Chemical and mineralogical forms of lead,zinc and cadmium in particle size fractions of some wastes,sediments and soils in Korea

Forms of Pb, Zn and Cd in the different size fractions (<2 μm, 2–53 μm and >53 μm) of waste dumps, stream sediments and surrounding soils from a former Au mine in Korea, were investigated chemically by sequential extraction analysis and mineralogically by XRD and analytical SEM, so as to clarify the relationships between chemical and mineralogical forms. Total concentrations for the waste dumps and the stream sediments range from 655 to 2920 mg/kg for Pb, 565 to 1191 mg/kg for Zn, and 24.4 to 71.4 mg/kg for Cd, while those for the surrounding soils do not exceed the natural background levels. Direct observations on the heavy mineral fractions of the waste dumps and the stream sediments indicates that the primary sphalerite is still the main pool of the Zn and Cd, while a large part of the primary galena has been changed into a carbonate-bound form. This is in a good agreement with the partitioning of chemical forms in the coarse fractions, in which most of the Zn (75.3 to 79.4% for the waste dumps) and Cd (54.8 to 60.1% for the waste dumps) are associated with the oxidizable form, while most of the Pb (68.8 to 71.0% for the waste dumps) is in the acid (NaOAc)-extractable form. On the other hand, the partitioning of metal forms in the clay fraction is characterised by the highest proportion of the reducible form for all metals (56.6 to 73.8% for Pb, 60.2 to 68.4% for Zn, and 27.1 to 36.8% for Cd in the waste dumps), suggesting precipitation of easily to moderately reducible oxides and hydroxides from the other forms during weathering. With the increase of pH, the dramatic changes of the acid-extractable Pb, the oxidizable Zn and Cd in the coarse fractions, and the exchangeable form, especially for Cd in the clay fraction indicate that pH is the prime factor controlling the partitioning of heavy metals.     

The influence of channel morphology on the chemical partitioning of Pb and Zn in contaminated river sediments

The chemical partitioning of Pb and Zn was investigated in contaminated stream sediments from the River Ystwyth in mid-Wales, with changes in metal/substrate fixation being related to variations in channel morphology. Confinement of the channel by bedrock (chute zones) is sufficient to create very turbulent flow conditions facilitating the precipitation of Mn(IV) on surfaces of sand sized particles (2000-63 μm). Phase specific extraction of Pb (easily reducible fraction) from this particle size range indicates significant adsorption on precipitated forms of Mn. Conversely, under meandering conditions, association with the moderately reducible fraction (Fe-oxides) was more influential in the physico-chemical partitioning of Pb. Thus oxyhydroxide “precipitation zones” are created which affect heavy metal partitioning. These phenomena are, however, not observed on silt and clay sized particle coatings (<63 μm). The partitioning of Zn is not influenced by channel morphology due to a combined influence of the greater solubility of ionic species and subsequent transfer in solution and to the prevalence of total sediment Zn as sphalerite (ZnS).     

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.     

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...     

Granulometric and chemical composition of the Sava River sediments upstream and downstream of the Krsko nuclear power plant

Total concentrations of 13 elements (K, Ca, Ti, Cr, Mn, Fe, Cu, Zn, Rb, Sr, Y, Zr, Pb) in the size-fractionated Sava River sediments upstream and downstream of the Krsko nuclear power plant together with metal speciation within bulk sediment have been investigated. Trace metals generally increase with decreasing particle size, however, because of entrapment of organic matter in the 0.63–1 mm fraction, concentrations in the coarser sediment fraction are higher than expected. Exchangeable Pb, Zn, Cu, Mn, Cr and Fe are generally found to represent a negligible fraction of the total metal concentration of the bulk sediment. Seasonal variations of the Pb, Zn and Cu concentrations in the <0.5 mm fraction reflect decreased values during the spring period. Heavy metal concentrations in the 2003 waste water discharges from the Krsko nuclear power plant released into the Sava River were much lower than their maximum allowed values. Combined rubidium and organic matter normalization of the Zn, Pb and Cu concentrations, which was applied on the minus 0.063 mm fraction, indicated three potential sources of contaminants.     

