Trace Metal Concentrations in an Intensive Agricultural Watershed in British Columbia,Canada1

Abstract: Effects of agricultural intensification and a naturally occurring landslide of asbestos material upon water and sediment quality in a transboundary watershed were investigated. The water and sediments of the Sumas River watershed were analyzed for copper (Cu), zinc (Zn), chromium (Cr), and nickel (Ni) concentrations in 1993/1994 and 2003/2004 and differences within sites over time were examined. Based upon a review of the literature, Cu and Zn were used as indicators of agricultural impacts while Cr and Ni were used as indicators of impacts from an asbestos landslide. Animal unit equivalents (AUEs) were calculated on a per area basis as an indicator of livestock density using detailed statistical census data. Whatman #42 filtered metals, bioavailable metals, and sediment‐bound metals (in the <63 μm fraction) were determined at 22 sites along the mainstem and tributaries, including two reference sites. Temperature, pH, and dissolved organic carbon (DOC) were also measured. The bioavailable metal fraction was determined using the diffusive gradient thin film technique (DGT). Sediment‐bound results were compared with British Columbia’s Interim Sediment Quality Guidelines (ISQGs) and Severe Effects Levels (SELs). A Wilcoxon signed rank test was used to determine if the concentrations of metals changed significantly within sites between 1993/1994 and 2003/2004. Spearman rank correlation analysis was used to determine relationships between trace metals, water quality parameters, and AUEs/hectare. The results indicate that Cu and Zn levels in sediments increased significantly to concentrations above the ISQGs of 35.7 mg/kg and 123 mg/kg, respectively from 1993/1994 to 2003/2004 in streams, where associated land use was dominated by intensive agriculture. Higher AUEs/hectare were significantly correlated with greater bioavailable levels of Zn as well as higher sediment‐bound Zn concentrations. Neither Cu nor Cr were detected by the DGTs on any of the sampling occasions. The Cr and Ni sediment concentrations were highest in Swift Creek, the headwater tributary affected by the natural landslide of asbestos material, and decreased in the Sumas River downstream from the point of input. Cr and Ni concentrations have increased in the mid‐region of the Sumas River since 1993/1994, suggesting downstream movement of the asbestos material over time. DGT results indicated that bioavailable Zn is significantly positively correlated to sediment‐bound Zn and livestock density, and bioavailable Ni is significantly correlated to sediment‐bound Ni.     

Changes in Extractable Metal Concentrations During Storage of Surface Water Samples Containing Sediments1

ABSTRACT: Changes in metal concentrations during storage of acidified water samples were studied. Water samples with high concentrations of suspended sediment were collected from the Fraser River, British Columbia. These samples were analyzed for “extractable” metals, which are defined to be the dissolved metals plus those metals extracted from suspended sediment by dilute mineral acid. Concentrations of extractable Cu, Fe, Pb, Zn, Ni, Co, Mn, and Cd were determined over time. Metal concentrations in these water samples were not stable and showed significant increases throughout the storage period. These results suggest that the extractable metal technique is inappropriate for the analysis of water samples containing suspended sediment.     

The characterization of total and leachable metals in foundry molding sands

Waste molding sands from the foundry industry have been successfully used as a component in manufactured soils, but concern over metal contamination must be addressed before many states will consider this beneficial use. Since there is little data available on this topic, the purpose of this study was to characterize total and leachable metals from waste molding sands. A total elemental analysis for Ag, Al, As, B, Ba, Be, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb, Sb, V, and Zn was conducted on 36 clay-bonded and seven chemically bonded molding sands. Total metal concentrations in the molding sands were similar to those found in agricultural soils. The leaching of metals (i.e. Ag, As, Ba, Be, Cd, Cr, Cu, Ni, Pb, Sb, and Zn) was assessed via the toxicity characteristic leaching procedure (TCLP), synthetic precipitation leaching procedure (SPLP), and ASTM water leach test. Based on the TCLP data, none of the 43 molding sands would meet the Resource Conservation and Recovery Act (RCRA) characteristic for toxicity due to high Ag, As, Ba, Cd, Cr, and Pb. Compared to the TCLP results, the metal concentrations were generally lower in the SPLP and ASTM extracts, which is likely related to the buffering capacity of the extraction fluids.     

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.     

