Multivariate statistics to investigate metal contamination in surface soil

The modification of soil composition in the urbanized area of Ankara due to wet-dry deposition and pollution-derived particles from the atmosphere is investigated by analyzing 120 surface soil samples, collected from the urbanized area and its un-urbanized surrounding, for major, minor and trace elements. Concentrations of elements from human activity (e.g. Cd, Pb, Cr, Zn, Cu and Ca) in the urbanized area were higher than their corresponding concentrations in global average soil and soil in un-urbanized areas outside the urbanized area. Metal contents in soil were very high in densely populated districts and around some industrial facilities. The only exception was Pb distribution, which was more dispersed, due to the nature of motor vehicle emissions. Alteration of the Cd, Zn, Cu and Cr content of soil was confined to the inhabited and industrial areas, whereas enrichment factors of these elements were close to unity in the remaining study area. Factor analysis identified two polluted soil factor associations. One factor includes elements, such as Zn and Cd, which had high factor scores in inhabited areas and the other factor (high loading of Pb) represents soil polluted by motor vehicle emissions.     

Characteristic levels of heavy metals in soil profiles of automobile mechanic waste dumps in Nigeria

The characteristic levels of heavy metals (Cd, Cr, Cu, Pb, Ni and Zn) of soil profiles of automobile mechanic waste dumps were studied. The concentration of heavy metals decreased with the depth of the profile and lateral distance from the dumpsites. The levels found in this study exceeded background concentrations and limits for agricultural and residential purposes. The distribution pattern of heavy metals in the soil profiles were in the following order Pb > Zn > Cu > Cd > Ni > Cr. The mechanic waste dumps represent potential sources of heavy metal pollution to environment. The elevated levels of heavy metals in these soil profiles constitute a serious threat to both surface and groundwater.     

Heavy metal distribution and chemical speciation in tailings and soils around a Pb-Zn mine in Spain

Soil pollution by lead, zinc, cadmium and copper was characterized in the mine tailings and surrounding soils (arable and pasture lands) of an old Spanish Pb-Zn mine. Sixty soil samples were analyzed, determining the total metal concentration by acid digestion and the chemical fractionation of Pb and Zn by the modified BCR sequential extraction method. Samples belonging to mine waste areas showed the highest values, with mean concentrations of 28,453.50 mg kg(-1) for Pb, 7000.44 mg kg(-1) for Zn, 20.57 mg kg(-1) for Cd and 308.48 mg kg(-1) for Cu. High concentrations of Pb, Zn and Cd were found in many of the samples taken from surrounding arable and pasture lands, indicating a certain extent of spreading of heavy metal pollution. Acidic drainage and wind transport of dust were proposed as the main effects causing the dispersion of pollution. Sequential extraction showed that most of the Pb was associated with non-residual fractions, mainly in reducible form, in all the collected samples. Zn appeared mainly associated with the acid-extractable form in mine tailing samples, while the residual form was the predominant one in samples belonging to surrounding areas. Comparison of our results with several criteria reported in the literature for risk assessment in soils polluted by heavy metals showed the need to treat the mine tailings dumped in the mine area.     

Plant-available zinc and lead in mine spoils and soils at the mines of Spain, Iowa

To investigate the forms of Zn and Pb and their plant availability in mine spoil long after its abandonment, we studied seven sites in the Mines of Spain, near Dubuque, IA. Ores of Zn and Pb were mined from dolomitic limestone primarily during the 19th century, and there had been no subsequent remediation of metals-contaminated spoil. From both mine spoil and undisturbed areas, we collected root-zone soil samples as well as samples of the dominant ground-level, native plants, aniseroot [Osmorhiza longistylis (Torr.) DC.] and black snakeroot (Sanicular marilandica L.). We determined Zn and Pb concentrations in both the plant tissue and in the soil samples after strong-acid digestion, and we fractionated the solid-phase forms of Zn, Pb, and P in the soil samples by using sequential extraction. Concentrations of total Zn and Pb were 10- to 20-fold greater in the spoil than in the undisturbed soils. Plants growing in the mine spoil had Zn concentrations two to four times greater and Pb concentrations more than 26 times greater than did plants growing in the undisturbed soils. The highest concentrations of Zn and Pb were in the CBD-extractable and the residual fractions in both undisturbed and mine spoil samples. Although the mine spoil contained large amounts of P, Zn, and Pb were available for uptake by the two plant species in amounts proportional to Zn and Pb concentrations in the rooting zone.     

