黄河包头段不同粒级沉积物中重金属形态分布特征

以黄河包头段为研究对象,探讨了该河段不同粒级沉积物中重金属的形态分布特征,并估算了各粒级沉积物对各形态重金属的贡献率。结果表明,铁锰氧化物结合态是黄河干流各粒级沉积物中Cu、Pb和Zn非稳定态的主导形态;总体上,黄河干支流沉积物中3种重金属各形态含量均随粒级增大而减小,表现明显的粒度效应;重金属形态分布的粒度效应是沉积...     

Particulate trace metal speciation in stream sediments and relationships with grain size: Implications for geochemical exploration

Sediment samples were collected from streambeds in an undisturbed watershed in eastern Quebec (Gaspé Peninsula). Two sampling sites were located on a stream draining an area of known mineralization (Cu, Pb, Zn) and two on a control stream. The sediment samples were separated into 8 distinct size classes in the 850 μm to <1 μm size range by wet sieving, gravity sedimentation or centrifugation. Each sediment subsample was then subjected to a sequential extraction procedure designed to partition the particulate heavy metals into five fractions: (1) exchangeable; (2) specifically adsorbed or bound to carbonates; (3) bound to Fe-Mn oxides; (4) bound to organic matter; (5) residual. The following metals were analyzed in each extract: Cu, Pb, Zn; Fe, Mn.Comparison of samples from the mineralized area with control samples revealed the expected increase in total concentrations for Cu, Pb and Zn. Non-detrital metals were mainly associated with Fe oxides (specifically adsorbed; occluded) and with organic matter or resistant sulfides. For a given sample, variation of trace metal levels in fractions 2 and 3 with grain size reflected changes in the available quantities of the inorganic scavenging phase (FeOx/MnOx); normalization with respect to Fe and Mn content in fraction 3 greatly reduced the apparent dependency on grain size.The results of this study suggest that a single reducing extraction (NH₂OH.HCl) could be used advantageously to detect anomalies in routine geochemical surveys. A second leaching step with acidified H₂O₂ could also be included, as the trace metal concentrations in fraction 4, normalized with respect to organic carbon content, also showed high {anomaly/background} ratios.     

Geochemical features of heavy metals in core sediments of northwestern Taihu Lake, China

Sequential core sediments from northwestern Taihu Lake in China were analyzed for grain size, organic carbon and heavy metal content. The sediments are composed of organic-poor clayey-fine silts. The chemical speciations of Cu, Fe, Mn, Ni, Pb, and Zn were also analyzed using the BCR sequential extraction procedure. Cu, Fe, Ni, and Zn are mainly associated with the residue fraction; Mn is concentrated mainly in exchangeable/carbonate fraction and residue fraction; and Pb mainly in Fe/Mn oxide fraction and organic/sulfide fraction. The exchangeable/carbonate fractions of Cu, Fe, Ni, Zn and Pb are lower. The fractions of Ni, Pb and Zn bound to the Fe/Mn oxide have significant correlations with reducible Mn; the organic/sulfide fractions of Cu, Mn, Ni, Pb, and Zn have significant correlations with TOC. The extractable fractions of Cu, Mn, Ni, Pb, and Zn are high at the top 4 cm of the core sediments as compared to those in the deeper layers, showing the anthropogenic input of heavy metals is due to rapid industrial development. The heavy metal pollution history of the sediments has been recorded since the late 1970s, determined by the result of ^137Cs dating.     

Trace Metal Speciation of USGS Reference Sample MAG-I

The USGS reference sample marine mud MAG-1 has been subjected to a sequential extraction procedure designed to partition the constituent trace metals into five fractions: I-exchangeable; II- bound to carbonates; III-bound to Fe-Mn oxides; IV- bound to organic matter; V- residual. The analytical approach involved successive chemical extractions and the subsequent determination of trace metal concentrations (Co, Cu, Ni, Pb, Zn; Fe, Mn) in the leachates by atomic absorption spectrophotometry. The chemical speciation results obtained on four replicate sub-samples demonstrate that the coefficients of variation for metal concentrations in the individual fractions are generally better than + 10%. Comparison with published values for total trace metal concentrations in the MAG-1 sample suggests that the overall accuracy of the chemical extraction procedure is satisfactory.     

