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.     

Mobility of Al, Co, Cr, Cu, Fe, Mn, Ni and V in sulphide-bearing fine-grained sediments exposed to atmospheric O2: an experimental study

 The major aim was to increase our knowledge on the behaviour of Al, Co, Cr, Cu, Fe, Mn, Ni and V in sulphide-bearing fine-grained sediments exposed to atmospheric oxygen. Samples of this type of sediment collected in a previous investigation at eight sites in western Finland were digested in HClO₄-HNO₃-HCl-HF at 200  °C and in HCl:HNO₃:H₂O at 95  °C (aqua regia), and subjected to extractions with ammonium acetate and hydrogen peroxide. Metals and S in the leachates were determined with ICP-AES. The results of the chemical analyses are compared with previously reported experimental data. The concentrations of Al and Fe in the sulphide-bearing fine-grained sediments are about 7% and 5%, respectively. Of the trace metals studied, Mn is most abundant followed in decreasing order by V>Cr>Ni>Cu>Co. On oxidation of the sediments, high proportions of Co, Mn and Ni, intermediate proportions of Cu but low proportions of Fe, Al, Cr and V are released. The extent of the release of a metal on oxidation is controlled either by (1) the level to which the pH of the sediments drops on oxidation (Al, Cu, Cr, V), (2) the amount of the metal associated with easily reduced phases (metal sulphides) in the sediments (Ni, Co) or (3) the sum of the amount associated with reduced phases and adsorbed on soil compounds (Mn). No control of the release of Fe on oxidation of the sediments was identified. Based on the results of the study it is argued that artificial drainage and the subsequent oxidation of sulphide-bearing sediments will result in extensive leaching of Co, Mn and Ni, moderate leaching of Cu and limited leaching of Cr and V into drainages. The major elements, Fe and Al, have the potential to be mobilised and leached in large amounts, though the proportions mobilised/leached will remain low. It is suggested that the identification of sulphide-bearing sediments with a high potential of metal release should be based on determination of metals in easily mobilised reduced compounds (dissolved e.g. in H₂O₂) and of the level to which the pH of the sediments drops on oxidation. Received: 16 October 1997 · Accepted: 9 March 1998     

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.     

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.     

Vertical distribution and water solubility of phosphorus and heavy metals in sediments of the St. Lucie Estuary, South Florida, USA

Accumulation and distribution of heavy metals and phosphorus in sediments impact water quality. There has been an increasing concern regarding fish health in the St. Lucie Estuary, which is related to increased inputs of nutrients and metals in recent decades. To investigate vertical changes of contaminants (P, Cd, Cr, Co, Cu, Ni, Pb, Zn, and Mn) in sediments of the St. Lucie Estuary in South Florida, 117 layer samples from six of the 210 to 420 cm depth cores were analyzed for their total and water-soluble P and heavy metals, clay, total Fe, Al, K, Ca, Mg, Na, and pH. Principal component analysis (PCA) was used in two sets of analytical data (total and water-soluble contaminant concentrations) to document changes of contaminants in each core of sediments. The PCA of total contaminants and minerals resulted in two factors (principal components). The first and second factors accounted for 61.7 and 17.2 % of the total variation in all variables, and contrast indicators associated with contaminants of P, Cd, Co, Cr, Ni, Pb, Zn, and Mn and accumulation of Fe and Al oxides, respectively. The first factor could be used for overall assessment of P and heavy metal contamination, and was higher in the upper 45–90 cm than the lower depths of each core. The concentrations of P and heavy metals in the surface layers of sediments significantly increased, as compared with those in the sediments deeper than 45–90 cm. The PCA of water-soluble contaminants developed two factors. The second factor (Cu–P) was higher in the upper than the lower depths of the sediment, whereas the highest score of the first factor (Cd–Co–Cr–Ni–Pb–Zn–Mn) occurred below 100 cm. The water-soluble Cu and P concentrations were mainly dependent on their total concentrations in the sediments, whereas the water-soluble Cd, Co, Cr, Ni, Pb, Zn, and Mn concentrations were mainly controlled by pH.     

