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1.
Environ Res ; 207: 112140, 2022 05 01.
Artigo em Inglês | MEDLINE | ID: mdl-34592255

RESUMO

There is no safe level of lead exposure. As exposure from point sources like lead paint have decreased, non-point sources such as drinking water have become a greater proportional source of total lead exposure. Even at low levels, lead exposure is shown to harm children, contributing to impaired development as well as learning and behavioral issues. This paper summarizes the key results of an Environmental Defense Fund (EDF) pilot study conducted at 11 child care facilities in 4 US states to evaluate approaches to testing and remediating lead in water at child care facilities. Over 75% of first draw samples contained lead levels under the 1 µg/L level recommended by the American Academy of Pediatrics (AAP). However, 10 of 11 child care facilities produced at least one sample above 1 µg/L. Fixture flushing, aerator cleaning, and fixture replacement were evaluated as remediation strategies. Fixture replacement was effective when initial lead was above 5 µg/L. Aerator cleaning did not have a measurable effect on lead levels for most fixtures but unexpectedly significantly increased lead levels in approximately 30% of fixtures. The 2021 Lead and Copper Rule (LCR) revision was applied to study data to determine whether updates would flag cases of low-level lead in child care settings and was found insufficient to prompt mitigation unless high lead was present at most taps.


Assuntos
Água Potável , Criança , Cuidado da Criança , Cobre , Água Potável/análise , Exposição Ambiental , Humanos , Chumbo/análise , Projetos Piloto , Estados Unidos
2.
Environ Sci Technol ; 50(2): 625-32, 2016 Jan 19.
Artigo em Inglês | MEDLINE | ID: mdl-26687028

RESUMO

Colloids have been implicated in influencing the transport of actinides and other adsorbed contaminants in the subsurface, significantly increasing their mobility. Such colloid-facilitated transport can be induced by changes in groundwater chemistry that occur, for example, when high ionic strength contaminant plumes are displaced by infiltrating rainwater. We studied the transport and mobility of Th(IV), as an analogue for Pu(IV) and other tetravalent actinides [An(IV)], in saturated columns packed with a natural heterogeneous subsurface sandy sediment. As expected, decreases in ionic strength both promoted the mobilization of natural colloids and enhanced the transport of previously adsorbed Th(IV). However, colloid-facilitated transport played only a minor role in enhancing the transport of Th(IV). Instead, the enhanced transport of Th(IV) was primarily due to the pH-dependent desorption of Th(IV) caused by the change in ionic strength. In contrast, the adsorption of Th(IV) had a marked impact on the surface charge of the sandy sediment, significantly affecting the mobility of the colloids. In the absence of Th(IV), changes in ionic strength were ineffective at releasing colloids while in the presence of Th(IV), decreases in ionic strength liberated significant concentrations of colloids. Therefore, under the conditions of our experiments which mimicked acidic, high ionic strength groundwater contaminant plumes, Th(IV) had a much greater effect on colloid transport than colloids had on Th(IV) transport.


Assuntos
Elementos da Série Actinoide/análise , Coloides/química , Água Subterrânea/química , Salinidade , Adsorção , Concentração de Íons de Hidrogênio , Concentração Osmolar
3.
Environ Sci Technol ; 47(6): 2661-9, 2013 Mar 19.
Artigo em Inglês | MEDLINE | ID: mdl-23387874

RESUMO

Colloids play an important role in governing the transport of radionuclides in geologic environments. As naturally occurring colloidal suspensions are compositionally heterogeneous, the subsurface fate of radionuclides may be sensitive to interactions among different kinds of colloids. Therefore, we investigated the adsorption equilibrium and desorption kinetics of uranium (U(VI)) in experiments conducted with compositionally homogeneous suspensions of colloidal SiO(2), ZnO, hydrous ferric oxide (HFO) or humic acids (HAs) as well as heterogeneous suspensions consisting of a colloidal metal oxide and HA. We found that interactions between HAs and ZnO or HFO greatly inhibited the sorption of U onto colloids in the heterogeneous suspensions. HA-ZnO interactions enhanced the desorption of U from the heterogeneous colloidal suspensions, while the association between HA and SiO(2) or HFO inhibited U desorption. Molecular-level characterizations reveal that HFO interacted with HAs by electrostatic interactions, association with aliphatic/aromatic carbon and inner-sphere complexation with carboxyl functional groups, while SiO(2) and ZnO mainly associated with HAs by weak interactions (e.g., van der Waals interactions). The present findings indicate that interactions between HA and metal-oxide colloids can substantially influence the desorption of U(VI) from these particles, thereby potentially affecting the mobility of this radionuclide in groundwater.


