Heavy metal migration at a landfill site,Sarnia, Ontario,Canada—I. Thermodynamic assessment and chemical interpretations

The transition metals Fe, Cu, Zn and Pb have diffused only 10–20 cm into the clay barrier at the Confederation Road landfill compared to 130 cm for porewater chloride. Other major dissolved species, including the alkali and alkaline earth metals, have also diffused out of waste landfill and into clay subsoils more rapidly than the metals. Redox potentials, E_h, indicate strongly reducing conditions (E_h= − 130 mV) in the clayey soil at the subsoil/waste interface and increase to +50 mV at a depth of 45 cm below the interface. pH values are close to 8 within the subsoil but the slightly lower values (7.8–8) near the interface may result from production of organic acids during degradation of the wastes. Thermodynamic analysis of subsoil pore waters indicates that Fe, Cu, Zn and Pb exist primarily as metal-hydroxy complexes of the forms [MeOH]⁺ and [Me(OH)₂]⁰, although a complex of [PbCl]⁺ may be significant, but not predominant. The analysis also demonstrates that the dissolved transition metal concentrations of the subsoil pore waters are controlled at carbonate mineral saturation levels, whereas Fe concentrations in leachate solutions associated with the wastes are controlled at FeS₂ saturation levels.Thermodynamic calculations and E_h-pH diagrams suggest that Fe(OH)₂, Zn(OH)₂ and Pb(OH)₂ are not stable phases in the solids of the subsoil. This means that observed “hydroxide” phases reported in the selective dissolution analysis by Yanful and Quigley (1986) have to be re-evaluated.     

Trace element concentrations of soils, plants and waters caused by a copper smelting plant and other industries, Northeast Turkey

The study area is situated in a large agricultural field which produces tobacco, maize, and other yearly cultivated vegetables in Tekkeköy, Samsun (NE-Turkey). In addition, a significant part of this area to the north along the Black Sea coast is occupied by several industrial plants such as a copper smelting plant (KB?), a fertilizer plant (Tügsa?) and industrial park facilities (IPF). In order to reveal their environmental impacts, heavy metal analyses were conducted on soil, plant leaves and water samples collected within an area of approximately 30 km² around these plants. Soil samples within an area of 10 km² around these facilities are found to be highly polluted with Cu, Zn, Pb, Fe and Mn. Pollution occurs at surface and sharply dies out at 20 cm downwards in soil profile. Since the region is polluted mostly with base metals, the copper smelting factory appears to be the main source of pollution as it processes the massive sulfidic ores of the Black Sea area. Plants show Cu, Pb, Zn and Fe pollution around KB? and Tügsa? and Cu and Pb around IPF. Pollutants observed in tobacco (Nicotiana tobacum) are Cu, Pb, Zn, Fe and S; in maize (Zea mays) Cu, Zn and Fe; and in cabbage (Brassica oleracea) Cu, Pb, Fe and S. The analyses of water samples collected from the study area reveal that Pb and, to a lesser degree, Cu and Fe pollution stem from KB?; Cu, Fe and Mn pollution from Tügsa?; Pb and minor amounts of Fe and Mn pollution from IPF. Factor analyses from analyzed metals and anionic complexes in water show three distinct groups: (a) an association of heavy metals with Na, K and Mg referring to pollution and acid leaching of soil, (b) an association of NH4, Fe, SO₄, Cl and Br indicating agricultural pollution and sea-water invasion in land near the shore line, and (c) HCO₃ behaving in a different manner in heavy metal precipitation.     

Monitoring and modelling of the solid-solution partitioning of metals and As in a river floodplain redox sequence

For a period of 2 a, pore water composition in a heavily contaminated river floodplain soil was monitored in situ. Pore water samples were collected 12 times over all seasons in a profile ranging from aerobic to sulphidic redox conditions, and As, Cd, Cr, Cu, Pb, Zn, Mn, Fe, Ca, Cl, SO₄, DOC, IOC and pH were determined. The variability of pH, IOC, DOC and Ca was found to be rather small during the year and within the profile (rsd < 0.04, 0.16, 0.24 and 0.22, respectively). The temporal variability of the metal and As concentrations was small, too, whereas changes with depth were distinct. Under sulphidic conditions, concentrations were below 1 μg L⁻¹ (Cd, Cu, Pb) or 10 μg L⁻¹ (Zn, As). The data set was compared with results from a geochemical model that was fully parameterised from literature data and included equilibrium speciation, sorption and mineral dissolution. The general pattern of the solid–solution partitioning of Cd, Cu, Zn and As in the profile was predicted well by mechanistic geochemical modelling on the basis of solid phase composition. Metals strongly bound to organic matter such as Cd and Cu were predicted better than metals mainly present within a mineral. Detailed information regarding the presence of colloidal Fe and Mn in pore water might improve the prediction of the solid–solution partitioning of a number of metals. The study also indicates that the chemical behaviour of Pb is still not understood sufficiently.     

