Spatio-temporal dynamics of heavy metals in sediments of the river estuarine system: Mahanadi basin (India)

Dynamics of heavy metals in the surface sediments of Mahanadi river estuarine system were studied for three different seasons. This study demonstrates that the relative abundance of these metals follows in the order of Fe > Mn > Zn > Pb > Cr > Ni ≥ Co > Cu > Cd. The spatial pattern of heavy metals supported by enrichment ratio data, suggests their anthropogenic sources possibly from various industrial wastes and municipal wastes as well as agricultural runoff. The metal concentrations in estuarine sediments are relatively higher than in the river due to adsorption/accumulation of metals on sediments during saline mixing, while there is a decreasing trend of heavy metal concentrations towards the marine side. The temporal variations for metals, such as Fe, Mn, Zn, Ni and Pb exhibit higher values during monsoon season, which are related to agricultural runoff. Higher elemental concentrations are observed during pre-monsoon season for these above metals (except Ni) at the polluted stations and for metals, such as Cr, Co and Cd at all sites, which demonstrate the intensity of anthropogenic contribution. R-mode factor analysis reveals that “Fe–Mn oxy hydroxide”, “organic matter”, “CaCO₃”, and “textural variables” factors are the major controlling geochemical factors for the enrichment of heavy metals in river estuarine sediment and their seasonal variations, though their intensities were different for different seasons. The relationships among the stations are highlighted by cluster analysis, represented in dendrograms to categorize different contributing sites for the enrichment of heavy metals in the river estuarine system.     

Heavy metals in nearshore sediments of Kalpakkam,southeast coast of India

Kalpakkam, a tiny fishing hamlet dotting the east coast, halfway between Chennai and Pondicherry has become prominent due to the Madras Atomic Power Station. The present study aims at assessing the spatial and temporal distribution pattern of heavy metals (Cd, Pb, Zn, Cu, Ni, Cr, and Fe) from 12 stations along the inner shelf of Bay of Bengal, India, during pre-monsoon (PRM), monsoon, and post-monsoon (POM) seasons. The order of occurrence of the metals in sediments of Kalpakkam is Cr > Zn > Ni > Cu > Pb > Cd (excluding Fe since unit is in %) and exhibits a unique seasonal pattern with the highest values (average) during POM except for Cd which shows highest (average) concentration during PRM. In order to determine the sample association according to their geochemical composition and their granulometric characteristics, a correlation matrix was generated and sediment pollution indices viz., sediment enrichment factor and geoaccumulation index were computed. The results confirm anthropogenic input of Cd to nearshore sediments of Kalpakkam. Sources of Cd can be attributed to dredging activities at Edaiyur, direct dumping and sewage sludge from anthropogenic activities, which reach the study area through the Buckingham Canal opening at the backwaters—Sadras and Edaiyur, and extreme use of antifouling paints by fishing trawlers.     

Identification and regional quantification of hydrochemical processes at the contact zone between anoxic groundwater and surface water in poldered floodplains (Oderbruch polder,Germany)

The hydrochemistry in the largest polder of the Oder River, named Oderbruch, is affected by long-term infiltration of water from the Oder into the aquifer below an alluvial loamy top layer of the polder. These exceptional hydraulic conditions are a result of dyke constructions which were built more than 250 a ago. The objective of this investigation is a better understanding and a characterisation of the contact zone between the anaerobic groundwater and the surface water of a vast drainage system. Induced by changing water levels, different hydraulic conditions occur, which strongly influence the hydrochemistry of the shallow aquifer and therefore the natural sink function of the polder area.Field investigations with a hydrochemical and hydraulic characterisation of selected drainage ditch locations show considerable chemical interactions between groundwater and surface water. Depending on the drainage ditch type, which is defined by the hydraulic situation, the redox processes create a chemical gradient combined with a distinct enrichment of Fe and Mn. The source of the high amounts of Fe and Mn in the groundwater are reduced Fe- and Mn-hydroxides from the aquifer sediments.Under exfiltrating conditions interrupted by dry phases, more than 50 g kg⁻¹ Fe and 0.25 g kg⁻¹ Mn have accumulated in the drainage ditch floor sediments since the construction of the drainage ditches 35 a ago. The results show a very effective fixation of trace metals in the drainage ditch sediments under these conditions. Under permanent exfiltration conditions, the enrichment of Fe and Mn is relatively low. The maximum Fe content was 4 g kg⁻¹ sediment and the Mn content reached only 0.4 g kg⁻¹. This is less than 10% of the mobile Fe²⁺ and less than 1% of the Mn²⁺ which migrates from the aquifer into the surface water.     