Surface metal enrichment and partitioning of metals in a dated sediment core from a Norwegian fjord

A 24-cm long sediment core from an oxic fjord basin in Ranafjord, Northern Norway, was sliced in 2 cm sections and analysed for As, Co, Cu, Ni, Hg, Pb, Zn, Mn, Fe, ignition loss and Pb-210. Partitioning of metals between silicate, non-silicate and non-detrital phases was assessed by leaching experiments, in an attempt to understand the mechanisms of surface metal enrichment in sediments. Relative to metal concentrations in sediments deposited in the 19th century, metals in near surface sediments were enriched in the following order: Pb > Mn > Hg > Zn > Cu > As > Fe. Cobalt and Ni showed no enrichment. The non-detrital fraction of Cu, Pb, Mn and Zn was significantly higher in the upper 10 cm than at greater depth in the core. This corresponds to sediments deposited since 1900, when mining activities started in the area. The enrichment of Cu, Pb and Zn is assumed to be mainly a result of mining, while Mn is apparently enriched in the surface due to migration of dissolved Mn and precipitation in the oxic surface layer. Elevated concentrations of As and Fe in the upper 4 cm are presumably due to discharges from a coke plant and an iron works respectively. The excess Hg present in the near surface sediments is tightly bound, either in coal particles or ore dust introduced by local industry, or via long distance transport of atmospheric particles. Calculations of metal flux to the sediments indicate an anthropogenic flux of Zn equal to its natural flux, while the flux of Pb shows a threefold increase above natural input.     

Heavy metal contamination in surface sediments of Gökçekaya Dam Lake,Eskişehir,Turkey

The present study to find seasonal (September 2010–June 2011) heavy metal (Cd, Pb, Cr, Co, Ni, Zn, Cu, Fe, As) contamination and the origins thereof in surface sediments of Gökçekaya Dam Lake, as constructed on Sakarya River, the third-longest river in Turkey and the largest river of the Northwestern Anatolia. Upon analyses for the purpose thereof, heavy metal contamination in annual average concentrations in the lake sediment varied, respectively, as Fe > Zn > Cr > Ni > Cu > Pb > Co > As > Cd. Statistical assessments performed in order to see whether the average values of the heavy metal contamination as measured at stations placed in the lake changed by seasonal periods. There found statistically significant differences especially in Cd, Zn, and Pb between seasonal periods. In accordance with the Sediment Quality Index, Gökçekaya Dam Lake sediment was classified as “highly polluted” in terms of the amount of anthropogenic contaminants of As, Cr, Cu, Ni, Pb, and Zn. Enrichment factor and geoaccumulation index values (I _geo) were calculated in order to geochemically interpret the source of contamination due to heavy metal concentration in the lake sediment and the level of pollution. The As, Co, Cr, Cu, Ni Pb, and Zn values demonstrated that the sediment was rich for anthropogenic contaminants. The lake was found especially rich for arsenic (14.97–34.70 mg/kg) and lead (68.75–98.65 mg/kg) in accordance with annual average values. In general the lake was geochemically characterized as “moderately contaminated” in terms of As, Co, Cr, Cu, Ni, Pb, and Zn content.     

Heavy metals in freshly deposited sediments of the Gomati River (a tributary of the Ganga River): effects of human activities

 The concentrations of various metals (Cr, Cu, Co, Fe, Mn, Ni, Pb, Zn, and Cd) were determined in recently deposited surface sediments of the Gomati River in the Lucknow urban area. Markedly elevated concentrations (milligrams per kilogram) of some of the metals, Cd (0.26–3.62), Cu (33–147), Ni (45–86), Pb (25–77), and Zn (90–389) were observed. Profiles of these metals across the Lucknow urban stretch show a progressive downstream increase due to additions from 4 major drainage networks discharging the urban effluents into the river. The degree of metal contamination is compared with the local background and global standards. The geoaccumulation index order for the river sediments is Cd>Zn>Cu>Cr>Pb. Significant correlations were observed between Cr and Zn, Cr and Cu, Cu and Zn and total sediment carbon with Cr and Zn. This study reveals that the urbanization process is associated with higher concentrations of heavy metals such as Cd, Cu, Cr, Pb, and Zn in the Gomati River sediments. To keep the river clean for the future, it is strongly recommended that urban effluents should not be overlooked before their discharge into the river. Received: 16 February 1996 · Accepted: 29 February 1996     