Assuntos
Coloides/química , Compostos Férricos/química , Substâncias Húmicas/análise , Dióxido de Silício/química , Urânio/isolamento & purificação , Óxido de Zinco/química , Adsorção , Cinética , Modelos Moleculares
4.
Environ Sci Technol ; 46(11): 5931-8, 2012 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-22533547

RESUMO

The risk stemming from human exposure to actinides via the groundwater track has motivated numerous studies on the transport of radionuclides within geologic environments; however, the effects of waterborne organic matter on radionuclide mobility are still poorly understood. In this study, we compared the abilities of three humic acids (HAs) (obtained through sequential extraction of a peat soil) to cotransport hexavalent uranium (U) within water-saturated sand columns. Relative breakthrough concentrations of U measured upon elution of 18 pore volumes increased from undetectable levels (<0.001) in an experiment without HAs to 0.17 to 0.55 in experiments with HAs. The strength of the HA effect on U mobility was positively correlated with the hydrophobicity of organic matter and NMR-detected content of alkyl carbon, which indicates the possible importance of hydrophobic organic matter in facilitating U transport. Carbon and uranium elemental maps collected with a scanning transmission X-ray microscope (STXM) revealed uneven microscale distribution of U. Such molecular- and column-scale data provide evidence for a critical role of hydrophobic organic matter in the association and cotransport of U by HAs. Therefore, evaluations of radionuclide transport within subsurface environments should consider the chemical characteristics of waterborne organic substances, especially hydrophobic organic matter.


Assuntos
Sedimentos Geológicos/química , Movimento (Física) , Compostos Orgânicos/análise , Urânio/análise , Adsorção , Carbono/análise , Coloides , Simulação por Computador , Meio Ambiente , Humanos , Substâncias Húmicas/análise , Cinética , Peso Molecular , Tamanho da Partícula , Fatores de Tempo
5.
J Contam Hydrol ; 129-130: 2-9, 2012 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-22136983

RESUMO

It is difficult to design column experiments to study transport processes involving slow geochemical reactions that require long residence times to reach equilibrium. We propose a sequential equilibration reactor (SER) setup to study such equilibrium geochemical reactive transport problems. The proposed system consists of sequentially operated batch reactors that directly mimic typical one-dimensional grids used in numerical reactive transport models. The SER experimental setup has the characteristics of batch experiments and provides complete control over the reaction time; in addition, the setup also includes certain simple transport features. We conducted several single-reactor and multiple-reactor SER experiments to investigate arsenic adsorption and transport on iron-oxide coated sand, at different pH, solid-solution ratio, and initial arsenic concentration conditions. The data generated from the experiments are compared against predictions from a geochemical transport code (PHREEQCI) that used previously developed surface complexation model parameters to describe the reaction system. The model predictions matched the SER experimental data well. The proposed SER system provides a flexible alternative to column experiments and allows better control over system parameters such as pH, reaction time, and solid-solution ratio.