宁沪高速公路句容段两侧土壤磁化率异常与重金属元素的关系研究

高速公路两侧土壤的磁化率从路中央向两侧具有逐渐降低的特征,相对应的样品中的重金属Cu、Pb、Zn、N i、Cr、Fe等元素的含量也具有从路中心向两侧逐渐降低的现象。相关分析表明,土壤磁化率与土壤中的Cu、Pb、Zn、N i、Cr、Fe的相关性显著,因而可以利用磁化率异常来指示高速公路两侧土壤的重金属污染状况。元素的赋存形态分析表明铁锰氧化物态与残渣态是Cu、Pb、Zn、N i、Cr、Fe的主要赋存形式;各元素的形态分析结果与土壤磁化率的相关统计分析表明,高速公路两侧土壤的磁化率与可交换态中的Cu、Pb、Zn、铁锰氧化物态中的Fe、Pb、Zn、有机还原态中的Cu、Cr、Fe、Zn和残渣态中的Cu、Pb、Zn、Cr、Co、N i具有明显的相关性。     

Laboratory and field evidence in support of the electrogeochemically enhanced migration of ions through glaciolacustrine sediment

Ionic aureoles, overlying or contiguous to massive sulphide occurrences, are postulated to have been emplaced as a result of natural galvanic forces. The occurrences of these galvanic forces, most commonly referred to as the self-potential or spontaneous polarization phenomena, are well documented, but ionic migration in response to these electrical forces remained to be proven conclusively.The purpose of this study was to attempt to document ionic migration attributable solely to electrogeochemical transport. Pleistocene glaciolacustrine sediments rich in clay-size particles was the geological substrate chosen to minimize migration processes other than those of electrogeochemical transport.Laboratory experiments which simulated a field situation and utilized the radioisotope ⁶⁵Zn as a tracer, revealed a readily detectable diffusion of Zn²⁺ into glaciolacustrine clay; the distance of penetration of the Zn²⁺ being significantly increased by the application of a DC electrical potential, similar in magnitude to a natural self-potential. The rate of diffusion was greatest around the margins of the cathodic electrode located at the base of the clay layers; the areas shown to have the greatest current density. The resulting pattern of Zn penetration into the clay, when viewed in a vertical section, showed a double peaked increase in Zn concentration on either side, and a distinct decrease in Zn penetration directly above this cathode. Extrapolation of the average diffusion coefficient found for Zn²⁺ (D₀ = 6.3 × 10⁻⁹cm s⁻¹) to other ions commonly associated with base metal deposits, revealed that only H⁺ could be expected to move through appreciable thicknesses (>20 m) of clay in the 8000 years since sediment deposition.The hypothesis that H⁺ would diffuse through varved clay, and that the resulting pattern would be predictably modified by a self-potential field generated by an oxidizing sulphide body, was tested over the Magusi River volcanogenic massive sulphide deposit near Noranda, Quebec. The organic soil horizon (H) and top of the clay soil layer (C) were sampled and analyzed for conductivity, pH, and other major and minor elements. The mineral horizon revealed distinct changes in conductivity, pH, Ca, Mg, and Fe above the contacts of the hanging wall and footwall of the sulphide horizon, thus producing a double-peaked “rabbit-ear” anomalous pattern. The H soil horizon, when corrections for variable “total” element and carbon concentrations were applied, showed clear anomalies in Fe and other pH sensitive elements. A ratio of EDTA Fe/TOTAL Fe to total organic carbon revealed the best “rabbit-ear” anomaly above the sulphide horizoon. The use of organic horizon geochemistry as a method of evaluating EM conductors overlain by water-saturated lacustrine sediments is recommended.     

