Mobilization of trace metals and inorganic compounds during resuspension of anoxic sediments from Trepangier Bayou, Louisiana

The release of trace metals (Mn, Ni, Co, Cu, Zn, Pb, and Cd) and inorganic compounds (As) from initially anoxic Trepangier Bayou sediments, Louisiana and the sources of the released metals were investigated. After 1 to 2 d aeration, significant amounts of trace metals (Mn, Zn, Cd, Ni, and Co) were released to the aqueous phase with increased acidity, primarily due to the oxidation of acid-volatile sulfide and ferrous iron and iron sulfide minerals. The addition of a bacterial inhibitor, NaN,, to the Trepangier sediment during resuspension inhibited metal release, suggesting that microbial catalysis can regulate metal mobilization during sediment resuspension. In a well buffered system, oxidation of iron sulfides alone did not appear to induce trace metal release. Moreover, when Trepangier sediment was resuspended in anoxic conditions at neutral pH, <1% of the trace metal content was released, whereas a significant release of metal was observed under acidic anoxic conditions. Although oxidation of iron sulfide minerals is an essential prerequisite for the release of Zn, Co, Cd, and Ni, carbonates and oxides also play a role. The trace metals and inorganic compounds investigated could be classified into three groups according to their release characteristics: (i) Mn, Zn, Cd, Ni, and Co; (ii) Fe, Pb, and As; and (iii) Cu. The groupings appeared to depend on the sources of compounds and their relative affinity, after oxidation, to iron oxyhydroxides or organic matter.     

Distribution of heavy metals in sediments of Igbede, Ojo and Ojora rivers of Lagos, Nigeria

The distribution of some heavy metals, namely Cd, Pb, Zn, Fe, Cu, Cr and Mn in epipellic sediments of Igbede, Ojo and Ojora rivers of Lagos was studied weekly in the early summer (November) of 2003. The levels of selected trace metals were determined using Atomic Absorption Spectrophotometer (UNICAM 969 AAS SOLAR). Trends in heavy metal burdens in the sediments revealed weekly variations in all the rivers assessed. Statistical analyses also showed different mean levels of trace metals in the aquatic environments, the distribution of which followed the sequence Fe > Zn > Mn > Pb > Cu > Cr > Cd, Fe > Zn > Cu > Mn > Pb > Cr > Cd and Fe > Zn > Mn > Cu > Cr > Pb > Cd in Igbede, Ojo and Ojora rivers respectively. Fe recorded the highest concentration levels (1,582.95 ± 96.57 μ g/g–1,910.34 ± 723.19 μ g/g) in all the sediments investigated while the Cd levels (0.06 ± 0.10 μ g/g–0.47 ± 0.36 μ g/g) were the lowest. Expectedly, trace metal concentrations in fine grain muddy sediments of the Igbede and Ojo coastline were much higher than those of Ojora which consist of coarse and sandy deposits covering the near shore area. Generally, the results obtained fell within tolerable limits stipulated by World Health Organization (WHO).     

Characteristic levels of heavy metals in sediments and dredged sediments of a municipal creek in the Niger delta, Nigeria

Characteristic levels of metal ions in post dredged sediment and dredged sediments materials of a municipal creek in the Niger Delta show that significant concentrations of heavy metals are found to be accumulated more on the surface (0–15cm depth) of the dredged material as compared to the sub surface (15–30cm) and post dredged sediments. The distribution patterns were in the following order Fe > Mn > Zn > Cu > Pb > Ni > Cd and Fe > Mn > Zn > Pb > Cu > Ni > Cd for the post dredged sediment and dredged sediment materials respectively. The levels of the various metals were far below the EPA screening levels for open water disposal, consequently total levels of heavy metal found in these sediments pose no problem by open-water or upland disposal     

Characteristics of slag, fly ash and deposited particles during melting of dewatered sewage sludge in a pilot plant