Assuntos
Arsênio/química , Compostos Férricos/química , Dióxido de Silício/química , Eliminação de Resíduos Líquidos/métodos , Adsorção , Arseniatos/química , Modelos Químicos , Propriedades de Superfície
6.
J Environ Manage ; 92(10): 2504-12, 2011 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-21665352

RESUMO

The ever-increasing growth of biorefineries is expected to produce huge amounts of lignocellulosic biochar as a byproduct. The hydrothermal carbonization (HTC) process to produce biochar from lignocellulosic biomass is getting more attention due to its inherent advantage of using wet biomass. In the present study, biochar was produced from switchgrass at 300 °C in subcritical water and characterized using X-ray diffraction, fourier transform infra-red spectroscopy, scanning electron micrcoscopy, and thermogravimetric analysis. The physiochemical properties indicated that biochar could serve as an excellent adsorbent to remove uranium from groundwater. A batch adsorption experiment at the natural pH (~3.9) of biochar indicated an H-type isotherm. The adsorption data was fitted using a Langmuir isotherm model and the sorption capacity was estimated to be ca. 2.12 mg of U g(-1) of biochar. The adsorption process was highly dependent on the pH of the system. An increase towards circumneutral pH resulted in the maximum adsorption of ca. 4 mg U g(-1) of biochar. The adsorption mechanism of U(VI) onto biochar was strongly related to its pH-dependent aqueous speciation. The results of the column study indicate that biochar could be used as an effective adsorbent for U(VI), as a reactive barrier medium. Overall, the biochar produced via HTC is environmentally benign, carbon neutral, and efficient in removing U(VI) from groundwater.


Assuntos
Carvão Vegetal/química , Recuperação e Remediação Ambiental/métodos , Água Subterrânea/química , Urânio , Purificação da Água/métodos , Adsorção , Concentração de Íons de Hidrogênio , Poaceae , Temperatura , Poluentes da Água , Poluição da Água , Abastecimento de Água
8.
Water Res ; 43(20): 5171-9, 2009 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-19748651

RESUMO

Mercury (Hg) immobilization using stabilized iron sulfide (FeS) nanoparticles was investigated through a series of batch and column experiments. The nanoparticles were prepared using a low-cost, food-grade cellulose (sodium carboxymethyl cellulose, CMC) as the stabilizer. The hydrodynamic diameter of fresh FeS-CMC nanoparticles was measured to be 38.5+/-5.4nm. Batch tests showed that the nanoparticles can effectively immobilize Hg in a clay loam sediment. The Hg distribution coefficient for the nanoparticles was determined to be 8930+/-1480L/g, which is >4 orders of magnitude greater than for the sediment. When the Hg-laden sediment was treated at an FeS-to-Hg molar ratio of 26.5, the Hg concentration leached into water was reduced by 97% and the TCLP (toxicity characteristic leaching procedure) leachability of Hg was reduced by 99%. Column tests showed that water-leachable mercury from the sediment containing 3120mg/L Hg was reduced by 67% and the TCLP leachability by >77% when the sediment was treated with 67 pore volumes (PVs) of a 0.5g/L FeS nanoparticle suspension. Column tests proved that the stabilized nanoparticles were highly mobile in the sediment and full breakthrough of the nanoparticles occurred at approximately 18 PVs.


Assuntos
Sedimentos Geológicos/química , Ferro/química , Mercúrio/análise , Nanopartículas Metálicas/química , Poluentes Químicos da Água/análise , Recuperação e Remediação Ambiental/métodos , Ferro/análise , Cinética , Mercúrio/química , Nanopartículas Metálicas/análise , Nanopartículas Metálicas/ultraestrutura , Sulfetos/análise , Sulfetos/química , Poluentes Químicos da Água/química
9.
J Environ Qual ; 37(6): 2116-24, 2008.
Artigo em Inglês | MEDLINE | ID: mdl-18948465

