiked with individual ionic metal standards and equilibrated. Spiking of the River Clyde sample revealed competition among different metals for hydrophobic ligands. Metal displacement from hydrophobic complexes was generally most significant following the addition of ionic Al or Pb, although the addition of either of these metals had little effect on the octanol-solubility of the other. In both river water samples hydrophobic metals were detected on the suspended particles retained by filtration following their extraction in n-octanol. In general, particulate Cu and Zn (up to 40%) were most available, and Al, Co and Pb most resistant (<1%) to octanol extraction. Distribution coefficients defining the concentration ratio of octanol-soluble particle-bound metal to octanol-soluble dissolved metal were in the range 10(3.3)-10(5.3)mlg(-1). The presence of hydrophobic dissolved and particulate metal species has implications for our understanding of the biogeochemical behaviour of metals in aquatic environments. Specifically, such species are predicted to exhibit characteristics of non-polar organic contaminants, including the potential to penetrate the lipid bilayer. Current strategies for assessing the bioavailability and toxicity of dissolved and particulate trace metals in natural waters may, therefore, require revision.     

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.     

Changes in speciation and leaching behaviors of heavy metals in dredged sediment solidified/stabilized with various materials

Solidification/stabilization (S/S) of sediments is frequently used to treat contaminants in dredged sediments. In this study, sediment collected from the Pearl River Delta (China) was solidified/stabilized with three different kinds of functional materials: cement, lime and bentonite. Lime primarily acted via induced increases in pH, while cements stabilization occurred through their silicate-based systems and the main function of bentonite was adsorption. The speciation and leaching behaviors of specific heavy metals before and after S/S were analyzed and the results showed that the residual speciation of Cd, Cr, Ni, Pb and Zn increased in all treatments except for Cu, as the exchangeable speciation, carbonate-bound speciation and Fe-Mn-oxide-bound speciation of Cu (all of which could be stabilized) were less than 2 % of the total amount. Pb leaching only decreased when pH increased, while the mobility of Cr and Ni only decreased in response to the silicate-based systems. The leached portion of the Fe-Mn-oxide-bound speciation followed the order Zn?>?Cu?>?Ni/Cd?>?Pb?>?Cr. The leached portion of organic-matter-bound species was less than 4 % for Cd, Cr, Ni and Pb, but 35.1 % and 20.6 % for Cu and Zn, respectively.     

Properties of biochars from conventional and alternative feedstocks and their suitability for metal immobilization in industrial soil

In contaminated soils, excessive concentrations of metals and their high mobility pose a serious environmental risk. A suitable soil amendment can minimize the negative effect of metals in soil. This study investigated the effect of different biochars on metal (Cu, Pb, Zn) immobilization in industrial soil. Biochars produced at 300 and 600 °C from conventional (MS, maize silage; WP, wooden pellets) and alternative (SC, sewage sludge compost; DR, digestate residue) feedstocks were used as soil amendments at a dosage of 10 % (w/w). The type of feedstock and pyrolysis temperature affected the properties of the biochars and their ability to immobilize metal in soil. Compared to production at 300 °C, all biochars produced at 600 °C had higher pH (6.2–10.7), content of ash (7.2–69.0 %) and fixed carbon (21.1–56.7 %), but lower content of volatile matter (9.7–37.2 %). All biochars except DR biochar had lower dissolved organic carbon (DOC) content (1.4–2.3 g C/L) when made at 600 °C. Only MS and SC biochars had higher cation exchange capacity (25.2 and 44.7 cmol/kg, respectively) after charring at 600 °C. All biochars contained low concentrations of Cd, Cu, Ni, Pb and Zn; Cd was volatilized to the greatest extent during pyrolysis. Based on FTIR analysis and molar ratios of H/C and O/C, biochars had a greater degree of carbonization and aromaticity after charring at 600 °C. The efficiency of the biochars in metal immobilization depended mainly on their pH, ash content, and concentration of DOC. SC and DR biochars were more effective for Cu and Zn immobilization than MS and WP biochars, which makes them attractive options for large-scale soil amendment.     

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.     

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.     