The mechanisms of forming iron-base metal gossan minerals

Laboratory studies of the weathering of sulphide ores have centred around using samples of ore as electrodes and accelerating the weathering processes by passing an electric current. The results of reacting 19 different ore types under varying conditions are compared with data from co-precipitating, Fe and Cu, Fe and Ni, Fe and Zn, Fe and Co, and Fe and Pb, over a pH range from 2 to 11. An electrochemical cell specially designed to fit onto an optical microscope has allowed direct observation of the changes in sulphide mineral grains as they are anodically weathered.These experiments are used to demonstrate that the pH of the environment during the weathering of sulphides to sulphates is the most important parameter in determining the initial gossan minerals that form. Factors that will cause the pH to be high are buffering from gangue and wallrock minerals, low iron content in the sulphide and a high metal to sulphur ratio in the sulphide. A low pH is favoured by the converse, namely a sulphide sufficiently massive to override the buffering effects of the wallrocks and any gangue minerals present, a high iron content in the sulphide and a low metal to sulphur ratio in the sulphide.Two mechanisms of iron hydrolysis dominate the weathering processes where iron is a major metal being released from a sulphide.

1. (1) The high pH process. Where there is sufficient buffering for the pH to remain at or above 7, most of the base metals including ferrous iron will be hydrolysed and pyroaurite type of minerals form for Ni, Zn and Co, while mixed Fe-Cu hydroxycarbonates and hydroxysulphates form for Cu, and mixed iron lead hydrocarbonates form for Pb. The iron is located in these initial compounds as a green rust where it is effectively bound as ferrous hydroxide. Subsequent oxidation of this hydroxide produces no further acid. 4Fe(OH)₂ + O₂ + 2H₂0 → 4Fe(OH)₃

2. (2) The low pH process. Where the buffering is insufficient and the pH is below 7, even though some of the ferrous iron will have precipitated as an equivalent to Fe(OH)₂, the solubility is such that sufficient Fe²⁺ will remain in solution so that further oxidation will produce acid. 4Fe²⁺ + O₂ + 1OH₂O → Fe(OH)₃ + 8H⁺ This acid will bring more of the Fe²⁺ into solution to create more acid and the pH will gradually fall even further, so that the gossan forming environment will be at a pH less than 5 and may be as low as 3. At these low pH values, the base metals are soluble and not prone to co-precipitation or adsorption with the gossan minerals. Only elements present in solution as anions, such as Se, As, Mo and Sb, are likely to be bound into gossans forming at low pH.

The results from weathering tests carried out on gossan minerals formed at higher pH show that these minerals are reasonably stable if treated with solutions that have a pH above 7, but they can break down if treated with a solution of pH 5. Thus they could be expected to be leached by rain water saturated with CO₂.When investigating a likely gossan, all aspects — the iron oxides, the silicates, the carbonates and penetrations into the footwall and hanging wall — should be examined carefully, being ever mindful of the effect that pH would have had during the formation and reworking of the minerals. The composition of gossan minerals, their adsorption properties, the solubilities of metal ions, the mechanisms of Fe precipitation, the co-precipitation of other metals with Fe, the stability of carbonates and the binding of humic materials are all pH dependent in the same way. At high pH, metals are immobilized; at low pH, they tend to be in solution.     

Multi-metal contaminant dynamics in temporarily flooded soil under sulfate limitation

In many river basins, floodplain soils have accumulated a variety of metal contaminants, which might be released during periods of flooding. We investigated the dynamics of copper, cadmium, lead, zinc, and nickel in a contaminated freshwater floodplain soil under a realistic sulfate-limited flooding regime in microcosm experiments. We found that most contaminants were initially mobilized by processes driven by the reductive dissolution of Fe(III) and Mn(IV, III) (hydr)oxides. Subsequently, bacterial sulfate respiration resulted in the transformation of the entire available sulfate (2.3 mmol/kg) into chromous reducible sulfur (CRS). Cu K-edge X-ray absorption fine structure (XAFS) spectroscopy revealed that the soil Cu speciation changed from predominantly Cu(II) bound to soil organic matter (SOM) intermittently to 14% metallic Cu(0) and subsequently to 66% copper sulfide (Cu_xS). These Cu_xS precipitates accounted for most of the formed CRS, suggesting that Cu_xS was the dominant sulfide phase formed in the flooded soil. Sequential metal extractions, in agreement with CRS results, suggested that easily mobilizable Cd was completely and Pb partially sequestered in sulfide precipitates, controlling their dissolved concentrations to below detection limits. In contrast, Zn and Ni (as well as Fe) were hardly sequestered into sulfide phases, so that micromolar levels of dissolved Zn and Ni (and millimolar dissolved Fe(II)) persisted in the reduced soil. The finding that Cu, Cd, and Pb were sequestered (but hardly any Zn, Ni, and Fe) is consistent with the thermodynamically predicted sulfide ladder following the increasing solubility products of the respective metal sulfides. The observation that Cd and Pb were sequestered in sulfides despite the presence of remaining SOM-bound Cu(II) suggested that the kinetics of Cu(II) desorption, diffusion, and/or Cu_xS precipitation interfered with the sulfide ladder. We conclude that the dynamics of multiple metal contaminants are intimately coupled under sulfate limitation by the relative thermodynamic stabilities and formation kinetics of the respective metal sulfides.     