Heavy metal mobility assessment in sediments from the Odiel River (Iberian Pyritic Belt) using sequential extraction

The Tessier sequential extraction scheme (SES) was applied to sediments from the Odiel river catchment (Iberian Pyritic Belt, SW of Spain), one of the most acid rivers on Earth, to assess the chemical association (exchangeable, carbonatic, bound to manganese and iron oxides, bound to organic matter and residual mineral) of heavy metals (Zn, Cd, Pb, Cu, Cr, Mn, Ni, Fe, and Hg). Sediments are very heterogeneous in their textural characteristics, showing different grain size. Twenty-seven samples were studied from from areas along the Odiel River, from the source to the mouth, with special interest in the Odiel Marshes Natural Park due to its ecological significance. Samples were classified as sandy (especially at the river mouth with low iron oxide and organic matter content) and clay-silty (in the middle of the river catchment with high iron oxide content). The numerous sandy samples with low pH values explain the low levels of metals upstream, although potential metals contributions arise from mining and ore. However, the presence of sulfate in the mining area and carbonate at the mouth may explain the high presence of lead and iron in these sandy zones. Some percentage of mobile Ni, Cu, and Zn were detected in the mining area, but the elevated relative percentage of exchangeable Cd in the estuary is even more remarkable. The percentage of Zn bound to carbonate is considerable in the catchment but especially in the estuary. However, Cu is only detected in the carbonate phase downstream, in spite of the low concentration of carbonate, which represents a drawback in the application of the Tessier SES to these types of samples. Finally, relatively high percentages of residual, non-mobile, Hg and Pb were observed, in the estuarine and mining areas, respectively. Sand, lime, and clay fractions of representative samples from Areas I, II, and III were used in a metal speciation study. Mainly, the elements analyzed had accumulated in the non-residual fractions. In the mining area of the Pyrite Belt, the elements analyzed are mainly bound to Fe–Mn oxides (Fe + Mn + Cu + Cr + Pb + Mn ± Zn) and the organic matter/sulfide fraction (Ni + Zn + Hg ± Cd), independent of sediment grain size. In conclusion, we show that the results of the study of chemical speciation in sediments from acid rivers are independent of the sediment grain size considered.     

Distribution and enrichment of heavy metals in a sediment core from the Pearl River Estuary

A sediment core collected from coastal zone near the Qiao Island in the Pearl River Estuary was analyzed for total metal concentrations, chemical partitioning, and physico-chemical properties. Three vertical distribution patterns of the heavy metals in the sediment core were identified, respectively. The dominant binding phases for Cu, Pb, Cr, and Zn were the residual and Fe/Mn oxides fractions. Cd in all sediments was mainly associated with exchangeable fraction. Influences of total organic carbon content and cation exchange capacity on the total concentrations and fractions of almost all the metals were not evident, whereas sand content might play an important role in the distributions of residual phases of Cr, Cu, Pb, and Zn. In addition, sediment pH had also an important influence on the Fe/Mn oxides, organic/sulfide and residual fractions of Cr, Cu, and Zn. Contamination assessment on the heavy metals in the sediment core adopting Index of Geoaccumulation showed that Cr, V, Be, Se, Sn, and Tl were unpolluted, while Cu, Ni, Pb, Zn, Cd, and Co were polluted in different degrees throughout the core. It was remarkable that the various pollution levels of the metals from moderate (for Cu, Pb, and Zn) to strong (for Cd) were observed in the top 45 cm of the profiles. The relative decrease of the residual fraction in the upper 45 cm of the core is striking, especially for Zn and Cu, and, also for Pb, and Cr. The change in fraction distribution in the upper 45 cm, which is very much contrasting to the one at larger depths, confirms that the residual fraction is related to the natural origin of these metals, whereas in the upper part, the non-residual fractions (mainly the Fe/Mn oxides fraction) are increased due to pollution in the last decade. The possible sources for Cu, Pb, Zn, and Cd contaminations were attributed to the increasing municipal and industrial wastewater discharges, agricultural runoff, atmospheric inputs, and runoff from upstream mining or smelting activities, which may be associated with an accelerating growth of economy in the Pearl River Delta region in the past decade.     

