Showing papers in "Environmental Science & Technology in 1996"

Mechanisms of Slow Sorption of Organic Chemicals to Natural Particles

Abstract: The use of equilibrium expressions for sorption to natural particles in fate and transport models is often invalid due to slow kinetics. This paper reviews recent research into the causes of slow sorption and desorption rates at the intraparticle level and how this phenomenon relates to contaminant transport, bioavailability, and remediation. Sorption kinetics are complex and poorly predictable at present. Diffusion limitations appear to play a major role. Contending mechanisms include diffusion through natural organic matter matrices and diffusion through intraparticle nanopores. These mechanisms probably operate simultaneously, but the relative importance of each in a given system is indeterminate. Sorption shows anomalous behaviors that are presently not well explained by the simple diffusion models, including concentration dependence of the slow fraction, distributed rate constants, and kinetic hysteresis. Research is needed to determine whether adsorption/desorption bond energies may play a role alon...

Gas/Particle Partitioning and Secondary Organic Aerosol Yields

Abstract: Secondary organic aerosol (SOA) formation is considered in the framework of the gas/particle partitioning absorption model outlined by Pankow Expressions for the fractional SOA yield (Y) are developed within this framework and shown to be a function of the organic aerosol mass concentration, M_o These expressions are applied to over 30 individual reactive organic gas (ROG) photooxidation smog chamber experiments Analysis of the data from these experiments clearly shows that Y is a strong function of M_o and that secondary organic aerosol formation is best described by a gas/particle partitioning absorption model In addition to the 30 individual ROG experiments, three experiments were performed with ROG mixtures The expressions developed for Y in terms of M_o, used in conjunction with the overall yield data from the individual ROG experiments, are able to account for the M_o generated in the ROG mixture experiments This observation not only suggests that SOA yields for individual ROGs are additive but that smog chamber SOA yield data may be confidently extrapolated to the atmosphere in order to determine the important ambient sources of SOA in the environment

Source Apportionment of Atmospheric Polycyclic Aromatic Hydrocarbons Collected from an Urban Location in Birmingham, U.K.

Abstract: Intensive seasonal sampling campaigns were undertaken at an urban location in Birmingham, U.K., in which high-volume samplers were used to collect particulate- and vapor-phase polycyclic aromatic hydrocarbons (PAHs) by means of filter papers and polyurethane foam plugs. Eighteen PAH species were determined by reversed-phase HPLC. Additionally, the suspended particle loading of the air was measured gravimetrically. Dichotomous stacked filter units (DSFUs) were run simultaneously with the high-volumes enabling the collection of particulate matter representative of fine (<2.1 μm) and coarse sized (2.1−10 μm) fractions. Filters from the DSFUs were analyzed for 19 metal species [by proton induced X-ray emission (PIXE)], ammonium, elemental carbon, and various anions. Metal and PAH concentrations were observed to be broadly in line with concentrations measured at other urban areas throughout the U.K. Chemical source apportionment studies took the form of principal component analysis (PCA) followed by multi-line...

Peer reviewed: tracking the distribution of persistent organic pollutants.

Abstract: Control strategies for these contaminants will require a better understanding of how they move around the globe.

Estimation of lead and arsenic bioavailability using a physiologically based extraction test

Abstract: The physiologically based extraction test (PBET) is an in vitro test system for predicting the bioavailability of metals from a solid matrix and incorporates gastrointestinal tract parameters representative of a human (including stomach and small intestinal pH and chemistry, soil-to-solution ratio, stomach mixing, and stomach emptying rates). For lead (Pb), the results of the PBET are linearly correlated with results from a Sprague-Dawley rat model (r2 = 0.93 between in vitro and in vivo results, n = 7). For arsenic (As), the results of the PBET are overpredicting bioavailability study results in rabbit and primate models (2−11% difference between in vitro and in vivo results, depending on the animal model). The PBET was not designed to supplant bioavailability studies using animal models, but rather to estimate Pb and As bioavailability when animal study results are not available. Dissolution of Pb in the acidic stomach environment was strongly pH dependent; the extent of dissolution decreased by 65% whe...

Microbial Reduction of Crystalline Iron(III) Oxides: Influence of Oxide Surface Area and Potential for Cell Growth

Abstract: Quantitative aspects of microbial crystalline iron(III) oxide reduction were examined using a dissimilatory iron(III) oxide-reducing bacterium (Shewanella alga strain BrY). The initial rate and lon...