The significance of organic matter degradation in the interpretation of historical pollution trends in depth profiles of estuarine sediment

The quantitative significance of organic matter degradation in bringing about the early diagenetic mobility of anthropogenic trace metals (Cu, Zn, Pb) is assessed specifically in relation to the use of estuarine sediments as historical records of pollution. A 1,500 mm salt-marsh sediment depth profile from Tites Point, Severn Estuary, England, was sampled at 10-mm intervals. Organic carbon determinations were carried out by a wet oxidation technique, and ‘organic fraction’ metals were separated by sequential leaching. Results demonstrated that organic phase metals are quantitatively significant in Severn Estuary sediments, particularly Cu and Zn (Cu>Zn), and that metals are probably released from this fraction during early diagenesis. The degree of release, and the apparent loss of the released trace metals from the sediment, would suggest that the use of estuarine sediments as historical records of pollution requires qualification.     

Downstream patterns of bed sediment-borne metals,minerals and organic matter in a stream system receiving acidic mine effluent: A preliminary study

Different downstream variation patterns were observed for a range of bed sediment-borne metals (aqua regia-extractable fraction) in a subtropical stream system receiving acid mine drainage. Mine-originated Fe tended to be deposited in the acidic (mean pH < 4.9) upstream reach in forms of goethite and/or hematite. In contrast, other metals tended to be transported farther downstream and settled in a low-gradient reach with high pH (mean pH > 5.6). The peak of sediment-borne Al, Be, Ca, Cd, Co, Cu, La, Mn, Ni and Zn corresponded very well with the peak of the sediment-borne organic matter, suggesting a close association between the water-borne organic colloids and the inorganic metal oxides/hydroxides during their transport. The marked increase in the sediment-borne Al and Pb started more upstream than the other metals, suggesting that the water-borne Al and Pb were more susceptible to pH rise-induced precipitation, as compared to the other metals. It appeared that the organic colloids played no important role in Pb transport and settlement. The iron precipitates had a limited role to play in affecting the transport and fates of other metals since they were predominantly formed and deposited in the acidic reach, which made them incapable of scavenging cationic metals by co-precipitation or adsorption.     

Sequential extraction and leaching characteristics of heavy metals in abandoned tungsten mine tailings sediments

The chemical speciation of potentially toxic elements (As, Cd, Cu, Pb, and Zn) in the contaminated soils and sulfides-rich tailings sediments of an abandoned tungsten mine in Korea was evaluated by conducting modified BCR sequential extraction tests. Kinetic and static batch leaching tests were also conducted to evaluate the potential release of As and other heavy metals by acidic rain water and the leaching behaviors of these heavy metals. The major sources of the elements were As-, Zn- and Pb-bearing sulfides, Pb carbonates (i.e., cerussite), and Pb sulfates (i.e., anglesite). The biggest pollutant fraction in these soil and tailing samples consists of metals bound to the oxidizable host phase, which can be released into the environment if conditions become oxidative, and/or to residual fractions. No significant difference in total element concentrations was observed between the tailings sediments and contaminated soils. For both sample types, almost no changes occurred in the mobility of As and the other heavy metals at 7 days, but the mobility increased afterwards until the end of the tests at 30 days, regardless of the initial pH. However, the mobility was approximately 5–10 times higher at initial pH 1.0 than at initial pHs of 3.0 and 5.0. The leached amounts of all the heavy metal contents were higher from tailings sediments than from contaminated soils at pH > 3.0, but were lower at pH < 3.0 except for As. Results of this study suggest that further dissolution of heavy metals from soil and tailing samples may occur during extended rainfall, resulting in a serious threat to surface and groundwater in the mine area.     

Isotopic evidence of lead sources in Loire River sediment

Sediments along the Loire River (central France) were investigated by means of Pb isotopes determined on the labile sediment fraction, or acid-extractable matter (AEM). The combination of trace elements and Pb isotopes allows deciphering the origin of the elements (i.e. natural or anthropogenic) and their history, in the sediment from two small watersheds (one draining basalt, the other one granite–gneiss), both in present-day suspended matter in Loire River water, and in sediment from the Loire estuary. Crustal weathering, as confirmed by the Pb-isotope ratios for most sample points, is the main source of Pb in the upstream part of the Loire River, as well as that transported in the middle part of the basin and in the estuary. Among anthropogenic sources, the use of Pb-isotopic compositions shows an influence of agriculturally-derived Pb inputs and a major input of Pb derived from gasoline, particularly in the estuary due to harbor activities.     

