Alexi Ernstoff

Exploring consumer exposure pathways and patterns of use for chemicals in the environment

Highlights • To assign use-related information to chemicals to help prioritize which will be given more scrutiny relative to human exposure potential.• Categorical chemical use and functional information are presented through the Chemical/Product Categories Database (CPCat).• CPCat contains information on >43,000 unique chemicals mapped to ∼800 terms categorizing their usage or function.• The CPCat database is useful for modeling and prioritizing human chemical exposures.

Micropollutant Fate in Wastewater Treatment: Redefining “Removal”

Lauren B. Stadler,*,† Alexi S. Ernstoff,‡ Diana S. Aga, and Nancy G. Love† †Department of Civil & Environmental Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States ‡Environmental Health Sciences, School of Public Health, University of Michigan, Ann Arbor, Michigan 48109, United States Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260, United States

A life cycle assessment framework combining nutritional and environmental health impacts of diet: a case study on milk

PurposeWhile there has been considerable effort to understand the environmental impact of a food or diet, nutritional effects are not usually included in food-related life cycle assessment (LCA).MethodsWe developed a novel Combined Nutritional and Environmental Life Cycle Assessment (CONE-LCA) framework that evaluates and compares in parallel the environmental and nutritional effects of foods or diets. We applied this framework to assess human health impacts, expressed in Disability Adjusted Life Years (DALYs), in a proof-of-concept case study that investigated the environmental and nutritional human health effects associated with the addition of one serving of fluid milk to the present average adult US diet. Epidemiology-based nutritional impacts and benefits linked to milk intake, such as colorectal cancer, stroke, and prostate cancer, were compared to selected environmental impacts traditionally considered in LCA (global warming and particulate matter) carried to a human health endpoint.Results and discussionConsidering potential human health effects related to global warming, particulate matter, and nutrition, within the context of this study, findings suggest that adding one serving of milk to the current average diet could result in a health benefit for American adults, assuming that existing foods associated with substantial health benefits are not substituted, such as fruits and vegetables. The net health benefit is further increased when considering an iso-caloric substitution of less healthy foods (sugar-sweetened beverages). Further studies are needed to test whether this conclusion holds within a more comprehensive assessment of environmental and nutritional health impacts.ConclusionsThis case study provides the first quantitative epidemiology-based estimate of the complements and trade-offs between nutrition and environment human health burden expressed in DALYs, pioneering the infancy of a new approach in LCA. We recommend further testing of this CONE-LCA approach for other food items and diets, especially when making recommendations about sustainable diets and food choices.

Effect of redox conditions on pharmaceutical loss during biological wastewater treatment using sequencing batch reactors

We lack a clear understanding of how wastewater treatment plant (WWTP) process parameters, such as redox environment, impact pharmaceutical fate. WWTPs increasingly install more advanced aeration control systems to save energy and achieve better nutrient removal performance. The impact of redox condition, and specifically the use of microaerobic (low dissolved oxygen) treatment, is poorly understood. In this study, the fate of a mixture of pharmaceuticals and several of their transformation products present in the primary effluent of a local WWTP was assessed in sequencing batch reactors operated under different redox conditions: fully aerobic, anoxic/aerobic, and microaerobic (DO concentration ≈0.3mg/L). Among the pharmaceuticals that were tracked during this study (atenolol, trimethoprim, sulfamethoxazole, desvenlafaxine, venlafaxine, and phenytoin), overall loss varied between them and between redox environments. Losses of atenolol and trimethoprim were highest in the aerobic reactor; sulfamethoxazole loss was highest in the microaerobic reactors; and phenytoin was recalcitrant in all reactors. Transformation products of sulfamethoxazole and desvenlafaxine resulted in the reformation of their parent compounds during treatment. The results suggest that transformation products must be accounted for when assessing removal efficiencies and that redox environment influences the degree of pharmaceutical loss.

