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Use of reversed-phase high-performance liquid chromatography-diode array detection for complete separation of 2,4,6-trinitrotoluene metabolites and EPA Method 8330 explosives: influence of temperature and an ion-pair reagent.

Explosives such as 2,4,6-trinitrotoluene (TNT), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) are widely distributed environmental contaminants. Complete chromatographic separation is necessary in order to accurately determine and quantify explosives and their degradation products in environmental samples and in (bio)transformation studies. The present study describes a RP-HPLC method with diode array detection using a LC-8 guard column, a Supelcosil LC-8 chromatographic column, and a gradient elution system. This gradient method is capable of baseline separating the most commonly observed explosives and TNT transformation metabolites including 2,4,6-triaminotoluene (TAT) in a single run. The TNT metabolites separated were 2-hydroxylamino-4,6-dinitrotoluene, 4-hydroxylamino-2,6-dinitrotoluene, 2,4-dihydroxylamino-6-nitrotoluene, 4,4',6,6'-tetranitro-2,2'-azoxytoluene, 2,2',6,6'-tetranitro-4,4'-azoxytoluene, 4,4',6,6'-tetranitro-2,2'-azotoluene, 2,2',6,6'-tetranitro-4,4'-azotoluene, 2-amino-4,6-dinitrotoluene, 4-amino-2, 6-dinitrotoluene, 2,6-diamino-4-nitrotoluene, 2,4-diamino-6-nitrotoluene, and TAT. The same gradient method at a different column temperature can also be used to baseline separate the explosives targeted in the Environmental Protection Agency (EPA) Method 8330 with approximately 22% reduction in total run time and 48% decrease in solvent consumption compared to previously published methods. Good separation was also obtained when all TNT metabolites and EPA Method 8330 compounds (a total of 23 compounds) were analyzed together; only 2,6-DANT and HMX co-eluted in this case. The influence of temperature (35-55 degrees C) and the use of an ion-pair reagent on the chromatographic resolution and retention were investigated. Temperature was identified as the key parameter for optimal baseline separation. Increased temperature resulted in shorter retention times and better peak resolution especially for the aminoaromatics investigated. The use of an ion-pair reagent (octanesulfonic acid) generally resulted in longer retention times for compounds containing amine functional groups, more baseline noise, and decreased peak resolution.

Chromatography, High Pressure Liquid↗

Public health concerns about caliciviruses as waterborne contaminants.

Caliciviruses are disseminated by the fecal-oral route and are found in contaminated surface and ground waters. The US Environmental Protection Agency (EPA) is interested in preventing calicivirus contamination in treated waters used for consumption, and these viruses are on the EPA's "contaminant candidate list" for regulatory consideration in drinking waters. These viruses also present a health threat for recreation and shellfish-growing waters. However, before EPA can make regulatory decisions regarding caliciviruses, significant information and technology needs must be established, including analytical methods for sampling, identifying, and quantifying the viruses; applicability of surrogates to determine their presence; efficacy of water and wastewater treatment or disinfection; waterborne occurrence levels and distribution; dose response; and the viruses' effect(s) on health. Future drinking-water regulations may need to ensure that treatments are adequate to remove caliciviruses from source waters. For recreation and shellfish-growing waters, surrogate indicators and health criteria may need to be based upon establishing risks of exposure to caliciviruses.

Caliciviridae↗

Regulating insect resistance management: the case of non-Bt corn refuges in the US.

In this paper, we analyze the insect resistance management (IRM) plan put in place by the US Environmental Protection Agency (EPA) to delay the evolution of resistance to Bt corn in natural populations of the European corn borer, Ostrinia nubilalis Hübner. This IRM plan is the most impressive mandatory IRM system ever developed. It forms a coherent whole and includes mandatory refuges, actions to increase growers' compliance and a program for monitoring the evolution of resistance. However, our analysis suggests that two components of this IRM plan are not entirely satisfactory: growers' compliance and monitoring of the evolution of resistance. Moreover, the implementation of these two components of IRM has been required of the registrants, whose incentives for IRM are probably lower than the social optimum. Our analysis suggests that alternatives to the IRM plan currently in place could improve these two components.

