Use of sequential leaching, mineralogy, morphology and multivariate statistical technique for quantifying metal pollution in highly polluted aquatic sediments--a case study: Brahmani and Nandira Rivers, India

The particle size distribution, geochemical composition and sequential leaching of metals (Fe, Mn, Ni, Cu, Co, Cr, Pb, Zn and Cd) are carried out in core sediments (<88 microm) from the Brahmani and Nandira Rivers, India. To confirm the contamination of downstream sediments by fly ash, mineralogical and morphological characterizations were carried out. High environmental risk of Co, Pb and Ni is due to their higher availability in exchangeable fraction. The metals like Zn, Cu and Mn represent an appreciable portion in the carbonate phase. Metals such as Zn, Pb, Cd, Co and Ni are associated with reducible phase may be due to adsorption. The organic bound Cu, Zn, and Pb seem to be second dominant fraction among non-lithogenous in Nandira sediments. Factor analysis data reveals that textural parameters, Fe-Mn oxy/hydroxides, organic precipitation and coal fly ash disposals, are individually responsible for the enrichment of heavy metals. The relationships among the stations are highlighted by cluster analysis to identify the contamination levels.     

Total concentrations and fractions of Cd, Cr, Pb, Cu, Ni and Zn in sewage sludge from municipal and industrial wastewater treatment plants

Heavy metals are one of the important factors that affect the final disposal of sewage sludge. In this paper, the metal mobility and bioavailability of heavy metals in sewage sludge were studied by using Community Bureau of Reference (BCR) sequential extraction procedure to get more information for the reasonable disposal of sludge. Sewage sludge was collected from five municipal wastewater treatment plants and three industrial wastewater treatment plants. The sludge was examined for and the total concentrations and different chemical fractions of Cd, Cr, Pb, Cu, Ni and Zn. The total metal concentrations of heavy metals in sludge varied greatly. The contents of Zn and Cu were the highest, followed by then Cr, Ni and Pb and the content of Cd was the least. There was no significant difference in total metal concentration between municipal and industrial wastewater treatment plants. Fractions extracted by the BCR sequential procedure were acid soluble/exchangeable, reducible and oxidizable fraction. Sludge pH was found to have profound effect on the chemical fractions of heavy metals. Acidic sludges (Xiamen and Jinlin Petrochemical Group Co., wastewater treatment plant) had higher proportion of the acid soluble/exchangeable fractions than in neutral sludge. In neutral sludges, Pb and Cr were principally distributed in between the oxidizable fraction and the residual fraction; Cu was in the oxidizable fraction; Cd mainly in the residual fraction in municipal wastewater treatment plants and had high percentage of acid soluble/exchangeable and reducible fractions in industrial wastewater treatment plants; Ni and Zn had higher percentage in the acid soluble/exchangeable and the oxidizable fraction.     

杭州下沙河道底泥重金属检测及污染分析

检测了杭州下沙河网区18条河道表层底泥重金属Cu、Zn、Pb、Cd、Ni的含量,分析了研究区域内的重金属污染情况,并用潜在生态危害指数法对河道底泥重金属污染情况进行评价,通过聚类分析法分析重金属的空间分布特征.结果表明,Cd污染最严重,超标率为94.44%,平均超标倍数为16.50,Cd的平均潜在生态风险为很高风险,Cu、Zn、Pb、Ni的平均潜在生态风险为低风险,重金属平均综合潜在生态风险属于高风险.重金属聚类分析结果显示Cd、Ni、Pb三种元素相关性显著,应受同一污染源因素影响;采样点聚类分析结果显示下沙河网河道底泥重金属污染分布较为均匀.     