Risk-Based High-Throughput Chemical Screening and Prioritization using Exposure Models and in Vitro Bioactivity Assays

We present a risk-based high-throughput screening (HTS) method to identify chemicals for potential health concerns or for which additional information is needed. The method is applied to 180 organic chemicals as a case study. We first obtain information on how the chemical is used and identify relevant use scenarios (e.g., dermal application, indoor emissions). For each chemical and use scenario, exposure models are then used to calculate a chemical intake fraction, or a product intake fraction, accounting for chemical properties and the exposed population. We then combine these intake fractions with use scenario-specific estimates of chemical quantity to calculate daily intake rates (iR; mg/kg/day). These intake rates are compared to oral equivalent doses (OED; mg/kg/day), calculated from a suite of ToxCast in vitro bioactivity assays using in vitro-to-in vivo extrapolation and reverse dosimetry. Bioactivity quotients (BQs) are calculated as iR/OED to obtain estimates of potential impact associated with each relevant use scenario. Of the 180 chemicals considered, 38 had maximum iRs exceeding minimum OEDs (i.e., BQs > 1). For most of these compounds, exposures are associated with direct intake, food/oral contact, or dermal exposure. The method provides high-throughput estimates of exposure and important input for decision makers to identify chemicals of concern for further evaluation with additional information or more refined models.

Defining Product Intake Fraction to Quantify and Compare Exposure to Consumer Products

There is a growing consciousness that exposure studies need to better cover near-field exposure associated with products use. To consistently and quantitatively compare human exposure to chemicals in consumer products, we introduce the concept of product intake fraction, as the fraction of a chemical within a product that is eventually taken in by the human population. This metric enables consistent comparison of exposures during consumer product use for different product-chemical combinations, exposure duration, exposure routes and pathways and for other life cycle stages. We present example applications of the product intake fraction concept, for two chemicals in two personal care products and two chemicals encapsulated in two articles, showing how intakes of these chemicals can primarily occur during product use. We demonstrate the utility of the product intake fraction and its application modalities within life cycle assessment and risk assessment contexts. The product intake fraction helps to provide a clear interface between the life cycle inventory and impact assessment phases, to identify best suited sentinel products and to calculate overall exposure to chemicals in consumer products, or back-calculate maximum allowable concentrations of substances inside products.

Multi-pathway exposure modeling of chemicals in cosmetics with application to shampoo

We present a novel multi-pathway, mass balance based, fate and exposure model compatible with life cycle and high-throughput screening assessments of chemicals in cosmetic products. The exposures through product use as well as post-use emissions and environmental media were quantified based on the chemical mass originally applied via a product, multiplied by the product intake fractions (PiF, the fraction of a chemical in a product that is taken in by exposed persons) to yield intake rates. The average PiFs for the evaluated chemicals in shampoo ranged from 3×10(-4) up to 0.3 for rapidly absorbed ingredients. Average intake rates ranged between nano- and micrograms per kilogram bodyweight per day; the order of chemical prioritization was strongly affected by the ingredient concentration in shampoo. Dermal intake and inhalation (for 20% of the evaluated chemicals) during use dominated exposure, while the skin permeation coefficient dominated the estimated uncertainties. The fraction of chemical taken in by a shampoo user often exceeded, by orders of magnitude, the aggregated fraction taken in by the population through post-use environmental emissions. Chemicals with relatively high octanol-water partitioning and/or volatility, and low molecular weight tended to have higher use stage exposure. Chemicals with low intakes during use (<1%) and subsequent high post-use emissions, however, may yield comparable intake for a member of the general population. The presented PiF based framework offers a novel and critical advancement for life cycle assessments and high-throughput exposure screening of chemicals in cosmetic products demonstrating the importance of consistent consideration of near- and far-field multi-pathway exposures.

Stochastic modeling of near-field exposure to parabens in personal care products.

