Application of sequential leaching, risk indices and multivariate statistics to evaluate heavy metal contamination of estuarine sediments: Dhamara Estuary, East Coast of India

In the present study, concentration of some selected trace metals (Fe, Mn, Ni, Co, Pb, Zn, Cu, Cr and Cd) are measured in Brahmani, Baitarani river complex along with Dhamara estuary and its near shore. Chemical partitioning has been made to establish association of metals into different geochemical phases. The exchangeable fraction is having high environmental risk among non-lithogeneous phases due to greater potential for mobility into pore water. The metals with highest bio-availability being Cd, Zn and Cr. The metals like Mn, Zn, Cd and Cu represent an appreciable portion in carbonate phase. Fe–Mn oxides act as efficient scavenger for most of the metals playing a prime role in controlling their fate and transport. Among non-lithogeneous phases apart from reducible, Cr showed a significant enrichment in organic phase. Risk assessment code values indicate that all metals except Fe fall under medium-risk zone. In estuarine zone Cd, Zn, Pb and Cr are released to 32.43, 26.10, 21.81 and 20 %, respectively, indicating their significant bio-availability pose high ecological risk. A quantitative approach has been made through the use of different risk indices like enrichment factor, geo-accumulation index and pollution load index. Factor analysis indicates that in riverine zone, Fe–Mn oxides/hydroxides seem to play an important role in scavenging metals, in estuarine zone, organic precipitation and adsorption to the fine silt and clay particles while in coastal zone, co-precipitation with Fe could be the mechanism for the same. Canonical discriminant function indicates that it is highly successful in discriminating the groups as predicted.     

Chemical fractionation of heavy metals in urban soils of Guangzhou, China

Knowledge of the total concentration of heavy metals is not enough to fully assess the environmental impact of urban soils. For this reason, the determination of metal speciation is important to evaluate their environment and the mobilization capacity. Sequential extraction technique proposed by the former European Community Bureau of Reference (BCR) was used to speciate Cd, Cu, Fe, Mn, Ni, Pb, and Zn in urban soils from Guangzhou into four operationally defined fractions: HOAc extractable, reducible, oxidizable, and residual. The Cu, Fe, Ni, and Zn were predominately located in the residual fraction, Pb in the reducible fraction, and Cd and Mn within the HOAc extractable fraction. The order of Cd in each fraction was generally HOAc extractable > reducible > residual > oxidizable; Cu and Fe were residual > reducible > oxidizable > HOAc extractable; Mn was HOAc extractable > residual > reducible > oxidizable; Ni and Zn were residual > reducible > HOAc extractable > oxidizable; and Pb was reducible > residual > oxidizable > HOAc extractable. Cadmium was identified as being the most mobile of the elements, followed by Mn, Zn, Ni, Cu, Pb and Fe. Iron–Mn oxides can play an important role in binding Cd, Cu, Ni, Pb, and Zn and in decreasing their proportion associated with the residual fraction in the soils. With total concentrations of Cd, Cu, Ni, Pb, Zn, and Mn increase, these metals more easily release and may produce more negative effects on the urban environment.     

Geochemical fractionation of trace elements in sediments of Hugli River (Ganges) and Sundarban wetland (West Bengal, India)

A sequential extraction procedure was carried out to determinate the concentrations of 11 elements (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Zn) in different geochemical phases of sediments collected along the Hugli (Ganges) River Estuary and in the Sundarban mangrove wetland, eastern coastal part of India. The chemical speciation of elements was determined using the three-step sequential extraction procedure described by the European Community Bureau of Reference. Total metal concentration was determined using a microwave-assisted acid digestion procedure. Metal concentrations were near the background level except for As for which a moderate pollution can be hypothesized. The mobility order of the metals was: Cd?>?Mn?>?Cu?>?Zn?>?As?>?Co?>?Pb?>?Ni?>?Fe?>?Cr?>?Al. The highest percentage of Cd (>60%) was found in the most labile phase. Residual fraction was prevailing for Fe, Cr and Al, while Pb was mainly associated with the reducible fraction. Data were compared with Sediment Quality Guidelines to estimate the relationship between element concentrations and adverse biological effects on benthic community, finding the possibility of some toxic effects due to the presence of As in the entire studied area and Cd, only in Calcutta.     