Effect of metal spiking on different chemical pools and chemically extractable fractions of heavy metals in sewage sludge

A laboratory experiment was conducted to study the effect of metal spiking and incubation on some properties and sequentially extractable chemical pools of some heavy metals (F1, two extractions with 0.1 M Sr(NO3)2; F2, one extraction with 1 M NaOAc (pH 5.0); F3, three extractions with 5% NaOCl (pH 8.5) at 90-95 degrees C; F4, three extractions with 0.2 M oxalic acid + 0.2 M ammonium oxalate + 0.1 M ascorbic acid (pH 3.0); and F5, dissolution of sample residue in HF-HClO4 (residual fraction,) and also 1 M CaCl2 and 0.005 M DTPA extractable heavy metals in sewage sludge. Metal spiking and incubation decreased pH and easily oxidizable organic C content of sludge but increased electrical conductivity. Metal spiking and incubation increased F1 fraction of all heavy metals, F2 fraction of Ni, Pb, Cu, and Cd, F3 fraction of Pb, Cu, and Cd, F4 or reducible fraction of Ni, Cu, and Cd and residual fraction of Zn and Pb, but decreased F2 fraction of Zn, F3 of Zn and Ni, F4 fraction of Zn and F5 fraction of Ni, Cu, and Cd. Metal spiking and incubation increased 1 M CaCl2 and 0.005 M DTPA extractable amounts of all heavy metals in sludge except for 0.005 M DTPA extractable Zn, which registered only very marginal decrease.     

Distribution of heavy metals in Lakes Doirani and Kerkini, Northern Greece

The distribution of heavy metals in two lakes of high ecological significance, Doirani and Kerkini, located in Northern Greece was studied. Eight metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) were determined in water, total suspended solids, fine and coarse sediments. Moreover, the modified BCR fractionation scheme was employed in sediments and suspended solids to determine soluble, oxidisable, reducible and residual fractions of metals. The Lake Doirani presents higher metal concentrations in aqueous phase than Lake Kerkini; Cd, Cu, Ni, Pb and Zn are above the chronic freshwater quality criteria for aquatic life. In both lakes, Fe and Mn are the most abundant elements in total suspended solids whereas Cd the less abundant. The Lake Kerkini exhibits higher concentrations of all the examined metals in sediments comparing to the Lake Doirani, however the concentrations are lower than the sediment quality guidelines. Cd in sediments is mainly in soluble fraction, Pb and Cu exhibit significant oxidisable fractions whereas, Cr and Fe associated mainly with residual fraction.     

Determination of heavy metals by ICP-OES and F-AAS after preconcentration with 2,2'-bipyridyl and erythrosine

The applicability of 2,2'-bipyridyl and erythrosine co-precipitation method for the separation and preconcentration of some heavy metals, such as Cd, Co, Cu, Ni, Pb and Zn in actual samples for their determination by ICP-OES and F-AAS was studied. Experimental conditions influencing the recovery of the investigated metals, such as pH, molar ratio of 2,2'-bipyridyl to erythrosine, the effect of time on co-precipitation were optimized. The analytical characteristics of the method (e.g. limit of detection, sensitivity, linear range and preconcentration factor) were obtained. The limits of detection LOD (ng mL(-1)) of the ICP-OES (F-AAS) method were: Cd: 4.0 (7.75), Co: 3.1 (57.2), Cu: 18 (10.3), Ni 21.3 (32.8), Pb: 35.9 (29.2) and Zn: 10.2 (6.90). The recovery of all the elements tested was more than 93%. The influence of inorganic matrix was examined. The proposed method was applied to determination of Cd, Co, Cu, Ni, Pb and Zn in vegetables and certified reference material (NCS ZC85006 Tomato).     

Heavy metal sorption and desorption capacity of soils containing endogenous contaminants

Soils on serpentinites in some regions of northwestern Spain have been the subject of agricultural management practices involving the use of fertilizers and various types of organic waste containing heavy metals. Although such practices have facilitated crop growth, they have also raised the natural contents in heavy metals of the soils. In this work, three ferralic Cambisols and another three mollic Leptosols with high Cr and Ni contents were used to study competitive sorption and desorption of six heavy metals via K(d100), which was employed as a measure of the ability of the soils to adsorb and retain each metal. Lead was found to be the metal sorbed and retained to the greatest extent, and Cd, Ni and Zn those sorbed and retained in the smallest amounts. Although the ferralic Cambisols were found to contain greater amounts of natural heavy metals, they exhibited an increased ability to adsorb and retain the body of metals relative to the mollic Leptosols by effect of their increased contents in clay and Fe, Mn and Al oxides, in addition to their higher ion-exchange capacity. Based on the results, Pb and Cu are strongly bound, and Zn, Cd and Ni weakly bound, to the soils. The ferralic Cambisols exhibited an increased capacity to adsorb and retain Cd, Ni, Zn and--especially--Cr than the mollic Leptosols; the latter, however, proved more effective in adsorbing and retaining Cu and Pb by virtue of their increased organic matter contents. Copper sorption and retention, and Pb retention, were found to be correlated with the content in organic matter and that in vermiculite--which was only present in the mollic Leptosols--in the clay fraction.     