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.     

Mineral components in a peat deposit: looking for signs of early mining and smelting activities in Silesia–Cracow region (Southern Poland)

The results of investigations (SEM/EDS and AAS) of a peat deposit, spanning 13,000 years of peat accumulation, are shown. The peat deposit is located in a region of shallow occurrence of Zn–Pb ores, near Tarnowskie Góry town, within the Cracow–Silesia district (southern Poland). Exploitation of lead, silver and iron during the medieval times (Twelfth and thirteenth century) was confirmed by historical documents whereas there are no unambiguous data showing that there was metal mining during the Romanian or earlier times in the region. The peat deposit is located within the influence of atmospheric Pb and Zn emission from a nearby Zn–Pb smelter. Two vertical peat profiles were investigated (120 and 140 cm depth of profile) showing variable concentrations of Zn up to 713 mg kg^?1, Pb up to 317 mg kg^?1, Cd up to 13 mg kg^?1 and Tl up to 31 mg kg^?1. The highest concentrations were recorded for the uppermost peat layers. SEM and EDS investigations revealed the occurrence of metalbearing, submicroscopic mineral components: Fe, Mn, Ti and Zn oxides and Zn and Pb carbonates. The top layer of the deposit contained Zn, Pb and Cd sulphides. The occurrence of aggregates of Au–Ag, Cu–Zn and Au–Ag–Cu alloys can be possibly related to pre-historical mining and smelting or be explained by geochemical transformations. The preservation of carbonates and oxides in the peat is discussed, indicating a generally neutral to alkaline peat water chemistry and maintenance of an oxidized environment in the fen.     

Mercury and other metal and metalloid soil contamination near a Pb/Zn smelter in east Hunan province, China

The spatial distributions of contaminant metals (Hg, Pb, Zn, Cd, Cu) and a metalloid (As) in vegetable plots and paddy fields located near a large scale Pb/Zn smelter in Hunan province, China, were investigated. Soil located 4 km from the smelter was severely contaminated, with maximum concentrations of Hg, Pb, Zn, Cd, Cu and As as high as 2.89, 1200, 3350, 41.1, 157 and 93 mg kg⁻¹, respectively. Concentrations of soil metal and As decreased with distance in the dominant wind direction. Single-factor assessment indicated pollution levels of Hg, Pb, Zn and Cd were most severe, while pollution levels for Cu and As were less severe. Results from a potential ecological risk assessment indicated high risk associated with the soil within a 4 km radius, with the contribution for each contaminant calculated as follows: Cd (70.0%), Hg (19.4%), Pb (4.8%), As (3.0%), Cu (1.7%) and Zn (1.1%). The forest soil in the nearby city park was also affected by the atmospheric depositions from smelting activities. Soil profiles demonstrated the pollutants were mostly accumulated in the upper 20 cm layer. Contamination of the topsoil with Hg, Pb, Zn, Cd, Cu and As indicated remediation should be considered.     

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.     

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.     

Heavy metal distribution and environmental status of Doon Valley soils, Outer Himalaya, India

 Doon Valley is surrounded by two major river systems (Ganga and Yamuna) on either side, with a water divide passing nearly across the centre of the valley, and is sandwiched between two mountain ranges in the fragile ecological systems of the Himalayan foothills. In total 398 soil samples were collected from the valley in a grid pattern (∼1 sample per 2 km²) and investigated for their heavy metal (Cr, Cu, Ni, Pb and Zn) abundances that are environmentally sensitive. Comparison of the heavy metal abundances with the contamination threshold values (CTV) revealed that most of these elemental abundances in Doon Valley soils fall well within the range of the uncontaminated to slightly contaminated category. In the case of Cr and Ni, a sizeable number of samples exceeded the CTV (250 and 100 mg kg^–1 respectively) with an overall background value of 109 and 52 mg kg^–1 respectively. Sites of high Cr and Ni mostly occur in the Ganga Catchment (GC) sector that includes even relatively undisturbed forestland. The source of this contamination is attributed to geological factors which indicate contribution from the mafic volcanics of the Lesser Himalaya. This is also consistent with the distribution pattern of Mn and Fe, though their abundance levels are not alarming. The background concentration of Pb is low (22 mg kg^–1) in Doon Valley soils; however, signs of gradual Pb contamination are palpable in and around the centre of the Dehra Dun city and along the highways. Aluminium normalized heavy metal ratios were found to exhibit narrow variability in the case of Cu, Ni and Cr and had good correlation with Al, indicating their affinity and association with the clay minerals. On the other hand, Pb and Zn seem to be associated with non-silicate sources. Received: 7 January 2000 · Accepted: 30 July 2000     