Animals↗

Hydrologic regionalisation impacts on wet-weather control selection.

Continuous simulation is performed using the US Environmental Protection Agency (USEPA) Storm Water Management Model (SWMM) to evaluate regional differences around the United States in hydrologic and water quality performance of wet-weather controls. Controls are characterised as being limited by peak inflow rate (i.e. any device with little or no storage, such as screens, filters and some proprietary devices) or by storage capacity (e.g., ponds, tanks). For flow-limited devices, results are presented in the form of percentage of annual runoff volume captured (passing through the device) for a given inflow capacity. For storage-limited devices, results are presented in two forms: percentage of annual runoff volume captured as a function of unit basin size and drawdown (drain) time, and as a percentage of total suspended solids captured, for the same two variables. Regional differences are apparent, driven mainly by variations in rainfall patterns around the country.

Demography↗

Proposed protocols for the determination of potential ocular effects of organophosphorus pesticides.

The US Environmental Protection Agency now requires ocular toxicity testing to support the registration of organophosphorus pesticides. As a first step toward guideline development for the conduct of these studies, preliminary protocols for ocular toxicity testing in the non-rodent and rodent are being proposed by the Office of Pesticide Programs. Proposed protocol parameters include determination of animal health status, measurement of plasma, erythrocyte and retinal cholinesterase activities, ocular assessment by routine ophthalmological examination, slit lamp biomicroscopy, fundic observations, tonometry, electroretinography and determination of objective refractivity, pupillary response and tracking. Gross and detailed histopathological examinations of ocular system components would also be conducted. Associated questions and concerns with regard to ocular toxicity testing are presented. The Agency plans to hold a workshop in the near future to discuss issues related to protocol refinement and guideline development.

Animals↗

A trichloroethylene risk assessment using a Monte Carlo analysis of parameter uncertainty in conjunction with physiologically-based pharmacokinetic modeling.

A Monte Carlo simulation is incorporated into a risk assessment for trichloroethylene (TCE) using physiologically-based pharmacokinetic (PBPK) modeling coupled with the linearized multistage model to derive human carcinogenic risk extrapolations. The Monte Carlo technique incorporates physiological parameter variability to produce a statistically derived range of risk estimates which quantifies specific uncertainties associated with PBPK risk assessment approaches. Both inhalation and ingestion exposure routes are addressed. Simulated exposure scenarios were consistent with those used by the Environmental Protection Agency (EPA) in their TCE risk assessment. Mean values of physiological parameters were gathered from the literature for both mice (carcinogenic bioassay subjects) and for humans. Realistic physiological value distributions were assumed using existing data on variability. Mouse cancer bioassay data were correlated to total TCE metabolized and area-under-the-curve (blood concentration) trichloroacetic acid (TCA) as determined by a mouse PBPK model. These internal dose metrics were used in a linearized multistage model analysis to determine dose metric values corresponding to 10(-6) lifetime excess cancer risk. Using a human PBPK model, these metabolized doses were then extrapolated to equivalent human exposures (inhalation and ingestion). The Monte Carlo iterations with varying mouse and human physiological parameters produced a range of human exposure concentrations producing a 10(-6) risk.

Administration, Inhalation↗

The medical waste audit. A framework for hospitals to appraise options and financial implications.

The generation, handling, and disposal of medical wastes involve virtually every department in the hospital. To enhance coordination, managers must comprehensively describe the total system and specify the roles of key functions and individuals. Hospitals produce about 77 percent of the approximately 500,000 tons of regulated medical waste produced annually in the United States. The amount produced by different hospitals varies, primarily because of differences in "waste-management practices." The Environmental Protection Agency is trying to develop a greater understanding of the types of medical wastes that are infectious, methods of transmission, and the likelihood of transmission in the handling and disposal of waste within the hospital environment. To ensure that medical waste is being handled and treated in the most cost-effective manner and with the least health risk to employees and the community, hospital administrators must undertake a comprehensive appraisal of the activities associated with the generation, handling, and disposal processes. A "medical waste audit" requires the following steps: Generation profile to identify origination points, categories or types of waste, and associated generation rates. Inventory of handling practices, including existing regulations, procedures and protocols, training programs, definitions regarding waste segregation, and documentation. Review of current disposal practices and existing and developing alternatives. Cost analysis

Accounting↗

Toxicity equivalency factors for PCBs?