Metal speciation and attenuation in stream waters and sediments contaminated by landfill leachate

The degree of metal contamination (Zn, Pb, Cu, Ni, Cd) has been investigated in the vicinity of an old unmonitored municipal landfill in Prague, Czech Republic, where the leachate is directly drained into a surface stream. The water chemistry was coupled with investigation of the stream sediment (aqua regia extract, sequential extraction, voltammetry of microparticles) and newly formed products (SEM/EDS, XRD). The MINTEQA2 speciation-solubility calculation showed that the metals (Zn, Pb, Cu, Ni) are mainly present as carbonate complexes in leachate-polluted surface waters. These waters were oversaturated with respect to Fe(III) oxyhydroxides, calcite (CaCO₃) and other carbonate phases. Three metal attenuation mechanisms were identified in leachate-polluted surface waters: (i) spontaneous precipitation of metal-bearing calcite exhibiting significant concentrations of trace elements (Fe, Mn, Mg, Sr, Ba, Pb, Zn, Ni); (ii) binding to Fe(III) oxyhydroxides (mainly goethite, FeOOH) (Pb, Zn, Cu, Ni); and (iii) preferential bonding to sediment organic matter (Cu). These processes act as the key scavenging mechanisms and significantly decrease the metal concentrations in leachate-polluted water within 200 m from the direct leachate outflow into the stream. Under the near-neutral conditions governing the sediment/water interface in the landfill environment, metals are strongly bound in the stream sediment and remain relatively immobile.     

The biogeochemical cycle of iron and associated elements in Lake Kinneret

Iron biogeochemical cycling and distribution between particulate, reactive (colloidal + dissolved, oxine-labile, Fe(II)) fractions were studied in the seasonally stratified, mesotrophic Lake Kinneret. This article presents various aspects of the Fe budget in the lake and relates them to the chemical reactivity of various physicochemical forms of Fe.The budget of Fe in Lake Kinneret is dominated by fluvial Fe load, rather than by internal recycling of Fe from the sediment, as shown by the fact that 75 to 94% of the variance in Fe concentrations in the lake can be explained by the fluctuation in the water discharge of the Jordan River. Iron associated with phytoplankton accounts for 9-16% of the bulk particulate Fe in the lake. However, within patches of the dominate algae, the dinoflagellate Peridinium gatunense, algal Fe accounts for more than 70% of the lake’s particulate Fe. The algal Fe is predominantly intracellular, and the Fe: chlorophyll a ratios were within the range of published values for dinoflagellates and cyanobacteria. Iron associated with particles larger than 0.025 μm (20-300 nM) accounts for 80-95% of total Fe in the epilimnion of Lake Kinneret throughout the year. In contrast, this fraction of Fe is dominant in the hypolimnion only during the period of lake mixing. Iron concentration of different size fractions (<0.025 μm, <0.2 μm and >0.025 μm) in the surface water covaried throughout the research period. These covariations suggest dynamic transformations of Fe between different size fractions, either due to partial dissolution/precipitation or desorption/adsorption. Oxine-labile Fe concentrations, the Fe fraction considered chemically labile and available for phytoplankton, ranged from 15 to 75 nM. In wintertime, the oxine-labile Fe accounts for only 10-20% of the total Fe, while in other seasons most of the Fe is oxine-labile. Oxine-labile Fe concentrations always exceed the 0.025 μm-filtered Fe, implying that some of the larger particles contain oxine labile-Fe, and therefore are reactive. The fraction of reactive particles in Lake Kinneret (10-80%) is high relative to that of the marine environments, and can most likely be attributed to its fluvial source, which contains a significant proportion of reactive Fe oxide and hydrous oxide particles.The annual variability in the epilimnetic concentrations of other trace elements and nutrients, such as Al, Mn, Cd, Zn, Pb, and P were studied and grouped according to their resemblance with river water discharge, redox processes, or biological uptake and scavenging. Distribution patterns of Al, Pb and Cd resembled that of Fe, suggesting that similar processes control the concentrations of these metals, namely significant contribution from the watershed, high affinity to particulate matter and little control of biota on their fate in the lake. Other elements such as Zn and P are more affected by biological uptake, while Mn is more affected by redox cycling within the lake.     