Speciation and ecological risk of heavy metals in intertidal sediments of Quanzhou Bay, China

The chemical speciation of nine heavy metals in intertidal sediments from Quanzhou Bay was determined using a modified sequential extraction procedure, proposed by the Commission of the European Community Bureau of Reference. The results show that Mn presents the highest percentage in the acid-soluble fraction, and Pb and Cu present the highest percentages in the reducible fraction. The highest percentages of Fe, V, Cr, Ni, Zn, and Co were found in the residual fraction. The mobility order of the heavy metals studied on the basis of the nonresidual content of the elements is Mn > Pb > Cu > Co > Zn > Ni > Cr > V > Fe. The assessment on potential ecological risk indices of some heavy metals indicates that Zn, Ni, and Cr show moderate contamination, while Cu and Pb show slighter contamination. On the whole, the comprehensive potential ecological risk index of Cu, Zn, Ni, Cr, and Pb in the sediments presents moderate degree.     

Pollution in the urban soils of Lianyungang,China, evaluated using a pollution index,mobility of heavy metals,and enzymatic activities

Soil samples from 16 urban sites in Lianyungang, China were collected and analyzed. A pollution index was used to assess the potential ecological risk of heavy metals and a sequential extraction procedure was used to evaluate the relative distribution of Cu, Zn, Pb, Cd, Cr, and As in exchangeable, carbonate, Fe/Mn oxide, organic/sulfide, and residual fractions. The mobility of heavy metals and urease (URE) activity, alkaline phosphatase (ALP) activity, and invertase (INV) activity of soils was determined. The results showed that the average concentrations of Cu, Zn, Pb, Cd, Cr, and As in Lianyungang soils were much higher than those in the coastal city soil background values of Jiangsu and China. Among the five studied regions (utilities, commercial, industrial, tourism, and roadside), the industrial region had the highest metal concentrations demonstrating that land use had a significant impact on the accumulation of heavy metals in Lianyungang soils. Compared to the other metals, Cd showed the highest ecological risk. According to chemical partitioning, Cu was associated with the organic/sulfides and Pb and Zn were mainly in the carbonate and the Fe/Mn oxide phase. The greatest amounts of Cd were found in exchangeable and carbonate fractions, while Cr and As were mainly in the residual fraction. Cd had the highest mobility of all metals, and the order of mobility (highest to lowest) of heavy metals in Lianyungang soils was Cd > Zn > Pb > Cu > As > Cr. Soil urease activity, alkaline phosphatase activity, and invertase activity varied considerably in different pollution degree sites. Soil enzyme activities had the lowest levels in roadside and industrial regions. Across all the soil data in the five regions, the total Cu, Zn, Pb, Cd, Cr, and As level was negatively correlated with urease activity, alkaline phosphatase activity, and invertase activity, but the relationship was not significant. In the industrial region, alkaline phosphatase activity had significant negative correlations with total Cu, Pb, Cr, Zn, Cd, and heavy metal fractions. This showed that alkaline phosphatase activity was sensitive to heavy metals in heavily contaminated regions, whereas urease and invertase were less affected. The combination of the various methods may offer a powerful analytical technique in the study of heavy metal pollution in street soil.     