Reduction of Nitro Aromatic Compounds by Zero-Valent Iron Metal

Abstract: The properties of iron metal that make it useful in remediation of chlorinated solvents may also lead to reduction of other groundwater contaminants such as nitro aromatic compounds (NACs). Nitrobenzene is reduced by iron under anaerobic conditions to aniline with nitrosobenzene as an intermediate product. Coupling products such as azobenzene and azoxybenzene were not detected. First-order reduction rates are similar for nitrobenzene and nitrosobenzene, but aniline appearance occurs more slowly (typical pseudo-first-order rate constants 3.5 × 10-2, 3.4 × 10-2, and 8.8 × 10-3 min-1, respectively, in the presence of 33 g/L acid-washed, 18−20 mesh Fluka iron turnings). The nitro reduction rate increased linearly with concentration of iron surface area, giving a specific reaction rate constant (3.9 ± 0.2 × 10-2 min-1 m-2 L). The minimal effects of solution pH or ring substitution on nitro reduction rates, and the linear correlation between nitrobenzene reduction rate constants and the square-root of mixing ra...

Kinetics of Halogenated Organic Compound Degradation by Iron Metal

Abstract: A combination of new and previously reported data on the kinetics of dehalogenation by zero-valent iron (Fe0) has been subjected to an analysis of factors effecting contaminant degradation rates. First-order rate constants (kobs) from both batch and column studies vary widely and without meaningful correlation. However, normalization of these data to iron surface area concentration yields a specific rate constant (kSA) that varies by only 1 order of magnitude for individual halocarbons. Correlation analysis using kSA reveals that dechlorination is generally more rapid at saturated carbon centers than unsaturated carbons and that high degrees of halogenation favor rapid reduction. However, new data and additional analysis will be necessary to obtain reliable quantitative structure−activity relationships. Further generalization of our kinetic model has been obtained by accounting for the concentration and saturation of reactive surface sites, but kSA is still the most appropriate starting point for design c...

Enhanced Photocatalytic Performance of Titania-Based Binary Metal Oxides: TiO2/SiO2 and TiO2/ZrO2

Abstract: Sol-gel prepared mixtures of silica or zirconia with titania are shown to have significantly higher activities than pure titania for the complete photocatalytic oxidation of ethylene. These higher activities are only apparent when the respective catalysts are stabilized by sintering. The differences become even more pronounced when the catalysts are used in a tubular reactor. Optimum mixture concentrations are found to be 12 wt % zirconia and 16 wt % silica in titania. Both catalyst types exhibit activity maxima with respect to sintering temperature. It is hypothesized that the maxima arise from opposing effects of densification and phase transformation versus beneficial sintering. A comparison of our catalyst compositions with literature in this area suggests that the increase in activity due to the addition of silica or zirconia may be a result of higher surface acidity. However, isoelectric point measurements employing the unsintered and sintered catalysts show no conclusive increase in surface acidity...

Uptake, Toxicity, and Trophic Transfer of Mercury in a Coastal Diatom

Abstract: The primary mechanisms controlling the accumulation of methylmercury and inorganic mercury in aquatic food chains are not sufficiently understood. Differences in lipid solubility alone cannot account for the predominance of methylmercury in fish because inorganic mercury complexes (e.g., HgCl2), which are not bioaccumulated in fish, are as lipid soluble as their methylmercury analogs (e.g., CH3HgCl). Mercury concentrations in fish are ultimately determined by methylmercury accumulation at the base of the food chain, which is governed by water chemistry, primarily pH and chloride concentration. Our studies of mercury speciation, toxicity, and phytoplankton uptake demonstrate that passive uptake of uncharged, lipophilic chloride complexes is the principal accumulation route of both methylmercury and inorganic mercury in phytoplankton. The predominance of methylmercury in fish, however, is a consequence of the greater trophic transfer efficiency of methyl- mercury than inorganic mercury. In particular, methy...

Metal ion binding by humic acid: application of the NICA-Donnan model.

Abstract: A Donnan-type model for nonspecific binding of electrolyte ions has been combined with the non-ideal competitive adsorption (NICA) model for specific binding to produce a model for ion binding to humic substances. The model considers site heterogeneity, non-ideality, multicomponent competition, and electrostatic interactions. The NICA-Donnan model was fitted to data for H, Ca, Cd, Cu, and Pb binding by a purified peat humic acid. The model fits were good and covered a wide range of pH and free metal concentrations. The parameters from these single metal data sets were then used to predict the competitive effect of Ca on Cd and Cu binding at various pHs. These predictions agreed well with the experimental data although there were some small but systematic differences. The new NICA-Donnan model also predicted reasonably well the increase in Cd and Cu binding on changing from a 0.1 M KNO3 background electrolyte to 0.01 M KNO3. A shortcoming of the model is that in some cases it significantly underestimated t...

