Measurement of asbestos emissions associated with demolition of abandoned residential dwellings.

Many cities are revitalizing their urban cores through the demolition of abandoned residential dwellings (ARDs). However, data regarding the emissions of asbestos during such an operation are sparse. We measured airborne asbestos emissions from emergency demolitions (demolitions on structures deemed too dangerous to enter and remove asbestos) of ARDs in Detroit. High-flow air sampling was conducted during ARD demolitions. Air samples were analyzed using Phased Contrast Microscopy (PCM), and a subset using Transmission Electron Microscopy (TEM). One hundred and one air samples were collected on 25 emergency demolitions. Fifty-four of the 101 PCM samples (53%) exceeded the limit of detection (LOD). However, only 2 of 46 TEM samples (4%) exceeded the LOD for asbestos; these latter samples were from two different demolitions and each contained a single chrysotile asbestos fiber. Using conservative exposure assumptions and commonly-accepted risk estimation formulae, we estimated the lifetime risk of mesothelioma and lung cancer combined to be less than one case per one million people. Emissions of airborne asbestos during emergency (unabated) ARD demolition operations appear to be negligible. As a result, the associated health risk for asbestos-related disease is also negligible. Reconsideration of current regulatory mandates for asbestos abatement in ARDs may be warranted.

Accumulation of DNAPL waste in subsurface clayey lenses and layers.

Chlorinated solvents like trichloroethylene (TCE) and tetrachloroethylene (PCE) are prevalent groundwater contaminants being detected more than half of the Superfund Sites. They are introduced into the subsurface due to improper disposal of hazardous wastes containing these chlorinated dense non-aqueous phase liquids (DNAPL). DNAPL wastes sink in the subsurface and form pools on clay layers. Further transport into the underlying clay layer is dominated by diffusion due to the low permeability of these soils and results in accumulation of contaminants therein overtime through diffusion. However, field evidence reported that mass storage of solvents in such zones was higher than what can be attributed to simple diffusion. To evaluate this finding, mass storage of TCE in a hypothetical aquitard after 30 years of diffusion was calculated. The diffusion coefficient reported in the field study resulted in mass storage of 137.7 g in this hypothetical aquitard whereas the mass calculated using the measured diffusion coefficient of TCE from pure solvent into water-saturated clayey soil was 25-65% of it (35.0-89.4 g). The calculated mass storage was even lower (8.2 g) if the measured diffusion coefficient of TCE from DNAPL waste into waste-contacted soil was used. So, mass of TCE accumulated through sole diffusion was not able to explain the one observed in the field. This excess mass in the field might be the mass of DNAPL entered into the cracks which were reported to form in clay layers as a result of the direct contact between water saturated clay and DNAPL waste. Mass of TCE in the cracks was calculated using reported average crack size and an assumed crack depth, and it appeared that cracks filled with DNAPL could increase the stored mass up to a minimum of 334 g which could easily account for the enhanced mass storage observed in the field.

Effective diffusion coefficients of DNAPL waste components in saturated low permeability soil materials.

Diffusion is regarded as the dominant transport mechanism into and out of low permeable subsurface lenses and layers in the subsurface. But, some reports of mass storage in such zones are higher than what might be attributable to diffusion, based on estimated diffusion coefficients. Despite the importance of diffusion to efforts to estimate the quantity of residual contamination in the subsurface, relatively few studies present measured diffusion coefficients of organic solutes in saturated low permeability soils. This study reports the diffusion coefficients of a trichloroethylene (TCE), and an anionic surfactant, Aerosol OT (AOT), in water-saturated silt and a silt-montmorillonite (25:75) mixture, obtained using steady-state experiments. The relative diffusivity ranged from 0.11 to 0.17 for all three compounds for the silt and the silt-clay mixture that was allowed to expand. In the case in which the swelling was constrained, the relative diffusivity was about 0.07. In addition, the relative diffusivity of 13C-labeled TCE through a water saturated silt-clay mixture that had contacted a field dense non-aqueous phase liquid (DNAPL) for 18months was measured and equaled 0.001. These experimental results were compared with the estimates generated using common correlations, and it was found that, in all cases, the measured diffusion coefficients were significantly lower than the estimated. Thus, the discrepancy between mass accumulations observed in the field and the mass storage that can attributable to diffusion may be greater than previously believed.