Speciation of metals in bed sediments and water of Qaraaoun Reservoir, Lebanon

Determination of only total element in sediments does not give an accurate estimate of the likely environmental impacts. Speciation study of metals in sediment provides information on the potential availability of metals (toxic) to biota under various environmental conditions. In water, the toxic metal specie is the free hydrated metal ion. The toxicity of metals depends especially on their chemical forms rather than their total metal content. The present study focuses on Qaraaoun Reservoir, Lebanon. Earlier studies focused only on total metal concentrations in sediment and water. The objective of this study was to determine metal speciation (Fe, Cr, Ni, Zn, Cu, Pb, Cd) in the (operationally defined) sediment chemical fractions and metal speciation in reservoir water. This would reflect on metal bioavailability and toxicity. Water samples and bed sediments were collected from nine sites during the dry season and a sequential chemical fraction scheme was applied to the <75-??m sieve sediment fraction. Metal content in each fraction was determined by the FAAS technique. The data showed that the highest percentages of total metal content in sediment fractions were for: Fe in residual followed by reducible, Cr and Ni in residual and in reducible, Cu in organic followed by exchangeable, Zn in residual and in organic, Pb in organic and carbonate, Cd was mainly in carbonate. Total metal content in water was determined by ICP-MS technique and aqueous metal speciation was predicted using AQUACHEM software interfaced to PHREEQC geochemical computer model. The water speciation data predicted that a high percentage of Pb and Ni were present as carbonate complex species and low percentages as free hydrated ions, highest percentage of Zn as carbonate complex species followed by free hydrated ion, highest percentage of Cd as free hydrated ion followed by carbonate complex species. The sensitivity attempt of free hydrated ion of Ni, Zn, Pb, and Cd in reservoir water revealed dependence of Zn and Cd on pH and alkalinity, while Ni and Pb were only dependent on pH.     

Vertical distribution of heavy metals in soil profile in a seasonally waterlogging agriculture field in Eastern Ganges Basin

The accumulation of heavy metals in soil and water is a serious concern due to their persistence and toxicity. This study investigated the vertical distribution of heavy metals, possible sources and their relation with soil texture in a soil profile from seasonally waterlogged agriculture fields of Eastern Ganges basin. Fifteen samples were collected at ～0.90-m interval during drilling of 13.11 mbgl and analysed for physical parameters (moisture content and grain size parameters: sand, silt, clay ratio) and heavy metals (Fe, Mn, Cr, Cu, Pb, Zn, Co, Ni and Cd). The average metal content was in the decreasing order of Fe?>?Mn?>?Cr?>?Zn?>?Ni?>?Cu?>?Co?>?Pb?>?Cd. Vertical distribution of Fe, Mn, Zn and Ni shows more or less similar trends, and clay zone records high concentration of heavy metals. The enrichment of heavy metals in clay zone with alkaline pH strongly implies that the heavy metal distributions in the study site are effectively regulated by soil texture and reductive dissolution of Fe and Mn oxy-hydroxides. Correlation coefficient analysis indicates that most of the metals correlate with Fe, Mn and soil texture (clay and silt). Soil quality assessment was carried out using geoaccumulation index (I _geo), enrichment factor (EF) and contamination factor (CF). The enrichment factor values were ranged between 0.66 (Mn) and 2.34 (Co) for the studied metals, and the contamination factor values varied between 0.79 (Mn) and 2.55 (Co). Results suggest that the elements such as Cu and Co are categorized as moderate to moderately severe contamination, which are further confirmed by I _geo values (0.69 for Cu and 0.78 for Co). The concentration of Ni exceeded the effects-range median values, and the biological adverse effect of this metal is 87 %. The average concentration of heavy metals was compared with published data such as concentration of heavy metals in Ganga River sediments, Ganga Delta sediments and upper continental crust (UCC), which apparently revealed that heavy metals such as Fe, Mn, Cr, Pb, Zn and Cd are influenced by the dynamic nature of flood plain deposits. Agricultural practice and domestic sewage are also influenced on the heavy metal content in the study area.     