Competitive Sorption between Atrazine and Other Organic Compounds in Soils and Model Sorbents

Abstract: This is part of a larger study that addresses the question of whether site-specific sorption of organic compounds takes place in soil organic matter (SOM). Competitive sorption is one indication that such interactions may take place. Competitive sorption was tested between atrazine (AT) and other co-solutes in water suspensions of natural and model sorbents. The co-solutes included several s-triazine analogs, a substituted benzene analog (5-chloro-1,3-dimethoxybenzene), and a dissimilar compound, trichloroethene (TCE). The sorbents included a mineral soil (3% OM), a peat soil (93% OM), soil humic acid particles (99% OM), rubbery polymers (polyethylene, cellulose, chitin), a glassy polymer [poly(2,6-diphenyl-p-phenylene oxide)], and a mesoporous silica gel. The rubbery polymers afforded linear single-solute isotherms and no competition, both consistent with ideal (Henry's law) partition sorption. The other sorbents, including the glassy polymer, gave nonlinear single-solute isotherms and significant compet...

Contribution of Sulfonate Groups and Alginate to Heavy Metal Biosorption by the Dry Biomass of Sargassum fluitans

Abstract: The mechanism of heavy metal complexation by the dry biomass of the brown seaweed Sargassum fluitans was investigated at the molecular level using different techniques. Simultaneous potentiometric and conductimetric titrations gave some information concerning the amount of strong and weak acidic functional groups in the biomass (0.25 ± 0.05 mequiv/g and 2.00 ± 0.05 mequiv/g, respectively). Those results were confirmed by the chemical identification of sulfonate groups (0.27 mequiv/g ± 0.03) and alginate (45% of the dry weight) corresponding to 2.25 mmol of carboxyl groups/g of biomass. Modification of these functional groups by methanolic hydrochloride or propylene oxide demonstrated the predominant role of alginate in the uptake of cadmium and lead. However, sulfonate groups can also contribute, to a lower extent, to heavy metal binding, particularly at low pH. Eventually, FTIR spectrophotometry on protonated or cadmium-loaded alginate and S. fluitans biomass physically demonstrated that cadmium binding ...

Environmental Photochemistry on Semiconductor Surfaces: Photosensitized Degradation of a Textile Azo Dye, Acid Orange 7, on TiO2 Particles Using Visible Light

Abstract: Photosensitized degradation of a textile azo dye, Acid Orange 7, has been carried out on TiO2 particles using visible light Mechanistic details of the dye degradation have been elucidated using diffuse reflectance absorption and FTIR techniques Degradation does not occur on Al2O3 surface or in the absence of oxygen The dependence of the dye degradation rate on the surface coverage shows the participation of excited dye and TiO2 semiconductor in the surface photochemical process Diffuse reflectance laser flash photolysis confirms the charge injection from the excited dye molecule into the conduction band of the semiconductor as the primary mechanism for producing oxidized dye radical The surface-adsorbed oxygen plays an important role in scavenging photogenerated electrons, thus preventing the recombination between the oxidized dye radical and the photoinjected electrons Diffuse reflectance FTIR was used to make a tentative identification of reaction intermediates and end products of dye degradation

Reductive Elimination of Chlorinated Ethylenes by Zero-Valent Metals

Abstract: To date it does not appear to have been demonstrated in the literature that halogenated ethylenes can undergo reductive {beta}-elimination to alkynes under environmental conditions. The purpose of this paper is to provide experimental evidence that such pathways may be involved in the reaction of chloroethylenes with zero-valent metals as well as to speculate on the significance of the products that may result. Calculations indicate that reductive {beta}-elimination reactions of chloroethylenes are in fact comparable energetically to hydrogenolysis at neutral pH. Experiments were therefore initiated to assess whether {beta}-elimination reactions of chlorinated ethylenes could occur in the presence of two zero-valent metals, Fe and Zn. 76 refs., 3 figs., 1 tab.

