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Analysis of partitioning tracer tests conducted in dense nonaqueous phase liquid (DNAPL) source zones relies on conceptual models that describe mass exchange between the DNAPL and aqueous phases. Such analysis, however, is complicated by the complex distribution of entrapped DNAPL mass and formation heterogeneity. Due to parameter uncertainty in heterogeneous regions and the desire to reduce model complexity, the effect of mass transfer limitations is often neglected, and an equilibrium-based model is typically used to interpret test results. This work explores the consequences of that simplifying assumption on test data interpretation and develops an alternative upscaled modeling approach to quantify effective mass transfer rates. To this end, a series of partitioning tracer tests is numerically simulated in heterogeneous two-dimensional PCE-DNAPL source zones, representative of a range of hydraulic conductivity and DNAPL mass distribution characteristics. The effective mass transfer coefficient corresponding to each test is determined by fitting an upscaled model to the simulated data, and regression analysis is performed to explore the correlation between various source zone metrics and the effective mass transfer coefficient. Results suggest that vertical DNAPL spreading, Reynolds number, pool fraction, and the effective organic phase saturation are the most significant parameters controlling tracer partitioning rates. Finally, a correlation for prediction of the effective (upscaled) mass transfer coefficient is proposed and verified using existing experimental data. The developed upscaled model incorporates the influence of physical heterogeneity on the rate of tracer partitioning and, thus, can be used for the estimation of source zone mass distribution characteristics from tracer test results. © 2015. American Geophysical Union.


Iavicoli I.,Catholic University of the Sacred Heart | Calabrese E.J.,University of Massachusetts Amherst | Nascarella M.A.,Gradient
Dose-Response | Year: 2010

Nanoparticles are particles with lengths that range from 1 to 100 nm. They are increasingly being manufactured and used for commercial purpose because of their novel and unique physicochemical properties. Although nanotechnology-based products are generally thought to be at a pre-competitive stage, an increasing number of products and materials are becoming commercially available. Human exposure to nanoparticles is therefore inevitable as they become more widely used and, as a result, nanotoxicology research is now gaining attention. However, there are many uncertainties as to whether the unique properties of nanoparticles also pose occupational health risks. These uncertainties arise because of gaps in knowledge about the factors that are essential for predicting health risks such as routes of exposure, distribution, accumulation, excretion and dose-response relationship of the nanoparticles. In particular, uncertainty remains with regard to the nature of the dose-response curve at low level exposures below the toxic threshold. In fact, in the literature, some studies that investigated the biological effects of nanoparticles, observed a hormetic dose-response. However, currently available data regarding this topic are extremely limited and fragmentary. It therefore seems clear that future studies need to focus on this issue by studying the potential adverse health effects caused by low-level exposures to nanoparticles. © 2010 University of Massachusetts.


Mayfield D.B.,Gradient | Fairbrother A.,Exponent, Inc.
Integrated Environmental Assessment and Management | Year: 2013

Wildlife toxicity reference values (TRVs) are routinely used during screening level and baseline ecological risk assessments (ERAs). Risk assessment professionals often adopt TRVs from published sources to expedite risk analyses. The US Environmental Protection Agency (USEPA) developed ecological soil screening levels (Eco-SSLs) to provide a source of TRVs that would improve consistency among risk assessments. We conducted a survey and evaluated more than 50 publicly available, large-scale ERAs published in the last decade to evaluate if USEPA's goal of uniformity in the use of wildlife TRVs has been met. In addition, these ERAs were reviewed to understand current practices for wildlife TRV use and development within the risk assessment community. The use of no observed and lowest observed adverse effect levels culled from published compendia was common practiceamong the majority of ERAs reviewed.We found increasing use over time of TRVs established in the Eco-SSL documents; however, Eco-SSL TRV values were not used in the majority of recent ERAs and there continues to be wide variation in TRVs for commonly studied contaminants (e.g., metals, pesticides, PAHs, and PCBs). Variability in the toxicity values was driven by differences in the key studies selected, dose estimation methods, and use of uncertainty factors. These differences result in TRVs that span multiple orders of magnitude for many of the chemicals examined. This lack of consistency in TRV development leads to highly variable results in ecological risk assessments conducted throughout the United States. © 2012 SETAC.


Mayfield D.B.,Gradient | Fairbrother A.,Exponent, Inc.
Chemosphere | Year: 2015

Rare earth elements (REEs or lanthanides) were measured in ten freshwater fish species from a reservoir in Washington State (United States). The REE distribution patterns were examined within fillet and whole body tissues for three size classes. Total concentrations (σREE) ranged from 0.014 to 3.0mgkg-1 (dry weight) and averaged 0.243mgkg-1 (dry weight). Tissue concentration patterns indicated that REEs accumulated to a greater extent in organs, viscera, and bone compared to muscle (fillet) tissues. Benthic feeding species (exposed to sediments) exhibited greater concentrations of REEs than pelagic omnivorous or piscivorous fish species. Decreasing REE concentrations were found with increasing age, total length or weight for largescale and longnose suckers, smallmouth bass, and walleye. Concentration patterns in this system were consistent with natural conditions without anthropogenic sources of REEs. These data provide additional reference information with regard to the fate and transport of REEs in freshwater fish tissues in a large aquatic system. © 2014 Elsevier Ltd.