In December 1990 the U.S. Environmental Protection Agency sponsored a workshop to discuss the applicability of an interim "toxicity equivalency factor" (TEF) approach to assessing risks posed by exposures to complex mixtures of polychlorinated biphenyls (PCBs). The group concluded that application of the TEF approach to PCBs would be less straightforward than it was in the case of chlorinated dibenzo-p-dioxins and dibenzofurans (CDDs/CDFs). It appears that "dioxin"-like properties of some PCB congeners are amenable to a TEF treatment that is compatible with that used for CDDs/CDFs. Such a scheme also seems to have utility in assessing risks to wildlife. Other non-"dioxin"-like toxic endpoints (e.g., neurotoxicity) appear to have a different structure-activity-related mechanism-of-action that requires a separate TEF scheme. The workshop identified data gaps in toxicology and analytical chemistry that hinder adoption of proposed TEF schemes for PCBs at this time.

Benzofurans↗

Survey of trihalomethanes and other volatile chemical contaminants in processed foods by purge-and-trap capillary gas chromatography with mass selective detection.

A limited number of soft drinks, juices, beers, and waters from processed vegetables were analyzed for trihalomethanes (THMs), benzene, and toluene by a modified Environmental Protection Agency (EPA) Method 524.2. The THMs, which include chloroform, bromodichloromethane, dibromochloromethane, and bromoform, are reaction by-products of water disinfection by chlorination. EPA Method 524.2 is a purge-and-trap capillary gas chromatographic method based on mass spectrometric detection which identifies and simultaneously measures purgeable volatile organic compounds in drinking water. Chloroform was present at concentrations ranging from none detected to 94 ng/g in the 44 foods analyzed. Bromoform was not found in any of the products at a detection limit of 0.1 ng/g. Residue levels of the other THMs ranged from none detected to highs of 12 and 2 ng/g for bromodichloromethane and dibromochloromethane, respectively. Benzene residues were typically < 5 ng/g, except for 7 and 9 ng/g in 2 foods. Toluene residues were typically < or = 3 ng/g except for 23, 29, and 75 ng/g in 3 canned foods.

Benzene↗

Methodologies for estimating emissions for the U.S. EPA's NOx SIP call, CER rule, and other complexities.

Emissions inventories play an important role in many air quality decisions, and the importance of obtaining correct emissions data challenges the emissions inventory community to continuously improve its estimation techniques. The Clean Air Act Amendments of 1990 requires states with ozone nonattainment areas (NAAs) to submit periodically a comprehensive, accurate, and actual inventory of ozone precursor emissions until the areas are redesignated to attainment. They require the states with NAAs to report peak ozone season daily and annual estimates of the inventories for the counties that are in nonattainment. The recently proposed U.S. Environmental Protection Agency's (EPA) NO(x) SIP call and the Consolidating Emissions Reporting (CER) rule are more demanding still. The CER rule requires the states to report statewide point source inventories, 3-yr cycle inventories, and NO(x) SIP call inventories by county for all source types, regardless of the attainment status; the estimating periods are peak ozone season daily, 5-month ozone season, and annual estimates. Furthermore, complexities in emissions inventories such as estimating the emissions with different seasonal and multiple controls exist. These complexities and methodologies for estimating emissions for different time periods are not addressed sufficiently either by the EPA's procedure manuals or by the Emissions Inventory Improvement Program guidance documents. This paper presents methodologies for estimating emissions for different time periods and multiple controls. These methodologies will help the EPA, state, and local government agencies to meet the evolving demands of emissions inventories and the reporting requirements of the NO(x) SIP call and the CER rules.