Fate of biosolids trace metals in a dryland wheat agroecosystem

Biosolids land application for beneficial reuse applies varying amounts of trace metals to soils. Measuring plant-available or total soil metals is typically performed to ensure environmental protection, but these techniques do not quantify which soil phases play important roles in terms of metal release or attenuation. This study assessed the distribution of Cd, Cr, Cu, Mo, Ni, Pb, and Zn associated with soluble/exchangeable, specifically adsorbed/carbonate-bound, amorphous Mn hydroxyoxide-bound, amorphous Fe hydroxyoxide-bound, organically complexed, and residual inorganic phases. Biosolids were applied every 2 yr from 1982 to 2002 (except in 1998) at rates of 0, 6.7, 13.4, 26.8, and 40.3 dry Mg biosolids ha(-)(1) to 3.6- by 17.1-m plots. In 2003, 0- to 20-cm and 20- to 60-cm soil depths were collected and subjected to 4 mol L(-1) HNO(3) digestion and sequential extraction. Trace metals were concentrated in the 0- to 20-cm depth, with no significant observable downward movement using 4 mol L(-1) HNO(3) or sequential extraction. The sequential extraction showed nearly all measurable Cd present in relatively mobile forms and Cr, Cu, Mo, Ni, Pb, and Zn present in more resistant phases. Biosolids application did not affect Cd or Cr fractionation but did increase relatively immobile Cu, Mo, and Zn phases and relatively mobile Cu, Ni, and Pb pools. The mobile phases have not contributed to significant downward metal movement. Long-term, repeated biosolids applications at rates considered several times greater than agronomic levels should not significantly contribute to downward metal transport and ground water contamination for soils under similar climatic conditions, agronomic practices, and histories.     

Assessment of contamination from arsenical pesticide use on orchards in the Great Valley region, Virginia and West Virginia, USA

Lead arsenate pesticides were widely used in apple orchards from 1925 to 1955. Soils from historic orchards in four counties in Virginia and West Virginia contained elevated concentrations of As and Pb, consistent with an arsenical pesticide source. Arsenic concentrations in approximately 50% of the orchard site soils and approximately 1% of reference site soils exceed the USEPA Preliminary Remediation Goal (PRG) screening guideline of 22 mg kg(-1) for As in residential soil, defined on the basis of combined chronic exposure risk. Approximately 5% of orchard site soils exceed the USEPA PRG for Pb of 400 mg kg(-1) in residential soil; no reference site soils sampled exceed this value. A variety of statistical methods were used to characterize the occurrence, distribution, and dispersion of arsenical pesticide residues in soils, stream sediments, and ground waters relative to landscape features and likely background conditions. Concentrations of Zn, Pb, and Cu were most strongly associated with high developed land density and population density, whereas elevated concentrations of As were weakly correlated with high orchard density, consistent with a pesticide residue source. Arsenic concentrations in ground water wells in the region are generally <0.005 mg L(-1). There was no spatial association between As concentrations in ground water and proximity to orchards. Arsenic had limited mobility into ground water from surface soils contaminated with arsenical pesticide residues at concentrations typically found in orchards.     

Total Contents and Sequential Extraction of Heavy Metals in Soils Irrigated with Wastewater,Akaki, Ethiopia