Assessment of heavy metal contamination status in sediments and identification of pollution source in Daye Lake,Central China

This research presents a detailed study which was performed to infer the quantity of metal (Cd, Cr, Pb, Zn, Cu and Fe) contents in sediments of Daye Lake, Central China. The geo-accumulation (I _geo) and potential ecological risk (PER) of these metals were assessed. The results reveal that: (1) the mean value of I _geo ranked an order of Fe (class 6) > Cd (class 5) > Pb (class 3) > Zn (class 2) > Cr (Class 1) > Cu (Class 0); (2) Potential ecological risk (PER) values calculated for all these metals at different sampled points in Daye Lake exceeded the value of very high risk. Multivariate statistical analyses were carried out to determine the relationship between these six metals and to identify the possible pollution sources, with the results suggesting that the metal content in the sediments has three patterns: the first pattern includes Pb, Cd and Cr which were mainly present due to discharged water by smelting industries; second pattern contains Zn and Cu which mainly originated from the waste residue of the copper mining industry; the third pattern is Fe which is mainly related to mine tailing leaches. This study indicates very high metal content levels in the sediments, which may have adverse risks (average PER = 7,771.62) for the lake’s ecosystem and human beings associated with Daye Lake.     

Potential ecological risk assessment,enrichment, geoaccumulation,and source identification of metals in the surface sediments of Choghakhor Wetland,Iran

This study reported the first comprehensive research on identification of metal concentrations (Fe, Mg, Mn, Pb, Cd, Cr) in order to provide baseline data for future studies, identify possible sources, determine degree of pollution, and identify potential ecological risks of metals in surface sediments from Iran’s Choghakhor Wetland. The order of metal concentration was as follows: Fe > Mg > Mn > Pb > Cd > Cr, with mean concentrations of 6140.35, 1647.32, 289.03, 1.10, and 0.45 µg/g of dry weight, respectively. These results reveal that Choghakhor Wetland is not heavily polluted compared to other regions. The results of enrichment factor (EF) and geoaccumulation index (I _geo) showed that Fe, Pb, Mg, Cr, and Mn presented low levels of contamination and probably originated from natural sources. On the other hand, the results of EF and I _geo indices suggested that Cd concentrations in sediments of Choghakhor Wetland originated from anthropogenic sources. Based on the results of three sets of sediment quality guidelines, only Cd concentration in sediments of Choghakhor Wetland is a threat for aquatic organisms of Choghakhor Wetland. The results of multivariate analysis such as principal component analysis and cluster analysis showed that Fe–Mn, Cr–Mg, and Pb groups originated from natural sources, while Cd concentrations in sediments of Choghakhor Wetland originated from both natural and anthropogenic sources (mainly chemical fertilizers). To our knowledge, this is the first study about metal concentrations in sediments of Choghakhor Wetland, and because of low levels of these metals, these concentrations can be considered background levels for future investigation.     