Air Pollutants↗

Assessing sites contaminated with unexploded ordnance: statistical modeling of ordnance spatial distribution.

More than 40,000 km2 of former military land in the United States are contaminated with unexploded ordnance (UXO). Cleanup costs are estimated to total as much as 140 billion dollars. The amount of contaminated acreage and total costs are likely to increase as the U.S. Department of Defense (DOD) follows through on recently announced plans to close an additional 22 domestic military bases. The U.S. Environmental Protection Agency(EPA) and DOD disagree on how these sites should be characterized to assess their risks and plan for cleanup. As a result, much potentially valuable land remains idle while remediation decisions are pending. One of the sources of disagreement is how the locations of UXO should be characterized, given that the exact spatial distribution of UXO is unknown in advance of cleanup. In this paper, we propose and test a new model to represent the spatial distribution of UXO. Unlike existing DOD models, the new model accounts for the tendency of UXO to cluster, presumably around targets at which soldiers aimed during training. We fit the cluster model to geographic data on UXO locations at two former military installations and show that it describes key characteristics of the data more accuratelythan the existing DOD model. We discuss how the choice of a UXO spatial distribution model could affect important decisions about cleaning up and reusing UXO-affected property.

Environmental Monitoring↗

Probabilistic risk assessment of cotton pyrethroids: V. Combining landscape-level exposures and ecotoxicological effects data to characterize risks.

Since their introduction, synthetic pyrethroid insecticides have generated regulatory concerns regarding their toxicity to fish and aquatic invertebrates. In this paper we assess the potential for risks to aquatic ecosystems in cotton-growing areas, focusing on cypermethrin as a suitable representative of the pyrethroid class and static water bodies (ponds and lakes) as worst-case water bodies because of low levels of dilution. Reviews of cypermethrin effects under laboratory and field conditions have characterized the potential aquatic effects of the chemical. Also, a landscape-level exposure characterization has been conducted in a worst-case cotton-growing county, Yazoo County, Mississippi, USA, to provide a more realistic exposure characterization than is possible using standard model scenarios. Risks were characterized using the standard tier I and II approaches of the U.S. Environmental Protection Agency. In addition, a probabilistic risk assessment was conducted by comparing landscape-level exposure calculations for ponds and lakes in Yazoo County (modified tier II analysis) with distributions of laboratory effect concentrations and with data from field studies. Risk characterization using tier I and tier II models demonstrated a level of concern for certain aquatic organisms. However, modified tier II analysis showed that exposure concentrations are unlikely to exceed concentrations that might cause ecologically significant effects. Indeed, in the vast majority of cases, concentrations in the modified tier II analysis were several orders of magnitude lower than those at which effects would be predicted on the basis of laboratory and field data. The conclusion of minimal potential for adverse ecological effects was also supported by field studies, which showed that impacts on aquatic systems were negligible, even at concentrations many times higher than the modified tier II exposure concentrations.

Animals↗

An evaluation of the urban stormwater pollutant removal efficiency of catch basin inserts.

In a storm sewer system, the catch basin is the interface between surface runoff and the sewer. Responding to the need to improve the quality of stormwater from urban areas and transportation facilities, and spurred by Phase I and II Stormwater Rules from the U.S. Environmental Protection Agency, several companies market catch basin inserts as best management practices for urban water quality management. However, little data have been collected under controlled tests that indicate the pollutant removal efficiency of these inserts when the inflow is near what can be expected to occur in the field. A stormwater simulator was constructed to test inserts under controlled and replicable conditions. The inserts were tested for removal efficiency of total suspended solids (TSS) and total petroleum hydrocarbons (TPH) at an inflow rate of 757 to 814 L/min, with influent pollutant concentrations of 225 mg/L TSS and 30 mg/L TPH. These conditions are similar to stormwater runoff from small commercial sites in the southeastern United States. Results from the tests indicate that at the test flowrate and pollutant concentration, average TSS removal efficiencies ranged from 11 to 42% and, for TPH, the removal efficiency ranged from 10 to 19%.