The Akaki River, laden with untreated wastes from domestic, industrial, and commercial sources, serves as a source of water for irrigating vegetable farms. The purpose of this study is to identify the impact of waste-water irrigation on the level of heavy metals and to predict their potential mobility and bioavailability. Zn and V had the highest, whereas Hg the lowest, concentrations observed in the soils. The average contents of As, Co, Cr, Cu, Ni, Zn, V, and Hg of both soils; and Pb and Se from Fluvisol surpassed the mean + 2 SD of the corresponding levels reported for their uncontaminated counterparts. Apparently, irrigation with waste water for the last few decades has contributed to the observed higher concentrations of the above elements in the study soils (Vertisol and Fluvisol) when compared to uncontaminated Vertisol and Fluvisol. On the other hand, Vertisol accommodated comparatively higher average levels of Cr, Cu, Ni, Zn, etc V, and Cd, whereas high contents of Pb and Se were observed in Fluvisol. Alternatively, comparable levels of Co and Hg were found in either soil. Except for Ni, Cr, and Cd in contaminated Vertisol, heavy metals in the soils were not significantly affected by the depth (0–20 and 30–50 cm). When the same element from the two soils was compared, the levels of Cr, Cu, Ni, Pb, Se, Zn, V, Cd at 0–20 cm; and Cr, Ni, Cu, Cd, and Zn at 30–50 cm were significantly different. Organic carbon (in both soils), CEC (Fluvisol), and clay (Vertisol) exhibited significant positive correspondences with the total heavy metal levels. Conversely, Se and Hg contents revealed perceptible associations with carbonate and pH. The exchangeable fraction was dominated by Hg and Cd, whereas the carbonate fraction was abounded with Cd, Pb, and Co. conversely, V and Pb displayed strong affinity to reducible fraction, where as Cr, Cu, Zn, and Ni dominated the oxidizable fraction. Cr, Hg, Se, and Zn (in both soils) showed preference to the residual fraction. Generally, a considerable proportion of the total levels of many of the heavy metals resided in non residual fractions. The enhanced lability is generally expected to follow the order: Cd > Co > Pb > Cu > Ni > Se > V and Pb > Cd > Co > Cu > Ni > Zn in Vertisol and Fluvisol, respectively. For the similar wastewater application, the soil variables influence the status and the distribution of the associated heavy metals among the different soil fractions in the study soils. Among heavy metals that presented relatively elevated levels and with potential mobility, Co, Cu, Ni (either soil), V (Vertisol), Pb, and Zn (Fluvisol) could pose health threat through their introduction into the food chain in the wastewater irrigated soils.     

Prediction of zinc, cadmium, lead, and copper availability to wheat in contaminated soils using chemical speciation, diffusive gradients in thin films, extraction, and isotopic dilution techniques

To predict the availability of metals to plants, it is important to understand both solution- and solid-phase processes in the soil, including the kinetics of metal release from its binding agent (ligand and/or particle). The present study examined the speciation and availability of Zn, Cd, Pb, and Cu in a range of well-equilibrated metal-contaminated soils from diverse sources using several techniques as a basis for predicting metal uptake by plants. Wheat (Triticum aestivum L.) was grown in 13 metal-contaminated soils and metal tissue concentrations (Zn, Cd, Pb, and Cu) in plant shoots were compared with total soil metal concentrations, total soluble metal, and free metal activities (pM2+) in soil pore waters, 0.01 M CaCl2-extractable metal concentrations, E values measured by isotope dilution, and effective metal concentrations, C(E), measured by diffusive gradients in thin films (DGT). In the DGT technique, ions are dynamically removed by their diffusion through a gel to a binding resin, while E values represent the isotopically exchangeable (labile) metal pools. Free metal activities (Zn2+, Cd2+, and Pb2+) in soil pore waters were determined using a Donnan dialysis technique. Plant Zn and Cd concentrations were highly related to C(E), while relationships for Zn and Cd with respect to the other measures of metals in the soils were generally lower, except for CaCl2-extractable Cd. These results suggest that the kinetically labile solid-phase pool of metal, which is included in the DGT measurement, played an important role in Zn and Cd uptake by wheat along with the labile metal in soil solution. Plant Pb concentrations were highly related to both soil pore water concentrations and C(E), indicating that supply from the solid phase may not be so important for Pb. Predictions of Cu uptake by wheat from these soils by the various measures of Cu were generally poor, except surprisingly for total Cu.     

Watershed-scale assessment of arsenic and metal contamination in the surface soils surrounding Miyun Reservoir,Beijing, China

Concentrations of As and selected metals were determined in surface soils of the Miyun Reservoir watershed of Beijing, China. The degree to which concentrations of As and metals exceeded the corresponding background concentration of soils was: Cr > Cu > Zn > As > Ni with no apparent anthropogenic contamination with Cd and Pb. Based on the results of a combination of multivariate statistics and geostatistical analysis, greater concentrations of Cr and Ni in soils were determined to be primarily from iron ore mining near where the Chaohe River enters the northeast portion of the reservoir. Agricultural activities were responsible for the observed elevated concentrations of Cu and Zn in soils. Relatively great concentrations of As were found in soils near the upstream regions of the Baihe River in Chicheng County where small gold mining activities have taken place. The greatest potential for adverse effects of Cr and Cu occurred along the eastern shore of Miyun Reservoir.     