This study examines slag, fly ash, and deposited particles during melting of dewatered sewage sludge in a pilot plant. In addition, the chemical composition of particles in flue gas was simulated using a thermodynamics program, namely FACTSage 5.2. The results showed that the main components of slag were Al, Fe, Ca, P and Si; the minor components were Na, K, Mg, Cu, and Zn. The main chemical compound of slag was Ca4(Mg,Fe)5(PO4)6. For fly ash particles, heavy metals with the highest concentrations were in the order of Zn and As, Pb, Cu, and Cd, respectively. For non-heavy metals, Al, Fe and P were also found in significant amounts. The majority of deposited particles were composed of elements of Zn, P, S, Na, Fe, Al, Si, and Ca and such chemical compounds as Zn3(PO4)2, AlPO4, FePO4 and Fe(OH)3 while the minority consisted of elements of As, Cu, and Pb. Moreover, the compositions of deposited particles in each chamber differed due to different flue gas temperatures inside. In the secondary chamber at 760 degrees C, the amounts of Fe and Al were higher than Zn, whereas, in the other chambers (600-400 degrees C), the amount of Zn was higher. In other words, at the lower temperature the deposition of Zn was higher than the deposition of Fe and Al. In the water cooling section, volatile elements (i.e. Zn, As, Cu, Pb) were found in the highest concentrations due to a big difference in temperature between the wall surface and flue gas. From the simulation results, most of the elements in the gas phase were found to be chloride compounds, whereas those in the solid phase were in the form of oxide, sulfate, and phosphate compounds.     

Spatial variations in selected metal contents and particle size distribution in an urban and rural atmosphere of Islamabad, Pakistan

Spatial variations in total suspended particulate matter (TSP) were investigated for distribution of metals and particle size fractions in the urban and rural atmosphere of Islamabad, Pakistan. The metals Na, K, Fe, Mn, Pb, Cd, Cr, Zn, Ni and Co, and the particle fractions <2.5, 2.5-10, 10-100 and >100 microm were included in the study. TSP samples were trapped on glass fibre filters using high volume samplers and quantification of metals was done using Atomic Absorption Spectrometry employing HNO(3) based wet digestion. At the urban site, Na was dominant at 2.384 microg/m(3) followed by K, Fe and Zn with 0.778, 0.667 and 0.567 microg/m(3) as mean concentrations, respectively. The metal levels for the rural site ranged from 0.002 microg/m(3) for Cd to 1.077 microg/m(3) for Na. However, compared with the urban site, mean Pb concentration showed an almost two-fold enhancement, i.e., 0.163 Vs. 0.327 microg/m(3). Metals and particle size source identification was done using Principal Component Analysis and Cluster Analysis. Five sources were traced out for the urban site: industrial, soil, automobile emissions, metallurgical industries and excavation activities. For the rural site, four sources were recorded: agricultural, automotive emissions, excavation activities and metallurgical units. Collectively, for both the sites, PM(10-100) emerged as a major contributor to TSP, followed by PM(2.5-10), PM(<2.5) and PM(>100) in that order. The metals showed in general positive relationship with fine particulate fractions (PM(2.5-10), PM(<2.5)), and negative correlation with coarse fractions (PM(10-100), PM(>100)). Comparison with the corresponding data from various Asian sites revealed that the levels of Na, K, Fe, Mn, Co and Ni for the present study were lower than those reported for grossly polluted cities of the world.     

Concentrations and pattern of Fe,Cu, Cr,and Zn contamination in the soils of Akure,Nigeria

An assessment was made on twenty-eight topsoils collected from seven sites with intense artisan activities in the city of Akure, Nigeria, using geochemical approach in order to establish anthropogenic influence on metal contamination and to assess the severity of the contamination in the urban environment. Concentrations of Fe, Cu, Zn, and Cr were determined in the samples by atomic absorption spectrophotometry. The results revealed between 137- and 165-fold elevation of Fe, between 17- and 94-fold elevation of Cu, between 50- and 137-fold elevation of Zn, and between 1- and 3-fold elevation of Cr in topsoil relative to background levels. This indicates that except for Cr, soil contaminations by the metals were due to anthropic sources such as mechanic and vulcanizers workshops. The current average levels of copper exceeded the target value in Nigeria and in many developed countries, while Zn and Cr are generally lower than the respective soil quality guidelines. The contamination/pollution index maps figured out mechanic workshop as the main source of diffuse contamination and also show the influence of the point sources of contamination to urban topsoils. Cu contamination found around the soils of the mechanic/battery charger workshop is potentially serious (severe pollution), and this may pose health risk to people dwelling around these sites or within the metropolis. Children could be at greater risk than adults, because of their hand-to-mouth behaviors that increase their exposure potential.     