pH effects in the adsorption of heavy metal ions by clays

The amount of hydroxonium or hydroxyl ion sorbed by the sodium form of clays (kaolin, illite or montmorillonite) has been found to increase in proportion with the amount added (i.e., data fits a Boedeker type equation). The adsorptive capacities, and bonding strengths (as evaluated from Langmuir isotherm plots) varied with clay type and nature of the adsorbing species (values for OH^? being greater than for H⁺).The presence of clay suspensions reduced the pH required for total precipitation of heavy metal ions (e.g., Cu, Pb, Cd, Zn), as hydroxy species, and this behaviour has been re-examined in terms of observed pM, pOH relationships and the effect of ligand additions.     

Enrichment pattern of leachable trace metals in roadside soils of Miri City,Eastern Malaysia

This article presents the results on distribution and enrichment pattern of acid-leachable trace metals (ALTMs) from roadside soil of Miri city, Sarawak, East Malaysia. The city is one of the fastest developing in the Malaysian region with huge petroleum resources. ALTMs Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn and Cd along with organic carbon and carbonates (CaCO₃) were analyzed in 37 soil sediments collected from roadside. The enrichment of ALTMs [especially Cu (0.4–13.1 μg g^?1), Zn (9.3–70.7 μg g^?1), Pb (13.8–99.1 μg g^?1)] in the roadside soils indicate that these metals are mainly derived from sources related to traffic exhausts, forest fires and oil refineries. The comparative study and enrichment pattern of elements indicates that Mn, Cu, Zn and Pb are enriched multi-fold than the unpolluted soil and Ni, Pb, Cd in some samples compared to Sediment Quality Guidelines like Lowest Effect Level (LEL) and Effects Range Low (ERL) in the region which is mainly due to the recent industrial developments in the region.     

Effects of grazing and livestock exclusion on soil physical and chemical properties in desertified sandy grassland,Inner Mongolia,northern China

Heavy grazing is recognized as one of the main causes of vegetation and soil degradation and desertification in the semiarid Horqin sandy grassland of northern China. Soil physical and chemical properties were examined under continuous grazing and exclusion of livestock for 8 years in a representative desertified sandy grassland. Exclosure increased the mean soil organic C, total N, fine sand and silt + clay contents, inorganic C (CaCO₃), electrical conductivity, and mineral contents (including Al₂O₃, K₂O, Na₂O, Fe₂O₃, CaO, MgO, TiO₂, MnO), microelements (Fe, Mn, Zn, B, Cu, Mo), and heavy metals (Pb, Cr, Ni, As, Hg, Cd, Se), and decreased the coarse sand content, bulk density, and SiO₂ in the top 100 cm of the soil. Livestock exclusion also improved available N, P, K, Fe, Mn, and Cu, exchangeable K⁺, and the cation exchange capacity, but decreased pH, exchangeable Na⁺, and available S, Zn, and Mo in the top 20 cm of the soil. The greatest change in soil properties was observed in the topsoil. The results confirm that the desertified grassland is recovering after removal of the livestock disturbance, but that recovery is a slow process.     

Particulate metal speciation in surficial sediments from Loch Dee, southwest Scotland, U.K.