Dechlorination of Trichloroethene in Aqueous Solution Using Fe0

Abstract: Flow-through column tests were conducted to investigate the products of degradation of aqueous trichloroethene (TCE) in contact with granular iron metal. The results indicated the degradation process to be pseudo-first-order and the rate constant to be relatively insensitive to the initial concentration of TCE over the range from about 1.3 to 61 mg/L. The principal degradation product was ethene, followed by ethane with substantially smaller amounts of other C1−C4 hydrocarbons. About 3.0−3.5% of the initial TCE appeared as chlorinated degradation products, including the three dichloroethene isomers and vinyl chloride. Although the chloride mass balance was generally between 98 and 102%, a maximum of 73% of the carbon could be accounted for in the identified products. Based on the low concentrations of chlorinated degradation products in the solution phase, it is proposed that most of the TCE remains sorbed to the iron surface until complete dechlorination is achieved.

Bioremediation of an Experimental Oil Spill on the Shoreline of Delaware Bay

Abstract: In the summer of 1994, a field study was undertaken in Delaware in which light crude oil was intentionally released onto plots to evaluate bioremediation. The objectives were to obtain credible statistical evidence to determine if bioremediation with inorganic mineral nutrients and/or microbial inoculation enhanced the removal of crude oil contaminating a sandy beach and to compute intrinsic and enhanced biodegradation rates. Biodegradation was tracked by GC/MS analysis of selected components, and the measured concentrations were corrected for abiotic removal by hopane normalization. A randomized block design was used to assess treatment effects. Three treatments were evaluated: a no-nutrient addition control, addition of water-soluble nutrients, and addition of water-soluble nutrients supplemented with a natural microbial inoculum from the site. Although substantial hydrocarbon biodegradation occurred in the untreated plots, statistically significant differences between treated and untreated plots were ...

Specific Adsorption of Nitroaromatic Explosives and Pesticides to Clay Minerals

Abstract: It is demonstrated that nitroaromatic compounds (NACs) may adsorb specifically and reversibly to natural clay minerals in aqueous suspension. Adsorption of NACs to clays is high when the exchangeable cations at the clays include K+ or NH4+ but is negligibly small for homoionic Na+-, Ca2+-, Mg2+-, and Al3+-clays. Highest adsorption coefficients (Kd values up to 60 000 L kg-1) are found for polynitroaromatic compounds including some important contaminants such as explosives (e.g., trinitrotoluene, trinitrobenzene, dinitrotoluidines) and dinitrophenol herbicides (e.g., DNOC, DINOSEB). Nonaromatic nitro compounds (e.g., RDX) generally exhibit very low Kd values. The specific adsorption of NACs can be rationalized by electron donor−acceptor (EDA) complex formation with oxygens present at the external siloxane surface(s) of clay minerals. Kd values of a given NAC and clay mineral can be estimated from known Kd values of other NACs, even when measured at other clay minerals. The affinity and the adsorption capac...

Fluorescence Characterization of IHSS Humic Substances: Total Luminescence Spectra with Absorbance Correction

Abstract: Total luminescence spectroscopy was applied to the fluorescence characterization of humic substances obtained from the International Humic Substances Society (IHSS). Results show that total luminescence spectra, represented as excitation−emission matrices (EEMs), may be used to discriminate between soil-derived and aquatic-derived IHSS humic substances and between humic and fulvic acids derived from the same source (soil or aquatic). Ionic strength in the range of 0−1 M KCl and humic substance concentration in the range of 5−100 mg/L had little effect on the fluorescence spectral characteristics of the humic substances, while pH had significant effects as expected. Absorbance correction was shown to be essential for accurate representation and comparison of the EEMs of the humic substances at high concentrations.

Kinetics of chromate reduction by ferrous iron

Abstract: Reduction of Cr(VI) to Cr(III) is environmentally favorable as the latter species is not toxic to most living organisms and also has a low mobility and bioavailability. Ferrous iron is one possible reductant implicated as a major contributor to the removal of Cr(VI) from suboxic and anoxic waters and soils. Despite the importance of this redox reaction, no mechanistic or kinetic information are available, which are needed to determine the rate of Cr(VI) reduction and to assess the role of oxygen in limiting this reaction. In this study we used a stopped-flow kinetic technique monitored by UV−VIS spectroscopy and an initial rate method to ascertain the rate constant and the rate dependence of each reactant. We observed that the rate of Cr(VI) removal conformed to −d[Cr(VI)]/dt = kcr[Fe(II)]0.6[Cr(VI)]1 where kcr = 56.3 (±3.7) mmol-0.6 min-1 L0.6. Based on this rate expression and that for the oxygenation of Fe(II), Cr(VI) reduction should be unaffected by oxygen except at pH values in excess of 8 even at m...