High-resolution profiles of trace metals assessed by DGT techniques in lake sediment porewaters

The technique of diffusive gradients in thin films (DGT) was applied to obtain high-resolution vertical profiles of trace metals in sediment porewater of a eutrophic lake, Lake Chaohu. All sampling sediments were under anaerobic conditions with Eh values below 0, the redox potential profile in M4 was relatively stable, and higher Eh values in M4 than that in M1 were observed due to hydrodynamic effects. Fe, Mn and As exhibited closely corresponding profiles due to the co-release of Fe and Mn oxides and the reduction of As. Higher Fe and Mn concentrations and lower As concentrations were observed in M1 of the western half-lake than those in M4 of the eastern half-lake due to different sources and metal contamination levels in the two regions. Cu and Zn showed increasing concentrations similar to Mn and Fe at 1–2 cm depth of sediments, while DGT measured Co, Ni, Cd and Pb concentrations decreased down to 3–4 cm in the profiles. Co, Ni, Cu, Zn, Cd and Pb showed insignificant regional concentration variances in the western and eastern half-lakes. According to the R(C _DGT/C _{centrifugation}) values, the rank order of metal labilities decrease as follows: Fe (>1) > Cu, Pb, Zn (>0.9) > Co, Ni, Cd (>0.3) > Mn, As (>0.1).     

Distribution and enrichment of trace metals and arsenic at the upper layer of sediments from Lerma River in La Piedad,Mexico: case history

Lerma River is one of the largest rivers in Mexico. Over the past 20 years, unplanned population growth occurred along its course and the river has been used as the only outlet for industrial and domestic wastewater disposal. The aim of the present study was to determine trace metals such as Cr, Ni, Cu, Zn, Fe, Pb, and arsenic concentrations at the upper layer of sediments of the Lerma River meander in La Piedad, Michoacan, Mexico. Sediment samples were collected from eight different sites during the rainy and dry seasons. All samples were physically characterized, and concentration values of trace metals and As were determined. On the basis of protection criteria for freshwater sediments, concentrations of Fe, Zn, Cu, Ni, and Pb were found to exceed the lowest effect level; moreover, the concentrations were found to exceed the severe effect level at some sites, particularly for Cu. Statistical analyses showed significant differences between sampling seasons for Fe and As, and among sites for Ni, Cu, Zn, and Pb. In addition, the enrichment factor indicates the following order Zn > Cr > Cu > Ni > Pb > As, and the geoaccumulation index (I _geo) indicates contamination in the following order Zn > Cr > Cu > Ni > As > Pb. The Lerma River meander in La Piedad shows a reduction in pollution by trace metals and arsenic near the drain area and downstream of the meander. However, there are significantly higher concentrations of these elements in sediments of sites located in the middle part of the city.     

Transport and sediment–water partitioning of trace metals in acid mine drainage: an example from the abandoned Kwangyang Au–Ag mine area, South Korea

Transport and sediment–water partitioning of trace metals (Cr, Co, Fe, Pb, Cu, Ni, Zn, Cd) in acid mine drainage were studied in two creeks in the Kwangyang Au–Ag mine area, southern part of Korea. Chemical analysis of stream waters and the weak acid (0.1 N HCl) extraction, strong acid (HF–HNO₃–HClO₄) extraction, and sequential extraction of stream sediments were performed. Heavy metal pollution of sediments was higher in Chonam-ri creek than in Sagok-ri creek, because there is a larger source of base metal sulfides in the ores and waste dump upstream of Chonam-ri creek. The sediment–water distribution coefficients (K _d) for metals in both creeks were dependent on the water pH and decreased in the order Pb ≈ Al > Cu > Mn > Zn > Co > Ni ≈ Cd. K _d values for Al, Cu and Zn were very sensitive to changes in pH. The results of sequential extraction indicated that among non-residual fractions, Fe–Mn oxides are most important for retaining trace metals in the sediments. Therefore, the precipitation of Fe(–Mn) oxides due to pH increase in downstream sites plays an important role in regulating the concentrations of dissolved trace metals in both creeks. For Al, Co, Cu, Mn, Pb and Zn, the metal concentrations determined by 0.1 N HCl extraction (Korean Standard Method for Soil Pollution) were almost identical to the cumulative concentrations determined for the first three weakly-bound fractions (exchangeable + bound to carbonates + bound to Fe–Mn oxides) in the sequential extraction procedure. This suggests that 0.1 N HCl extraction can be effectively used to assess the environmentally available and/or bioavailable forms of trace metals in natural stream sediments.     