Boroumand A.,Gradient | Abriola L.M.,Tufts University
Water Resources Research | Year: 2015

Analysis of partitioning tracer tests conducted in dense nonaqueous phase liquid (DNAPL) source zones relies on conceptual models that describe mass exchange between the DNAPL and aqueous phases. Such analysis, however, is complicated by the complex distribution of entrapped DNAPL mass and formation heterogeneity. Due to parameter uncertainty in heterogeneous regions and the desire to reduce model complexity, the effect of mass transfer limitations is often neglected, and an equilibrium-based model is typically used to interpret test results. This work explores the consequences of that simplifying assumption on test data interpretation and develops an alternative upscaled modeling approach to quantify effective mass transfer rates. To this end, a series of partitioning tracer tests is numerically simulated in heterogeneous two-dimensional PCE-DNAPL source zones, representative of a range of hydraulic conductivity and DNAPL mass distribution characteristics. The effective mass transfer coefficient corresponding to each test is determined by fitting an upscaled model to the simulated data, and regression analysis is performed to explore the correlation between various source zone metrics and the effective mass transfer coefficient. Results suggest that vertical DNAPL spreading, Reynolds number, pool fraction, and the effective organic phase saturation are the most significant parameters controlling tracer partitioning rates. Finally, a correlation for prediction of the effective (upscaled) mass transfer coefficient is proposed and verified using existing experimental data. The developed upscaled model incorporates the influence of physical heterogeneity on the rate of tracer partitioning and, thus, can be used for the estimation of source zone mass distribution characteristics from tracer test results. © 2015. American Geophysical Union. All Rights Reserved.


Lewandowski T.A.,Gradient | Peterson M.K.,Gradient | Charnley G.,HealthRisk Strategies LLC
Food and Chemical Toxicology | Year: 2015

Ensuring adequate iodine intake is important, particularly among women of reproductive age, because iodine is necessary for early life development. Biologically based dose-response modeling of the relationships among iodide status, perchlorate dose, and thyroid hormone production in pregnant women has indicated that iodide intake has a profound effect on the likelihood that exposure to goitrogens will produce hypothyroxinemia. We evaluated the possibility of increasing iodine intake to offset potential risks from perchlorate exposure. We also explored the effect of dietary exposures to nitrate and thiocyanate on iodine uptake and thyroid hormone production. Our modeling indicates that the level of thyroid hormone perturbation associated with perchlorate exposures in the range of current regulatory limits is extremely small and would be overwhelmed by other goitrogen exposures. Our analysis also shows that microgram levels of iodine supplementation would be sufficient to prevent the goitrogenic effects of perchlorate exposure at current regulatory limits among at risk individuals. The human health risks from supplementing drinking water with iodine are negligible; therefore, this approach is worthy of regulatory consideration. © 2015 The Authors.


Briggs N.L.,Gradient | Long C.M.,University of Cambridge
Atmospheric Environment | Year: 2016

An increasing number of air pollution source apportionment studies in Europe and the United States have focused on the black carbon (BC) fraction of ambient particulate matter (PM) given its linkage with adverse public health and climate impacts. We conducted a critical review of European and US BC source apportionment studies published since 2003. Since elemental carbon (EC) has been used as a surrogate measure of BC, we also considered source apportionment studies of EC measurements. This review extends the knowledge presented in previous ambient PM source apportionment reviews because we focus on BC and EC and critically examine the differences between source apportionment results for different methods and source categories. We identified about 50 BC and EC source apportionment studies that have been conducted in either Europe or the US since 2003, finding a striking difference in the commonly used source apportionment methods between the two regions and variations in the assigned source categories. Using three dominant methodologies (radiocarbon, aethalometer, and macro-tracer methods) that only allow for BC to be broadly apportioned into either fossil fuel combustion or biomass burning source categories, European studies generally support fossil fuel combustion as the dominant ambient BC source, but also show significant biomass burning contributions, in particular in wintertime at non-urban locations. Among US studies where prevailing methods such as chemical mass balance (CMB) and positive matrix factorization (PMF) models have allowed for estimation of more refined source contributions, there are fewer findings showing the significance of biomass burning and variable findings on the relative proportion of BC attributed to diesel versus gasoline emissions. Overall, the available BC source apportionment studies provide useful information demonstrating the significance of both fossil fuel combustion and biomass burning BC emission sources in Europe and the US, although further studies are needed to evaluate the uncertainties and comparability of the methodologies. © 2016 Elsevier Ltd