Total Contents and Sequential Extraction of Heavy Metals in Soils Irrigated with Wastewater,Akaki, Ethiopia

The Akaki River, laden with untreated wastes from domestic, industrial, and commercial sources, serves as a source of water for irrigating vegetable farms. The purpose of this study is to identify the impact of waste-water irrigation on the level of heavy metals and to predict their potential mobility and bioavailability. Zn and V had the highest, whereas Hg the lowest, concentrations observed in the soils. The average contents of As, Co, Cr, Cu, Ni, Zn, V, and Hg of both soils; and Pb and Se from Fluvisol surpassed the mean + 2 SD of the corresponding levels reported for their uncontaminated counterparts. Apparently, irrigation with waste water for the last few decades has contributed to the observed higher concentrations of the above elements in the study soils (Vertisol and Fluvisol) when compared to uncontaminated Vertisol and Fluvisol. On the other hand, Vertisol accommodated comparatively higher average levels of Cr, Cu, Ni, Zn, etc V, and Cd, whereas high contents of Pb and Se were observed in Fluvisol. Alternatively, comparable levels of Co and Hg were found in either soil. Except for Ni, Cr, and Cd in contaminated Vertisol, heavy metals in the soils were not significantly affected by the depth (0–20 and 30–50 cm). When the same element from the two soils was compared, the levels of Cr, Cu, Ni, Pb, Se, Zn, V, Cd at 0–20 cm; and Cr, Ni, Cu, Cd, and Zn at 30–50 cm were significantly different. Organic carbon (in both soils), CEC (Fluvisol), and clay (Vertisol) exhibited significant positive correspondences with the total heavy metal levels. Conversely, Se and Hg contents revealed perceptible associations with carbonate and pH. The exchangeable fraction was dominated by Hg and Cd, whereas the carbonate fraction was abounded with Cd, Pb, and Co. conversely, V and Pb displayed strong affinity to reducible fraction, where as Cr, Cu, Zn, and Ni dominated the oxidizable fraction. Cr, Hg, Se, and Zn (in both soils) showed preference to the residual fraction. Generally, a considerable proportion of the total levels of many of the heavy metals resided in non residual fractions. The enhanced lability is generally expected to follow the order: Cd > Co > Pb > Cu > Ni > Se > V and Pb > Cd > Co > Cu > Ni > Zn in Vertisol and Fluvisol, respectively. For the similar wastewater application, the soil variables influence the status and the distribution of the associated heavy metals among the different soil fractions in the study soils. Among heavy metals that presented relatively elevated levels and with potential mobility, Co, Cu, Ni (either soil), V (Vertisol), Pb, and Zn (Fluvisol) could pose health threat through their introduction into the food chain in the wastewater irrigated soils.     

Geochemical properties and pollution assessment of heavy metals in the sediments of Daechung Lake,Korea

In order to examine the forms, sources, and pollution of heavy metals—arsenic (As), aluminum (Al), cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe), nickel (Ni), lead (Pb), and zinc (Zn)—in Daechung Lake, Korea, sediment samples were collected in November 2014. Daechung Lake was constructed to supply water for human consumption, agricultural use, and industrial use as well as to generate electric power. The lake is stratified in the summer and surrounded mostly by agricultural and mining areas. Our results indicate that the heavy metals (except As and Cd) displayed similar concentrations at all of the sampling stations. As and Cd were high in locations where fine sediments had built up. Based on the enrichment factor of the metals, the sediments collected from all of the sampling stations were highly polluted by As and Cd. Therefore, deposition of heavy metals in Daechung Lake is possibly controlled by grain size and anthropogenic activity, such as drainage from abandoned mines, agricultural activities, and/or the release of wastewater. The most dominant forms for all of the metals were oxide and silicate forms. This suggests that the sediments of Daechung Lake are not highly sulfidic. However, the sediment samples were collected after the collapse of seasonal stratification. Therefore, future studies should include elucidation of major sources for As and Cd and the collection of sediments during months of stratification.     