恬矿库周围土壤中重金属存在形态特征研究

通过对大冶铜绿山铜铁矿尾矿库周围土壤中重金属形态分析实验,研究了重金属各种形态在土壤中的分布特征。由对比实验可知,尾矿库周围土壤中Ｃｕ、Ｐｂ、Ｚｎ、Ｃｄ等重金属含量都显著地高于对照样品,书经受到重金属的严重污染。土壤中重金属形态分布征为：ｗ（Ｃｒ、Ｚｎ、Ｆｅ）;可变换态〈碳酸盐态〈有机态〈铁锰氧化态〈残渣态;ｗ（Ｃｕ、Ｐｂ）：可变换态〈碳酸盐态〈有机态〈残渣态〈铁锰氧化态;ｗ（Ｃｄ）：残渣态,有机     

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.     

Assessment of the pseudo total metal content in alluvial sediments from Danube River,Serbia

We used elemental carbon, nitrogen, hydrogen and sulfur as well as ratios of hydrogen and nitrogen with total organic carbon for investigation of source and conditions of organic matter in alluvial Danube sediments. We also determined the pseudo total concentrations of metals presented as a sum of extracted concentration after five sequential extraction steps. The pseudo total metal concentrations were found to be (mg kg⁻¹) for Mn, 666; Fe, 25,852; Mg, 16,193; K, 2,063; Ni, 32.4; Zn, 72.2; Pb, 15.0; Cu, 26.0 and for Cr, 15.9. Correlation analysis and two multivariate analysis methods (principal component and cluster analysis) were helpful in determining the associations between the pseudo total extracted fractions of metals and with elemental carbon, hydrogen, nitrogen, sulfur, total inorganic and organic carbon. These correlations will help us to identify substrates of trace metals in different oxic/anoxic conditions. The correlation results of the trace metals and Fe, K, Mg and Mn suggest their adsorption, mainly onto Fe and Mn (hydro)oxides and K alumosilicates, whereas correlations of metals with sulfur indicate that they were precipitated as Fe-sulfides.     

太湖沉积物中重金属的地球化学形态及特征分析

用连续提取法分析了太湖沉积物5种重金属的地球化学形态,对地球化学形态的组成和地理特征进行了分析研究.重金属地球化学形态配分的共同特点是可交换态最低,残渣态最高.两种形态中Cd的可交换态最高,Cr的残渣态最高,可交换态最低.Cd的碳酸盐态较高,Cr的最低;Pb、Cd的Fe-Mn氧化态较高,Cu的偏低;Cu的有机态最高,Cd的最低;Zn的地球化学形态比例大都处于中间.地域上变化较大的元素是Cd和Cu,变化不明显的元素有Pb和Zn.化学成分中Fe2O3、MnO与重金属地球化学形态的相关性最好,TOC与Cu的形态相关系数最高.综合对比分析表明,太湖沉积物重金属的生物有效性以Cd为最高,其次为Pb.     

Mechanism of enrichment of trace metals on fine sludges collected from filtration plants

Fine sludges were collected from five filtration plants, and the partitioning of ten metals (Ag, Cd, Mn, Zn, Pb, Cu, Sn, Co, Ni, and Fe) in them was determined by selective leaching techniques. (1) The available amounts, which shows the total of each metal leached between 1 M CH₃COONH₄ and 30 percent H₂O₂, for Ag, Cd and Mn, ranged from 51 to 98 percent for five sludges. (2) The available amounts for Zn, Pb, Cu, and Sn were 47–92 percent for five sludges. (3) The most important fraction for Co, Ni, and Fe, except the Inagawa sludge, which is markedly polluted by organic matter, was the crystalline particle. Therefore, the above metals, except Co, Ni, and Fe, are thought to be enriched on ion-exchangeable sites, organic matter, hydrous Fe/Mn oxides, and sulfides in fine sludges.     