RESUMO

In-situ stabilization using phosphate (P) amendments, such as P-based fertilizers and rock, are a potentially cost-effective and minimally disruptive alternative for stabilizing Pb in soils. We examined the effect of time (0-365 d), in vitro extraction pH (1.5 vs. 2.3), and dosage of three P-based amendments on the bioaccessibility (as a surrogate for oral bioavailability) of Pb in 10 soils from U.S. Department of Defense facilities. Initial untreated soil bioaccessibility consistently exceeded the U.S. Environmental Protection Agency default value of 60% relative bioavailability, with higher bioaccessibility consistently observed at an in vitro extraction pH of 1.5 vs. 2.3. Although P-based amendments statistically (P < 0.05) reduced bioaccessibility in many instances, with reductions dependent on the amendment and dosage, large amendment dosages (approximately 20-25% by mass to yield 5% P by mass) were required to reduce average bioaccessibility by approximately 25%. For most amendment combinations, reductions continued to occur for periods up to 1 yr, indicating that the observed reductions were not merely experimental artifacts of the in vitro extraction procedure. Although our results indicated that reductions in Pb bioaccessibility with P amendments are technically feasible, relatively large amendment masses were required to achieve relatively modest reductions in bioaccessibility. The cost and potential environmental implications of adding such large amounts of P may limit the practicality of in situ immobilization for some Pb-contaminated soils, industrial and firing range soils in particular.


Assuntos
Chumbo/química , Chumbo/metabolismo , Fosfatos/química , Poluentes do Solo/química , Poluentes do Solo/metabolismo , Solo/análise , Armas de Fogo , Resíduos Industriais , Indústrias
10.
J Environ Qual ; 37(5): 1733-40, 2008.
Artigo em Inglês | MEDLINE | ID: mdl-18689734

RESUMO

A study of the potential negative consequences of adding phosphate (P)-based fertilizers as amendments to immobilize lead (Pb) in contaminated soils was conducted. Lead-contaminated firing range soils also contained elevated concentrations of antimony (Sb), a common Pb hardening agent, and some arsenic (As) of unknown (possibly background) origin. After amending the soils with triple superphosphate, a relatively soluble P source, column leaching experiments revealed elevated concentrations of Sb, As, and Pb in the leachate, reflecting an initial spike in soluble Pb and a particularly dramatic increase in Sb and As mobility. Minimal As, Sb, and Pb leaching was observed during column tests performed on non-amended control soils. In vitro extractions tests were performed to assess changes in Pb, As, and Sb bioaccessibility on P amendment. Lead bioaccessibility was systematically lowered with increasing P dosage, but there was much less of an effect on As and Sb bioaccessibility than on mobility. Our results indicate that although P amendments may aid in lowering the bioaccessibility of soil-bound Pb, it may also produce an initial increase in Pb mobility and a significant release of Sb and As from the soil, dramatically increasing their mobility and to a lesser extent their bioavailability.


Assuntos
Fertilizantes/análise , Chumbo/química , Fósforo/química , Poluentes do Solo/química , Solo/análise , Antimônio/química , Arsênio/química
11.
Environ Pollut ; 156(2): 504-14, 2008 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-18367298

RESUMO

Elemental mercury (Hg(0)) is a metal with a number of atypical properties, which has resulted in its use in myriad anthropogenic processes. However, these same properties have also led to severe local subsurface contamination at many places where it has been used. As such, we studied the influence of various parameters on Hg(II) sorption onto pyrite (pH, time, Hg(II) concentration), a potential subsurface reactive barrier. Batch sorption studies revealed that total Hg(II) removal increases with both pH and time. X-ray absorption spectroscopy analysis showed that a transformation in the coordination environment at low pH occurred during aging over 2 weeks, to form an ordered monolayer of monodentate Hg-Cl complexes on pyrite. In column studies packed with pure quartz sand, the transport of Hg(II) was significantly retarded by the presence of a thin pyrite-sand reactive barrier, although dissolved oxygen inhibited Hg(II) sorption onto pyrite in the column.


Assuntos
Poluentes Ambientais/química , Recuperação e Remediação Ambiental/métodos , Ferro/química , Mercúrio/química , Sulfetos/química , Absorciometria de Fóton , Adsorção , Monitoramento Ambiental/métodos , Poluentes Ambientais/análise , Concentração de Íons de Hidrogênio , Ferro/análise , Mercúrio/análise , Microscopia Eletrônica de Varredura , Quartzo , Sulfetos/análise , Tempo
12.
J Contam Hydrol ; 95(1-2): 30-41, 2008 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-17706833