A mechanism of basal spacing reduction in sodium smectitic clay materials in contact with DNAPL wastes.

There has been concern regarding the possible attack of clays in aquitards, slurry walls and landfill liners by dense nonaqueous phase liquid (DNAPL) wastes, resulting in cracking. Despite the fact that a reduction in basal spacing in sodium smectitic clay materials has been linked to cracking, no plausible mechanism by which this reduction occurs in contact with waste DNAPLs has been formulated. To elucidate a mechanism, screening studies were conducted that showed that the combination of an anionic surfactant (AOT), a nonionic surfactant (TritonX-100) and a chlorinated solvent, tetrachloroethylene (PCE), could replicate the basal spacing reduction and cracking behavior of water-saturated bentonite caused by two waste DNAPLs obtained from the field. FTIR measurements of this system showed a displacement of the HOH bending band of water symptomatic of desiccation. Sorption measurements showed that the uptake of AOT by bentonite increased eight fold in the presence of TritonX-100 and PCE. The evidence presented here supports a mechanism of syneresis, involving the extraction of water from the interlayer space of the clay through the synergistic sorption of a nonionic and anionic surfactant mixture. It is speculated that the solvation of water in reverse micellar aggregates is the process driving the syneresis.

Dependence of particle concentration effect on pH and redox for arsenic removal by FeS-coated sand under anoxic conditions.

FeS has been recognized as a good scavenger for arsenic under anoxic conditions. To create a suitable adsorbent for flow-through reactors such as permeable reactive barriers, it has been suggested that this material may be coated onto sand. However, previous work on FeS-coated sand has focused on batch reactors, while flow-through reactors usually have higher solid-solution ratios. To ascertain whether differences in the solid-solution ratio (SSR) are important in this system, batch sorption experiments were conducted as a function of pH using As(III) and FeS-coated sands at various solid-solution ratios. The results showed little variation in the distribution coefficient with SSR at pH 7 and 9. However, at pH 5, the results showed lower values of the distribution coefficient at lower SSRs, the reverse of typically reported SSR effects. Measured pe values showed a dependence on SSR, which, when coupled with chemical modeling of the Fe-As-S-H2O system, suggested a change in the removal mechanism with SSR, from adsorption to a reduced Fe(II) oxyhydroxide phase (represented by Fe2(OH)5) to precipitation as As2S3 or AsS. On the other hand, at pH 7 and 9, arsenite adsorption is the most probable removal mechanism regardless of the pe. Thus, this study identified variations in pH and redox conditions, and the removal mechanisms that these parameters govern, as the reason for the apparent SSR effect.

Impact of DNAPL contact on the structure of smectitic clay materials.

Smectitic clays have a flexible structure that may be impacted by contact with dense nonaqueous phase liquids (DNAPLs) present at hazardous waste sites. Measurements of the basal spacing of air-dry clays contacted with pure chlorinated solvents and chlorinated DNAPL wastes showed that the intraparticle spacing is similar to that in air. Basal spacings of water-saturated clays contacted with pure chlorinated solvents are similar to those in contact with water, even after extended equilibration times (300 d). In contrast, contact with chlorinated DNAPL wastes reduced the basal spacing of water-saturated sodium smectites in a relatively short time frame, resulting in cracks that were as large as 1mm in aperture. The penetration of these wastes into the intraparticle spacing of clay and the resultant cracking may contribute to the accumulation of chlorinated compounds in clay layers observed in the field and the extended remediation times associated with this mass storage.

Estimation of age- and sex-specific background human serum concentrations of PCDDs, PCDFs, and PCBs in the UMDES and NHANES populations.