Regional geochemical reconnaissance in the Belgian Ardennes: Secondary dispersion patterns in stream sediments

Two geochemical stream sediment surveys were conducted in the Belgian Ardennes for Fe, Cu, Pb, Zn, Co, Ni and Mn. The geological setting is of quartzo-pelitic rocks of Early Devonian and Cambro-Ordovician age. One survey covers the Ourthe and Salm valleys, the other the Lesse and Lomme drainage basins. Results of these surveys show the geochemical similarity of the two regions. Anomalies have been ascribed to four factors: human activity, Fe-Mn enrichment, known mineralization and potential mineralization. Mean values of metal concentration and statistical dispersion are identical. This results from similar physico-chemical conditions which induce the same types of surficial metallic association. The stream environment is characterized by two main phases, an oxidizing phase where Fe-Mn oxides trap trace metals, and a reducing phase where organic matter and secondary sulphides are bound with Pb, Zn and Cu. In oxidizing conditions, Cu and Ni show a greater affinity for the Fe-oxides while Zn and especially Co are related to the Mn-oxides. Pb has only a weak relationship with the Fe-Mn oxides but is also associated with the organic matter and the secondary sulphides in the reducing environment. Consequently, one may propose the following scale of mobility: Zn > Ni-Mn > Cu-Co > Pb > Fe.     

Environmental geochemistry of El Temsah Lake sediments, Suez Canal district, Egypt

The heavy metal contents of Mn, Ni, Cu, Zn, Cr, Co, Pb, Cd, Fe, and V in the surface sediments from five selected sites of El Temsah Lake was determined by graphite furnace atomic absorption spectrophotometer. Geochemical forms of elements were investigated using four-step sequential chemical extraction procedure in order to identify and evaluate the mobility and the availability of trace metals on lake sediments, in comparison with the total element content. The operationally defined host fractions were: (1) exchangeable/bound to carbonate, (2) bound to Fe/Mn oxide, (3) bound to organic matter/sulfides, and (4) acid-soluble residue. The speciation data reveals that metals Zn, Cd, Pb, Ni, Mn, Cu, Cr, Fe, and V are sink primarily in organic and Fe–Mn oxyhydroxides phases. Co is mainly concentrated in the active phase. This is alarming because the element is enriched in Al Sayadin Lagoon which is still the main site of open fishing in Ismailia. Average concentration of the elements is mostly above the geochemical background and pristine values of the present study. There is a difference on the elemental composition of the sediment collected at the western lagoon (Al Sayadin Lagoon), junction, the shoreline shipyard workshops, and eastern beach of the lake. Depending upon the nature of elements and local pollution source, high concentration of Zn, Pb, and Cu are emitted by industrial wastewater flow (shoreline workshops), while sanitary and agricultural wastewater (El Bahtini and El Mahsama Drains) emit Co and Cd in Al Sayadin Lagoon. On the other hand, there is a marked decrease in potentially toxic heavy metal concentrations in the sediments at the most eastern side of the lake, probably due to the successive sediment dredging and improvements in water purification systems for navigation objective. These result show that El Temsah receives concentrations in anthropogenic metals that risk provoking more or less important disruptions, which are harmful and irreversible on the fauna and flora of this lake and on the whole ecobiological equilibrium.     

Coupled physicochemical and bacterial reduction mechanisms for passive remediation of sulfate- and metal-rich acid mine drainage