RESUMO

Understanding the fundamentals of arsenic adsorption and oxidation reactions is critical for predicting its transport dynamics in groundwater systems. We completed batch experiments to study the interactions of arsenic with a common MnO2(s) mineral, pyrolusite. The reaction kinetics and adsorption isotherm developed from the batch experiments were integrated into a scalable reactive transport model to facilitate column-scale transport predictions. We then completed a set of column experiments to test the predictive capability of the reactive transport model. Our batch results indicated that the commonly used pseudo-first order kinetics for As(III) oxidation reaction neglects the scaling effects with respect to the MnO2(s) concentration. A second order kinetic equation that explicitly includes MnO2(s) concentration dependence is a more appropriate kinetic model to describe arsenic oxidation by MnO2(s) minerals. The arsenic adsorption reaction follows the Langmuir isotherm with the adsorption capacity of 0.053micromol of As(V)/g of MnO2(s) at the tested conditions. The knowledge gained from the batch experiments was used to develop a conceptual model for describing arsenic reactive transport at a column scale. The proposed conceptual model was integrated within a reactive transport code that accurately predicted the breakthrough profiles observed in multiple column experiments. The kinetic and adsorption process details obtained from the batch experiments were valuable data for scaling to predict the column-scale reactive transport of arsenic in MnO2(s)-containing sand columns.


Assuntos
Arsênio/química , Compostos de Manganês/química , Modelos Teóricos , Oxirredução , Óxidos/química , Poluentes da Água/química , Adsorção , Arsênio/análise , Poluentes da Água/análise
13.
Environ Toxicol Chem ; 26(11): 2253-9, 2007 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-17941725

RESUMO

The widespread contamination of groundwater resources associated with methyl-tert-butyl ether (MtBE) use has prompted a search for replacement oxygenates in gasoline. Among the alternatives currently under development are higher methyl-tert-alkyl ethers, notably methyl-tert-hexyl ether (MtHxE) and methyl-tert-octyl ether (MtOcE). As was the case with MtBE, the introduction of these ethers into fuel supplies guarantees their migration into groundwater resources. In the present study, a screening-level risk assessment compared predicted well water concentrations of these ethers to concentrations that might cause adverse effects. A physicochemical model which has been successfully applied to the prediction of MtBE concentrations in community water supply wells (CSWs) was used to predict well water concentrations of MtHxE and MtOcE. The results indicate that these ethers are likely to contaminate water supply wells at slightly lower levels than MtBE as a result of migrating from leaking underground fuel tanks to CSWs. Because very little data is available on the physicochemical and environmental properties of MtHxE and MtOcE, estimation methods were employed in conjunction with the model to predict well water concentrations. Model calculations indicated that MtHxE and MtOcE will be present in many CSWs at concentrations approaching the concentrations that have caused widespread public health concern for MtBE. Based on these results and the possibility that MtHxE and MtOcE are potential carcinogens, testing of the toxicological properties of these ethers is recommended before they are used to replace MtBE in gasoline.


Assuntos
Carcinógenos Ambientais/análise , Gasolina/análise , Éteres Metílicos/análise , Oxigênio/análise , Poluentes Químicos da Água/análise , Abastecimento de Água , Animais , Humanos , Oxigênio/química , Medição de Risco
14.
Artigo em Inglês | MEDLINE | ID: mdl-17654151

RESUMO

We investigated the use of various iron amendments (metallic Fe and soluble Fe(II)- and Fe(III)-halide salts) to reduce arsenic (As) bioaccessibility (as a surrogate for oral bioavailability) in contaminated soils. Soluble Fe(II)- and Fe(III)-salts were more effective than metallic Fe in reducing As bioaccessibility. Adding soluble Fe(III)-salts to soil reduces As bioaccessibility in two ways, by increasing the Fe(III) (hydr)oxide content and by lowering the soil pH. A detailed investigation into the effect of soil moisture when adding Fe(III) amendments indicated that the reaction can occur in situ if sufficient (>or=30% moisture) is added. If the amendments are added to the soil without moisture, a reduction in bioaccessibility will occur in the extraction fluid itself (i.e., an experimental artifact not reflecting a true in situ reduction in bioaccessibility). Adding Fe (III)-salts to nine As-contaminated soils at a Fe:As molar ratio of 100:1 reduced the average bioaccessibility in the soils by approximately a factor of two. Greater reductions in As bioaccessibility can be achieved by increasing the Fe:As molar ratio. These results suggest decreasing As bioaccessibility and bioavailability in soil by adding Fe amendments may be an effective strategy to remediate As-contaminated soils.