Age- and sex-specific estimates of serum dioxin concentrations are important for comparisons among populations. However, such comparisons are problematic because populations have different age and sex structures and values are typically reported only in broad age ranges that are not comparable across studies. There are few studies that report congener-specific serum concentrations, and none that provide these by sex for age as a continuous function. We combined the NHANES 2003-2004 data with the University of Michigan Dioxin Exposure Study (UMDES) referent population 2005 data to achieve stable and accurate estimates of mean and quantiles of serum dioxins by sex over ages 18-85. Survey-weighted linear and quantile regression models were fitted on the combined data with the log-transformed congener concentration as outcome and age, sex, and data source as covariates. Formulas are provided to allow calculations of age- and sex-specific mean and quantile estimates over ages 18-85. For instance, the geometric mean, median, 75th percentile, and 95th percentile of serum TEQ for men aged 50 can be estimated, respectively, from the formulas as 18.33, 19.02, 22.60, and 30.37 pg g(-1) lipids among the Michigan general population, and as 15.71, 15.89, 22.60, and 29.90 pg g(-1) lipids among US non-Hispanic whites. These methods and results are useful for comparing the congener-specific human serum dioxin concentrations in any individual to the general population mean, median, 75th percentile, and 95th percentile, and for comparing the serum dioxin concentration in any group of interest to the US and the Michigan general populations.

Impact of dissolved silica on arsenite removal by nano-particulate FeS and FeS-coated sand.

This work evaluated the inhibitory effect of dissolved silica on arsenite adsorption to nanoparticulate FeS (NP-FeS) or mackinawite and FeS-coated sand (CS-FeS) sorbents. Arsenite retention by the NP-FeS solid was not affected by dissolved silicate over a wide range in pH, in contrast to the known inhibitory effect of dissolved silica on As(III) uptake by Fe-(hydr)oxide systems. However, some inhibition was observed in CS-FeS system at pH 9. This latter result is attributed to the co-existence of both FeS and small amounts of Fe-(hydr)oxide phases on the sand surface. Given the ubiquitous presence of dissolved Si in groundwater, FeS-based sorbents may have an advantage for As retention compared to those based on Fe-(hydr)oxides in reducing subsurface environments.

Permeability of iron sulfide (FeS)-based materials for groundwater remediation.

Iron sulfide (FeS) has been extensively assessed as a reactive medium to remove both metals and halogenated organics from groundwater. However, to address its suitability as a material for permeable reactive barriers (PRBs), its propensity for solids and gas production, which result in reduced permeability, must be evaluated. The reduction in permeability for sands coated with FeS (as mackinawite), under the anoxic conditions often encountered at contaminated groundwater sites, was examined through column experiments and geochemical modeling under conditions of high calcium and nitrate, which have been previously shown to cause significant permeability reduction in zero-valent iron (ZVI) systems. The column experiments showed negligible production of both solids and gases. The geochemical modeling predicted a maximum reduction in permeability of 1% due to solids and about 30% due to gas formation under conditions for which a complete loss of permeability was predicted for ZVI systems. This difference in permeability reduction is driven by the differences in thermodynamic stability of ZVI and FeS in aqueous solutions. The results suggest that geochemical conditions that result in high permeability losses for ZVI systems will likely not be problematic for FeS-based reactive materials.

X-ray absorption and photoelectron spectroscopic study of the association of As(III) with nanoparticulate FeS and FeS-coated sand.