Contaminant dispersion at the rehabilitated Mary Kathleen uranium mine, Australia

This study reports on the transfer of contaminants from waste rock dumps and mineralised ground into soils, sediments, waters and plants at the rehabilitated Mary Kathleen uranium mine in semi-arid northwest Queensland. Numerous waste rock dumps were partly covered with benign soil and the open pit mine was allowed to flood. The mineralised and waste calc-silicate rock in the open pit and dumps has major (>1 wt%) Ca, Fe and Mg, minor (>1,000 ppm) Ce, La, Mn, P and S, subminor (>100 ppm) Ba, Cu, Th and U, and trace (<100 ppm) As, Ni, Pb, Y and Zn values. Consequently, chemical and physical weathering processes have acted on waste rock and on rock faces within the open pit, mobilising many elements and leading to their dispersion into soils, stream sediments, pit water and several plant species. Chemical dispersion is initiated by sulfide mineral breakdown, generation of sulfuric acid and formation of several soluble, transient sulfate minerals as evaporative efflorescent precipitates. Radiation doses associated with the open pit average 5.65 mSv year⁻¹; waste dumps commonly have lower values, especially where soil-covered. Surface pit water is slightly acid, with high sulfate values accompanied by levels of U, Cu and Ni close to or above Australian water guideline values for livestock. Dispersion of U and related elements into soils and stream sediments occurs by physical (erosional) processes and from chemical precipitation. Plants growing in the mine void, on waste dumps and contaminated soil display evidence of biological uptake of U, LREE, Cu and Th and to a lesser degree of As, Ni, Pb, Y and Zn, with values being up to 1–2 orders of magnitude above background sites for the same species. Although rehabilitation procedures have been partly successful in reducing dispersion of U and related elements into the surrounding environment, it is apparent that 20 years after rehabilitation, there is significant physical and chemical mobility, including transfer into plants.     

Heavy metal contamination of coastal lagoon sediments by anthropogenic activities: the case of Nador (East Morocco)

Nador lagoon sediments (East Morocco) are contaminated by industrial iron mine tailings, urban dumps and untreated wastewaters from surrounding cities. The lagoon is an ecosystem of biological, scientific and socio-economic interests but its balance is threatened by pollution already marked by biodiversity changes and a modification of foraminifera and ostracods shell structures. The aim of the study is to assess the heavy metal contamination level and mobility by identifying the trapping phases. The study includes analyses by ICP-AES and ICP-MS, of, respectively, major (Si, Al, Mg, Ca, Fe, Mn, Ti, Na, K, P) and trace elements (Sr, Ba, V, Ni, Co, Cr, Zn, Cu, As, Pb, Cd) in sediments and suspended matter, heavy metals enrichment factors calculations and sequential extractions. Results show that sediments contain Zn, Cu, Pb, V, Cr, Co, As, Ni with minimum and maximum concentrations, respectively, of 4–1190 μg/g, 4–466 μg/g, 11–297 μg/g, 11–194 μg/g, 9–139 μg/g, 1–120 μg/g, 4–76 μg/g, 2–62 μg/g. High concentrations in Zn are also present in suspended matter. The enrichment factors show contamination in Zn, Pb and As firstly induced by the mining industry and secondly by unauthorized dumps and untreated wastewaters. Cr and Ni are bound to clays, whereas V, Co, Cu and Zn are related to oxides. Thus, the risk in metal mobility is for the latter elements and lies in the oxidation–reduction-changing conditions of sediments.     