Assuntos
Arsênio/análise , Monitoramento Ambiental/métodos , Recuperação e Remediação Ambiental/métodos , Ferro/química , Poluentes do Solo/análise , Solo/análise , Arsênio/farmacocinética , Disponibilidade Biológica , Humanos , Modelos Biológicos , Solo/normas , Poluentes do Solo/farmacocinética , Estados Unidos
15.
Chemosphere ; 68(7): 1218-23, 2007 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-17349670

RESUMO

The migration of uranium(VI) in subsurface environments is strongly influenced by its adsorption/desorption reactions at the solid/solution interface. Phosphate is often present in subsurface systems and was shown to significantly affect U(VI) adsorption in previous batch experiments. In this study, column experiments were conducted to investigate the effects of phosphate on U(VI) adsorption and transport under flow conditions. The adsorption of U(VI) and phosphate was very low on pure quartz sand with negligible effects on U(VI) and phosphate transport. However, U(VI) and phosphate transport was retarded in a column packed with goethite-coated sand. The presence of phosphate, either as a co-solute with U(VI) or pre-adsorbed, greatly increased U(VI) adsorption and retardation. U(VI) and phosphate adsorption in our column experiments were rate-limited, and the adsorption of U(VI) and phosphate was not reversible, with kinetic limitations more pronounced for desorption than for adsorption. This study demonstrated the importance of phosphate in controlling U(VI) mobility in subsurface environments and helped illustrate some phenomena potentially applicable to U(VI) adsorption and transport in natural systems, especially where U(VI) adsorption is rate-limited.


Assuntos
Compostos de Ferro/química , Fosfatos/química , Urânio/química , Adsorção , Cinética , Minerais
16.
J Colloid Interface Sci ; 310(1): 8-17, 2007 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-17306821

RESUMO

The adsorption of Si on goethite (alpha-FeOOH) has been studied in batch experiments that cover the natural range of Si concentrations as found in the environment. The results have been interpreted and quantified with the charge distribution (CD) and multi-site surface complexation (MUSIC) model in combination with an extended Stern (ES) layer model option. This new double layer approach (ES) accounts for ordering of interfacial water molecules leading to stepwise changes in the location of electrolyte ions near the surface [T. Hiemstra, W.H. Van Riemsdijk, J. Colloid Interface Sci. 301 (2006) 1]. The Si adsorption on goethite peaks at a pH of approximately 9 and decreases at lower and higher pH values. Thermodynamically, the pH-dependency of silicic acid adsorption is related to the value of the proton co-adsorption and can also be linked to the Si charge distribution in the interface as is discussed. Based on published EXAFS data, the adsorption of Si on goethite was modeled as the formation of a bidentate surface complex. The ionic charge distribution (CD) of this complex can be calculated from the geometry of this surface complex, optimized with molecular orbital/density functional theory (MO/DFT), and combined with a correction for water dipole orientation. The resulting CD value has been applied successfully in the description of the adsorption data. The use of a theoretical CD value has the practical advantage of a reduction of the number of adjustable parameters with a factor 2. To describe the adsorption at a high Si loading, formation of a Si polymer, e.g. a tetramer, is proposed. Such a species is only contributing to the overall adsorption at solution concentrations above about 10(-4) M, where super saturation with respect to quartz exists. The adsorbed silica polymer hydrolyzes at high pH. The reactive ligand of the polymer is quite acid (logK approximately 6.5-7.1), which is typically for the triple bond SiO(-1) surface groups of polymerized Si, like amorphous SiO(2)(s), and the triple bond SiO(-1) ligand of the aqueous dimer Si(2)O(OH)(5)O(-1)(aq). The applied model correctly predicts the change of particles charge and the shift in IEP due to proton release upon Si adsorption.