Historical environmental pollution trend and ecological risk assessment of trace metals in marine sediments off Adyar estuary,Bay of Bengal,India

Geochemical, mineralogical and textural analyses were carried out in core sediments off Adyar estuary, Bay of Bengal, India to record the contamination trend from urban and industrial activities during the historical past. Quartz, feldspar, kaolinite, chlorite and illite were the main lithogenic and clay minerals; carbonate was the predominant biogenic mineral. Trace metals (Fe, Al, Cu, Cr, Ni, Pb and Zn) indicate more enrichment in the surface sediment layers due to recent anthropogenic activities. The mean anthropogenic factor (AF) values for trace metals in core sediments decreased in the following order: Cr > Ni > Zn > Cu > Pb. The pollution load index (PLI) values in Adyar core sediments ranged from 1 to 1.25 with an average of 1.07. Based on AF, PLI, and sediment quality guidelines values for trace metals, significant metal enrichment and ecological risk were obtained in upper-most sediment layer. Multivariate statistical methods such as correlation matrix, principal component analysis and cluster analysis were carried out to find the relationships among the texture size, metals and minerals. The pollution of Adyar estuarine sediments was started in the 1960s, responding to the rapid economic development in Chennai coastal and Adyar estuarine region in the last five decades. Despite these high concentrations in the upper layer, development and expansion of industries are still continuing. The stricter regulations for the discharge and remediation of sediments are urgent for the conservation of environments and human health.     

Distribution and speciation of heavy metals in surface sediments from the Yangtze estuary and coastal areas

The concentrations and speciation of heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb and Zn) in the sediments of the nearshore area, river channel and coastal zones of the Yangtze estuary, China, were systematically investigated in this study. The concentrations of all heavy metals except Ni in the sediments of the nearshore area were higher than those of the river channel and coastal zones. In the nearshore area, the concentrations of most heavy metals except Hg in the sediments of the southern branch were higher than those of the northern branch because of the import of pollutants from the urban and industrial activities around. When compared with the threshold effect level (TEL) and geochemical background levels, Cr, Ni and As accumulated and posed potential adverse biological effects. The speciation analysis suggested that Cd, Pb and Zn in the sediments of the three zones showed higher bioavailability than the other heavy metals, and thus posed ecological risk. Significant correlations were observed among Cr, Cu, Ni and Zn (r > 0.77) in the nearshore area, Ni, Cu, Zn and Pb (r > 0.85) in the river channel and Ni, Cu, Cr, Pb and Zn (r > 0.75) in the coastal zone. Principal component analysis (PCA) indicated that the discharge of unban and industrial sewage, shipping pollution and the properties of the sediments (contents of Fe, Mn, Al, TOC, clay and silt) dominated the distribution of heavy metal in the nearshore area, river channel and coastal zones of the Yangtze estuary.     

Diagenetic processes on metals in hypersaline mudflat sediments from a subtropical saltmarsh (SE Gulf of California): Postdepositional mobility and geochemical fractions

To understand the biogeochemical cycles of trace metals (Cd, Cu, Fe, Mn, Ni and Zn) in a hypersaline subtropical marsh, geochemical studies of both interstitial and solid phases were conducted on sediment cores from Chiricahueto marsh, SE Gulf of California. The sequential extraction procedure proposed by Tessier was used to estimate the percentages of the metals present in each geochemical phase of the sediment. Metal concentrations in the solid phase were found to be enriched in the upper layers and mainly associated with reactive fractions such as organic matter, Fe–Mn oxyhydroxides and carbonates (46–74% of Ni, Mn and Cd, and 11–19% of Cu and Zn). Principal factor analysis (PFA) and Spearman correlation analysis revealed a strong positive association of metals and their reactive phases with OC (the diagenetic component), and a negative or non-association with the mud content, Al, Fe and Li (the lithogenic component). Diagenetically released metals are mainly mobilized within hypersaline sediments by buoyancy transport (>90% of total flux) in response to an extreme salinity gradient by input of fresh groundwater (3–6 psu cm⁻¹). The molecular diffusion due to the gradient of metals in porewater (maximum and higher levels at 5–7 and below 20 cm depth, respectively) is significantly less important to the advective transport. Most of the metals mobilized by diffusion–advection processes are re-precipitated in the sediments by authigenic minerals, only <10% of most metals are extruded out to the overlying water column. Authigenic accumulation rates were estimated as 1.42–7.09 mg m⁻² a⁻¹ for Cd; 58.8–378 for Cu; 6922–17,985 for Fe; 38.2–345 for Mn; 20.8–263 for Ni; and 282–2956 mg m⁻² a⁻¹ for Zn. The Mn–Fe oxyhydroxides (40–85% of reactive metals) in the upper oxic–suboxic layers (<5 cm below surface) and sulfide minerals (75–97%) in anoxic sediment layers (7–18 cm) constitute the main scavengers for metals.     