Analysis and assessment on heavy metal sources in the coastal soils developed from alluvial deposits using multivariate statistical methods

An investigation on heavy metal sources, i.e., Cu, Zn, Ni, Pb, Cr, and Cd in the coastal soils of Shanghai, China, was conducted using multivariate statistical methods (principal component analysis, clustering analysis, and correlation analysis). All the results of the multivariate analysis showed that: (i) Cu, Ni, Pb, and Cd had anthropogenic sources (e.g., overuse of chemical fertilizers and pesticides, industrial and municipal discharges, animal wastes, sewage irrigation, etc.); (ii) Zn and Cr were associated with parent materials and therefore had natural sources (e.g., the weathering process of parent materials and subsequent pedo-genesis due to the alluvial deposits). The effect of heavy metals in the soils was greatly affected by soil formation, atmospheric deposition, and human activities. These findings provided essential information on the possible sources of heavy metals, which would contribute to the monitoring and assessment process of agricultural soils in worldwide regions.     

Fractionation of metals in street sediment samples by using the BCR sequential extraction procedure and multivariate statistical elucidation of the data

The concentrations of metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in street sediment samples were determined by flame atomic absorption spectrometry (FAAS) using the modified BCR (the European Community Bureau of Reference) sequential extraction procedure. According to the BCR protocol for extracting the metals from the relevant target phases, 1.0 g of specimen of the sample was treated with 0.11 M acetic acid (exchangeable and bound to carbonates), 0.5M hydroxylamine hydrochloride (bound to iron- and manganese-oxides), and 8.8M hydrogen peroxide plus 1M ammonium acetate (bound to sulphides and organics), sequentially. The residue was treated with aqua regia solution for recovery studies, although this step is not part of the BCR procedure. The mobility sequence based on the sum of the BCR sequential extraction stages was: Cd approximately Zn ( approximately 90%)>Pb ( approximately 84%)>Cu ( approximately 75%)>Mn ( approximately 70%)>Co ( approximately 57%)>Ni ( approximately 43%)>Cr ( approximately 40%)>Fe ( approximately 17%). Enrichment factors as the criteria for examining the impact of the anthropogenic emission sources of heavy metals were calculated, and it was observed that the highest enriched elements were Cd, Pb, and Zn in the dust samples, average 190, 111, and 20, respectively. Correlation analysis (CA) and principal component analysis (PCA) were applied to the data matrix to evaluate the analytical results and to identify the possible pollution sources of metals. PCA revealed that the sampling area was mainly influenced from three pollution sources, namely; traffic, industrial, and natural sources. The results show that chemical sequential extraction is a precious operational tool. Validation of the analytical results was checked by both recovery studies and analysis of the standard reference material (NIST SRM 2711 Montana Soil).     

Speciation of heavy metals by modified BCR sequential extraction procedure in different depths of sediments from Sungai Buloh, Selangor, Malaysia

The sequential extraction procedure proposed by the European Standard, Measurements and Testing (SM&T) program, formerly the Community Bureau of Reference (BCR), was applied for partitioning of heavy metals (HMs) in river sediments collected along the course of Sungai Buloh and the Straits of Malacca in Selangor, Malaysia. Eight elements (V, Pb, Cd, Cr, Co, Ni, Cu and Zn) from seven stations (S1-S7) and at different depths were analyzed using the modified BCR Sequential Extraction Procedure (SEP) in combination with ICP-MS to obtain the metal distribution patterns in this region. The results showed that heavy metal contaminations at S2 and S3 was more severe than at other sampling sites, especially for Zn, Cu, Ni and Pb. Nevertheless, the element concentrations from top to bottom layers decreased predominantly. The samples from the Straits of Malacca (S4-S7) the highest contamination factors obtained were for Co, Zn and Pb while the lowest were found for V and Cr, similar to Sungai Buloh sediments. The sediments showed a low risk for V, Cr, Cu and Pb with RAC values of less than 10%, but medium risk for Co, Zn (except S3), Cd at S1 and S2 and Ni at S1, S3 and S5. Zn at S3 and Cd at S3-S7 showed high risk to our sediment samples. There is not any element of very high risk conditions in the selected samples.     