17.
J Air Waste Manag Assoc ; 56(10): 1484-92, 2006 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-17063870

RESUMO

Methyl tertiary hexyl ether (MtHxE) and methyl tertiary octyl ether (MtOcE) are currently being developed as replacement oxygenates for methyl tertiary butyl ether (MtBE) in gasoline. As was the case with MtBE, the introduction of these ethers into fuel supplies guarantees their introduction into the environment as well. In this study, a screening-level risk assessment was performed by comparing predicted environmental concentrations (PEC) of these ethers to concentrations that might cause adverse effects to humans or ecosystems. A simple box model that has successfully estimated urban air concentrations of MtBE was adapted to predict atmospheric concentrations of MtHxE and MtOcE. Expected atmospheric concentrations of these ethers were also estimated using the European Union System for the Evaluation of Substances (EUSES) multimedia fate model, which simultaneously calculates PECs in the various environmental compartments of air, water, soil, and sediment. Because little or no data are available on the physicochemical, environmental, and toxicological properties of MtHxE and MtOcE, estimation methods were used in conjunction with EUSES to predict both the PECs and the concentrations at which these ethers might pose a threat. The results suggest that these ethers would contaminate the air of a moderately sized U.S. city (Boston, MA) at levels similar to those found previously for MtBE. The risk assessment module in EUSES predicted risk characterization ratios of 10(-3) and 10(-2) for MtHxE and MtOcE, respectively, in Boston, and 10(-2) and 10(-1) in very large urban centers, suggesting that these ethers pose only a minimal threat to ecosystems at the anticipated environmental concentrations. The assessment also indicates that these compounds are possible human carcinogens and that they may be present in urban air at concentrations that pose an unacceptable cancer risk. Therefore, testing of the toxicological properties of these compounds is recommended before they replace MtBE in gasoline.


Assuntos
Exposição Ambiental/efeitos adversos , Poluentes Ambientais/análise , Poluentes Ambientais/toxicidade , Éteres Metílicos/análise , Éteres Metílicos/toxicidade , Animais , Clorófitas , Daphnia , Exposição Ambiental/análise , Peixes , Gasolina , Humanos , Modelos Teóricos , Oligoquetos , Oxigênio , Medição de Risco , Relação Estrutura-Atividade
18.
Environ Sci Technol ; 40(10): 3243-7, 2006 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-16749688

RESUMO

U(VI) adsorption onto goethite-coated sand was studied in batch experiments ata solid-to-solution ratio (SSR) ranging from 33.3 to 333 g/L. Batch kinetic experiments revealed that the presence of 10(-4) M phosphate increased both the initial rate and ultimate extent of U(VI) adsorption compared with phosphate-free systems. Our experimental U(VI) adsorption isotherms were independent of SSR in phosphate-free systems. However, the U(VI) adsorption isotherm became dependent on SSR in phosphate-containing systems (with a lower SSR resulting in stronger U(VI) adsorption). A surface complexation model (SCM) was used to conceptualize the interactions in systems containing U(VI), phosphate, and goethite contributing to this SSR effect. The SCM accounted for the effects of SSR on U(VI) adsorption reasonably well. This study implies that the extrapolation of batch-measured adsorption parameters of U(VI) (and potentially other radionuclides and metal(loid)s as well) to field conditions should be done with caution, especially in the presence of strongly interacting ligands.