Comparison of three sequential extraction procedures for partitioning of heavy metals in car park dusts

The aim of this study was to elucidate the amount of metal released at each step by using different extractants in three sequential extraction schemes for the partitioning of metal contents of car park deposited dust samples. For this purpose, three different sequential extraction procedures (SEP) were employed for the metal fractionation in car park dust samples collected from the campus of Erciyes University, Kayseri, Turkey. While two of the sequential extraction procedures contain five steps the other, namely the BCR sequential extraction scheme, has three steps. The first two methods fractionate metals to be exchangeable, bound to carbonates, bound to Mn oxides, bound to Fe oxides and bound to organic matter, and the BCR protocol fractionates the metals as acid soluble and exchangeable, reducible, and oxidisable. Determination of the metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn was performed by flame atomic absorption spectrometry (FAAS). The results obtained by the three methods were compared and showed that the amount of metal released at each step of the leaching procedure depended both on the type of reagents used and the sequence in which they were applied. The most mobile elements were Cd, Pb and Zn which are metals potentially toxic to the environment and are also known to originate from traffic. The calculated enrichment factors for Cd and Pb were substantially high (73.5-187 and 18.4-27.5, respectively) and somewhat lower for Zn (5.1-6.8). These results confirm that they are important metal pollutants for car parks. Detection limits and recoveries were found in the range of 0.01-1.39 microg ml(-1) and 68-126%, respectively, for the metals studied and the three sequential extraction procedures.     

Heavy Metal Levels in Biota and Sediments in the Northern Coast of the Marmara Sea

Concentration of Cd, Co, Cr, Ni, Zn, Fe, Mn, Pb and Cu were determinedin biota and sediment samples collected from the Marmara Sea in Turkey. The levels of Zn, Fe, Mn, Pb and Cu in the macroalgae are higher than previous studies in the Marmara Sea. Moreover, Cu and Zn concentrations at the present study are significantly high than Bosphorus and Black Sea algae. The order heavy metal concentrations in the mussel samples was: Fe > Zn > Ni > Mn > Cu > Pb > Cr > Cd > Co. The metal concentrations are generally lower when compared with the Black Sea mussels except Pb. At the same time, concentrations of Pb, Cu and Zn in the mussel species are lower when compared with the results in the Aegean Sea. The ranges of Mn and Cu in the tested fish samples are higher than Black Sea fish. On the other hand, Cd, Co, Cr, Zn and Pb concentrations are lower. The northern coast of the Marmara Sea having the highest metal concentrations in sediments as follows: Co, Cr, Ni, Fe at ?arköy ; Pb, Cu at M. Ere?li; Cd, Zn, Mn at Menek?e. The heavy metal levels in the sediment samples are lower than other areas in the Marmara Sea.     

Spatial patterns of heavy metals in soil under different geological structures and land uses for assessing metal enrichments

One hundred and thirty composite soil samples were collected from Hamedan county, Iran to characterize the spatial distribution and trace the sources of heavy metals including As, Cd, Co, Cr, Cu, Ni, Pb, V, Zn, and Fe. The multivariate gap statistical analysis was used; for interrelation of spatial patterns of pollution, the disjunctive kriging and geoenrichment factor (EF_G) techniques were applied. Heavy metals and soil properties were grouped using agglomerative hierarchical clustering and gap statistic. Principal component analysis was used for identification of the source of metals in a set of data. Geostatistics was used for the geospatial data processing. Based on the comparison between the original data and background values of the ten metals, the disjunctive kriging and EF_G techniques were used to quantify their geospatial patterns and assess the contamination levels of the heavy metals. The spatial distribution map combined with the statistical analysis showed that the main source of Cr, Co, Ni, Zn, Pb, and V in group A land use (agriculture, rocky, and urban) was geogenic; the origin of As, Cd, and Cu was industrial and agricultural activities (anthropogenic sources). In group B land use (rangeland and orchards), the origin of metals (Cr, Co, Ni, Zn, and V) was mainly controlled by natural factors and As, Cd, Cu, and Pb had been added by organic factors. In group C land use (water), the origin of most heavy metals is natural without anthropogenic sources. The Cd and As pollution was relatively more serious in different land use. The EF_G technique used confirmed the anthropogenic influence of heavy metal pollution. All metals showed concentrations substantially higher than their background values, suggesting anthropogenic pollution.     