Characteristics and accumulation of heavy metals in sediments originated from an electroplating plant

Heavy metals in river water and sediments originated from an electroplating plant in Jiangsu Province of China were studied and analyzed for their environmental impact. The results indicated that the wastewater from the plant degraded the quality of the aquatic environment downstream from the plant. In surface water, considerable concentrations of Cu, Ni, Zn, Mn and Cr were present at the sites near the plant. Unsafe levels of Cu were observed at all sites, and unsafe levels of Ni, Zn, and Cr were present at some sites. Significant accumulation of Ni, Cu, Zn and Cr was identified, and heavy metal longitudinal distribution in sediments was similar to that in water. The contents of Ni, Cu and Cr at all sites and Zn at some sites were likely to result in harmful effects on the environment. The risks posed by Ni, Cu, Zn and Cr in water and sediments decreased with increasing downstream distance. Moreover, a modified sequential extraction procedure was employed to determine exchangeable, carbonate-bound, iron-manganese oxide bound, organic matter bound and residual fractions of metals in sediments. The results showed that Ni was distributed in every fraction except for iron-manganese oxide bound, significant Mn exhibited in exchangeable fractions, and high percentage of Cu was in the organic matter and residual fractions. Residual fraction was the dominant fractions for Pb and Zn. According to RACs, Ni and Mn posed a high risk to the environment, Zn exhibited medium to high risk, Cu had low to high risk, and Pb possessed a low to medium risk.     

Cadmium distribution in sediment profiles of the six main rivers in southern Taiwan

Dynamic cadmium distribution has been studied in six main rivers flowing through the largest, most highly developed and polluted area of southern Taiwan. Sediment profile samples were also analyzed for Cu, Cr, Zn, Ni, Pb, Co, Mn, Fe, carbonates, Mn-oxides, Fe-oxides and organic matter in order to characterize the geochemical environment and to identify the pollutant sources. Higher Cd concentrations (about 3.5 mg/kg) at depths of 0-10 cm have been detected in the samples of Yenshui, Ell-ren and Potzu rivers, associated to the history of industrial activity in their catchments. According to the linear correlation coefficient (r) between Cd and the geochemical components, carbonates are the primary Cd binding phase in the Ell-ren river (r=0.85), and Cd comes from the same pollutant sources of those containing Cr, Ni, Cu and Zn (r>0.80). Cadmium concentration in the Potzu and Peikang river sediments is probably due to waste deposits rich in Cr and Cu (0.54相似文献   

Assessment of the metal pollution, potential toxicity and speciation of sediment from Algeciras Bay (South of Spain) using chemometric tools

A study to determine total and mobile heavy metals concentrations in sediments from Algeciras Bay was performed and pollution hotspots were identified. The effects on aquatic organisms were established using sediment quality guidelines (SQGs). Ni and Cr exceeded the effect range medium and low levels, respectively, around industrial area. Potential toxicity of metals was determined by diethylenetriaminepenta-acetic acid (DTPA) extractions and low alert levels of Co, Cu, Zn, Cd, Ni and Pb were exceeded at most sampling sites. Three pollution indicators were used showing significant values for As, Ni, Cr, Pb and Cd. Sediment speciation using the sequential extraction BCR procedure was carried out, being Cd, Zn, Pb and As the most available metals. Principal component, cluster and ANOVA analyses were performed in order to assess the sources of metals and the influence of seasonality and anthropogenic activities on the sediment quality. Two principal component analysis (PCA) factors were obtained identifying the sampling sites affected by anthropogenic activities; Ni-Cr and Zn-Cu-V clusters were also obtained associated with stainless steel and petrochemical industrial activities. ANOVA showed the outstanding sites because of total metal concentration and significant differences among sampling sites by the acid extractable and reducible fractions for all metals except for Ba and V.     