Pyritization of iron and trace metals in anoxic fjord sediments (Nordåsvannet fjord,western Norway)

The accumulation and storage of trace metals in coastal sediments is an environmental concern. It is, therefore, important to understand better how these metals are bound or released under different redox conditions. This study of Fe and trace metal fixation under continuously anoxic conditions in the bottom sediments and the lower water column of the Nordåsvannet fjord in western Norway contributes further to such understanding. It allows investigation of both an end member redox state and one important mechanism of Fe and trace metal accumulation in sediments, the pyritization of Fe and trace metals. Pyrite formation occurs both in the water column and in the sediments of the Nordåsvannet fjord and favours the fixing of Fe and trace metals in the bottom sediments of the fjord. Thus, these sediments act as a continuous sink for Fe and trace metals. The DOP, and the degrees of trace metal pyritization for Mo, Ni and Cr correlate with organic matter content. While it is generally thought that Fe is the factor limiting pyrite formation in anoxic environments, this study found that degrees of pyritization of Fe (DOP) are clearly below 100%, and the availability of metabolizable organic matter is limiting pyrite formation. This is an important finding, because it indicates that increased supply of organic and mineral matter by higher runoff from land would further enhance the fixation of these metals in the fjord sediments, as would higher organic matter availability from increased productivity due to higher nutrient supply. The metals stored in the bottom sediments could be released into the biogeochemical cycle if redox conditions were to change from anoxic to suboxic or oxic. The fjord would then become a source rather than a sink for these metals.     

Spatial geochemical variation of major and trace elements in the marine sediments of Mumbai Harbor Bay

The resulting concentration data sets of major (Na, K, Mg, Ca and Fe) and trace elements (Cu, Ni, Co and Mn) in bed and suspended sediments were used to evaluate the enrichment factor for anthropogenic influences and principal component analysis for identifying the origin of source contributions in the studied area. Normalization of metals to Fe indicated that high enrichment factors in the bed sediment were in the order of Co > Cu > Na > Ca > Ni except Mg, K and Mn while for suspended sediments, only Co has a high enrichment factor. High enrichment of Co and Cu reflected the contamination of sediments from anthropogenic sources. The high influence of Na and Ca in sediments may be caused for seawater salinization factor. A significant positive correlation among enrichment factors of various elements of interest suggests a common origin/identical behavior during transport in the sediment system.     

Distribution and immobilization of heavy metals in Pliocene aquifer sediments in Wadi El Natrun depression, Western Desert