Heavy metals in an urban watershed in southeastern Michigan

The occurrence of heavy metals in the soil was measured over a period of several years to determine background concentrations in a heavily urbanized watershed in southeastern Michigan. A spatially dispersed sample was collected to capture the inherent variability of the soils and historic land use. The analysis focused on 14 metals (antimony, arsenic, barium, beryllium, cadmium, chromium, copper, lead, mercury, nickel, selenium, silver, thallium, and zinc) that are part of the USEPA's list of the 129 most common pollutants. Metal concentrations were measured at three depths: near-surface (<0.5 m), shallow subsurface (0.5-10 m), and depths greater than 10 m across six soil units in glacial terrain. Additional analyses assessed the metal concentrations in each depth profile across three general land use categories: residential, commercial, and industrial. Metal concentrations were the highest in the near-surface with Pb present at concentrations averaging 15.5 times that of background in industrial areas and approximately 16 times background in residential areas. Cadmium, Hg, and Zn were also present in surface soils at levels of several times that of background. The highest concentrations of each of these metals were present in the clay-rich soils located in the eastern, more urbanized and industrialized part of the watershed. Metals detected at elevated concentrations decreased in concentration with increasing depth and distance from the urbanized and industrialized center of the watershed. Statistically significant differences in the concentrations of heavy metals were also noted between the land use categories, with Cd, Cr, Cu, Pb, Ni, and Zn observed within industrial areas at mean concentrations several times greater than background levels.     

Cottongrass effects on trace elements in submersed mine tailings

Phytostabilization may limit the leakage of metals and As from submersed mine tailings, thus treatment of acid mine drainage with lime could be reduced. Tall cottongrass (Eriophorum angustifolium Honckeny) and white cottongrass (E. scheuchzeri Hoppe) were planted in pots with unlimed (pH 5.0) and limed (pH 10.9) tailings (containing sulfides) amended with sewage sludge (SS) or a bioashsewage sludge mixture (ASM). Effects of the amendments on plant growth and plant element uptake were studied. Also, effects of plant growth on elements (Cd, Cu, Pb, Zn, and As), pH, electrical conductivity (EC), and concentrations of SO4(2-), in the drainage water as well as dissolved oxygen in tailings, were measured. Both plant species grew better and the shoot element concentrations of white cottongrass were lower in SS than in ASM. Metal concentrations were lowest in drainage water from limed tailings, and plant establishment had little effect on metal release, except for an increase in Zn levels, even though SO4(2-) levels were increased. In unlimed tailings, plant growth increased SO4(2-) levels slightly; however, pH was increased and metal concentrations were low. Thus, metals were stabilized by plant uptake and high pH. Amendments or plants did not affect As levels in the drainage water from unlimed tailings. Thus, to reduce the use of lime for stabilizing metals, phytostabilization with tall cottongrass and white cottongrass on tailings is a sound possibility.     

Elemental contaminants in groundwater: A study of trace metals from residential area in the vicinity of an industrial area in Lagos, Nigeria

Groundwater (well water) from a residential area within the vicinity of an industrial estate in Lagos, Nigeria were sampled and analysed by Flame Atomic Absorption Spectroscopy for their heavy metals content. This was with a view of assessing the quality of the water, which was being used for domestic activities, especially, drinking usually without treatment. Total trace metal determination by mineral acid digestion of water samples was applied. This method proved to be better than an extractive concentration technique in the quality assurance protocols with the recovery range being 90.7 ± 0.006–97.6 ± 0.003%. Mean concentration of trace metals in water samples ranged from Fe: 0.05–0.47 mg l⁻¹; Al: 0.1–1.54 mg l⁻¹; Cu: 0.14–1.39 mg l⁻¹; Zn: 0.04–0.43 mg l⁻¹; Cd: trace–0.02 mg l⁻¹; Pb: trace–0.03 mg l⁻¹, Mn: 0.01–0.18 mg l⁻¹ and Ni: 0.02–0.11 mg l⁻¹. Physical parameters of water samples examined were within the drinking water safety limits except for conductivity. Results generally indicate the presence of heavy metal constituents in groundwater samples. Detection of metals such as cadmium and lead which have serious health implications above WHO and USEPA limits in drinking water gives cause for concern.     