Assessment of heavy metal contamination and its mobilization from municipal solid waste open dumping site

Influence of heavy metals was investigated by conducting various tests on the samples collected from Nonthaburi dumpsite in Thailand. The heavy metal concentration in the solid waste and its mobility potential based on its binding forms was studied. The sequential extraction method was used to determine the binding forms of metals. From the analysis, Zn was found to be highest concentrated heavy metal compared to Mn, Cu, Cr, Cd, Pb, Ni and Hg in the solid waste. From the sequential extraction, Mn, Zn and Cd mostly found in reducible form, showed its susceptibility to be leached easily. Cu and Cr were found predominantly in oxidizable form and stable under anaerobic condition. Pb and Ni were present in residual form, which is inert. The estimated individual contamination factor (C(f)(i)), showed Zn with highest affinity to leach. The concentration level of all the heavy metals in the leachate except for Cr was noticed to be below the National effluent standards. Though, indicated to be safe for disposal, its effect in any concentration proved toxic to the plant life from the seed germination toxicity test using synthetic chelate ethylene diamine tetraacetic acid (EDTA).     

Heavy metals in urban soils with various types of land use in Beijing, China

Heavy metal concentrations of Cd, Cr, Cu, Ni, Pb and Zn were investigated for 127 urban soil samples collected from business area (BA), classical garden (CG), culture and education area (CEA), public green space (PGS), residential area (RA) and roadside area (RSA) in Beijing. The distribution of Cd, Cu, Pb and Zn was mainly affected by anthropogenic sources, with their mean concentrations much higher than the background values of Beijing, while Cr and Ni were from natural sources. Among the 6 types of land use, the concentrations of Cd, Cu, Pb and Zn in CG were significantly higher than those in the other 5 types of land use (p<0.05), which were due to their historical use such as pigments, wood preservation and brassware. For the other 5 types of land use except CG, the mean concentration of Cd in RSA was significantly higher than those in BA, CEA, PGS and RA (p<0.05), suggesting Cd was mainly from traffic sources. The distribution maps revealed that the concentrations of Cu, Pb and Zn showed decreasing trends from the center to the suburb of Beijing, they increased with the age of the urban area.     

Removal of metals from landfill leachate by sorption to activated carbon, bone meal and iron fines

Sorption filters based on granular activated carbon, bone meal and iron fines were tested for their efficiency of removing metals from landfill leachate. Removal of Al, As, Ca, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Mo, Ni, Pb, Sr and Zn were studied in a laboratory scale setup. Activated carbon removed more than 90% of Co, Cr, Cu, Fe, Mn and Ni. Ca, Pb, Sr and Zn were removed but less efficiently. Bone meal removed over 80% of Cr, Fe, Hg, Mn and Sr and 20-80% of Al, Ca, Cu, Mo, Ni, Pb and Zn. Iron fines removed most metals (As, Ca, Co, Cr, Cu, Fe, Mg, Mn, Pb, Sr and Zn) to some extent but less efficiently. All materials released unwanted substances (metals, TOC or nutrients), highlighting the need to study the uptake and release of a large number of compounds, not only the target metals. To remove a wide range of metals using these materials two or more filter materials may need to be combined. Sorption mechanisms for all materials include ion exchange, sorption and precipitation. For iron fines oxidation of Fe(0) seems to be important for metal immobilisation.     