Trace metal fractionation in the Pichavaram mangrove–estuarine sediments in southeast India after the tsunami of 2004

The geochemistry of coastal sediments of southern India was altered after the tsunami in 2004. A five-step sequential extraction procedure was applied to assess the effects of tsunami on mobility and redistribution of selected elements (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn). Ten surface sediments and three cores were analyzed for different metal fractions (exchangeable, carbonate, reduced, oxidized, and residual). Total metal concentrations increased in mangrove sediments after the tsunami, but their spatial distribution did not show significant variation (except Mn). The sediments were mixed by the tsunami, and there was lack of variation in metal concentrations in different fractions with depth (except Pb and Mn). High concentrations of Pb and Zn occurred in the oxide fractions, whereas Cu, Cr, Cd, and Ni were high in the organic and sulfide-rich fractions. Metals in the residual fraction (lattice bound) had the highest concentration suggesting their non-availability and limited biological uptake in the system. Most of the metals (except Mn) do not constitute a risk based on the different geochemical indices.     

Levels and speciation of heavy metals in soils of industrial Southern Nigeria

A knowledge of the total content of trace metals is not enoughto fully assess the environmental impact of polluted soils. Forthis reason, the determination of metal species in solution isimportant to evaluate their behaviour in the environment andtheir mobilization capacity. Sequential extraction procedure wasused to speciate five heavy metals (Cd, Pb, Cu, Ni and Zn) fromfour contaminated soils of Southern Nigeria into sixoperationally defined geochemical species: water soluble,enchangeable, carbonates, Fe-Mn oxide, organic and residual.Metal recoveries were within ± 10% of the independentlydetermined total Cd, Pb, Cu, Ni and Zn concentrations. The highest amount of Cd (avg. 30%) in the nonresidual fractionswas found in the exchangeable fraction, while Cu and Zn weresignificantly associated with the organic fraction. Thecarbonate fraction contained on average 14, 18.6, 12.6, 13 and11% and the residual fraction contained on average 47, 18, 33,50 and 25% of Cd, Pb, Cu, Ni and Zn respectively. Assuming thatmobility and bioavailability of these metals are related to thesolubility of the geochemical form of the metals, and that theydecrease in the order of extraction sequence, the apparentmobility and potential bioavailability for these five metals inthe soil were: Pb > Zn > Cu > Ni > Cd. The mobility indexes ofcopper and nickel correlated positively and significantly withthe total content of metals, while mobility indexes of cadmiumand zinc correlated negatively and significantly with the totalcontent of metals.     

Heavy metals in Yeniçağa Lake and its potential sources: soil,water, sediment,and plankton

The distribution and accumulation of heavy metals (Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Mo, Cd, Sn, Ba, Pb) in the water, sediments, plankton of Yeniça?a Lake, and its potential sources (creeks, sewage, artesian well, soil) were investigated during 1-year study period as monthly or seasonally. Element analyses were performed by ICP–MS. Results showed that the trace and toxic elements (Al, As, Mn, Pb, Fe) concentration in lake water and/or its feeding sources were above the recommended water standards (WHO, EC, EPA, TS-266). It was found that the maximum accumulation of the heavy metals iron, aluminum, manganese, zinc, and barium in the sediment of Yeniça?a Lake. The accumulation order of trace metals were Fe > Al > Mn > Zn > Ba > Ni > Cr > As > Cu > Pb > Co > Mo > Sn > Cd in the lake, creeks sediment, and soil samples. The similar results suggest that the accumulation of heavy metals in the sediment is a natural process. Metals accumulated in the lake are naturally mixed from the soil. However, the presence of heavy metals in the analysis of artesian well water and sewage reveals that the transportation occurs also from the groundwater to the lake. The results obtained in plankton in Yeniça?a Lake showed that aluminum, iron, manganese, zinc, and barium were most accumulated elements in the plankton. The lower averages of lead prevalent in the water and sediment during some months were seen to have a significant mean accumulation in the plankton.     