Preliminary assessment of the occurrence and possible sources of MTBE in groundwater in the United States, 1993-1994

Abstract: The 1990 Clean Air Act Amendments require fuel oxygenates to be added to gasoline used in some metropolitan areas to reduce atmospheric concentrations of carbon monoxide or ozone. Methyl tert-butyl ether (MTBE) is the most commonly used fuel oxygenate and is a relatively new gasoline additive. Nevertheless, out of 60 volatile organic chemicals analyzed, MTBE was the second most frequently detected chemical in samples of shallow ambient groundwater from urban areas that were collected during 1993-1994 as part of the U.S. Geological Survey's National Water-Quality Assessment program. Samples were collected from five drinking water wells, 12 springs, and 193 monitoring wells in urban areas. No MTBE was detected in drinking water wells. At a reporting level of 0.2 μg/L, MTBE was detected most frequently in shallow groundwater from urban areas (27% of 210 wells and springs sampled in eight areas) as compared to shallow groundwater from agricultural areas (1.3% of 549 wells sampled in 21 areas) or deeper groundwater from major aquifers (1.0% of 412 wells sampled in nine areas). Only 3% of the shallow wells sampled in urban areas had concentrations of MTBE that exceed 20 μg/L, which is the estimated lower limit of the United States Environmental Protection Agency draft drinking water health advisory. Because MTBE is persistent and mobile in groundwater, it can move from shallow to deeper aquifers with time. In shallow urban groundwater, MTBE generally was not found with benzene, toluene, ethylbenzene, or xylene (BTEX) compounds, which commonly are associated with gasoline spills. This disassociation causes uncertainty as to the source of MTBE. Possible sources of MTBE in groundwater include point sources, such as leaking storage tanks, and non-point sources, such as recharge of precipitation and stormwater runoff.

Colloid Transport in Geochemically Heterogeneous Porous Media: Modeling and Measurements

Abstract: The transport of colloids in geochemically heterogeneous porous media is investigated. A model describing the transport and deposition of colloids onto heterogeneously charged mineral grains is developed and applied to column experiments. The model characterizes mineral grain surfaces according to a patchwise charge distribution, with individual patches being either favorable or unfavorable for deposition depending on their electrostatic charge. Separate rate expressions are used in the model to depict favorable and unfavorable deposition kinetics. Declining deposition kinetics that are produced when previously retained particles block subsequent at tachment of colloids are quantified in the model by dynamic blocking functions. Column experiments involving colloid transport in geochemically heterogeneous porous media were performed using silica colloids and quartz sand. Surface charge heterogeneity was introduced into the porous medium by coating a fraction of the quartz sand with iron oxyhydroxide. Theor...

Measurement of Polycyclic Aromatic Hydrocarbons Associated with Size-Segregated Atmospheric Aerosols in Massachusetts

Abstract: Size-segregated atmospheric aerosols were collected from urban and rural locations in Massachusetts using a micro-orifice impactor. The samples were analyzed for polycyclic aromatic hydrocarbons (PAH) with molecular weights between 178 and 302, using gas chromatography/mass spectrometry. Fifteen PAH were quantified in the urban samples and nine in the rural samples. The quantification results are in good agreement with available ambient monitoring data. In the urban samples, PAH were distributed among aerosol size fractions based on molecular weight. PAH with molecular weights between 178 and 202 were approximately evenly distributed between the fine (aerodynamic diameter 2 μm) aerosols. PAH with molecular weights greater than 228 were associated primarily with the fine aerosol fraction. In the rural samples, low and high molecular weight PAH were associated with both the fine and coarse aerosols. Slow mass transfer by vaporization and condensation is proposed to e...