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.     

Storage of sediment-associated nutrients and contaminants in river channel and floodplain systems

Samples of fine-grained channel bed sediment and overbank floodplain deposits were collected along the main channels of the Rivers Aire (and its main tributary, the River Calder) and Swale, in Yorkshire, UK, in order to investigate downstream changes in the storage and deposition of heavy metals (Cr, Cu, Pb, Zn), total P and the sum of selected PCB congeners, and to estimate the total storage of these contaminants within the main channels and floodplains of these river systems. Downstream trends in the contaminant content of the <63 μm fraction of channel bed and floodplain sediment in the study rivers are controlled mainly by the location of the main sources of the contaminants, which varies between rivers. In the Rivers Aire and Calder, the contaminant content of the <63 μm fraction of channel bed and floodplain sediment generally increases in a downstream direction, reflecting the location of the main urban and industrialized areas in the middle and lower parts of the basin. In the River Swale, the concentrations of most of the contaminants examined are approximately constant along the length of the river, due to the relatively unpolluted nature of this river. However, the Pb and Zn content of fine channel bed sediment decreases downstream, due to the location of historic metal mines in the headwaters of this river, and the effect of downstream dilution with uncontaminated sediment. The magnitude and spatial variation of contaminant storage and deposition on channel beds and floodplains are also controlled by the amount of <63 μm sediment stored on the channel bed and deposited on the floodplain during overbank events. Consequently, contaminant deposition and storage are strongly influenced by the surface area of the floodplain and channel bed. Contaminant storage on the channel beds of the study rivers is, therefore, generally greatest in the middle and lower reaches of the rivers, since channel width increases downstream. Comparisons of the estimates of total storage of specific contaminants on the channel beds of the main channel systems of the study rivers with the annual contaminant flux at the catchment outlets indicate that channel storage represents <3% of the outlet flux and is, therefore, of limited importance in regulating that flux. Similar comparisons between the annual deposition flux of specific contaminants to the floodplains of the study rivers and the annual contaminant flux at the catchment outlet, emphasise the potential importance of floodplain deposition as a conveyance loss. In the case of the River Aire the floodplain deposition flux is equivalent to between ca. 2% (PCBs) and 36% (Pb) of the outlet flux. With the exception of PCBs, for which the value is ≌0, the equivalent values for the River Swale range between 18% (P) and 95% (Pb). The study emphasises that knowledge of the fine-grained sediment delivery system operating in a river basin is an essential prerequisite for understanding the transport and storage of sediment-associated contaminants in river systems and that conveyance losses associated with floodplain deposition exert an important control on downstream contaminant fluxes and the fate of such contaminants.     

Geomorphological assessment of sediment contamination in an urban stream system

Little is known about the influence of fluvial-geomorphological features on the dispersal of sediment-related contaminants in urban drainage systems. This study investigates the relation between reach-scale geomorphological conditions and network-scale patterns of trace-element concentrations in a partially urbanized stream system in East-Central Illinois, USA. Robust statistical analysis of bulk sediment samples reveals that levels of Cr, Cu, Pb, Ni, and Zn exceed contamination thresholds in the portion of the watershed in close proximity to potential sources of pollution—in this case storm-sewer outfalls. Although trace-element concentrations decrease rapidly downstream from these sources, substantial local variability in metal levels exists within contaminated reaches. This local variability is related to reach-scale variation in fluvial-geomorphic conditions, which in turn produces variation in the degree of sorting and organic-matter content of bed material. Metal concentrations at contaminated sites also exhibit considerable variability over time.Analytical tests on specific size fractions of material collected at a highly contaminated site indicate that Cr and Ni are concentrated in the 0.063 to 0.250 mm fraction of the sediment. This fraction also has elevated concentrations of Zr. SEM analysis shows that the fine sand fraction contains shards of stainless steel within a matrix of zircon sand, an industrial material associated with a nearby alloy casting operation. Samples of suspended load and bedload at the contaminated site also have elevated amounts of trace metals, but concentrations of Ni and Cr in the bedload are less than concentrations in the bed material, suggesting that these trace elements are relatively immobile. On the other hand, amounts of Cu and Zn in the bedload exceed concentrations in the bed material, implying that these trace metals are preferentially mobilized during transport events.     