Associations of cadmium, zinc, and lead in soils from a lead and zinc mining area as studied by single and sequential extractions

An exploratory study of the area surrounding a historical Pb?CZn mining and smelting area in Zawar, India, detected significant contamination of the terrestrial environment by heavy metals. Soils (n?=?87) were analyzed for pH, EC, total organic matter (TOM), Pb, Zn, Mn, and Cd levels. The statistical analysis indicated that the frequency distribution of the analyzed parameters for these soils was not normal. The median concentrations of metals in surface soils were: Pb 420.21 ?? g/g, Zn 870.25 ?? g/g, Mn 696.70 ?? g/g, and Cd 2.09 ?? g/g. Zn concentrations were significantly correlated with Cd (r?=?0.867), indicating that levels of Cd are dependent on Zn. However, pH, electrical conductivity and total organic matter were not correlated significantly with Cd, Pb, Zn, and Mn. To assess the potential mobility of Cd, Pb, and Zn in soils, single (EDTA) as well as sequential extraction scheme (modified BCR) were applied to representative (n?=?23) soil samples. The amount of Cd, Pb, and Zn extracted by EDTA and their total concentrations showed linear positive correlation, which are statistically significant (r values for Cd, Pb, and Zn being 0.901, 0.971, and 0.795, respectively, and P values being <0.001). The correlation coefficients indicate a strong relation between EDTA-extractable metal and total metal. These results appear to justify the use of ??total?? metal contents as a useful preliminary indicator of areas where the risks of metal excess or deficiency are high. The EDTA extractability was maximum for Cd followed by Pb and Zn in soils from all the locations. As indicated by single extraction, the apparent mobility and potential bioavailability of metals in soils followed the order: Cd ?? Pb >?> Zn. Soil samples were sequentially extracted (modified BCR) so that solid pools of Cd, Zn, and Pb could be partitioned into four operationally defined fractions viz. acid-soluble, reducible, oxidizable, and residual. Cadmium was present appreciably (39.41%) in the acid-soluble fraction and zinc was predominantly associated (32.42%) with residual fraction. Pb (66.86%) and Zn (30.44%) were present mainly in the reducible fraction. Assuming that the mobility and bioavailability are related to solubility of geochemical forms of metals and decrease in the order of extraction, the apparent mobility and potential metal bioavailability for these contaminated soil samples is Cd > Zn > Pb.     

Monitoring of total and bioavailable heavy metals concentration in agricultural soils

The aim of this paper is to evaluate total and bioavailable concentration of heavy metals in agricultural soils in order to estimate their distribution, to identify the possible correlations among toxic elements and the pollution sources, to distinguish the samples in relation to sampling site or to sampling depth, and to evaluate the available fraction providing information about the risky for plants. In particular, we reinvestigated total concentrations of As, Be, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, V, and Zn and available concentrations of As, Be, Cd, Cr, Cu, Hg, Ni, Pb, Sb, and Zn in soil from Apulia (Southern Italy). Analytical results showed that total concentrations, for all soils, are in the range permitted by regulations in force in Italy, but some soils evidence slight enrichment of Cd, Cr, Cu, Pb, and Zn. All the heavy metals in the available fraction were below the detection limits of the analytical techniques used except Cu, Ni, Pb, and Zn.     