The Pliocene aquifer receives inflow of Miocene and Pleistocene aquifer waters in Wadi El Natrun depression. The aquifer also receives inflow from the agricultural activity and septic tanks. Nine sediment samples were collected from the Pliocene aquifer in Wadi E1 Natrun. Heavy metal (Cu, Sr, Zn, Mn, Fe, Al, Ba, Cr, Ni, V, Cd, Co, Mo, and Pb) concentrations of Pliocene aquifer sediments were investigated in bulk, sand, and mud fractions. The determination of extractable trace metals (Cu, Zn, Fe, Mn, and Pb) in Pliocene aquifer sediments using sequential extraction procedure (four steps) has been performed in order to study environmental pathways (e.g., mobility of metals, bounding states). These employ a series of successively stronger chemical leaching reagents which nominally target the different compositional fractions. By analyzing the liquid leachates and the residual solid components, it is possible to determine not only the type and concentration of metals retained in each phase but also their potential ecological significance. Cu, Sr, Zn, Mn, Fe, and Al concentrations are higher in finer sediments than in coarser sediments, while Ba, Cr, Ni, V, Cd, Co, Mo, and Pb are enriched in the coarser fraction. The differences in relative concentrations are attributed to intense anthropogenic inputs from different sources. Heavy metal concentrations are higher than global average concentrations in sandstone, USEPA guidelines, and other local and international aquifer sediments. The order of trace elements in the bulk Pliocene aquifer sediments, from high to low concentrations, is Fe?>?Al?>?Mn?>?Cr?>?Zn?>?Cu?>?Ni?>?V?>?Sr?>?Ba?>?Pb?>?Mo?>?Cd?>?Co. The Pliocene aquifer sediments are highly contaminated for most toxic metals, except Pb and Co which have moderate contamination. The active soluble (F0) and exchangeable (F1) phases are represented by high concentrations of Cu, Zn, Fe, and Mn and relatively higher concentrations of Pb and Cd. This may be due to the increase of silt and clay fractions (mud) in sediments, which act as an adsorbent, retaining metals through ion exchange and other processes. The order of mobility of heavy metals in this phase is found to be Pb?>?Cd?>?Zn?>?Cu?>?Fe?>?Mn. The values of the active phase of most heavy metals are relatively high, indicating that Pliocene sediments are potentially a major sink for heavy metals characterized by high mobility and bioavailability. Fe–Mn oxyhydroxide phase is the most important fraction among labile fractions and represents 22% for Cd, 20% for Fe, 11% for Zn, 8% for Cu, 5% for Pb, and 3% for Mn. The organic matter-bound fraction contains 80% of Mn, 72% of Cu, 68% of Zn, 60% of Fe, 35% of Pb, and 30% of Cd (as mean). Summarizing the sequential extraction, a very good immobilization of the heavy metals by the organic matter-bound fraction is followed by the carbonate-exchangeable-bound fraction. The mobility of the Cd metal in the active and Fe–Mn oxyhydroxide phases is the highest, while the Mn metal had the lowest mobility.     

Vertical geochemical variations and arsenic mobilization in the shallow alluvial aquifers of the Chapai-Nawabganj District, northwestern Bangladesh: implication of siderite precipitation

Core sediments from three disturbed boreholes (JOR, GHAT, and RAJ) and two undisturbed boreholes (DW1 and DW2) were collected in the study area of the Chapai-Nawabganj district of northwestern Bangladesh for geochemical analyses. In the study area, groundwater samples from fourteen As-contained private wells and five nested piezometers at both the DW1 and DW2 boreholes were also collected and analyzed. The groundwater arsenic concentrations in the uppermost aquifer (10–40 m of depth) range from 3 to 315 μg/L (mean 47.73 ± 73.41 μg/L), while the arsenic content in sediments range from 2 to 14 mg/kg (mean 4.36 ± 3.34 mg/kg). An environmental scanning electron microscope (ESEM) with an energy dispersive X-ray spectrometer was used to investigate the presence of major and trace elements in the sediments. Groundwaters in the study area are generally the Ca–HCO₃ type with high concentrations of As, but low levels of Fe, Mn, NO₃ ^? and SO ₄ ^?2 . The concentrations of As, Fe, Mn decrease with depth in the groundwater, showing vertical geochemical variations in the study area. Statistical analysis clearly shows that As is closely associated with Fe and Mn in the sediments of the JOR core (r = 0.87, p < 0.05 for Fe and r = 0.78, p < 0.05 for Mn) and GHAT core (r = 0.95, p < 0.05 for Fe and r = 0.93, p < 0.05 for Mn), while As is not correlated with Fe and Mn in groundwater. The comparatively low Fe and Mn concentrations in some groundwater and the ESEM image revealed that siderite precipitated as a secondary mineral on the surface of the sediment particles. The correlations along with results of sequential extraction experiments indicated that reductive dissolution of FeOOH and MnOOH represents a mechanism for releasing arsenic into the groundwater.     