The geochemical partitioning of ten elements in stratified Holocene sediments from Loch Dee, southwest Scotland, has been established by use of a five-stage sequential extraction procedure. Samples from below 15 cm sediment depth show minimal evidence of modification by anthropogenic contamination or active diagenesis and hold Fe, Mg, Cu, Cd, Co, Pb, and Ni primarily in detrital silicates or organic complexes, while Mn, Ca, and Zn reside largely in adsorbed and reducible oxide phases. In the uppermost ca 15 cm of sediment, enhanced total concentrations of Zn, Cu, and Pb reflect increased atmospheric deposition during the postindustrial period. Of these metals, only Pb displays any notable adjustment of partitioning in the enriched zone, showing disproportionate accumulation in labile oxides and organic-Pb phases. The lack of Pb and Zn carbonates in the contaminated horizon may reflect inherent thermodynamic instability under the acid surface and pore-water conditions of Loch Dee. Increments to total Mn and Co in the surficial ca 5 cm of sediment are attributable to the accumulation of secondary oxides and adsorbed species, consistent with precipitation from the interstitial pore-waters across a sedimentary redox front. The presence of metals such as Zn and Cd in soluble or acid-volatile phases in the interfacial sediment has implications for the future management of the Loch Dee basin, with leaching into the overlying waters likely, given the continuation of current trends of lake acidification.     

Mine waste dumps and heavy metal pollution in abandoned mining district of Boccheggiano (Southern Tuscany, Italy)

 Mining activity in the Boccheggiano-Fontalcinaldo area (Southern Tuscany) dates back at least to the 16th century AD and lasted up to very recent times. Copper-rich hydrothermal veins, massive pyrite deposits, and their gossans were exploited. Two mine waste dumps (Fontalcinaldo, Fontebona), one flotation tailings impoundment (Gabellino), and one roasting/smelting waste dump (Merse-Ribudelli) in the study area were selected to ascertain the environmental effects of such protracted mining activity. Primary waste mineralogy is mainly characterized by pyrite, gypsum, quartz, carbonates, chlorites, and micas. Secondary oxidation mineralogy includes Fe and Cu sulfates and hydroxy sulfates, Cu carbonates, Fe and Al oxyhydroxides, and other phases [neogenic cassiterite at Fontalcinaldo; probable calkinsite, (Ce,La)₂(CO₃)₃· 4H₂O, at Fontebona]. Mine waste samples show extremely variable contents of toxic elements (Cu, Pb, Zn, Bi, Cd, As), with average values in the order of hundreds to thousands of parts per million (except for Bi and Cd). In some samples, the abundance of proper minerals of these metals cannot account for the entire metal load. Conceivably, either solid solution substitutions or adsorption processes contribute to the intake of released metals into newly formed minerals. Release and transport of pollutants was affected to variable degrees by acid-neutralization processes. The highest metal and acid concentrations occur close to the investigated wastes and rapidly decrease moving downstream some hundreds of meters or less, with the partial exception for Mn and Fe. Other than dilution effects, this phenomenon may be ascribed to metal adsorption and precipitation of solid phases. Received: 16 April 1995 · Accepted: 14 December 1995     

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.     

Selenium and heavy metals content in some Mediterranean soils

The study of metal contents in industrial, agricultural or/and polluted soils compared with natural or unpolluted soils is currently necessary to obtain reference values and to assess soil contamination. Nonetheless, very few works published appear in international journals on elements like Se, Li and Sr in Spanish soils. This study determines the total levels of Se, Li, Sr, As, Cd, Co, Cr, Cu, Ni, Pb, V, Zn, Fe, Mn and Ba in 14 natural (unpolluted) soils (Gypsisols, Leptosols, Arenosols and Acrisols), 14 agricultural soils (Anthrosols, Fluvisols and Luvisols), and 4 industrial–urban affected-surface soil horizons (Anthrosols and Fluvisols) of Eastern Spain. The geochemical baseline concentrations (GBC) and reference values (RV) have been established, and the relationships among elements and also between soil properties and elemental concentrations have been analysed. The RV obtained in this study were (mg kg⁻¹): Se 2.68, Li 115, Sr 298, Cd 0.97, Co 35, Cr 217, Cu 46, Ni 50, Pb 137, V 120, Zn 246, Fe 124,472, Mn 2691, and Ba 743. The RV for Se and Li were used as a preliminary approach to assess soil contamination in Spanish soils. The results confirm human impact on Sr, As, Cd, Cr, Cu, Ni, Pb and Zn soil concentrations, but evidence no deviation from natural Se, Li, Co, V, Fe, Mn and Ba concentrations. The results obtained from the statistical analysis reveal significant correlations between some elements and clay and soil organic matter (SOM) contents, indicating that metal concentrations are controlled by soil composition. One particularly interesting finding is the high correlation coefficients obtained between SOM and Se, Cd, Cr, V, Fe, and Mn, and between clay and Cd, Zn, V, Fe and Mn. Once again, these facts confirm the role of SOM and clay minerals in soil functions and that soil is an ecosystem element responsible for maintaining environmental quality.