Inventory compilation and distribution of heavy metals in wastewater from small-scale industrial areas of Delhi, India

Delhi has the highest cluster of small-scale industries (SSI) in India. There are generally less stringent rules for the treatment of waste in SSI due to less waste generation within each individual industry. This results in SSI disposing of their wastewater untreated into drains and subsequently into the river Yamuna, which is a major source of potable water in Delhi, thus posing a potential health and environmental risk to the people living in Delhi and downstream. To study the quantity, quality and distribution of heavy metals in liquid waste from industrial areas, wastewater, suspended materials and bed sediments were collected from industrial areas and from the river Yamuna in Delhi. This study has also focused on the efficiency of production processes in small-scale industries in India. Heavy metals such as Fe, Mn, Cu, Zn, Ni, Cr, Cd, Co and Pb were detected using a GBC 902 atomic absorption spectrometer. The concentration of heavy metals observed was as follows: Fe 2-212, Mn 0.3-39, Cu 0.2-20, Zn 0.2-5, Ni 0.6-6, Cr 0.2-53, Cd 0.08-0.2, Co 0.013-0.55, Pb 0.3-0.7 mg L(-1) in wastewater; Fe 5842-78 000, Mn 585-10 889, Cu 206-7201, Zn 406-9000, Ni 22-3621, Cr 178-10 533, Co 17-114, Cd 13-141, Pb 67-50 171 mg kg(-1) in suspended material; and Fe 3000-84000, Mn 479-1230, Cu 378-8127, Zn 647-4010, Ni 164-1582, Cr 139-3281, Co 20-54, Cd 37-65, Pb 228-293 mg kg(-1) in bed residues. This indicates that SSI could be one of the point sources of metals pollution in the river system.     

An assessment of heavy metal contamination in soils of fresh water aquifer system and evaluation of eco-toxicity by lithogenic implications

The chemistry of heavy metals in sediments with respect to bio-availability and chemical reactivity is regulated by pH, texture, and organic matter contents of the sediments and specific binding form and coupled reactivity of the metals within. To focus on the metal distribution (Fe, Mn, Pb, Cd, Zn, Co, Cu, and Cr) and behavior in a fresh water aquifer system along with the ecological toxicity parameters, a four-step sequential extraction method was applied on 18 Eastern Ghats’ type sediments from fluorosis-hit Nayagarh district, India. Geo-accumulation index of metals in the sediments indicates that they are practically uncontaminated and/or less contaminated with and Fe, Mn, and Cu; contaminated to moderately contaminated with Pb, Zn, and Cr; and strongly contaminated with Cd. Rather, more than 80 % recovered Cd metal concentration in sediments constitute the labile fractions. Temporal clustering of metal fractions indicates transition metal fraction distribution claiming the sediment pH regulation. Similarly, base metal distribution accounts for organic carbon and soil conductivity due to their greater availability in exchangeable and sulfide fractions. Correlation analysis and factor analysis scores demonstrate lack of inter-relationship between transition group and base metal fractions. High fluoride concentration in ground water is associated with high sodium-bicarbonate-iron affinity with elevated pH values (i.e., >7.0) and high positive factor score with the total iron concentration in ground water.     

Distribution and solid-phase speciation of toxic heavy metals of bed sediments of Bharali tributary of Brahmaputra River

Heavy metal (Fe, Mn, Zn, Cu, Ni, Pb, and Cd) concentrations and their chemical speciations were investigated for the first time in bed sediments of Bharali River, a major tributary of the Brahmaputra River of the Eastern Himalayas. Levels of Fe, Mn, Pb, and Cd in the bed sediments were much below the average Indian rivers; however, Cu and Zn exhibit levels on the higher side. Enrichment factors (EF) of all metals was greater than 1 and a higher trend of EF was seen in the abandoned channel for most metals. Pb showed maximum EF of 32 at site near an urban center. The geoaccumulation indices indicate that Bharali river is moderately polluted. The metals speciations, done by a sequential extraction regime, show that Cd, Cu, and Pb exhibit considerable presence in the exchangeable and carbonate fraction, thereby showing higher mobility and bioavailability. On the other hand, Ni, Mn, and Fe exhibit greater presence in the residual fraction and Zn was dominant in the Fe?CMn oxide phase. Inter-species correlations at three sites did not show similar trends for metal pairs indicating potential variations in the contributing sources.     