Iron sulfide (FeS) has been demonstrated to have a high removal capacity for arsenic (As) in reducing environments. However, FeS may be present as a coating, rather than in nanoparticulate form, in both natural and engineered systems. Frequently, the removal capacity of coatings may be different than that of nanoparticulates in batch systems. To assess the differences in removal mechanisms between nanoparticulate FeS and FeS present as a coating, the solid phase products from the reaction of As(III) with FeS-coated sand and with suspensions of nanoparticulate (NP) FeS were determined using x-ray absorption spectroscopy and x-ray photoelectron spectroscopy. In reaction with NP FeS at pH 5, As(III) was reduced to As(II) to form realgar (AsS), while at pH 9, As(III) adsorbed as an As(III) thioarsenite species. In contrast, in the FeS-coated sand system, As(III) formed the solid phase orpiment (As(2)S(3)) at pH 5, but adsorbed as an As(III) arsenite species at pH 9. These different solid reaction products are attributed to differences in FeS concentration and the resultant redox (pe) differences in the FeS-coated sand system versus suspensions of NP FeS. These results point to the importance of accounting for differences in concentration and redox when making inferences for coatings based on batch suspension studies.

FeS-coated sand for removal of arsenic(III) under anaerobic conditions in permeable reactive barriers.

Iron sulfide (as mackinawite, FeS) has shown considerable promise as a material for the removal of As(III) under anoxic conditions. However, as a nanoparticulate material, synthetic FeS is not suitable for use in conventional permeable reactive barriers (PRBs). This study developed a methodology for coating a natural silica sand to produce a material of an appropriate diameter for a PRB. Aging time, pH, rinse time, and volume ratios were varied, with a maximum coating of 4.0 mg FeS/g sand achieved using a pH 5.5 solution at a 1:4 volume ratio (sand: 2 g/L FeS suspension), three days of aging and no rinsing. Comparing the mass deposited on the sand, which had a natural iron-oxide coating, with and without chemical washing showed that the iron-oxide coating was essential to the formation of a stable FeS coating. Scanning electron microscopy images of the FeS-coated sand showed a patchwise FeS surface coating. X-ray photoelectron spectroscopy showed a partial oxidation of the Fe(II) to Fe(III) during the coating process, and some oxidation of S to polysulfides. Removal of As(III) by FeS-coated sand was 30% of that by nanoparticulate FeS at pH 5 and 7. At pH 9, the relative removal was 400%, perhaps due to the natural oxide coating of the sand or a secondary mineral phase from mackinawite oxidation. Although many studies have investigated the coating of sands with iron oxides, little prior work reports coating with iron sulfides. The results suggest that a suitable PRB material for the removal of As(III) under anoxic conditions can be produced through the deposition of a coating of FeS onto natural silica sand with an iron-oxide coating.

Estimation of background serum 2,3,7,8-TCDD concentrations by using quantile regression in the UMDES and NHANES populations.

BACKGROUND: The goal of the present study was to quantify the population-based background serum concentrations of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) by using data from the reference population of the 2005 University of Michigan Dioxin Exposure Study (UMDES) and the 2003-2004 National Health and Nutrition Examination Survey (NHANES). METHODS: Multiple imputation was used to impute the serum TCDD concentrations below the limit of detection by combining the 2 data sources. The background mean, quartiles, and 95th percentile serum TCDD concentrations were estimated by age and sex by using linear and quantile regressions for complex survey data. RESULTS: Any age- and sex-specific mean, quartiles, and 95th percentiles of background serum TCDD concentrations of study participants between ages 18 and 85 years can be estimated from the regressions for the UMDES reference population and the NHANES non-Hispanic white population. For example, for a 50-year-old man in the reference population of UMDES, the mean, quartiles, and 95th percentile serum TCDD concentrations are estimated to be 1.1, 0.6, 1.1, 1.8, and 3.3 parts per trillion, respectively. The study also shows that the UMDES reference population is a valid reference population for serum TCDD concentrations for other predominantly white populations in Michigan. CONCLUSION: The serum TCDD concentrations increased with age and increased more over age in women than in men, and hence estimation of background concentrations must be adjusted for age and sex. The methods and results discussed in this article have wide application in studies of the concentrations of chemicals in human serum and in environmental samples.

Wettability hysteresis and its implications for DNAPL source zone distribution.