Assessment of metal contamination in dregded sediments using fractionation and Self-Organizing Maps

Although total metal content is frequently the initial approach for measuring pollution, no information is provided about mobility and environmental risk. In this paper, a metal fractionation (sequential extraction) technique and artificial neural networks (Self-Organizing Maps, SOMs) have been used jointly to evaluate the pollution level of the sediments dredged from the dry dock of a former shipyard in the Bilbao estuary (Bizkaia, Spain). The load pollution index (LPI) for the upper, middle and bottom layers of the sediments was 7.65, 8.22 and 10.01, respectively, for six metals (Cu, Mn, Ni, Cr, Pb and Zn). This showed that upper sediments were less polluted than the lower ones. Consequently, a reduction in the pollution level of metal discharged into the river in recent years was confirmed. According to fractionation results, the most mobile minor elements were Cu, Pb and Zn, as they are mainly associated with the non-residual fractions. The statistical approach of Self-Organizing Maps (SOMs) revealed that Ni, Pb and Zn amounts in the residual fraction followed the same pattern associated with simultaneous discharges of slags into the river. However, other hazardous discharge sources are responsible for the high accumulation of those metals in the non-residual fractions.     

Removal of Cu, Pb and Zn in an applied electric field in calcareous and non-calcareous soils

The pH dependency of the removal of Cu, Zn and Pb by electrodialytic soil remediation from different industrially polluted soils was examined. From 18 experiments performed with five different soils, it was found that the order of mobilization due to a pH decrease was Zn>Cu>Pb. It was found, too, that each of the elements was removed at higher soil pH in calcareous soils (about 12% carbonates) than in soils with a carbonate content of less than 3.7%. In soils rich in carbonates, precipitation of heavy metal carbonates is an important retention mechanism and the heavy metal carbonates are dissolved at higher pH values than the pH at which heavy metals are desorbed in non-calcareous soils. Thus, the relation between the soil pH and the mobility of the heavy metal in the electric field is not only dependent on the heavy metal in focus, but also on the fraction of the heavy metal precipitated as carbonates.     

Potential use of treated wastewater and sludge in the agricultural sector of the Gaza Strip

Twelve elements (Ag, Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) were analyzed in 120 composite samples of influent and effluent wastewater; the results revealed that domestic wastewater influent contains considerable amounts of heavy metals and the partially functional treatment plants of Gaza are able to remove 40–70% of most metals during the treatment process. Heavy metals in 31 industrial wastewater effluents are within the ranges of international standards. All industries of Gaza are light; although they have no treatment facilities, their effluents are being discharged to municipal sewerage system and the existing treatment plants are capable of absorbing the industrial effluents with no significant impact on treatment bioprocesses.Thirty parameters were determined in 35 sludge samples: P, AOX, C, S, CaCO₃, Mg, Ca, Na, K, Li, Cu, Zn, Ni, Pb, Mn, Fe, Cr, Co, Cd, As, Hg, Ti, Se, Br, Rb, Th, Sr, Y, U, and Zr. Although there are no treatment facilities for sludge within the treatment plants, the results indicated that sludge in general is clean of heavy metals. Only Zinc and AOX showed anomalous concentrations; more than 85% of sludge samples showed that averages of zinc and AOX are 2,000 mg/kg and 550 mg Cl/kg, respectively, which exceed the standards of all industrial countries for sludge to be used in land application.     

Stabilization of an elevated heavy metal contaminated site

Heavy metal contamination is a common problem that is encountered at many uncontrolled sites. Immobilization is seen as a promising technology for heavy metal remediation. Here, we report a remediation case study of an elevated and multi-metal contaminated site containing Cd, Cu, Ni, Pb, and Zn. In a laboratory test, when the soil was stabilized with reagent grade stabilizers (CaHPO(4) and CaCO(3)), the toxicity characteristic leaching procedure (TCLP) extractable concentrations of Cd, Cu, Pb, and Zn were reduced by more than 87%. The greatest reduction was shown with Pb (99.8%). In the field, Ca(H(2)PO(4))(2) due to lower cost and higher solubility replaced CaHPO(4). The TCLP results of the field treatment showed that the extractable concentrations of Cd, Cu, Pb, and Zn were significantly reduced after 30 days of stabilization. The reduction ratios were 98% (Cd), 97% (Cu), 99% (Pb), and 96% (Zn). Although, the reduction ratio of Ni was only 65%, the average extractable concentration was still less than 4.0mg/l. The percent reduction can, therefore, be considered reasonable. The significant reduction of extractable metal concentrations showed that the stabilizers, a combination of Ca(H(2)PO(4))(2) and CaCO(3), successfully immobilized heavy metals on the site.