Exposure of caged mussels to metals in a primary-treated municipal wastewater plume

The biological availability of metals in municipal wastewater effluents is strongly influenced by the physical and chemical conditions of both the effluent and the receiving water. Aquatic organisms are exposed to both dissolved and particulate (food ingestion) forms of these metals. In the present study, the distribution of metals in specific tissues was used to distinguish between exposure routes (i.e. dissolved vs. particulate phase) and to examine metal bioavailability in mussels exposed to municipal effluents. Caged Elliptio complanata mussels were deployed at sites located between 1.5 km upstream and 12 km downstream of a major effluent outfall in the St. Lawrence River. Metals in surface water samples were fractionated by filtration techniques to determine their dissolved, truly-dissolved (<10 kDa), total-particulate and acid-reactive-particulate forms. At the end of the exposure period (90 days), pooled mussel soft tissues (digestive gland, gills, gonad, foot and mantle) were analyzed for several metals. The results showed that gills and digestive gland were generally the most important target tissues for metal bioaccumulation, while gill/digestive gland metal ratios suggest that both exposure routes should be considered for mussels exposed to municipal effluents. We also found that Ag and Cd in the dispersion plume nearest the outfall, in contrast to other metals such as Cu and Zn, are more closely associated with colloids and were generally less bioavailable than at the reference site in the St. Lawrence River.     

Cu and Zn mobilization in soil columns percolated by different irrigation solutions

We investigated the effects of different concentrations of nitrate and ammonium in irrigation water on the mobilization of Zn and Cu in repacked soil columns with a metal-polluted topsoil and unpolluted subsoils over two and a half years. Soil solution samples were collected by suction cups installed at vertical distances of a few centimeters and analyzed for dissolved organic carbon (DOC), Cu, and Zn (total and labile). During high N treatments the pH decreased and the presence of exchangeable cations resulted in Zn mobilization from the surface soil. The nitrogen input stimulated the biological activity, which affected both concentration and characteristics of DOC and consequently Cu speciation. Metal leaching through the boundary between the polluted topsoil and the unpolluted subsoils increased soil-bound and dissolved metals within the uppermost 2 cm in the subsoils. Our study shows that agricultural activities involving nitrogen fertilization can have a strong influence on metal leaching and speciation.     

Geochemical behavior of metals and metalloids in an estuary affected by acid mine drainage (AMD)

The Tinto and Odiel rivers in southwest Spain drain the world’s largest sulfide mineral formation: the Iberian Pyrite Belt which has been worked since 2,500 BC. The Tinto and Odiel estuarine zones include both an extensive area of salt marsh and an intensively industrialized urban area. As a consequence of pyrite oxidation, the Tinto and Odiel rivers are strongly acidic (pH?<?3) with unusually high and quite variable metal concentrations. In this study, seasonally varying concentrations of dissolved major and trace elements were determined in the acid mine drainage affected estuary of the Ría de Huelva. During estuarine mixing, ore-derived metal concentrations exhibit excellent correlations with pH as the main controlling parameter. As pH increases, concentrations of dissolved ore-associated elements are attenuated, and this process is enhanced during the summer months. The decrease in Fe and Al concentrations ranged from 80 to 100 % as these elements are converted from dissolved to sediment-associated forms in the estuary. Coprecipitation/adsorption processes also removed between 60 and 90 % of the originally dissolved Co, Cu, Mn, Pb, Zn, and Th; however, Cd and Ni exhibited a greater propensity to remain in solution, with an average removal of approximately 60 %. On the other hand, As and U exhibited a different behavior; it is likely that these elements remain in dissolved forms because of the formation of U carbonates and soluble As species. Concentrations of As remain at elevated levels in the outer estuary (average?=?48 μg L^?1) which exceeds concentrations present in the Tinto River. Nevertheless, the estuary has recently witnessed improvements in water quality, as compared to results of several previous studies reported in the 1990s.     

Impact of industrial and mine drainage wastes on the heavy metal distribution in the drainage basin and estuary of the Sado River (Portugal)

This paper presents results from a survey of the heavy metal distribution in sediments in the drainage basin and estuary of the Sado River (Portugal). In the drainage basin, heavy metals originate mostly from pyrite outcrop erosion and mining activities (Cd, Zn, Cu and locally Hg, Pg), and also from crust erosion (Sn, Ni, Ti, Zr). These sources are not correlated with the particulate organic carbon (POC) and so the metals are thought to be in inorganic forms in this area. Anthropogenic heavy metal sources (urban and industrial) are found in the lower estuary (Sn, Cd, Hg, Zn, Pb and Cu) along with high POC concentrations. In this zone, these metals are thought to be strongly adsorbed onto organic particles. Furthermore, organo-metallic species are likely to be present, as demonstrated in the case of Sn, since methyl- and butyl-tin species were detected in sediments from this area. This suggests the need for the detection of organo-metallic species to understand the heavy metal geochemical cycles. No long-term changes in metal concentrations are found in sediment cores, except in the middle estuary (Zn, Cu) due to the development of mining activities on an industrial scale in the 1860s.