Metal distribution and stability in constructed wetland sediment

The A-01 wetland treatment system (WTS) is a surface flow wetland planted with giant bulrush [Schoenoplectus californicus (C.A. Mey.) Palla] that is designed to remove Cu and other metals from the A-01 National Pollution Discharge Elimination System (NPDES) effluent at the Savannah River Site near Aiken, SC. Copper, Zn, and Pb concentrations in water were usually reduced 60 to 80% by passage through the treatment system. The Cu concentrations in the wetland sediments increased from about 4 to 205 and 796 mg kg(-1), respectively, in the organic and floc sediment layers in cell 4A over a 5-yr period. Metal concentrations were higher in the two top layers of sediment (i.e., the floc and organic layers) than in the deeper inorganic layers. Sequential extraction was used to evaluate remobilization and retention of Cu, Pb, Zn, Mn, and Fe in the wetland sediment. Metal remobilization was determined by the potentially mobile fraction (PMF) and metal retention by the recalcitrant factor (RF). The PMF values were high in the floc layer but comparatively low in the organic and inorganic layers. High RF values for Cu, Zn, and Pb in the organic and inorganic layers indicated that these metals were strongly bound in the sediment. The RF values for Mn were lower than for the other elements especially in the floc layer, indicating low retention or binding capacity. Retention of contaminants was also evaluated by distribution coefficient (Kd) values. Distribution coefficient (Kd) values were lower for Cu and Zn than for Pb, indicating a smaller exchangeable fraction for Pb.     

DISSOLVED HEAVY METALS IN SHALLOW GROUND WATER IN A SOUTHEASTERN MICHIGAN URBAN WATERSHED1

ABSTRACT: The occurrence of dissolved heavy metal concentrations in shallow ground water were measured at 126 sites within an urban watershed in southeastern Michigan. A total of 1,140 samples were collected from the first saturated zone, and the mean concentrations of 11 heavy metals (arsenic, barium, cadmium, chromium, copper, lead, mercury, nickel, selenium, silver, and zinc) were obtained and compared to their corresponding mean concentrations within surface soil. The results suggest that former and current land use processes have resulted in significant adverse impacts on the study region. Levels of Cr 20 to 30 times the maximum contaminant level (MCL) have been detected in the ground water beneath industrial sites. In addition, Cd and Pb have been found at levels exceeding their MCLs where surface soils are clay‐rich, and in sandy soils at more than 10 times their MCLs. The high levels of Cr in ground water strongly suggest that the chromium is in a hexavalent form, and this likelihood is supported by current studies. Given the hydraulic connection between the watershed's surface waters and the Great Lakes, these findings raise significant ecological and public health concerns.     

Understanding heavy metal and suspended solids relationships in urban stormwater using simulated rainfall

Urban stormwater from simulated rainfall on three different landuses in Queensland State, Australia (residential, industrial, commercial) was analysed for heavy metals and physico-chemical parameters such as Dissolved Organic Carbon (DOC) and Total Suspended Solids (TSS). Rainfall events were simulated using a specially designed rainfall simulator for paved surfaces. Event mean concentration samples were separated into five different particle sizes and analysed individually for eight metal elements (Zn, Fe, Cr, Cd, Cu, Al, Mn and Pb). Multivariate data analysis was carried out for the data thus generated. It was found that DOC and TSS influence the distribution of the metals in the different particle size classes. Zn was correlated with DOC at all three sites. Similarly, Pb, Fe and Al were correlated with TSS at all sites. The distribution of Cu was found to vary between the three sites, whilst Cd concentrations were too low to assess any relationships with other parameters. No correlation between Electrical Conductivity (EC), pH and heavy metals was found at the three sites. The identification of physico-chemical parameters influencing the distribution process kinetics of heavy metals in urban stormwater will significantly enhance the efficiency of urban stormwater management systems.     

Arsenic, cadmium, and lead in California cropland soils: role of phosphate and micronutrient fertilizers

Phosphate and micronutrient fertilizers contain potentially harmful trace elements, such as arsenic (As), cadmium (Cd), and lead (Pb). We investigated if application of these fertilizer increases the As, Cd, and Pb concentrations of the receiving soils. More than 1000 soil samples were collected in seven major vegetable production regions across California. Benchmark soils (no or low fertilizer input) sampled in 1967 and re-sampled in 2001 served as a baseline. Soils were analyzed for total concentrations of As, Cd, Pb, P, and Zn. The P and Zn concentrations of the soils were indicators of P fertilizer and micronutrient inputs, respectively. Results showed that the concentrations of these elements in the vegetable production fields in some production areas of California had been shifted upward. Principal component analysis and cluster analysis showed that the seven production areas could be sorted into three categories: (i) enrichment of As, Cd, and Pb, which was associated with the enrichment of P and Zn in one of the seven areas surveyed; (ii) enrichment of As, which was associated with enrichment of Zn in two of the seven areas surveyed; and (iii) no remarkable correlation between enrichment of As, Cd, and Pb and enrichment of P and Zn in the other four areas surveyed.     