Impact of historical metalworks on the concentrations of major and trace elements in sediments: a case study in Finland

The concentrations of major and trace elements were determined (aqua regia leach and ICP-AES analyses) in stream, lake and dredged sediments downstream of the historical Antskog iron- and copperworks, S.Finland. The levels of Ag, Cd, Cu, Pb and Zn are highly elevated in all studied sediment types: roughly half of the studied lake-sediment samples contain >5 ppm Ag, >15 ppm Cd, >0.1% Cu, >0.1% Pb and >0.3% Zn. In the dredged sediment material located onshore, the concentrations of Ag, Cu and Pb are comparable to those in the polluted lake-sediment samples, while in stream sediments elevated metal concentrations are found especially in samples characterised by high concentrations of organic material. The source of the elevated metal concentrations is the historical metalworks at Antskog, mainly the copperworks of the 19th century. Compared to the limit values for contaminated soils in Finland, the concentrations of Cu, Pb and Zn are on average elevated by factors >10 in the polluted horizons of lake sediments, >5 in the dredged sediment located onshore and >2 at the most heavily contaminated site in the stream. Since the surface waters in the area are used for agricultural purposes and for various leisure activities, it is necessary to make further detailed investigations into the extent of the metal pollution and to determine species, mobility and bioavailability of the metals.     

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).     

Organic matter-metal interactions in Recent sediments: the role of humic substances

Atomic emission spectrographic analysis of the trace inorganic constituents of marine humic substances gave the following range of concentrations: Si, 200 ppm to > 2%; Al, 400 ppm to ~ 1%; Fe, 600–3000 ppm; Ca, 600 ppm to > 2%; Mg, 20–6000 ppm; Na, 600 ppm to > 2%; Ag, < 6–600 ppm; B, < 60–1000 ppm; Cu, 600–4000 ppm; Mn, 8–100 ppm; Mo, <20–3000 ppm; Ni, 100–1000 ppm; Pb, < 40–600 ppm; Sn, 40–600 ppm; Ti, < 20–2500 ppm; V, 20–200 ppm; Zn, 350–4500 ppm; Zr, < 60–500 ppm.Humic substances contain a sizeable portion of the Cu, Mo and Zn found in sediments, but are less important for Ni, Co and Pb, and are insignificant for the Mn, V and Fe content. The metals are mostly introduced into the humates during their diagenetic formation in sediment by dissolution of metals from various mineralogical phases. A precursor of the sedimentary humates, the polymeric organic material dissolved in interstitial water, contains most of the Cu and Zn, about half of the Ni, Fe and Co, and very little of the Mn found in interstitial water. Comparison of the data on humates with that obtained by H₂O₂ treatment of sediments indicates that Cu, Zn and possibly most of the Mo are associated with organic matter, but that Ni and Co are associated with sulfides.     

Distribution of Cu,Co, As,and Fe in mine waste,sediment, soil,and water in and around mineral deposits and mines of the Idaho Cobalt Belt,USA

The distribution of Cu, Co, As and Fe was studied downstream from mines and deposits in the Idaho Cobalt Belt (ICB), the largest Co resource in the USA. To evaluate potential contamination in ecosystems in the ICB, mine waste, stream sediment, soil, and water were collected and analyzed for Cu, Co, As and Fe in this area. Concentrations of Cu in mine waste and stream sediment collected proximal to mines in the ICB ranged from 390 to 19,000 μg/g, exceeding the USEPA target clean-up level and the probable effect concentration (PEC) for Cu of 149 μg/g in sediment; PEC is the concentration above which harmful effects are likely in sediment dwelling organisms. In addition concentrations of Cu in mine runoff and stream water collected proximal to mines were highly elevated in the ICB and exceeded the USEPA chronic criterion for aquatic organisms of 6.3 μg/L (at a water hardness of 50 mg/L) and an LC50 concentration for rainbow trout of 14 μg/L for Cu in water. Concentrations of Co in mine waste and stream sediment collected proximal to mines varied from 14 to 7400 μg/g and were highly elevated above regional background concentrations, and generally exceeded the USEPA target clean-up level of 80 μg/g for Co in sediment. Concentrations of Co in water were as high as in 75,000 μg/L in the ICB, exceeding an LC50 of 346 μg/L for rainbow trout for Co in water by as much as two orders of magnitude, likely indicating an adverse effect on trout. Mine waste and stream sediment collected in the ICB also contained highly elevated As concentrations that varied from 26 to 17,000 μg/g, most of which exceeded the PEC of 33 μg/g and the USEPA target clean-up level of 35 μg/g for As in sediment. Conversely, most water samples had As concentrations that were below the 150 μg/L chronic criterion for protection of aquatic organisms and the USEPA target clean-up level of 14 μg/L. There is abundant Fe oxide in streams in the ICB and several samples of mine runoff and stream water exceeded the chronic criterion for protection of aquatic organisms of 1000 μg/L for Fe. There has been extensive remediation of mined areas in the ICB, but because some mine waste remaining in the area contains highly elevated Cu, Co, As and Fe, inhalation or ingestion of mine waste particulates may lead to human exposure to these elements.     