Relationships between bacterial tolerance levels and forms of copper and zinc in soils

The effects of various fractions of copper (Cu) and zinc (Zn) on soil bacteria were evaluated by the heavy metal tolerance level of the bacterial community (IC50) in soil samples collected near a mine. The IC50 values had no relationship with the total concentrations of Zn and Cu in the soils, but were weakly correlated with the 0.05 M CaCl2-extractable form of each metal in the soils (Cu: R2 = 0.670, p < 0.01; Zn: R2 = 0.453, p < 0.05). It was found that the IC50 correlated strongly with the total concentration of each metal in the extracts from water-saturated soil samples, described below as "soil solution" (Cu: R2 = 0.789, p < 0.01; Zn: R2 = 0.617, p < 0.01). The speciation of these metals in the soil solutions was estimated using an equilibrium thermodynamic computer model, SOILCHEM. Simulated free Cu ion ranged from 18 to 98% of total Cu, and organic complexes of Cu ranged from < 1 to 56%. In all samples, Zn existing as the free ion was estimated to be more than 80% of total Zn in the soil solutions. The IC50 values were also correlated with the estimated free metal ion activities, but with slightly lower correlation coefficients than found for total concentration in the soil solutions (Cu: R2 = 0.735, p < 0.01; Zn: R2 = 0.610, p < 0.01). The results suggest that not only high metal ion activities, but also total dissolved metal concentrations in soil solutions may affect the bacterial community.     

Nitrogen fertilization effects on stream water cadmium concentration

High transition metal concentrations were previously unexpectedly observed in soil water extracted by suction lysimeters following forest N fertilization. This observation called for additional measurements to investigate if the finding is a general phenomenon and, if so, whether stream water concentrations of transition metals could increase as a result of N fertilization. The measured levels of Cd in the preliminary findings were well above health limits for drinking water. Hence, the problem could be of major concern. Here we report on soil water and stream water concentrations at two partly fertilized watersheds. All sites were situated in the central part of Sweden. The N application (150 kg N ha(-1) in the form of calcium ammonium nitrate) resulted in increased concentrations of nitrate, and a pulse of acidity through the soil profile, which increased the solubility of transition metals (mainly Cd and Zn) and Al. Stream water concentrations of transition metals, on the other hand, were not affected during the studied period by the increased solubility of transition metals in the soil. The data imply that the solubilized transition metals probably insolubilize further down the soil profile, and that there is no risk from forest N fertilization (at normal soil pH levels) of transition metal levels increasing in nearby surface waters. To our knowledge, this is the first time this side effect of N fertilization has been considered.     

Effect of liming on the distribution of heavy metals in untreated industrial sewage sludge produced in Pakistan for the cultivation of <Emphasis Type="Italic">Sorghum bicolor</Emphasis> (L.)

The recycling of sewage sludge on agriculture land represents an alternative, advantageous, disposal of this waste material. The aim of the present study was to evaluate the feasibility of using industrial sewage sludge, produced in Pakistan, as a fertiliser. Agricultural soil amended with 25% (w/w) sewage sludge with or without lime treatment was used for growing a variety of sorghum (PARC-SS-1). The mobility of the heavy metals (HMs) (Cd, Cu, Cr, Ni, Pb and Zn) and metalloid (As) in the untreated industrial waste water sewage sludge (UIWS) samples were assessed by applying a modified BCR (Community Bureau of Reference) sequential extraction procedure. The single extraction procedure comprised of the application of mild extractant (CaCl₂) and water for the estimation of the proportion of easily soluble metal fractions. The precision and accuracy of BCR was evaluated by using a certified reference material of soil amended with sewage sludge BCR 483. The plant available metal contents, as extracted by the deionised water and 0.01 M CaCl₂ solution and exchangeable fraction of BCR sequential, decreased with lime application in the range of 10–44% for As, Cr, Ni, Pb and Zn, except in the cases of Cd and Cu, where their mobility was increased by 10% and 24%, respectively. Sludge amendment enhanced the dry weight yield of sorghum and the increase was more obvious after liming up to 25%. The uptake of HMs were lower in test samples (3.2–21.8%), except for Cu and Cd, which was higher (4%), while they were below the permissible limit of these metals. The present experiment demonstrates that liming was important in factors facilitating the growth of sorghum in sludge-amended soil.     