Potential ecological risk assessment of heavy metal contamination in sediment and water body around Dhaka export processing zone,Bangladesh

Sediments and surface water contamination by the industrial effluents containing heavy metals is the most detrimental environmental impact. Therefore, the present work attempts to determine the status of eight heavy metal distribution in sediments and water samples, and their ecological risks’ assessment in the studied area. The distribution pattern of heavy metals in the water and sediment follows the sequences: Zn > Cu > Pb > Cr > Mn > Ni > As > Cd and Mn > Zn > Cr > Pb > Cu > Ni > As > Cd, respectively. Gross water pollution is observed at different sampling points of Dhalai Beel and Bangshi River. The comparison of sedimentary mean metal concentrations with several environmental contamination monitoring parameters, viz, threshold effect level (TEL), probable effect level (PEL), and severe effect lever (SEL) indicates that the metal levels are less than PEL except Cr. Moreover, the level of contamination degree (C _d) and modified degree of contamination (mC _d) indicates ‘low’ and ‘nil to low’ degree of contamination, respectively. Pollution load indices (PLI) of the studied area are lower than unity, indicates no pollution. Furthermore, a toxic-response factor is applied to assess the potential ecological risk of these heavy metals into the water body. The results of this study exhibit a low potential ecological risk of heavy metals. The Pearson’s correlation and cluster analysis are also performed to assess the heavy metal interactions in water and sediment samples.     

Heavy metal partitioning in river sediments severely polluted by acid mine drainage in the Iberian Pyrite Belt

This study provides a geochemical partitioning pattern of Fe, Mn and potentially toxic trace elements (As, Cd, Cr, Cu, Ni, Pb, Zn) in sediments historically contaminated with acid mine drainage, as determined by using a 4-step sequential extraction scheme. At the upperstream, the sediments occur as ochreous precipitates consisting of amorphous or poorly crystalline oxy-hydroxides of Fe, and locally jarosite, whereas the estuarine sediments are composed mainly of detrital quartz, illite, kaolinite, feldspars, carbonates and heavy minerals, with minor authigenic phases (gypsum, vivianite, halite, pyrite). The sediments are severely contaminated with As, Cd, Cu, Pb and Zn, especially in the vicinity of the mining pollution sources and some sites of the estuary, where the metal concentrations are several orders of magnitude above background levels. Although a significant proportion of Zn, Cd and Cu is present in a readily soluble form, the majority of heavy metals are bonded to reducible phases, suggesting that Fe oxy-hydroxides have a dominant role in the metal accumulation. In the estuary, the sediments are potentially less reactive than in the riverine environment, because relevant concentrations of heavy metals are immobilised in the crystalline structure of minerals.     

Regional geochemical baseline concentration of potentially toxic trace metals in the mineralized Lom Basin,East Cameroon: a tool for contamination assessment

The distribution of trace metals in active stream sediments from the mineralized Lom Basin has been evaluated. Fifty-five bottom sediments were collected and the mineralogical composition of six pulverized samples determined by XRD. The fine fraction (<?150 µm) was subjected to total digestion (HClO₄?+?HF?+?HCl) and analyzed for trace metals using a combination of ICP-MS and AAS analytical methods. Results show that the mineralogy of stream sediments is dominated by quartz (39–86%), phyllosilicates (0–45%) and feldspars (0–27%). Mean concentrations of the analyzed metals are low (e.g. As?=?99.40 µg/kg, Zn?=?573.24 µg/kg, V?=?963.14 µg/kg and Cr?=?763.93 µg/kg). Iron and Mn have significant average concentrations of 28.325 and 442 mg/kg, respectively. Background and threshold values of the trace metals were computed statistically to determine geochemical anomalies of geologic or anthropogenic origin, particularly mining activity. Factor analysis, applied on normalized data, identified three associations: Ni–Cr–V–Co–As–Se–pH, Cu–Zn–Hg–Pb–Cd–Sc and Fe–Mn. The first association is controlled by source geology and the neutral pH, the second by sulphide mineralization and the last by chemical weathering of ferromagnesian minerals. Spatial analysis reveals similar distribution trends for Co–Cr–V–Ni and Cu–Zn–Pb–Sc reflecting the lithology and sulphide mineralization in the basin. Relatively high levels of As were concordant with reported gold occurrences in the area while Fe and Mn distribution are consistent with their source from the Fe-bearing metamorphic rocks. These findings provide baseline geochemical values for common and parallel geological domains in the eastern region of Cameroon. Although this study shows that the stream sediments are not polluted, the evaluation of metal composition in environmental samples from abandoned and active mine sites for comparison and environmental health risk assessment is highly recommended.     