Goodman J.E.,Gradient | Loftus C.T.,Gradient | Zu K.,Gradient
Annals of Epidemiology | Year: 2015

Purpose: Despite evidence from experimental studies indicating that the herbicide, 2,4-dichlorophenoxyacetic acid (2,4-D), is not carcinogenic, several epidemiology studies have evaluated links between 2,4-D and cancer. Some suggest that 2,4-D is associated with non-Hodgkin's lymphoma (NHL), gastric cancer, and prostate cancer, but results have been inconsistent. We conducted meta-analyses to evaluate the weight of epidemiology evidence for these cancers. Methods: We identified articles from PubMed, Scopus, and TOXLINE databases and reference lists of review articles. We evaluated study quality and calculated summary risk estimates using random effects models. We conducted subgroup and sensitivity analyses when possible. Results: We identified nine NHL, three gastric cancer, and two prostate cancer studies for inclusion in our meta-analyses. We found that 2,4-D was not associated with NHL (relative risk [RR]=0.97, 95% confidence interval [CI]=0.77-1.22, I2=28.8%, Pheterogeneity=19), and this result was generally robust to subgroup and sensitivity analyses. 2,4-D was not associated with gastric (RR=1.14, 95% CI=0.62-2.10, I2=54.9%, Pheterogeneity=11) or prostate cancer (RR=1.32, 95% CI=0.37-4.69, I2 87.0%, Pheterogeneity=01). Conclusions: The epidemiology evidence does not support an association between 2,4-D and NHL, gastric cancer, or prostate cancer risk. © 2015 The Authors.


Beyer L.A.,Gradient | Beck B.D.,Gradient | Lewandowski T.A.,Gradient | Lewandowski T.A.,Brooklyn College
Critical Reviews in Toxicology | Year: 2011

The animal testing protocols used today to evaluate the carcinogenicity of chemicals are very different from those used in the earlier part of the 20th century. To explore how cancer bioassays have changed over time, we surveyed the literature discussing test design and interpretation from the 1930s to the present. We also analyzed compendia of bioassays published by the US Public Health Service (US PHS) from 1938 to 1978, and evaluated the data to understand the evolution of testing methodology (e.g., animals used, test duration) and the types of chemicals being studied. The cancer bioassay evolved in several stages. At the beginning of the 20th century, animal bioassays were primarily used to re-create known human diseases, whereas in the 1940s to 1960s, animal bioassays were largely used to evaluate the safety of chemicals in foods, drugs, and cosmetics. Beginning in the late 1960s and 1970s, chemicals primarily associated with occupational or environmental exposures were also evaluated. Testing strategies now emphasize a suite of tests including multiple in vitro tests and both short-term and long-term animal tests. The objectives of testing are broader, too, with test goals encompassing information regarding mode of action and other parameters aimed at evaluating potential species differences (e.g., in toxicokinetics) and their relevance for evaluating human risks. It is important to consider this evolution when evaluating the testing methodology and scientific conclusions in earlier eras. As toxicology continues to develop, testing methods will continue to change in concert with increased knowledge and understanding. © 2011 Informa Healthcare USA, Inc.


Hughes M.F.,U.S. Environmental Protection Agency | Beck B.D.,Gradient | Chen Y.,New York University | Lewis A.S.,Gradient | Thomas D.J.,U.S. Environmental Protection Agency
Toxicological Sciences | Year: 2011

The metalloid arsenic is a natural environmental contaminant to which humans are routinely exposed in food, water, air, and soil. Arsenic has a long history of use as a homicidal agent, but in the past 100 years arsenic, has been used as a pesticide, a chemotherapeutic agent and a constituent of consumer products. In some areas of the world, high levels of arsenic are naturally present in drinking water and are a toxicological concern. There are several structural forms and oxidation states of arsenic because it forms alloys with metals and covalent bonds with hydrogen, oxygen, carbon, and other elements. Environmentally relevant forms of arsenic are inorganic and organic existing in the trivalent or pentavalent state. Metabolism of arsenic, catalyzed by arsenic (13 oxidation state) methyltransferase, is a sequential process of reduction from pentavalency to trivalency followed by oxidative methylation back to pentavalency. Trivalent arsenic is generally more toxicologically potent than pentavalent arsenic. Acute effects of arsenic range from gastrointestinal distress to death. Depending on the dose, chronic arsenic exposure may affect several major organ systems. A major concern of ingested arsenic is cancer, primarily of skin, bladder, and lung. The mode of action of arsenic for its disease endpoints is currently under study. Two key areas are the interaction of trivalent arsenicals with sulfur in proteins and the ability of arsenic to generate oxidative stress. With advances in technology and the recent development of animal models for arsenic carcinogenicity, understanding of the toxicology of arsenic will continue to improve.

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