Fractionation of eleven elements by chemical bonding from airborne particulate matter collected in an industrial city in Argentina

A four-step chemical sequential extraction procedure was used to evaluate the distribution of Al, As, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn in airborne particulate matter collected on glass fibre filters using a high-volume sampler. Two sets of samples were collected in 2001 (winter and summer campaigns) in representative zones of an industrial city of Argentina. The leaching scheme was applied to PM-10 particles and consisted in extracting the elements in four fractions, namely soluble and exchangeable elements; carbonates, oxides and reducible elements; bound to organic matter and sulfidic metals; and residual elements. Metals and metalloids at microg g(-1) level were determined in each fraction by inductively coupled plasma optical emission spectrometry (ICP OES). Analyte concentration varied from 14 microg g(-1) (equivalent to 1.0 ng m(-3)) for As to 11.8 mg g(-1) (equivalent to 2,089 ng m(-3)) for Al. Seven elements, namely Al, Cr, Fe, Mn, Pb, Ti and Zn showed similar distributions in both seasons while As was distributed in a significantly different manner in each season. The results exhibited low As contents in the first and second fractions that could be associated with routine coal combustion and a high content in the third and fourth fractions of the summer samples that could be linked to the use of pesticides. Aluminium, As, Cu, Mn, Ni, Ti, V and Zn were found in different percentages in the more bioavailable aqueous fraction with As, Mn, V and Zn exhibiting solubilities greater than 1% while Cr and Pb being insoluble. The content of Al, Cr, Cu, Fe, Ni, Pb, and Zn in the residual fraction was, in average, higher than 50%. A comparative assessment of the use of the underlying information available from fractionation studies compared to that obtained from total element content was done for Fe and Mn. It showed that the results obtained using chemical sequential extraction procedures allowed further discrimination of the potential air pollution sources.     

Fractionation and ecological risk of metals in urban river sediments in Zhongshan City, Pearl River Delta

Surface sediments collected from nine urban rivers located in Zhongshan City, Pearl River Delta, were analyzed for total concentration of metals with digestion and chemical fractionation adopting the modified European Community Bureau of Reference (BCR) sequential extraction procedure. The results showed that concentration and fractionation of metals varied significantly among the rivers. The total concentration of eight metals in most rivers did not exceed the China Environmental Quality Standard for Soil, Grade III. The potential ecological risk of metals to rivers were related to the land use patterns, in the order of manufacturing areas > residential areas > agriculture areas. The concentration of Pb in the reducible fraction was relatively high (60.0-84.3%). The dominant proportions of Cd, Zn and Cu were primary in the non-residual fraction (67.0%, 71.8% and 81.4% on average respectively), while the percentages of the residual fractions of Cr and Ni varied over a wide range (43-85% and 24-71% respectively). The approaches of the H?kanson ecological risk index and Secondary Phase Enrichment Factor were applied for ecological risk assessment and metal enrichment calculation. The results indicated Hg and Cd had posed high potential ecological risk to urban rivers in this region. Meanwhile, there was widespread pollution and high enrichment of Cu in river sediments in this region. Multiple regression analysis showed that five water quality parameters (pH, DO, COD(Mn), NH(4)(+)-N, TP) had little influence on the distribution of metal fractionation. This result revealed that the ecological risk of metals was not eliminated along with the improvement in water quality. Correlation studies showed that among the metals, Group A (Cd, As, Pb, Zn Hg, r = 0.730-0.924) and Group B (Cr, Cu, Ni, r = 0.815-0.948) were obtained, and the metal contaminations were from industrial activities rather than residential.