The use of the fine fractions of stream sediments in geochemical exploration in arid and semi-arid terrains

Partitioning of Cu, Pb, Zn, U, As and Mo between the minus 70 μm and minus 200 μm fractions of stream sediments from arid and semi-arid terrains is examined in the light of published case histories supplemented by new data. The advantages of selecting a particular fraction for routine sampling in such arid environments are assessed in terms of five criteria: (1) homogeneity of background population; (2) definition of threshold; (3) absolute element abundance levels; (4) contrast between anomalous and background populations; and (5) length of dispersion train. The most homogeneous background population distributions and improved definition of the threshold between background and anomaly occur in the very fine, minus 70 μm fraction of stream sediments for the majority of elements, in particular for Zn, Cu, U and As. Data for Pb and Mo do not consistently favour either size fraction in the case histories studied. Increased abundance levels of elements which are normally close to the analytical detection limit (U, Mo, As) occur most frequently in the minus 70 μm fraction, although Cu, Pb and Zn levels are commonly higher in the coarser fraction. In addition the finer size fraction better defines the anomalous population and provides the longer dispersion trains for Cu, Pb, Zn, U and As in the majority of case histories.The data examined indicate that the minus 70 μm fraction provides more useful information, in many instances, than the minus 200 μm fraction. The evidence suggests that problems expected with the use of the fine fraction — dilution through the abundance of wind blown material, and insufficient fine sediment — do not restrict the use of this fraction in stream sediment surveys in arid terrains.     

Geographical variations of trace elements in sediments of the major rivers in eastern China

 A total of 26 geographically and hydrologically diverse sediment samples were collected from 12 major rivers in eastern China. The <63-μm fraction of the sediments was analysed for both total concentrations of Cu, Zn, Pb and Cd, and their associations with various geochemical phases. The geographical variations of sediment-bound trace metals can be related to the bedrock types and weathering processes in the corresponding river basins. The rivers in southern China had notably higher concentrations of trace metals in sediments because of abundant non-ferrous mineral deposits and stronger weathering process in the region. A large proportion of trace metals in these sediments was associated with iron and manganese oxides and organic matter. Relative low levels of trace metals were found in river sediments in northern China, and a significant proportion of the metals was bound to organic matter, carbonates, and the residual fraction. The sediments in the Yellow River, originating from special loess, had the lowest concentrations of trace metals. Most of the trace metals were associated with the carbonates and residual phases. Received: 24 March 2000 · Accepted: 11 July 2000     

Geochemical behaviour and relative mobility of metals (Mn, Cd, Zn and Pb) in recent sediments of a retention pond along the A-71 motorway in Sologne, France

 Retention ponds have been dug along some of the motorways in France to minimize environmental pollution by keeping pollutants from spreading over the surrounding area. In the current work, eight core samples were collected from the bottom of a retention pond located along the A-71 motorway in Sologne to study the pollution of sediment by heavy metals and their diagenetic behaviour. The vertical concentration profiles of metals (Pb, Zn, Cd, Fe and Mn) in sediment as well as in interstitial water were determined. Especially in the case of the sediment, a sequential extraction method was employed to investigate how the movement of each metal is associated with the other metals and with other solid phases such as organic matter. In addition, to investigate the relative mobility of the metals, the distribution coefficients (K_D) were also determined. The concentrations of the metals were always found to be highest in the topmost layer of sediment. This so-called surface enrichment is caused by a substantial increase of the non-detrital fraction of these metals at the sediment surface. For instance, the accumulation of Pb and Zn is associated with the increase in the "fraction II" in the sequential extraction. The accumulation of Cd at the surface (0–2 cm) is partly due to the liberation of Cd from the particles during early diagenesis. However, the major factor contributing to the accumulation of Cd at the sediment surface is attributed to the dissolution of Cd from polluted roadside soil during the periods of rainstorms and its subsequent redeposition on the sediment surface after being carried to the retention pond. K_D values for Zn and Cd were found to decrease with depth, while K_D values for Pb increased. Based on the K_D values, the relative mobilities of the studied metals were determined to be as follows: Mn>Zn>Cd>Pb, for the upper layer, and Mn>Cd>Zn>Pb, for the layers below. Received: 28 October 1996 / Accepted: 21 November 1996     