Exposure assessment is a key step in determining risks to chemicals in consumer goods, including personal care products (PCPs). Exposure models can be used to estimate exposures to chemicals in the absence of biomonitoring data and as tools in chemical risk prioritization and screening. We apply a PCP exposure model based on the product intake fraction (PiF), which is defined as the fraction of chemical in a product that is taken in by the exposed population, to estimate chemical intake based on physicochemical properties and PCP usage characteristics. The PiF can be used to estimate route and pathway-specific exposures during both the use and disposal stages of a product. As a case study, we stochastically quantified population level exposures to parabens in PCPs, and compared estimates with biomarker values. We estimated exposure based on the usage of PCPs in the female US population, taking into account population variability, product usage characteristics, paraben occurrence in PCPs and the PiF. Intakes were converted to urine levels and compared with National Health and Nutrition Examination Survey (NHANES) biomonitoring data. Results suggest that for parabens, chemical exposure during product use is substantially larger than environmentally mediated exposure after product disposal. Modeled urine concentrations reflect well the NHANES variation of three orders of magnitude across parabens for the 50th, 75th, 90th, and 95th percentiles and were generally in good agreement with measurements, when taking uncertainty into account. This study presents an approach to estimate multi-pathway exposure to chemicals in PCPs and can be used as a tool within exposure-based screening of chemicals as well in higher tier exposure estimates.

LCA of Chemicals and Chemical Products

This chapter focuses on the application of Life Cycle Assessment (LCA) to evaluate the environmental performance of chemicals as well as of products and processes where chemicals play a key role. The life cycle stages of chemical products, such as pharmaceuticals drugs or plant protection products, are discussed and differentiated into extraction of abiotic and biotic raw materials, chemical synthesis and processing, material processing, product manufacturing, professional or consumer product use, and finally end-of-life. LCA is discussed in relation to other chemicals management frameworks and concepts including risk assessment, green and sustainable chemistry, and chemical alternatives assessment. A large number of LCA studies focus on contrasting different feedstocks or chemical synthesis processes, thereby often conducting a cradle to (factory) gate assessment. While typically a large share of potential environmental impacts occurs during the early product life cycle stages, potential impacts related to chemicals that are found as ingredients or residues directly in products can be dominated by the product use stage. Finally, methodological challenges in LCA studies in relation to chemicals are discussed including the choice of functional unit, defining the system boundaries, quantifying emissions for many thousands of marketed chemicals, characterising emissions in terms of toxicity and other impacts, and finally interpreting LCA results. The chapter is relevant for LCA students and practitioners who wish to gain basic understanding of LCA studies of products or processes with chemicals as a key aspect.

Toward Harmonizing Ecotoxicity Characterization in Life Cycle Impact Assessment

Ecosystem quality is an important area of protection in life cycle impact assessment (LCIA). Chemical pollution has adverse impacts on ecosystems on a global scale. To improve methods for assessing ecosystem impacts, the Life Cycle Initiative hosted by the United Nations Environment Programme established a task force to evaluate the state-of-the-science in modeling chemical exposure of organisms and the resulting ecotoxicological effects for use in LCIA. The outcome of the task force work will be global guidance and harmonization by recommending changes to the existing practice of exposure and effect modeling in ecotoxicity characterization. These changes will reflect the current science and ensure the stability of recommended practice. Recommendations must work within the needs of LCIA in terms of 1) operating on information from any inventory reporting chemical emissions with limited spatiotemporal information, 2) applying best estimates rather than conservative assumptions to ensure unbiased comparison with results for other impact categories, and 3) yielding results that are additive across substances and life cycle stages and that will allow a quantitative expression of damage to the exposed ecosystem. We describe the current framework and discuss research questions identified in a roadmap. Primary research questions relate to the approach toward ecotoxicological effect assessment, the need to clarify the methods scope and interpretation of its results, the need to consider additional environmental compartments and impact pathways, and the relevance of effect metrics other than the currently applied geometric mean of toxicity effect data across species. Because they often dominate ecotoxicity results in LCIA, we give metals a special focus, including consideration of their possible essentiality and changes in environmental bioavailability. We conclude with a summary of key questions along with preliminary recommendations to address them as well as open questions that require additional research efforts. Environ Toxicol Chem 2018;37:2955-2971.