Treatment of acid mine drainage (AMD) highly rich in sulfate and multiple metal elements has been investigated in a continuous flow column experiment using organic and inorganic reactive media. Treatment substrates that composed of spent mushroom compost (SMC), limestone, activated sludge and woodchips were incorporated into bacterial sulfate reduction (BSR) treatment for AMD. SMC greatly assisted the removals of sulfate and metals and acted as essential carbon source for sulfate-reducing bacteria (SRB). Alkalinity produced by dissolution of limestone and metabolism of SRB has provided acidity neutralization capacity for AMD where pH was maintained at neutral state, thus aiding the removal of sulfate. Fe, Pb, Cu, Zn and Al were effectively removed (87–100%); however, Mn was not successfully removed despite initial Mn reduction during early phase due to interference with Fe. The first half of the treatment was an essential phase for removal of most metals where contaminants were primarily removed by the BSR in addition to carbonate dissolution function. The importance of BSR in the presence of organic materials was also supported by metal fraction analysis that primary metal accumulation occurs mainly through metal adsorption onto the organic matter, e.g., as sulfides and onto Fe/Mn oxides surfaces.     

Effectiveness of sulfate-reducing passive bioreactors for treating highly contaminated acid mine drainage: II. Metal removal mechanisms and potential mobility

Column bioreactors were used for studying mechanisms of metal removal, assessment of long-term stability of spent reactive mixtures, as well as potential metal mobility after treating highly contaminated acid mine drainage (AMD; pH 2.9–5.7). Several physicochemical, microbiological, and mineralogical analyses were performed on spent reactive mixtures collected from 4 bioreactors, which were tested in duplicate for two hydraulic retention times (7.3d and 10d), with downward flow over an 11-month period. Consistent with the high metal concentrations in the AMD feed, and with low metal concentrations measured in the treated effluent, the physicochemical analyses indicated very high concentrations of metals (Fe, Mn, Cd, Ni, and Zn) in the top and bottom layers of the reactive mixtures from all columns. Moreover, the concentrations of Fe (50.8–57.8 g/kg) and Mn (0.53–0.70 g/kg) were up to twice as high in the bottom layers, whereas the concentrations of Cd (6.77–13.3 g/kg), Ni (1.80–5.19 g/kg) and Zn (2.53–13.2 g/kg) were up to 50-times higher in the top layers. Chemical extractions and elemental analysis gave consistent results, which indicated a low fraction of metals removed as sulfides (up to 15% of total metals recovered in spent reactive mixtures). Moreover, Fe and Mn were found in a more stable chemical form (residual fraction was 42–74% for Mn and 30–77% for Fe) relative to Cd, Ni or Zn, which seemed more weakly bound (oxidisable/reducible fractions) and showed higher potential mobility. Besides identifying (oxy)hydroxide and carbonate minerals, the mineralogical analyses identified metal sulfides containing Fe, Cd, Ni and Zn. Metal removal mechanisms were, therefore, mainly adsorption and other binding mechanisms with organic matter (for Cd, Ni and Zn), and the precipitation as (oxy)hydroxide minerals (for Fe and Mn). After 15 months, however, the column bioreactors did not lose their capacity for removing metals from the AMD. Although the metals were immobile during the bioreactor treatment, their mobility could increase from spent reactive mixtures, if stored inappropriately. Metal recovery by acidic leaching of spent substrates at the end of bioreactor operation could be an alternative.     

Partitioning of heavy metals into mineral and organic fractions in a sediment core from Tokyo Bay

Sediment core was collected from Tokyo Bay. The surface enrichment of heavy metals due to human activities is recognized in the sediment. Partitioning of Cu, Zn, Fe and Mn into sulfide, carbonate, organic and silicate fractions has been determined with selective chemical leaching techniques for ²¹⁰Pb-dated sediment core samples. The heavy metal contents of silicate fractions without exchangeable sites are almost constant against depth in sediment core. However, the Cu, Zn and Mn contents of sulfide, carbonate and organic fractions vary with depth. Most Cu and Zn in the polluted sediment layer are associated with the iron sulfide fraction.     