Tracing subsurface migration of contaminants from an abandoned municipal landfill

This paper aims at determining of inorganic leachate contamination for a capped unsanitary landfill in the absence of hydrogeological data. The 2D geoelectrical resistivity imaging, soil physicochemical characterization, and surface water analysis were used to determine contamination load and extent of selective heavy metal contamination underneath the landfill. The positions of the contaminated subsoil and groundwater were successfully delineated in terms of low resistivity leachate plumes of <10 Ωm. Leachate migration towards the reach of Kelang River could be clearly identified from the resistivity results and elevated concentrations of Fe in the river downslope toe of the site. Concentration of Fe, Mn, Ca, Na, K, Mg, Cu, Cr, Co, Ni, Zn, and Pb was measured for the subsoil samples collected at the downslope (BKD), upslope (BKU), and the soil-waste interface (BKI), of the landfill. The concentration levels obtained for most of the analyzed heavy metals significantly exceed the normal range in typical municipal solid waste landfill sites. The measured heavy metal contamination load in the subsoil is in the following order Fe ? Mn > Zn > Pb > Cr > Cu. Taking into consideration poor physical and chemical characteristics of the local soil, these metals first seem to be attenuated naturally at near surface then remobilize unavoidably due to the soil acidic environment (pH 4.2-6.18) which in turn, may allow an easy washing of these metals in contact with the shallow groundwater table during the periodic fluctuation of the Kelang River. These heavy metals are believed to have originated from hazardous industrial waste that might have been illegally dumped at the site.     

The diagenetic geochemistry and contamination assessment of iron,cadmium, and lead in the sediments from the Shuangtaizi estuary,China

Sediment and pore water samples have been collected from the coastal tidal flat in the Shuangtaizi estuary, China, in order to investigate the geochemical behavior of iron, cadmium, and lead during diagenesis and to assess the degree of contamination. The calculated enrichment factors and geoaccumulation indices for separate elements show that anthropogenic activities have had no significant influence on the distribution of Fe and Pb in the study area, whereas the distribution of Cd has been closely influenced in this way. The high percentage of exchangeable Cd (average of 56.34%) suggests that Cd represents a potential hazard to benthic organisms in the estuary. The calculated diffusive fluxes of metals show that the most mobilized metal is Fe (9.22 mg m^?2 a^?1), followed by Cd (0.54 mg m^?2 a^?1) and Pb (0.42 mg m^?2 a^?1). Low Fe²⁺ contents in surface pore water, alongside high chromium-reducible sulfur contents, and low acid-volatile sulfur, and elemental sulfur contents at 0–25 cm depth in sediments show that Fe²⁺ is formed by the reduction of Fe oxides and is transformed first to a solid phase of iron monosulfides (FeS) and eventually to pyrite (FeS₂). The release of adsorbed Pb due to reductive dissolution of Fe/Mn oxides during early diagenesis could be a source of Pb²⁺ in pore water. From the relatively low total organic carbon contents measured in sediments (0.46–1.28%, with an average of 0.94%) and the vertical variation of Cd²⁺ in pore water, sulfide or Fe/Mn oxides (instead of organic matter) are presumed to exert a significant influence on carrying or releasing Cd by the sediments.