Assuntos
Fosfatos/química , Poluentes Radioativos do Solo/análise , Urânio/química , Poluentes Radioativos da Água/análise , Adsorção , Cinética , Ligantes , Resíduos Radioativos , Solubilidade
19.
Environ Sci Technol ; 39(20): 7875-82, 2005 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-16295850

RESUMO

The effects of high aqueous carbonate concentrations on arsenic mobility and transport in the subsurface were studied in synthetic iron oxide-coated sand column experiments. Elevated aqueous carbonate concentrations in groundwater have been studied and linked, by some authors, to increased aqueous As concentrations in natural waters. This study found that increasing carbonate concentrations had relatively little effect on As(V) adsorption to the iron oxide-coated sand surface at pH 7. The adsorption of As(V) decreased marginally when the CO2(g) partial pressure increased from 10(-3.5) to 10(-1.8) atm, despite a 50-fold increase in total dissolved carbonate (0.072 to 3.58 mM). Increasing the CO2(g) partial pressure to 10(-10) atm resulted in only a slight decrease in As(V) adsorption and increase in mobility, despite a >300-fold increase in total dissolved carbonate (to 22.7 mM). When compared to phosphate, a known competitive anion, carbonate mobilized less adsorbed As(V) than was mobilized by phosphate, even when present in much higher concentrations than phosphate. This was also true for an experiment with lower pore water velocity and an experiment where As(II) was introduced instead of As(V). Our experiments conclude that while carbonate anions do compete with As for adsorption to iron oxide-coated sand, the competitive effect is relatively small with regard to the total concentration of adsorbed As and the potential competitive effects of phosphate.


Assuntos
Arsênio/química , Carbonatos/química , Dióxido de Silício/química , Adsorção , Dióxido de Carbono/análise , Compostos Férricos , Concentração de Íons de Hidrogênio , Cinética , Pressão Parcial , Espectrofotometria Atômica
20.
Environ Sci Technol ; 39(18): 7102-10, 2005 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-16201635

RESUMO

At As-contaminated sites, where the ingestion of soil by children is typically the critical human-health exposure pathway, information on the bioavailability of soil-bound As is often limited. The influence of various soil physical and chemical properties (iron and manganese oxides, pH, cation exchange capacity, total inorganic and organic carbon, and particle size) on As(III) adsorption, sequestration, bioaccessibility (as a surrogate for oral bioavailability), and oxidation was investigated in 36 well-characterized soils by use of a physiologically based extraction test (PBET). These results were compared to an earlier published study with As(V) on the same set of soils. The properties of the soils were able to explain >80% of the variability in the adsorption and sequestration (as measured by the reduction in bioaccessibility over time) of As(III) in these soils. The initial bioaccessibility of As(III) was significantly higher than the initial bioaccessibility of As(V) on the same set of soils. However, over a 6-month period of aerobic aging, a significant portion of the solid-phase As(III) on these soils was oxidized to As(V), decreasing its bioaccessibility markedly. A multivariable linear regression model previously developed to predict the steady-state bioaccessibility of As(V) in soils was able to predict the bioaccessibility in As(III)-spiked soils within a root-mean-square error (RMSE) of 16.8%. Generally, soils having a higher iron oxide content and lower soil pH exhibited lower bioaccessibility. This model was also able to predict the in vivo bioavailability of As in contaminated soils previously used in an independent juvenile swine dosing trial within an RMSE of 15.5%, providing a greatly improved yet conservative estimate of bioavailability relative to the typical default assumption of 100%. However, the model was not able to accurately predict the bioavailability of As in a different set of contaminated soils previously used in an independent Cebus monkey dosing trial, consistently overpredicting the bioavailability, resulting in an RMSE of 42.7%. This model can be used to provide an initial estimate of As bioavailability in soil to aid in screening sites and justifying expensive site-specific animal feeding studies. Further, as the model is based on major soil properties, the resulting estimates are valid as long as the major soil properties do not change, thus providing some confidence in the long-term applicability of the estimates.


Assuntos
Arsênio/análise , Oxigênio/análise , Poluentes do Solo/análise , Adsorção , Envelhecimento , Disponibilidade Biológica , Carbono/análise , Cátions , Compostos Férricos/análise , Compostos Férricos/farmacologia , Concentração de Íons de Hidrogênio , Ferro/análise , Cinética , Modelos Lineares , Compostos de Manganês/análise , Modelos Estatísticos , Análise Multivariada , Oxirredução , Óxidos/análise , Solo/análise , Espectrofotometria , Fatores de Tempo
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