Grain size and geochemical partitioning of heavy metals in sediments of the Damodar River – a tributary of the lower Ganga, India

 The distribution of Si, Al, Fe, Mn, Cu, Zn, Ni and Cr in different grain-size fractions and geochemical association of Fe, Mn, Cu and Zn with <63-μm size fraction of bed sediments of Damodar River has been studied. In general, concentrations of heavy metals tend to increase as the size fractions get finer. However at two sites, near mining areas, the coarser particles show similar or even higher heavy metal concentrations than finer ones. The higher residence time and/or presence of coarser particles from mining wastes are possibly responsible for higher metal content in the coarser size fractions. The chemical fractionation study shows that lithogenic is the major chemical phase for heavy metals. Fe and Mn are the major elements of the lithogenic lattice, constituting 34–63% and 22–59%, respectively, of total concentrations. Fe-Mn oxide and organic bound fractions are significant phases in the non-lithogenic fraction. The carbonate fraction is less significant for heavy metal scavenging in the present environment and shows the following order of abundance Zn>Cu>Mn>Fe. The exchangeable fraction of the Damodar sediments contains very low amounts of heavy metals suggesting poor bioavailability of metals. Received: 18 August 1998 · Accepted: 1 December 1998     

Heavy metal relationships in a Pennsylvania soil

Soils of loamy sand on weathered, sandy dolomite were cored from six holes up to 70 ft beneath a municipal waste landfill in central Pennsylvania. Mn, Fe, Ni, Co, Cu, Zn, Cd, Pb, and Ag were determined in exchangeable and non-exchangeable forms in total and < 15 μm soil samples. Most of these metals were bound in Mn oxides, non-exchangeable with 0.5 M CaCl₂. The Mn oxides (often X-ray amorphous) identified when crystalline as todorokite occurred chiefly as coatings on quartz grains.Somewhat higher amounts of acid leachable trace metals were found in the < 15 μm size fraction than in the total soil samples; however, trace metal/Mn ratios were similar in both. In general, the initial mild soil leaching, which dissolved chiefly Mn oxides, gave MnFeX>Co>Ni>Pb>Zn> Cu>Cd>Ag. The final leaching, which dissolved chiefly ferric oxides, gave Fe>Mn>Ni>Zn>Co> Cu>Pb>Cd>Ag. Samples taken from an unpolluted site and from the same soils affected for seven years by leachate from the refuse had similar metal contents.Soil extractable Co, Ni, Cu, and Zn could be predicted from the Mn extracted. Based in part on factor analysis of the data, Mn-rich oxides had at least tenfold higher heavy metal percentages than Fe-rich oxides (crystalline component goethite), reflecting their greater coprecipitation potential. Because of this potential and because of the generally higher solubility of Mn than Fe oxides, more heavy metals may be released from Mn-rich than from Fe-rich soils by disposal of organic-bearing wastes. However, leaching of the moisture-unsaturated soils in situ is rarely severe enough to completely dissolve both Mn and Fe oxides. Based on the Mn content, Cd, Cu, and Pb were depleted in soil moisture beneath the landfill relative to their amounts in the soil. This depletion may reflect factors including heterogeneity in metal content of the soil oxides; preferential resorption of these metals; and removal of the Cd, Cu, and Pb as organic precipitates or as inorganic precipitates such as carbonates.     

Seasonal variation of particulate heavy metals in the Lower Paraíba do Sul River, R.J., Brazil

 Temporal and spatial variability of particulate metal concentrations (Cu, Cr, Zn, Mn and Fe) were investigated in the lower drainage basin of the Paraíba do Sul River. The results showed that the spatial variability was not important for all the studied metals, however, temporal variations seems to be considerable. In general, two distinct behaviors were observed for particulate heavy metals: (1) metal concentration increase together with water flow (Fe and Cu) and (2) concentration decrease with increasing water flux (Zn, Cr and Mn). The Fe and Cu behavior is probably due to the strong association of these metals with surface runoff, although their sources seem to be distinct. Iron probably originates from the regional soils rich in iron oxides, and Cu is possibly associated to the large-scale use of copper fungicides in the sugar cane plantations. The opposite trend observed for Zn, Cr and Mn probably reflects the importance of the industrial and urban effluents as a secondary source of these elements for the system. Their behavior is probably associated with the dilution effect caused by the input of a suspended matter poor in these metals originated from the surface runoff during the rainy season. Received: 4 March 1998 · Accepted: 30 June 1998     

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.