Seasonal Flushing of Pollutant Concentrations and Loads in Urban Stormwater1

Schiff, Kenneth C. and Liesl L. Tiefenthaler, 2011. Seasonal Flushing of Pollutant Concentrations and Loads in Urban Stormwater. Journal of the American Water Resources Association (JAWRA) 47(1):136‐142. DOI: 10.1111/j.1752‐1688.2010.00497.x Abstract: Despite broad observations of first flush within storms, the scientific understanding of seasonal flushing remains incomplete. Seasonal flushing occurs when initial storms of the season have greater concentrations or loads than storms later in the season. The goal of this study was to census stormwater concentrations and loads from an arid, urban watershed to quantify seasonal flushing. Samples were collected every 15 min during the 1997‐1998 wet season from the Santa Ana River and analyzed for total suspended solids. Initial storms of the season generated event mean concentrations 3‐10 times the event mean concentration of storms later in the season. Cumulative flow‐weighted mean concentrations were calculated as the season progressed. Early season storms discharged only 6% of the annual volume, but influenced flow‐weighted mean concentrations well past the midpoint of the wet season. Mass‐based estimates also indicated a disproportionate load in the early portion of the year; over 52% of the annual load was discharged in the first 30% of the annual volume from the highly urbanized lower watershed. Other stormwater pollutants, including six trace metals (Cd, Cr, Cu, Pb, Ni, Zn), were highly correlated with total suspended solids and also exhibited a significant seasonal flush.     

Industrial impact on marsh soils at the Bahia Blanca Ria, Argentina

The Bahia Blanca Estuary is located in southern Buenos Aires province, Argentina. The area is linked to a petrochemical industrial complex, whose raw materials and final products contaminate the surrounding areas via atmospheric pollution and effluents, which are dumped in the estuary waters. To establish the effects of the industrial waste disposal on the nearest coastal soils, 17 samples were taken at different distances from the loading dock and the outfall pipes of the industrial complex. Later, the physicochemical characteristics of the soil samples, their hydrocarbon contents, sulfides, sulfates, Zn, Cu, and Pb were analyzed and a comparison was made to control samples, which were not affected by the industrial outfall. Hydrocarbons, Zn, Cu, and Pb contents were found at levels that modified the physical and chemical characteristics of the soils. The resistance to penetration shows that the thinner the film of water that surrounds the particles or aggregates, the smaller the migration of organic micelle, which settle on the surface of the contact material. This is demonstrated by the degree of cohesion reached by the particles and the strong influence on the index of hydrophobicity. The high porosity shows that the continuity of the porous space of the soil matrix is impeded by the presence of pollutants, which generate areas that are highly limiting to water flow. The oxidation-reduction potential and the low concentrations of soluble forms of Cu and Pb compared with their concentrations precipitated as sulfides confirm the action of the pollutants.     

宝山区农用土壤中重金属的监测与评价

在研究的8种重金属元素中,Cd、Cr、Cu、Pb、Zn、Ni的平均值都超过上海市土壤背景值,但均低于国家土壤环境二级标准。与上海优质农产地环境标准相比较,重金属含量平均值超过标准的有Cr、Pb、Zn,但研究区土壤中8种重金属含量的平均值均低于绿色食品产地环境技术条件和无公害食品产地环境技术条件。宝山区7个城镇农业土壤按多因子潜在生态危害指数评价,庙行镇的生态风险指数最高,月浦镇的生态风险指数最低。从宝山区农田土壤重金属含量的整体情况来看:多因子潜在生态评价值为119.08,宝山区农田土壤达到轻微生态危害。     

Distribution and movement of sludge-derived trace metals in selected Nigerian soils

Use of metal-rich sewage sludge as soil fertilizer may result in trace- metal contamination of soils. This study was conducted to evaluate the effects of long-term sludge application on trace-metal (Zn, Cu, Pb, and Ni) distribution and potential bioavailability in Nigerian soils under a tropical wet-dry climate. Total metal analyses, sequential chemical fractionation, and DTPA extractions were carried out on samples of control and sludge-amended pedons in Nigeria (a Rhodic Kandiustult and two Rhodic Kandiustalfs from Nigeria, respectively). The sewage sludge applied to the soils contained higher levels of Zn and Cu than Pb and Ni. The control pedon contained low levels of all four metals. Soil enrichment factors (EF) were calculated for each metal in the sludge-amended pedons. Compared with the control soil, the sludge-amended pedons showed elevated levels of Zn and Cu, reflecting the trace-metal composition of the sewage sludge. Zinc and Cu in the sludge-amended soils were strongly enriched at all depths in the profile, indicating that they had moved below the zone of sludge application. The sequential extraction and DTPA analyses indicated that the sludge-amended soils contained more readily extractable and bioavailable metal ions than the unamended soil.     