A novel continuous-flow sequential extraction procedure for metal speciation in solids

A continuous-flow extraction system was developed to speed up, facilitate, and improve the accuracy of the chemical fractionation of metals in solid materials. A three-step sequential extraction scheme was used to evaluate the novel system by analyzing calcium (Ca), iron (Fe), manganese (Mn), copper (Cu), and zinc (Zn) in a soil certified reference material (National Institute of Standards and Technology [NIST] SRM 2710). In the proposed system, extraction occurred in a closed chamber through which extractants were passed sequentially. The extracts were collected in a number of subfractions for subsequent name atomic absorption analysis. Apart from the advantages of simplicity, speed, and less risk of the contamination that flow analysis systems usually possess, the continuous-flow system can improve the accuracy of chemical fractionation of metals by sequential extraction. The system ensures that extraction is performed at designated pH values without any need of adjustment. Variation of sample weight to chamber volume ratios from 1:12 to 1:40 had no effect on the extractability of the metals studied. In the extraction of the acid soluble fraction, concentrations of acetic acid in the range 0.11 to 0.5 mol L(-1) had no significant effect on the amounts of metals extracted, except Fe. Increasing the concentration of hydroxylamine in the reducible fraction step from 0.04 to 0.5 mol L(-1) affected the extraction efficiency for Fe, Mn, and Zn. The extraction profile, rather than a single value of extracted concentration, of each element offers additional information about the kinetics of leaching processes and chemical associations between elements in the solid materials.     

Bioproduction of ferric sulfate used during heavy metals removal from sewage sludge

Toxic metals removal from wastewater sewage sludge can be achieved through microbial processes involving Acidithiobacillus ferrooxidans. The oxidation of ferrous ions by A. ferrooxidans, cultured in sewage sludge filtrate, was studied in both batch and continuous flow stirred tank reactors. Sewage sludge filtrate containing natural nutrients (phosphorus and nitrogen) was recovered as effluent following the dehydration of a primary and secondary sludge mixture. Batch and continuous flow stirred tank reactor tests demonstrated that A. ferrooxidans were able to grow and completely oxidize ferrous iron in a culture medium containing more than 80% (v v(-1)) sewage sludge filtrate with 10 g Fe(II) L(-1) added. Toxic levels were reached when total organic carbon in the sewage sludge filtrate exceeded 250 mg L(-1). The ferric iron solution produced in the sludge filtrate by A. ferrooxidans was used to solubilize heavy metals in primary and secondary sludge. The solubilization of Cu, Cr, and Zn yielded 71, 49, and 80%, respectively. This is comparable with the yield percentages obtained using a FeCl(3) solution. The cost of treating wastewater sewage sludge by bioproducing a ferric ion solution from sewage sludge is three times less expensive than the conventional method requiring a commercial ferric chloride solution.     

Photosynthesis, chlorophyll integrity, and spectral reflectance in lichens exposed to air pollution

The major objective of the present study was to identify the relationship of physiologial parameters of the photosynthetic system with the elemental content of the lichen Ramalina lacera (With.) J.R. Laund. Thalli of R. lacera were collected in an unpolluted site and transplanted in a national park and an industrial region in Israel for 8 mo. Analyses of photosynthetic activity, chlorophyll integrity, spectral reflectance, and amount of 11 metals were performed after this period of exposure. The normalized difference vegetation index (NDVI), indicative of the spectral reflectance response of the thallus, correlated with photosynthetic rate and chlorophyll and K content and correlated inversely with amounts of Ba, Cr, Cu, and Ni. The NDVI appears to enable the detection of early signs of pollutant-induced stress before changes in other physiological parameters become apparent. Elevated amounts of Cr, Cu, Fe, Mn, Ni, and Zn in lichens transplanted to an industrial area and the correlation of Mn and Ni, Mn and V, Ni and V, Fe and Mn, Fe and V, and Fe and Zn point for the greater part to metal processing in a steel smelter. Correlations of Cr and Ni, Cu and Ni, Zn and Cu, Cu and Mn, and Zn and Ni could be related to metal processing in the industrial area but indicate also vehicular activity as a possible originator.     

Metal release from bottom sediments of Ocoee Lake No. 3, a primary catchment area for the Ducktown Mining District