Near- and mid-infrared diffuse reflectance spectroscopy for measuring soil metal content

Rapid and nondestructive methods such as diffuse reflectance infrared spectroscopy provide potentially useful alternatives to time-consuming chemical methods of soil metal analysis. To assess the utility of near-infrared reflectance spectroscopy (NIRS) and diffuse mid-infrared reflectance spectroscopy (DRIFTS) for soil metal determination, 70 soil samples from the metal mining region of Tarnowskie Gory (Upper Silesia, Poland) were analyzed by both chemical and spectroscopic methods. Soils represented a wide range of pH (4.0-8.0), total carbon (5.1-73.2 g kg(-1)), and textural classes (from sand to silty clay loam). Soils had various contents of metals (14-4500 mg kg(-1) for Zn, 18-6530 mg kg(-1) for Pb, and 0.17-34 mg kg(-1) for Cd), ranging from natural background levels to high contents indicative of industrial contamination in the region. Soil samples were scanned at the wavelengths from 400 to 2498 nm (near-infrared region) and from 2500 to 25000 nm (mid-infrared region). Calibrations were developed using the one-out validation procedure under partial least squares (PLS) regression. Mid-infrared spectroscopy markedly outperformed NIRS. Iron, Cd, Cu, Ni, and Zn were successfully predicted using DRIFTS. The coefficients of determination (R(2)) between actual and predicted contents were 0.97, 0.94, 0.80, 0.99, and 0.96 for those metals, respectively. Only Pb content was predicted poorly. Calibrations using NIRS were less accurate. Root mean squared deviation (RMSD) values were from 1.27 (Pb) to 3.3 (Ni) times higher for NIRS than for DRIFTS. Results indicate that DRIFTS may be useful for accurate predictions of metals if samples originate from one region.     

Stability constants for the complexation of various metals with a rhamnolipid biosurfactant

The presence of toxic metals in natural environments presents a potential health hazard for humans. Metal contaminants in these environments are usually tightly bound to colloidal particles and organic matter. This represents a major constraint to their removal using currently available in situ remediation technologies. One technique that has shown potential for facilitated metal removal from soil is treatment with an anionic microbial surfactant, rhamnolipid. Successful application of rhamnolipid in metal removal requires knowledge of the rhamnolipid-metal complexation reaction. Therefore, our objective was to evaluate the biosurfactant complexation affinity for the most common natural soil and water cations and for various metal contaminants. The conditional stability constant (log K) for each of these metals was determined using an ion-exchange resin technique. Results show the measured stability constants follow the order (from strongest to weakest): Al3+ > Cu2+ > Pb2+ > Cd2+ > Zn2+ > Fe3+ > Hg2+ > Ca2+ > Co2+ > Ni2+ > Mn2+ > Mg2+ > K+. These data indicate that rhamnolipid will preferentially complex metal contaminants such as lead, cadmium, and mercury in the presence of common soil or water cations. The measured rhamnolipid-metal stability constants were found in most cases to be similar or higher than conditional stability constants reported in the literature for metal complexation with acetic acid, oxalic acid, citric acid, and fulvic acids. These results help delineate the conditions under which rhamnolipid may be successfully applied as a remediation agent in the removal of metal contaminants from soil, as well as surface waters, ground water, and wastestreams.     

Characteristics of slag, fly ash and deposited particles during melting of dewatered sewage sludge in a pilot plant

This study examines slag, fly ash, and deposited particles during melting of dewatered sewage sludge in a pilot plant. In addition, the chemical composition of particles in flue gas was simulated using a thermodynamics program, namely FACTSage 5.2. The results showed that the main components of slag were Al, Fe, Ca, P and Si; the minor components were Na, K, Mg, Cu, and Zn. The main chemical compound of slag was Ca4(Mg,Fe)5(PO4)6. For fly ash particles, heavy metals with the highest concentrations were in the order of Zn and As, Pb, Cu, and Cd, respectively. For non-heavy metals, Al, Fe and P were also found in significant amounts. The majority of deposited particles were composed of elements of Zn, P, S, Na, Fe, Al, Si, and Ca and such chemical compounds as Zn3(PO4)2, AlPO4, FePO4 and Fe(OH)3 while the minority consisted of elements of As, Cu, and Pb. Moreover, the compositions of deposited particles in each chamber differed due to different flue gas temperatures inside. In the secondary chamber at 760 degrees C, the amounts of Fe and Al were higher than Zn, whereas, in the other chambers (600-400 degrees C), the amount of Zn was higher. In other words, at the lower temperature the deposition of Zn was higher than the deposition of Fe and Al. In the water cooling section, volatile elements (i.e. Zn, As, Cu, Pb) were found in the highest concentrations due to a big difference in temperature between the wall surface and flue gas. From the simulation results, most of the elements in the gas phase were found to be chloride compounds, whereas those in the solid phase were in the form of oxide, sulfate, and phosphate compounds.     