Subsurface heterogeneity at sites contaminated with nonaqueous phase liquids (NAPLs) reduces the effectiveness of traditional remediation measures. One cause may be the increased proportion of NAPL that is hydraulically isolated due to capillary trapping in heterogeneously-wetted materials. This study examines the wettability of ten materials, ranging from minerals, such as calcite and dolomite, to carbonaceous materials, such shale and coal, in air and water, NAPL and air, and NAPL and water systems. The wettability differed depending on which phase the solid material was initially immersed in: the less crystalline solids, if initially contacted by water were water-wet, but if initially contacted by NAPL were NAPL-wet. This difference, termed here wettability hysteresis, was observed for a suite of halogenated NAPLs and was independent of equilibration time. The degree of wettability hysteresis was greatest in the NAPL and water systems, with the magnitude of the difference increasing with the carbonaceous materials. Since the degree of capillary trapping in subsurface materials is related to wettability, the phenomenon of wettability hysteresis suggests that system history is a factor that may increase the heterogeneity of NAPL source zones.

Geostatistical modeling of the spatial distribution of soil dioxin in the vicinity of an incinerator. 2. Verification and calibration study.

A key component in any investigation of cause-effect relationships between point source pollution, such as an incinerator, and human health is the availability of measurements and/or accurate models of exposure at the same scale or geography as the health data. Geostatistics allows one to simulate the spatial distribution of pollutant concentrations over various spatial supports while incorporating both field data and predictions of deterministic dispersion models. This methodology was used in a companion paper to identify the census blocks that have a high probability of exceeding a given level of dioxin TEQ (toxic equivalents) around an incinerator in Midland, MI. This geostatistical model, along with population data, provided guidance for the collection of 51 new soil data, which permits the verification of the geostatistical predictions, and calibration of the model. Each new soil measurement was compared to the set of 100 TEQ values simulated at the closest grid node. The correlation between the measured concentration and the averaged simulated value is moderate (0.44), and the actual concentrations are clearly overestimated in the vicinity of the plant property line. Nevertheless, probability intervals computed from simulated TEQ values provide an accurate model of uncertainty: the proportion of observations that fall within these intervals exceeds what is expected from the model. Simulation-based probability intervals are also narrower than the intervals derived from the global histogram of the data, which demonstrates the greater precision of the geostatistical approach. Log-normal ordinary kriging provided fairly similar estimation results for the small and well-sampled area used in this validation study; however, the model of uncertainty was not always accurate. The regression analysis and geostatistical simulation were then conducted using the combined set of 53 original and 51 new soil samples, leading to an updated model for the spatial distribution of TEQ in Midland, MI.

Influence of organic acid and organic base interactions on interfacial properties in NAPL--water systems.

Interfacial properties play an important role in determining the transport and distribution of waste nonaqueous phase liquids (NAPLs) in groundwater. To develop a better understanding of the solute interactions governing the interfacial properties of waste NAPLs, this study examined the interfacial tension and contact angle of a tetrachloroethylene/water/quartz system containing octanoic acid and dodecylamine as a function of pH. The results showed that interactions between these solutes affected the system's interfacial properties significantly, producing a positive synergism. For example, octanoic acid, which by itself does not affect wettability, could reverse the wettability of quartz in the presence of dodecylamine. The significant reduction in interfacial tension and increase in contact angle around neutral pH was, based on the results of speciation modeling, attributed to the formation of a complex composed of the protonated organic base and deprotonated organic acid, whose formation also peaks around neutral pH. Thus, measures of the content of only one class of compounds, such as the base number, are inadequate descriptors of a NAPL's ability to alter wettability.

Prediction of two-phase capillary pressure-saturation relationships in fractional wettability systems.