Heavy metal content and distribution in surface sediments of the Seyhan River, Turkey

Chemical fractionation of seven heavy metals (Cd, Cr, Cu, Mn, Ni, Pb and Zn) was studied using a modified three-step sequential procedure to assess their impacts in the sediments of the Seyhan River, Turkey. Samples were collected from six representative stations in two campaigns in October 2009 and June 2010, which correspond to the wet and dry seasons, respectively. The total metal concentrations in the sediments demonstrated different distribution patterns at the various stations. Cadmium was the only metal that was below detection at all stations during both sampling periods. Metal fractionation showed that, except for Mn and Pb, the majority of metals were found in the residual fraction regardless of sampling time, indicating that these metals were strongly bound to the sediments. The potential mobility of the metals (non-residual fractions) is reflected in the following ranking: Pb > Mn > Zn > Cu > Ni > Cr in October 2009 and Mn > Pb > Zn > Cu > Ni > Cr in June 2010. The second highest proportion of metals was bound to organic matter/sulfides, originating primarily from anthropogenic activities. Non-residual metal fractions for all stations were highest in June 2010, which may be linked to higher organic matter concentrations in the sediment samples with 1.40% and 15.1% in October 2009 and June 2010, respectively. Potential sediment toxicity was evaluated using the Risk Assessment Code (RAC). Based on RAC classification, Cd and Cr pose no risk, Cu and Ni pose low risk, Pb and Zn were classified as medium risk metals, while the environmental risk from Mn was high. In addition, based on the sediment quality guidelines (SQG), the Seyhan River can be classified as a river with no, to moderate, toxicological risks, based on total metal concentrations.     

Metal contamination in sediments of the western Bohai Bay and adjacent estuaries, China

Twelve sediment cores were collected in July 2007 in open waters of western Bohai Bay, the Port of Tianjin, and the adjacent estuaries of the Haihe and Yongding Rivers. While overall concentrations of trace metals at incremental depths in these cores met the Marine Sediment Quality (GB18668-2002) criteria of China, the magnitude of both metal enrichment factors (EF) and geoaccumulation indices (I(geo)) suggested that pollution with Ag, Cd, Cr, Cu and Zn was occurring in the estuaries and Port. Risk analysis also suggested that Ag and Ni concentrations were sufficiently elevated as to cause adverse biological effects in the study area. Although metal concentrations in western Bohai Bay were of less concern, a positive relationship between EF values and excess (210)Pb activity for several metals suggested that their concentrations were increasing over time.     

Heavy metal release from contaminated soils: comparison of column leaching and batch extraction results

Heavy metals in soils may adversely affect environmental quality. In this study, we investigated the release of Zn, Cd, Pb, and Cu from four contaminated soils by column leaching and single and sequential batch extractions. Homogeneously packed soil columns were leached with 67 mL/g 10(-2) M CaCl2 to investigate the exchangeable metal pool and subsequently with 1400 mL/g 10(-2) M CaCl2 adjusted to pH 3 to study the potential of metal release in response to soil acidification. In two noncalcareous soils (pH 5.7 and 5.1), exchange by Ca resulted in pronounced release peaks for Zn and Cd that were coupled to the exchange of Mg by Ca, and 40 to 70% of total Zn and Cd contents were rapidly mobilized. These amounts compared well with exchangeable pools determined in single and sequential batch extractions. In two soils with near-neutral pH, the effluent concentrations of Zn and Cd were several orders of magnitude lower and no pronounced elution peaks were observed. This behavior was also observed for Cu and Pb in all four soils. When the soils were leached at pH 3, the column effluent patterns reflected the coupling of CaCO3 dissolution (if present) and other proton buffering reactions, proton-induced metal release, and metal-specific readsorption within the soil column. Varying the flow rate by a factor of five had only minor effects on the release patterns. Overall, Ca exchange and subsequent acidification to pH 3 removed between 65 and 90% of total Zn, Cd, Pb, and Cu from the four contaminated soils.