Novel passive co-treatment of acid mine drainage and municipal wastewater

A laboratory-scale, four-stage continuous-flow reactor system was constructed to test the viability of high-strength acid mine drainage (AMD) and municipal wastewater (MWW) passive co-treatment. Synthetic AMD of pH 2.6 and acidity of 1870 mg L(-1) as CaCO3 equivalent containing a mean 46, 0.25, 2.0, 290, 55, 1.2, and 390 mg L(-1) of Al, As, Cd, Fe, Mn, Pb, and Zn, respectively, was added at a 1:2 ratio with raw MWW from the City of Norman, OK, to the system which had a total residence time of 6.6 d. During the 135-d experiment, dissolved Al, As, Cd, Fe, Mn, Pb, and Zn concentrations were consistently decreased by 99.8, 87.8, 97.7, 99.8, 13.9, 87.9, and 73.4%, respectively, pH increased to 6.79, and net acidic influent was converted to net alkaline effluent. At a wasting rate of 0.69% of total influent flow, the system produced sludge with total Al, As, Cd, Cr, Cu, Fe, Pb, and Zn concentrations at least an order of magnitude greater than the influent mix, which presents a metal reclamation opportunity. Results indicate that AMD and MWW passive co-treatment is a viable approach to use wastes as resources to improve water quality with minimal use of fossil fuels and refined materials.     

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.     

阿尔金山保护区地表水部分重金属背景值调查与分析

根据实地考察,采集了阿尔金山保护区主要地表水体的水质样本。受考察期限和水质样本保存要求与期限限制,只对样本中铜、锌、镉等重金属指标进行了检测,分析了各指标与《地表水环境质量标准》中不同标准限值的关系,及其在地理空间上的分布规律。本次考察分析的结果可作为后期水质考察的背景信息,是进一步开展保护区水环境调查和研究的基础。     

柴窝堡湖表层底泥重金属污染评价

研究了乌鲁木齐市柴窝堡湖表层底泥的重金属含量,并采用Hakanson潜在生态危害指数法对底泥中的重金属潜在生态风险进行评价。结果表明:底泥中Cu、Zn、Pb、Cd含量均超出乌鲁木齐市土壤背景值。除湖心区外,Cd在5个监测区域中的潜在生态危害均为中等;其它重金属在5个采样点的潜在生态危害均为轻微。各重金属间的相关性分析表明,Zn与Cu,Pb与Cd、Cu呈显著正相关,说明这4种元素污染源可能相同。柴窝堡湖表层底泥受到Cu、Zn、Pb、Cd污染,需采取相应措施防止重金属由底泥进入水相。     

On-farm evaluation of aluminum sulfate (alum) as a poultry litter amendment: effects on litter properties

Aluminum sulfate [alum; Al2(SO4)3] amendment of poultry litters has been suggested as a best management practice to help reduce the potential environmental effects of poultry production. Past research has shown that alum treatment reduced NH3 emissions from litters, decreased the loss in runoff of P and trace metals from litter-amended soils, improved poultry health, and reduced the costs of poultry production. We conducted a large scale, "on-farm" evaluation of alum as a poultry (broiler) litter amendment on the Delmarva peninsula to determine the effect of alum on (i) litter properties and elemental composition and (ii) the solubility of several elements in litter that are of particular concern for water quality (Al, As, Cu, P, and Zn). Alum was applied over a 16-mo period to 97 poultry houses on working poultry farms; 97 houses on other farms served as controls (no alum). Litter samples were analyzed initially and after approximately seven alum applications. We found that alum decreased litter pH and the water solubility of P, As, Cu, and Zn. Alum-treated houses also had higher litter total N, NH4-N, and total S concentrations and thus a greater overall fertilizer value than litters from the control houses. Higher litter NH4-N values also suggest that alum reduced NH3 losses from litters. Thus, alum appears to have promise as a best management practice (BMP) for poultry production. Future research should focus on the long-term transformations of P, Al, As, Cu, and Zn in soils amended with alum-treated litters.     

Iron and Zinc status in soils, water and staple food cultivars in Itakpe, Kogi State of Nigeria

The levels of iron (Fe) and zinc (Zn) were quantitatively determined in soil and water samples as well as in staple food cultivars in Itakpe, Nigeria's major iron mining town. The survey was conducted to establish a baseline pollution index for Fe and Zn in the Itakpe environment and to evaluate the role of foods as an exogenous source of these metals among the inhabitants. Exceedingly high levels of both metals characterized the staple food cultivars in the town.     

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.