Trace elements contamination of agricultural soils affected by sulphide exploitation (Iberian Pyrite Belt,Sw Spain)

Agricultural soils of the Riotinto mining area (Iberian Pyrite Belt) have been studied to assess the degree of pollution by trace elements as a consequence of the extraction and treatment of sulphides. Fifteen soil samples were collected and analysed by ICP-OES and INAA for 51 elements. Chemical analyses showed an As–Cu–Pb–Zn association related with the mineralisation of the Iberian Pyrite Belt. Concentrations were 19–994 mg kg⁻¹ for As, 41–4,890 mg kg⁻¹ for Pb, 95–897 mg kg⁻¹ for Zn and of 27–1,160 mg kg⁻¹ for Cu. Most of the samples displayed concentrations of these elements higher than the 90th percentile of the corresponding geological dominium, which suggests an anthropogenic input besides the bedrock influence. Samples collected from sediments were more contaminated than leptosols because they were polluted by leachates or by mining spills coming from the waste rock piles. The weathering of the bedrock is responsible for high concentrations in Co, Cr and Ni, but an anthropogenic input, such as wind-blown dust, seems to be indicative of the high content of As, Cu, Pb and Zn in leptosols. The metal partitioning patterns show that most trace elements are associated with Fe amorphous oxy-hydroxides, or take part of the residual fraction. According to the results obtained, the following mobility sequence is proposed for major and minor elements: Mn, Pb, Cd, > Zn, Cu > Ni > As > Fe > Cr. The high mobility of Pb, Cu and Zn involve an environmental risk in this area, even in soils where the concentrations are not so high.     

Historical changes in distribution and partitioning of natural and anthropogenic shares of heavy metals in sediment core from the southern Caspian Sea

Distribution of seven major and trace elements (aluminum, iron, calcium, cobalt, copper, vanadium and manganese) and total organic matter were assessed for sediment cores, collected from the southwest of Caspian Sea sediment in September 2008. Sedimentation rate of 0.9?cm/year was obtained based on ²¹⁰ Pb and ¹³⁷ Cs activity study of sediment cores. The major and trace metal distributions over whole lengths of core lengths (14?C168?cm) were found to be uniform (except for Al, Fe and Ca). Such uniform distribution of elements over whole lengths of the cores of the study area indicates similarity among the lithogenous material delivered into the Caspian Sea by rivers running into the southern coast. Enrichment factor (EF) and modified Muller??s formula of geoaccumulation index I _poll (intensity of pollution) evaluated the degree of sediment contamination. The results of pollution indices are indicative of non-pollution status in the area of study. From the first to third transect, Al, Fe and Mn concentrations increase. Heavy metal concentrations show relatively lower elemental concentrations in the third transect, possibly due to distance from anthropogenic sources. Cluster analysis shows Cu and Co grouped in different clusters, while Mn, V and Fe display closer similarity coefficients and similar sources. The results of partition studies reveal the percentile of loose ions portion of the metals as: $$ {\text{Cu}}\, (25.4\%) > {\text{Co}}\,(15.1\%)> {\text{Mn}}\,( {7.5\% }) > {\text{V}}\, (5.8\%) > {\text{Fe}}\,(0.2\%) $$ It shows that Cu and Co are the most mobile metals that can be easily released into water under changing environmental conditions. There seems to be a slight increasing trend in the pollution level of the sediments of the study area for copper and cobalt over the last 60?years.     