Ocoee Lake No. 3 is the first reservoir receiving suspended sediments contaminated with trace metals discharged by acid mine effluents from the Ducktown Mining District, Tennessee. Bottom sediments (0-5 cm) from the lake were sampled to assess the potential for future adverse environmental effects if no remediation controls or activities are implemented. The sediments were found to include a major component (173 +/- 19 g kg(-1)) that dissolved in 6 mol L(-1) HCl within 24 h. This acid-soluble and relatively labile fraction contained high concentrations of Fe (460 +/- 40 g kg(-1)), Al (99 +/- 11 g kg(-1)), Mn (10 +/- 8 g kg(-1)), Cu (2000 +/- 700 mg kg(-1)), Zn (1300 +/- 200 mg kg(-1)), and Pb (300 +/- 200 mg kg(-1)). When the pH of water in contact with the sediment was decreased experimentally from 6.4 to 2.6, the concentrations of dissolved trace metals increased by factors of 2200 for Pb, 160 for Cu, 21 for Zn, 9 for Cd, 8 for Ni, and 5 for Co. The order in which metals were released with decreasing pH was the reverse of that reported for pH-dependent sorption of these metals in upstream systems. Substantial release of trace metals from the sediment was observed even by a modest decrease of pH from 6.4 to 5.9. Therefore, the metal-rich sediment of the lake should be considered as potentially hazardous to bottom-dwelling aquatic species and other organisms in the local food chain. In addition, if the reservoir is dredged or if the dam is removed, the accumulated sediment may have to be treated for recovery of sorbed metals.     

Understanding heavy metal and suspended solids relationships in urban stormwater using simulated rainfall

Urban stormwater from simulated rainfall on three different landuses in Queensland State, Australia (residential, industrial, commercial) was analysed for heavy metals and physico-chemical parameters such as Dissolved Organic Carbon (DOC) and Total Suspended Solids (TSS). Rainfall events were simulated using a specially designed rainfall simulator for paved surfaces. Event mean concentration samples were separated into five different particle sizes and analysed individually for eight metal elements (Zn, Fe, Cr, Cd, Cu, Al, Mn and Pb). Multivariate data analysis was carried out for the data thus generated. It was found that DOC and TSS influence the distribution of the metals in the different particle size classes. Zn was correlated with DOC at all three sites. Similarly, Pb, Fe and Al were correlated with TSS at all sites. The distribution of Cu was found to vary between the three sites, whilst Cd concentrations were too low to assess any relationships with other parameters. No correlation between Electrical Conductivity (EC), pH and heavy metals was found at the three sites. The identification of physico-chemical parameters influencing the distribution process kinetics of heavy metals in urban stormwater will significantly enhance the efficiency of urban stormwater management systems.     

Speciation of Cd,Cu, Zn,Fe and Pb in sediments sampled from Lake Victoria basin,Kenya

Speciation studies revealed that the heavy metals in sediments of Lake Victoria Basin, Kenya, are highly bioavailable with % average values of 73.3, 66.9, 65.6, 57.1 and 55.8 for Zn, Pb, Fe, Cu and Cd respectively being recorded. The high percentages were attributed to the anthropogenic sources of these metals upstream and within the shores of Lake Victoria. Large loads of floating organic matter were witnessed on the surface of water, and this most likely contributed to the high % of organic matter of 7.58 recorded in this study. High % of organic matter in sediments contributes significantly to bioavailability of heavy metals in sediments.     

micro-XANES and micro-XRF investigations of metal binding mechanisms in biosolids

Micro-X-ray fluorescence (micro-XRF) microprobe analysis and micro-X-ray absorption near-edge structure (micro-XANES) spectroscopy were employed to identify Fe and Mn phases and their association with selected metals in two biosolids (limed composted [LC] and Nu-Earth) before and after treatment to remove organic carbon (OC). Spatial correlations derived from elemental mapping of XRF images showed strong correlations between Fe and Cd, Cr, Pb, or Zn (r2= 0.65-0.92) before and after removal of most of the OC. The strong correlation between Fe and Cu that was present in intact samples disappeared after OC removal, suggesting that Cu was associated with OC coatings that may have been present on Fe compounds. Except for Fe and Cr, the spatial correlations of metals with Mn were improved after treatment to remove OC, indicating that the treatment may have altered more than the OC in the system. The Fe micro-XANES spectra of the intact biosolids sample showed that every point had varying mixtures of Fe(II and III) species and no two points were identical. The lack of uniformity in Fe species in the biosolids sample illustrates the complexity of the materials and the difficulty of studying biosolids using conventional analytical tools or chemical extraction techniques. Still, these microscopic observations provide independent information supporting the previous laboratory and field hypothesis that Fe compounds play a major role in retention of environmentally important trace elements in biosolids. This could be due to co-precipitation of the metals with Fe, adsorption of metals by Fe compounds, or a combination of both mechanisms.     

