A New Audit Technique for EPA Method 25

A simple, inexpensive, and accurate technique for evaluating or auditing the sampling, recovery, and analytical phases of EPA Source Reference Method 25 has been developed. The technique involves spiking a U-shaped stainless steel cartridge containing Tenax® with known quantities of selected organic compounds and thermally desorbing them at temperatures from 160°C to 180°C to generate organic vapors quantitatively. The major advantages of this technique are that no other measurement methods can be used to determine the generated organic concentrations in lieu of Method 25; and that the cartridge can easily be taken to the field for evaluation. The organic compounds generated in test runs are collected and analyzed using the Method 25 procedure. The generation of organics is quantitative and recoveries were found to be 100 ± 10%. The time required for desorption of the majority of organics is generally less than forty-five minutes at a flow rate of 100 mL/min; however, based on laboratory experience the recommended sampling time is sixty minutes. These spiked cartridges are stable at room temperature over a two-month period. Results of interlaboratory studies showed close agreement with the expected concentrations based on calculations from the mass loadings and sample volumes.     

Pilot-Scale Demonstration of an Innovative Treatment for Vapor Emissions

ABSTRACT

Researchers from the National Renewable Energy Laboratory recently conducted a pilot-scale study at McClellan Air Force Base (AFB) in Sacramento, CA. The objective of the test was to determine the effectiveness of an ambient-temperature, solar-powered photocatalytic oxidation treatment unit for destroying emissions of chlorinated organic compounds from an air stripper. This paper reports test results and discusses applications and limitations of the technology.

A 10-standard-cubic-foot-per-minute (SCFM) (28.3 L/min) slip stream of air from an air stripper at Operative Unit 29-31 at McClellan AFB was passed through a reactor that contained a lightweight, perforated, inert support coated with photoactive titanium dioxide. The reactor faced south and was tilted at a 45° angle from vertical so that the light-activated catalyst received most of the available sunlight. An online portable gas chro-matograph with two identical columns simultaneously analyzed the volatile organic compounds contained in the reactor inlet and outlet air streams. Summa canister grab samples of the inlet and outlet were also collected and sent to a certified laboratory for U.S. Environmental

Protection Agency Method TO-14 analysis and verification of our field analyses. Three weeks of testing demonstrated that the treatment system's destruction and removal efficiencies (DREs) are greater than 95% at 10 SCFM with UV intensities at or greater than 1.5 milliwatts/square centimeter (mW/cm²). DREs greater than 95% at 20 SCFM were obtained under conditions where UV irradiation measured at or greater than 2 mW/cm². In Sacramento, this provided 6 hours of operation per clear or nearly clear day in April. A solar tracking system could extend operating time. The air stream also contained trace amounts of benzene. We observed no loss of system performance during testing.     

Comparison of Stream Invertebrate Response Models for Bioassessment Metrics1

Waite, Ian R., Jonathan G. Kennen, Jason T. May, Larry R. Brown, Thomas F. Cuffney, Kimberly A. Jones, and James L. Orlando, 2012. Comparison of Stream Invertebrate Response Models for Bioassessment Metrics. Journal of the American Water Resources Association (JAWRA) 48(3): 570-583. DOI: 10.1111/j.1752-1688.2011.00632.x Abstract: We aggregated invertebrate data from various sources to assemble data for modeling in two ecoregions in Oregon and one in California. Our goal was to compare the performance of models developed using multiple linear regression (MLR) techniques with models developed using three relatively new techniques: classification and regression trees (CART), random forest (RF), and boosted regression trees (BRT). We used tolerance of taxa based on richness (RICHTOL) and ratio of observed to expected taxa (O/E) as response variables and land use/land cover as explanatory variables. Responses were generally linear; therefore, there was little improvement to the MLR models when compared to models using CART and RF. In general, the four modeling techniques (MLR, CART, RF, and BRT) consistently selected the same primary explanatory variables for each region. However, results from the BRT models showed significant improvement over the MLR models for each region; increases in R² from 0.09 to 0.20. The O/E metric that was derived from models specifically calibrated for Oregon consistently had lower R² values than RICHTOL for the two regions tested. Modeled O/E R² values were between 0.06 and 0.10 lower for each of the four modeling methods applied in the Willamette Valley and were between 0.19 and 0.36 points lower for the Blue Mountains. As a result, BRT models may indeed represent a good alternative to MLR for modeling species distribution relative to environmental variables.     

Canine toys and training devices as sources of exposure to phthalates and bisphenol A: Quantitation of chemicals in leachate and in vitro screening for endocrine activity

Chewing and mouthing behaviors exhibited by pet dogs are likely to lead to oral exposures to a variety of environmental chemicals. Products intended for chewing and mouthing uses include toys and training devices that are often made of plastics. The goal of the current study was to determine if a subset of phthalates and bisphenol A (BPA), endocrine disrupting chemicals commonly found in plastics, leach out of dog toys and training devices (bumpers) into synthetic canine saliva. In vitro assays were used to screen leachates for endocrine activity. Bumper leachates were dominated by di-2-ethylhexyl phthalate (DEHP) and BPA, with concentrations reaching low μg mL⁻¹ following short immersions in synthetic saliva. Simulated chewing of bumpers during immersion in synthetic saliva increased concentrations of phthalates and BPA as compared to new bumpers, while outdoor storage had variable effects on concentrations (increased DEHP; decreased BPA). Toys leached substantially lower concentrations of phthalates and BPA, with the exception of one toy which leached considerable amounts of diethyl phthalate. In vitro assays indicated anti-androgenic activity of bumper leachates, and estrogenic activity of both bumper and toy leachates. These results confirm that toys and training devices are potential sources of exposure to endocrine disrupting chemicals in pet dogs.     