Relationship of manganese-iron oxides and associated heavy metals to grain size in stream sediments

The distribution of ammonium citrate-leachable lead, zinc and cadmium among size fractions in stream sediments is strongly influenced by the presence of hydrous Mn-Fe oxides in the form of coatings on sediment grains. Distribution curves showing leachable metals as a function of particle size are given for eight samples from streams in New York State. These show certain features in common; in particular two concentrations of metals, one in the finest fractions, and a second peak in the coarse sand and gravel fraction. The latter can be explained as a result of the increasing prevalence and thickness of oxide coatings with increasing particle size, with the oxides serving as collectors for the heavy metals. The distribution of Zn and Cd in most of the samples closely parallels that of Mn; the distribution of Pb is less regular and appears to be related to Fe in some samples and Mn in others. The concentration of metals in the coarse fractions due to oxide coatings, combined with the common occurrence of oxide deposition in streams of glaciated regions, raises the possibility of using coarse materials for geochemical surveys and environmental heavy-metal studies.     

Occurrence forms of trace metals in recent bottom sediments from the White and Barents Seas

For the first time based on determination of the geochemical occurrence forms of trace metals the main processes that control the accumulation of elements (Al, Mn, Fe, Mo, Cr, Ni, Co, Cu, Pb, Cd, and As) in the recent sediment cores from the White Sea and Barents Sea were quantified. A high-resolution study of the bottom sediment cores allowed us to estimate the short-term variations (periodicity of 10–15 years) in the accumulation of metals to reveal the periods of maximum Fe and Mn contents in the amorphous hydroxides fraction, which serve as effective adsorbents of the trace elements majority, including heavy metals. The Mn/Fe ratio in the amorphous hydroxides phase can be considered as geochemical indicators of early diagenesis.     

Arsenic and lead mobility: From tailing materials to the aqueous compartment

This study concerns the mineralogy of the tailings of a former Ag–Pb mine (Auzelles district, France) and the contribution of the waste materials to the heavy metal dissemination in the environment. Accumulation of metals in fish flesh was reported and this pollution is attributed to past mining activities. Tailings were studied to establish the major transfer schemes of As and Pb in order to understand their mobility that leads to contamination of a whole ecosystem. Mineralogical investigation, solubility and compliance tests were performed to assess the stability of the metal-bearing phases. Among the various metallic elements measured, As and Pb show the highest bulk concentrations (up to 0.7% and 6.3% respectively) especially for samples presenting near neutral pH values. According to X-ray diffraction (XRD), Scanning Electron Microscopy (SEM-EDX), Electron Probe Micro-Analysis (EPMA) and micro-Raman spectrometry (μRS), tailings mineralogy still contain primary minerals such as sulfides (e.g., galena, pyrite), phosphates (monazite, apatite) and/or carbonates (e.g., (hydro-)cerussite, dolomite, siderite). Sulfates (e.g., anglesite, lanarkite, plumbojarosite and beudantite) are the main secondary metal-bearing phases with other interesting phases accounting for metals mobility such as Fe and/or Pb and/or Mn oxides (e.g., lepidocrocite, goethite -up to 15 wt% of Pb was measured-, plumboferrite-type phase, mimetite). The lowest Pb solubilities were obtained at pH 8–9 and at a larger range than for As for which the lowest solubilities are reached around pH 6–7. At this minimum solubility pH value, Pb concentrations released still over exceed the National Environmental Quality Standards (NEQS), whatever the samples. The highest solubility is reached at pH 2 for both elements whatever the considered sample. This represents up to 51% of total Pb and up to 46% of total As remobilized and concentrations exceeding the NEQS. As and Pb released mainly depends on the Fe/Mn oxides (e.g., goethite, lepidocrocite) and carbonates (cerussite) which are the less stable phases. Compliance tests also show that Pb concentrations released are higher than the upper limit for hazardous waste landfills. Determination of the mineralogy allows understanding both the solubility and leaching test experiments results, as well as to forecast the impact of the residues on the water quality at a mid-term scale.