Effect of organic matter oxidation on the fractionation of copper, zinc, lead, and arsenic in sewage sludge and amended soils

Long-term land application of sewage sludge (SS) has caused concern over the potential release of trace metals into the environment following the degradation of organic matter (OM). This study was performed to assess the impact of OM degradation on the relative distribution of Cu, Zn, Pb, and As in SS and SS-amended soils. Three SSs of different ages and two soils treated with SS were subjected to incubation and direct chemical oxidation using diluted HO, followed by a sequential extraction. The majority of Cu, Pb, and As were bound to OM, whereas the majority of Zn was bound with Fe/Mn oxides for all three SSs. Incubation of SS for 6 mo did not result in a substantial decrease in OM content or a change in the relative distribution of Cu, Zn, Pb, and As. Direct OM oxidation to 30 and 70% by diluted HO resulted in a significant decrease in organically bound Cu but increased its exchangeable, carbonate-bound, and Fe/Mn-bound fractions. Oxidation of OM slightly decreased organically bound Zn but significantly increased exchangeable Zn in all SSs. Oxide- and carbonate-bound Zn also decreased following OM oxidation. Exchangeable fractions of As and Pb were minute before and after OM degradation, indicating that release into the environment would be unlikely. The relative distribution of Cu, Zn, Pb, and As in SS-treated soils was similar to that of SS, suggesting a dominant role of SS properties in controlling metal distribution following OM oxidation. Overall, OM oxidation increased the mobility and bioavailability of Zn and Cu, whereas it had less impact on Pb and As.     

Trace Metal Concentrations in an Intensive Agricultural Watershed in British Columbia,Canada1

Abstract: Effects of agricultural intensification and a naturally occurring landslide of asbestos material upon water and sediment quality in a transboundary watershed were investigated. The water and sediments of the Sumas River watershed were analyzed for copper (Cu), zinc (Zn), chromium (Cr), and nickel (Ni) concentrations in 1993/1994 and 2003/2004 and differences within sites over time were examined. Based upon a review of the literature, Cu and Zn were used as indicators of agricultural impacts while Cr and Ni were used as indicators of impacts from an asbestos landslide. Animal unit equivalents (AUEs) were calculated on a per area basis as an indicator of livestock density using detailed statistical census data. Whatman #42 filtered metals, bioavailable metals, and sediment‐bound metals (in the <63 μm fraction) were determined at 22 sites along the mainstem and tributaries, including two reference sites. Temperature, pH, and dissolved organic carbon (DOC) were also measured. The bioavailable metal fraction was determined using the diffusive gradient thin film technique (DGT). Sediment‐bound results were compared with British Columbia’s Interim Sediment Quality Guidelines (ISQGs) and Severe Effects Levels (SELs). A Wilcoxon signed rank test was used to determine if the concentrations of metals changed significantly within sites between 1993/1994 and 2003/2004. Spearman rank correlation analysis was used to determine relationships between trace metals, water quality parameters, and AUEs/hectare. The results indicate that Cu and Zn levels in sediments increased significantly to concentrations above the ISQGs of 35.7 mg/kg and 123 mg/kg, respectively from 1993/1994 to 2003/2004 in streams, where associated land use was dominated by intensive agriculture. Higher AUEs/hectare were significantly correlated with greater bioavailable levels of Zn as well as higher sediment‐bound Zn concentrations. Neither Cu nor Cr were detected by the DGTs on any of the sampling occasions. The Cr and Ni sediment concentrations were highest in Swift Creek, the headwater tributary affected by the natural landslide of asbestos material, and decreased in the Sumas River downstream from the point of input. Cr and Ni concentrations have increased in the mid‐region of the Sumas River since 1993/1994, suggesting downstream movement of the asbestos material over time. DGT results indicated that bioavailable Zn is significantly positively correlated to sediment‐bound Zn and livestock density, and bioavailable Ni is significantly correlated to sediment‐bound Ni.     