Interlaboratory evaluation of trace element determination in workplace air filter samples by inductively coupled plasma mass spectrometry

Inductively coupled plasma mass spectrometry (ICP-MS) is becoming more widely used for trace elemental analysis in the occupational hygiene field, and consequently new ICP-MS international standard procedures have been promulgated by ASTM International and ISO. However, there is a dearth of interlaboratory performance data for this analytical methodology. In an effort to fill this data void, an interlaboratory evaluation of ICP-MS for determining trace elements in workplace air samples was conducted, towards fulfillment of method validation requirements for international voluntary consensus standard test methods. The study was performed in accordance with applicable statistical procedures for investigating interlaboratory precision. The evaluation was carried out using certified 37-mm diameter mixed-cellulose ester (MCE) filters that were fortified with 21 elements of concern in occupational hygiene. Elements were spiked at levels ranging from 0.025 to 10 μg filter(-1), with three different filter loadings denoted "Low", "Medium" and "High". Participating laboratories were recruited from a pool of over fifty invitees; ultimately twenty laboratories from Europe, North America and Asia submitted results. Triplicates of each certified filter with elemental contents at three different levels, plus media blanks spiked with reagent, were conveyed to each volunteer laboratory. Each participant was also provided a copy of the test method which each participant was asked to follow; spiking levels were unknown to the participants. The laboratories were requested to prepare the filters by one of three sample preparation procedures, i.e., hotplate digestion, microwave digestion or hot block extraction, which were described in the test method. Participants were then asked to analyze aliquots of the prepared samples by ICP-MS, and to report their data in units of μg filter(-1). Most interlaboratory precision estimates were acceptable for medium- and high-level spikes (RSD <25%), but generally yielded greater uncertainties than were anticipated at the outset of the study.     

Environmental contaminants in freshwater fish and their risk to piscivorous wildlife based on a national monitoring program

Organochlorine chemical residues and elemental concentrations were measured in piscivorous and benthivorous fish at 111 sites from large U.S. river basins. Potential contaminant sources such as urban and agricultural runoff, industrial discharges, mine drainage, and irrigation varied among the sampling sites. Our objectives were to provide summary statistics for chemical contaminants and to determine if contaminant concentrations in the fish were a risk to wildlife that forage at these sites. Concentrations of dieldrin, total DDT, total PCBs, toxaphene, TCDD-EQ, cadmium, chromium, mercury, lead, selenium, and zinc exceeded toxicity thresholds to protect fish and piscivorous wildlife in samples from at least one site; most exceedences were for total PCBs, mercury, and zinc. Chemical concentrations in fish from the Mississippi River Basin exceeded the greatest number of toxicity thresholds. Screening level wildlife risk analysis models were developed for bald eagle and mink using no adverse effect levels (NOAELs), which were derived from adult dietary exposure or tissue concentration studies and based primarily on reproductive endpoints. No effect hazard concentrations (NEHC) were calculated by comparing the NOAEL to the food ingestion rate (dietary-based NOAEL) or biomagnification factor (tissue-based NOAEL) of each receptor. Piscivorous wildlife may be at risk from a contaminant if the measured concentration in fish exceeds the NEHC. Concentrations of most organochlorine residues and elemental contaminants represented no to low risk to bald eagle and mink at most sites. The risk associated with pentachloroanisole, aldrin, Dacthal, methoxychlor, mirex, and toxaphene was unknown because NOAELs for these contaminants were not available for bald eagle or mink. Risk differed among modeled species and sites. Our screening level analysis indicates that the greatest risk to piscivorous wildlife was from total DDT, total PCBs, TCDD-EQ, mercury, and selenium. Bald eagles were at greater risk to total DDT and total PCBs than mink, whereas risks of TCDD-EQ, mercury, and selenium were greater to mink than bald eagle.     

Legal and technical defensibility of data and the Triad approach

The Triad approach was developed primarily to limit decision uncertainty during cleanups at hazardous waste sites. The fundamental principles of the Triad approach include development of a site characterization model and use of emerging technologies, which can provide data at a higher density than could be affordably collected using traditional data collection methodologies, to refine the model in essentially real time. New data formats are used collaboratively with data in traditional formats to iteratively pin down the relative concentration, nature, and extent of contaminants, thus minimizing decision uncertainties. This article examines the potential admissibility as evidence in legal proceedings of data collected by technologies designed to improve the density of information that are commonly used during the course of Triad‐type projects. The article explains that such criteria may vary depending on the purpose for which the evidence is to be used (e.g., as direct evidence to prove site conditions or as support for the testimony of an expert witness) and the court in which the legal proceeding would take place (e.g., federal court or state court). Admissibility in federal courts of data both as direct evidence and as support for expert witness testimony is covered. © 2005 Wiley Periodicals, Inc.     

A Pluralist–Expressivist Critique of the Pet Trade

Elizabeth Anderson’s “pluralist–expressivist” value theory, an alternative to the understanding of value and rationality underlying the “rational actor” model of human behavior, provides rich resources for addressing questions of environmental and animal ethics. It is particularly well-suited to help us think about the ethics of commodification, as I demonstrate in this critique of the pet trade. I argue that Anderson’s approach identifies the proper grounds for criticizing the commodification of animals, and directs our attention to the importance of maintaining social practices and institutions that respect the social meanings of animals. Her theory alone, however, does not adequately address the role of the state in this project. Drawing on social contract theory to fill this gap, I conclude that the state’s role in regulating the pet trade should be limited to ensuring the welfare of animals in the stream of commerce, not prohibiting their mass marketing altogether.