Effects of Fulvic Acid on Fe(II) Oxidation by Hydrogen Peroxide

Abstract: Iron redox cycling can catalyze the oxidation of humic substances and increase the rate of oxygen consumption in surface waters rich in iron and organic carbon. This study examines the role of Fenton`s reaction [oxidation of Fe(II) by hydrogen peroxide] in this catalytic cycle. A number of competing processes were observed in model systems containing dissolved Fe, hydrogen peroxide, and Suwannee River fulvic acid. First, the effective rate constant of Fenton`s reaction increased with increasing fulvic acid concentration, indicating the formation Fe(II)-fulvate complexes that react more rapidly with hydrogen peroxide than Fe(II)-aquo complexes. This effect was significant at pH 5 but negligible at pH 3. A second effect was scavenging of the HO{sup .} radical produced in Fenton`s reaction by fulvic acid, forming an organic radical. The organic radical reduced oxygen to HO{sub 2}{sup .}/O{sub 2}{sup .-}, which then regenerated hydrogen peroxide by reaction with Fe(II). Finally, Fe(III) was reduced by a dark reaction with fulvic acid, characterized by an initially fast reduction followed by slower processes. The behavior of Fe(II) and hydrogen peroxide over time in the presence of fulvic acid and oxygen could be described by a kinetic model taking all of these reactions into account. The netmore » result was an iron redox cycle in which hydrogen peroxide as well as oxygen were consumed (even though direct oxidation of Fe(II) by oxygen was not significant), and the oxidation of fulvic acid was accelerated. 56 refs., 7 figs., 1 tab.« less

Effect of Bromide Ion on Haloacetic Acid Speciation Resulting from Chlorination and Chloramination of Aquatic Humic Substances

Abstract: The objective of this study was to investigate the effect of bromide ion on the distribution of haloacetic acid (HAA) species resulting from the chlorination and chloramination of waters containing aquatic humic substances. Aquatic humic substances were extracted from a surface water and a groundwater and were chlorinated and chloraminated under standard conditions at pH 8 and pH 6 in the presence of bromide concentrations ranging from 0 to 25 μM (0−2 mg/L). The treated waters were analyzed for all nine of the HAA species containing bromine and chlorine. Standards for bromodichloroacetic acid and dibromochloroacetic acid were not commercially available but were synthesized for use in this study. Bromochloro-, bromodichloro-, and dibromochloroacetic acid were readily formed and constituted at least 10% of the total HAA concentration in waters containing as little as 1.2 μM (0.1 mg/L) bromide. The mixed bromochloro HAA species were major components of the total HAA concentration at bromide concentrations fo...

Emission factors for polycyclic aromatic hydrocarbons from biomass burning

Abstract: Emission factors for 19 polycyclic aromatic hydrocarbons were measured during wind tunnel simulations of open burning for agricultural and forest biomass fuels including cereal grasses, agricultural tree prunings, and fir and pine wood (slash). Yields of total PAH varied from 5 to 683 mg kg-1 depending principally on burning conditions and to a lesser extent on fuel type. Barley straw and wheat straw loaded at 400−500 g m-2 emitted much higher levels of PAH, including benzo[a]pyrene, than other cereal and wood fuel types burning under more robust conditions. As anticipated, total PAH emission rates increased with increasing particulate matter emission rates and with declining combustion efficiency.

Environmental Stability of Selected Petroleum Hydrocarbon Source and Weathering Ratios

Abstract: Weathering and biodegradation alter the composition of spilled oil, making it difficult to identify the source of the release and to monitor its fate in the environment Using intertidal sediment and terrestrial soil data that cover a wide range of oil weathering states, we show that ratios of alkylated dibenzothiophenes and phenanthrenes are useful for source identification even up to 98% depletion of total polycyclic aromatic hydrocarbons (PAHs) Furthermore, we find that some ratios of alkylated naphthalenes, phenanthrenes, and chrysenes can qualitatively assess the extent of weathering an oil has undergone since a spill These source and weathering ratios appear to successfully describe oil depletion and to identify sources in subtidal sediment data from the M/C Haven spill in Italy, the Exxon Valdez spill in Alaska, and a North Sea oil spill

Direct Determination of Lead Speciation in Contaminated Soils by EXAFS Spectroscopy

Abstract: Direct determination of the chemical form of trace metals in soils still remains a challenge for instrumental analytical techniques. This paper examines the potential of EXAFS spectroscopy to speciate and quantify the form of trace metals in the solid fraction of soil materials using lead as a case study. Three soils contaminated by different sorts of industrial activities, including the synthesis of lead organometallics for gasoline antiknocks, Pb−Zn smelting, and recycling of lead acid battery, were investigated. In soil contaminated by alkyl-tetravalent lead compounds, lead was found to be divalent and complexed to salicylate and catechol-type functional groups of humic substances. Lead sulfate and silica-bound lead are the predominant forms in the vicinity of the battery reclamation area. Near the smelter, lead was found to be divalent and coordinated to O,OH ligands. It is present in several chemical forms, which prevented them from being identified individually. The multiplicity of lead species in s...