Capillary pressure/saturation data are often difficult and time consuming to measure, particularly for non-water-wetting porous media. Few capillary pressure/saturation predictive models, however, have been developed or verified for the range of wettability conditions that may be encountered in the natural subsurface. This work presents a new two-phase capillary pressure/saturation model for application to the prediction of primary drainage and imbibition relations in fractional wettability media. This new model is based upon an extension of Leverett scaling theory. Analysis of a series of DNAPL/water experiments, conducted for a number of water/intermediate and water/organic fractional wettability systems, reveals that previous models fail to predict observed behavior. The new Leverett-Cassie model, however, is demonstrated to provide good representations of these data, as well as those from two earlier fractional wettability studies. The Leverett-Cassie model holds promise for field application, based upon its foundation in fundamental scaling principles, its requirement for relatively few and physically based input parameters, and its applicability to a broad range of wetting conditions.

Estimation of primary drainage three-phase relative permeability for organic liquid transport in the vadose zone.

The modeling of transport of organic liquid contaminants through the vadose zone often requires three-phase relative permeabilities. Since these are difficult to measure, predictive models are usually used. The objective of this study is to assess the ability of eight common models to predict the drainage relative permeability to oil in a three-phase system (water-oil-air). A comparison of the models' estimates using data set from Oak [Oak, M.J., 1990. Three-phase relative permeability of water-wet Berea. In: Seventh Symposium on Enhanced Oil Recovery, Paper SPE/Doe 20183. Tulsa, OK, April 22-25] showed that they provide very different predictions for the same system. The goodness of the models does not increase with the amount of data or computation that the models require. Also, the calculations showed how different interpretations of the models and of the terminology associated with them can significantly impact the predictions. Thus, considerable error may be introduced into the simulations of organic liquid transport in the vadose zone depending on the selection and interpretation of the three-phase relative permeability model.

Conductivity reduction due to emulsification during surfactant enhanced-aquifer remediation. 1. Emulsion transport.

Surfactant-enhanced aquifer remediation (SEAR) is a promising technology for the remediation of subsurface zones contaminated with organic liquids. To ensure the success of SEAR, the potential reduction in hydraulic conductivity must be evaluated. The objective of this study was to examine the process of conductivity reduction due to the transport of an emulsion, generated by mixing tetrachloroethylene with 4% solutions of two nonionic surfactants, in packed beds of sand-sized silica particles. The injection of the emulsion resulted in a 75-85% reduction in conductivity, depending on the properties of the surfactant and the porous medium. The greater viscosity of the emulsion relative to that of water accounted for about 25% of the reduction. The remainder was attributed to the clogging of the porous medium by the emulsion. The relative sizes of the emulsion droplets and the packed bed's pores, coupled with measurements of zeta potential of the emulsion droplets and silica particles, suggested that multilayer deposition was the principal mechanism of clogging. This hypothesis was corroborated by direct observation of the emulsion transport process in a micromodel. To simulate the reduction in hydraulic conductivity in these systems accurately, it was necessary to modify the emulsion transport model by Soo and Radke to include the phenomena of viscosity variation and multilayering.

Conductivity reduction due to emulsification during surfactant enhanced-aquifer remediation. 2. Formation of emulsion in situ.

Permeability reduction due to surfactant emulsification can impact the effectiveness of surfactant-enhanced aquifer remediation (SEAR). The objective of this study was to examine the process of in situ emulsification in systems composed of tetrachloroethylene (PCE) and solutions of two nonionic surfactants selected for their ability to enhance solubility. The injection of the surfactant solutions into columns packed with sand-sized silica particles containing residual saturations of PCE resulted in the formation of an emulsion with an average droplet diameter of 0.1-0.2 microm, about an order of magnitude smaller than that of the ex situ formed emulsion. The measurements of hydraulic conductivity showed an initial decrease, followed by a gradual increase, with a final steady-state reduction of about 35% after the injection of 7-8 pore volumes of surfactant solution, of which about 8% could be attributed to the deposition of the emulsion. To describe the observed trends, the modified emulsion transport model from Part 1 was modified to include the processes of the formation of the emulsion and the reduction of the PCE residual. The good comparison between the simulations and the experimental data suggests that the model correctly reflects the multiple processes controlling the hydraulic conductivity of the packed columns during surfactant solution injection.