Experimental oxidative dissolution of sphalerite in the Aznalcollar sludge and other pyritic matrices

After the collapse on 25 Apr. 1998 of the Aznalcóllar mine tailings dike in southwestern Spain, 45 km2 of the Guadiamar valley were covered by a pyritic sludge containing up to 2% sphalerite (ZnS). Later, the sludge was mechanically removed and calcium carbonate was plowed into the soil to immobilize heavy metals. By June 2001 more than 60% of the sulfides in the residual sludge had oxidized and soil Zn contents reached locally phytotoxic levels. Therefore, the oxidative dissolution of sphalerite in the sludge and other pyritic samples was examined. Flow-through oxidation experiments showed that: (i) about 5 and 17% of the sludge Fe and Zn were in soluble form, respectively, because the sludge sample had been partly oxidized in the field; (ii) the oxidation rates of the residual pyrite and sphalerite were similar; (iii) the overall sulfide oxidation rate was relatively unaffected by the addition of calcite; and (iv) poorly crystalline Fe (hydr)oxides containing Zn in occluded form and Zn (hydroxi)carbonates were formed in the presence of calcite. The rate of oxidation of reference sphalerite greatly increased when it was incorporated in the sludge or in a reference pyrite matrix. This enhancement was due to galvanic interaction because pyrite oxidation was depressed in the presence of sphalerite. Oxidation by Fe3+ ions was less important because the oxidation rates of native sphalerite were not greater at low than at high pH. The fast oxidation rate of sphalerite in the Aznalcóllar sludge indicates a need for quick adoption of remediation measures in similar accidents elsewhere. The use of calcite amendments has little influence on the oxidation rate but does result in the accumulation of Zn in relatively insoluble forms.     

Phytoextraction of heavy metals by willows growing in biosolids under field conditions

Biosolids produced by sewage treatment facilities can exceed guideline thresholds for contaminant elements. Phytoextraction is one technique with the potential to reduce these elements allowing reuse of the biosolids as a soil amendment. In this field trial, cuttings of seven species/cultivars of Salix(willows) were planted directly into soil and into biosolids to identify their suitability for decontaminating biosolids. Trees were irrigated and harvested each year for three consecutive years. Harvested biomass was weighed and analyzed for the contaminant elements: As, Cd, Cu, Cr, Hg, Pb, Ni, and Zn. All Salix cultivars, except S. chilensis, growing in soils produced 10 to 20 t ha(-1) of biomass, whereas most Salix cultivars growing in biosolids produced significantly less biomass (<6 t ha(-1)). Salix matsudana (30 t ha(-1)) and S. × reichardtii A. Kerner (18 t ha(-1)) had similar aboveground biomass production in both soil and biosolids. These were also the most successful cultivars in extracting metals from biosolids, driven by superior biomass increases and not high tissue concentrations. The willows were effectual in extracting the most soluble/exchangeable metals (Cd, 0.18; Ni, 0.40; and Zn, 11.66 kg ha(-1)), whereas Cr and Cu were extracted to a lesser degree (0.02 and 0.11 kg ha(-1)). Low bioavailable elements, As, Hg, and Pb, were not detectable in any of the aboveground biomass of the willows.     

Metal contamination of surface water,sediment and <Emphasis Type="Italic">Tympanotonus fuscatus</Emphasis> var. <Emphasis Type="Italic">radula</Emphasis> of Iko River and environmental impact due to Utapete gas flare station,Nigeria

Inter-seasonal studies on the trace metal load of surface water, sediment and Tympanotonus fuscatus var. radula of Iko River were conducted between 2003 and 2004. The impact of anthropogenic activities especially industrial effluent, petroleum related wastes, gas flare and episodic oil spills on the ecosystem are remarkable. Trace metals analyzed included cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe), lead (Pb), manganese (Mn), nickel (Ni), vanadium (V) and zinc (Zn). Sediment particle size analysis revealed that they were characteristically psammitic and were predominantly of medium to fine grained sand (>73%), less of silt (<15%) and clay (<10%). These results correlated with low levels of trace elements such as Pb (0.03 ± 0.02 mg kg⁻¹), Cr (0.22 ± 0.12 mg kg⁻¹), Cd (0.05 ± 0.03 mg kg⁻¹), Cu (0.04 ± 0.02 mg kg⁻¹) and Mn (0.23 ± 0.22 mg kg⁻¹) in the sediment samples. This observation is consistent with the scarcity of clayey materials known to be good scavengers for metallic and organic contaminants. Sediments indicated enhanced concentration of Fe, Ni and V, while other metal levels were relatively low. The concentrations of all the metals except Pb in surface water were within the permissible levels, suggesting that the petroleum contaminants had minimal effect on the state of pollution by trace metals in Iko River. Notably, the pollutant concentrations in the sediments were markedly higher than the corresponding concentrations in surface water and T. fuscatus tissues, and decreased with distance from point sources of pollution.