Impact of mining activities on sediments in a semi-arid environment: San Pedro River, Sonora, Mexico

A study of the San Pedro River (SPR), which is located in a semi-arid region in Sonora, Mexico, was conducted to evaluate the chemical, spatial and temporal (mobilization) trends of potentially harmful metals in its sediment in the rainy and dry seasons. High total concentrations of metals were detected in the following order: Fe > Cu > Mn > Zn > Pb > Cd. All studied metals except for Pb were increased during the dry season showing the effect of climate on the metal distribution in sediments. The results of sequential extraction indicated that the residual and Fe/Mn oxide fractions were the most important with regard to retaining potentially harmful metals in the sediments. In the exchangeable carbonate and Fe oxide fractions, high concentrations of metals were detected, representing high environmental risk. The geoaccumulation index shows slight to moderate contamination in most samples, and sampling point E4 (related to cattle activity) shows strong contamination for Cd, Cu, Pb and Zn. Enrichment factors (EFs) demonstrate anthropogenic origins for Pb (EF: 3–57), Cd (EF: 6–73) and Cu (EF: 1.5–224). This study shows that sediments are impacted by anthropogenic activities related to the mining industry, untreated wastewater discharges from the city of Cananea and cattle activities. Metal mobility in the SPR can disrupt the development of aquatic species in the river.     

Different types of fine-grained sediments associated with acid mine drainage in the Libiola Fe–Cu mine area (Ligurian Apennines,Italy)

Different types of fine-grained chemical precipitates were characterized in the surroundings of the pyrite-chalcopyrite mine of Libiola (Northern Italy). Both water chemistry and sediment composition were used to investigate metal mobility near the mine area. Local drainage waters were very acidic (with a pH as low as 2.5) and were rich in dissolved metals (Fe, Al, Cu, Zn, Mn, Ni). Sediments associated with low pH water (pH <4.5) were ochreous mixtures of schwertmannite and goethite with traces of jarosite. Their chemistry was dominated by Fe and they had, compared to other sediments investigated, low concentrations of other metals. When the acidity decreased gradually, other precipitates formed. At a pH of approximately 5, a poorly crystalline, whitish, Al-rich precipitate occurred. At a pH between 6 and 7, a poorly crystalline, blue, Cu (Zn) rich phase was present. These “sequential” precipitation events progressively reduced the metal loading typical of the acidic mine water when there was a gradual mixing with normal water. When a sudden mixing between normal waters (pH ∼8, Ca–HCO₃, low metal bearing) and acidic waters took place, a rapid flocculation occurred of mixed precipitates containing Fe, Al and trace elements.     

Colloidal and truly dissolved metal(oid) fractionation in sediment pore waters using tangential flow filtration

The partitioning of trace metal(oid)s between colloidal and “truly” dissolved fractions in sediment pore waters is often overlooked due to the analytical challenge; indeed, only small volumes are available and filtration membranes are rapidly clogged. Moreover, metal(oid)s are subject to co-precipitate with Fe. In this study, tangential flow filtration (TFF) was assessed for the fractionation of Fe, Mn, Cu, As, Co, Ni, Zn and Cd in sediment pore waters with a 5 kDa cut-off size membrane. Five natural sediments were collected and used for different tests. Results on blank samples showed that this technique was appropriate for Fe, Mn, Co, Zn, As and Cd. Although the applied concentration factors (CF) were low (<7.4) due to the small available volume of pore waters (50 mL), it was shown that colloidal concentrations obtained from the TFF procedure were similar whatever the applied concentration factor. The mass balance approach showed satisfying results (100 ± 25%) for Mn, Co, Zn and As. Mass balances were higher than 130% and highly variable for Cd, Ni and Cu. For Fe, mass balance was reproducible but low (71 ± 10%), probably due to sorption of positively charged Fe oxides on the membrane. Applying this method to five contrasting metal(oid)-contaminated sediments, it was shown that Mn, As, Co and Fe were mainly present in the “truly” dissolved phase (<5 kDa). This technique is a necessary step to assess sediment toxicity and bioavailability of metal(oid)s and could be of great interest for emergent pollutants such as nanometals.