Drainage, Sanitary↗

Assessment of recent ozone short-term epidemiologic studies.

The U.S. Environmental Protection Agency (EPA) revised the National Ambient Air Quality Standards (NAAQS) for ozone in 1997 based largely on short-term ozone studies published up to 1995. The U.S. EPA's conclusions must now be updated because (1) the agency did not consider many new studies published since 1995 and (2) the agency did not critically review the studies published before 1995 (i.e., it accepted the stated conclusions). In this article, we examine many recently published short-term ozone studies including 17 hospital admissions studies, 10 mortality studies, and 6 summer-camp studies. Almost all of these studies reported a significant association between ambient levels of ozone and adverse health effects. However, on close examination, it is apparent that there are mixed findings from one study to another and even within the results of a single study. Moreover, questionable statistical analyses and failure to consider confounders make a number of the reported findings doubtful and even negative.

Acute Disease↗

Approaches for exposure characterization and data needs for hazardous waste site assessment.

This article provides an understanding of the approaches for determining exposure and dose to populations in the vicinity of hazardous waste sites. A review of the federal legislation and jurisdiction for assessments is provided, and the approaches of the U.S. Environmental Protection Agency and the Agency for Toxic Substances and Disease Registry are compared. These methods strive to aid in the evaluation of public health impacts of contaminants that were, are, or may be released to the community, and they are concerned with various aspects of the contaminant fate, human contact, and toxic response for chemicals of concern. Such approaches have been designed for generic contamination scenarios, but they aim to be applicable to a wide range of chemicals and sites in the real world. Along with any modeling framework for exposure and dose characterization, detailed information or real data are requisite for the completion of any site-specific assessment. What kinds of data are needed and where they may be found are also discussed. A comprehensive framework for exposure characterization, recently proposed by Georgopoulos and Lioy, is outlined. The framework is one employing the following elements: chemodynamic analyses of sources and receptors; characterization of the target population; toxicokinetic/toxicodynamic analyses; uncertainty/error analyses; and evaluation of the characterization performance.

Environmental Exposure↗

The NAS perchlorate review: questions remain about the perchlorate RfD.

Human exposure to perchlorate is commonplace because it is a contaminant of drinking water, certain foods, and breast milk. The U.S. Environmental Protection Agency (EPA) conducted a perchlorate risk assessment in 2002 that yielded a reference dose (RfD) based on both the animal and human toxicology data. This assessment has been superceded by a recent National Academy of Science (NAS) review that derived a perchlorate RfD that is 20-fold greater (less stringent) than that derived by the U.S. EPA in 2002. The NAS-derived RfD was put on the U.S. EPA's Integrated Risk Information System (IRIS) database very quickly and with no further public review. In this commentary we raise concerns about the NAS approach to RfD development in three areas of toxicity assessment: the dose that the NAS described as a no observable adverse-effect level is actually associated with perchlorate-induced effects; consideration of uncertainties was insufficient; and the NAS considered the inhibition of iodine uptake to be a nonadverse effect. We conclude that risk assessors should carefully evaluate whether the IRIS RfD is the most appropriate value for assessing perchlorate risk.

Adult↗

Analysis of flour and food samples for cry9C from bioengineered corn.

StarLink corn is a variety of yellow corn that has been genetically modified by the insertion of an altered cry9C gene into the plant genome. resulting in expression of the insecticidal Cry9C protein. The U.S. Environmental Protection Agency has approved StarLink corn for use in animal feed but not in food intended for human consumption. Therefore, under the U.S. Food, Drug, and Cosmetic Act, any food intended for human consumption in which the presence of StarLink corn is indicated by the presence of either the Cry9C protein or the cry9C gene would be considered adulterated. Extraction and PCR-based methods were used to detect the presence of the cry9C DNA initially in corn flour and corn meal, and then these methods were extended to the analysis of processed corn products, including taco shells, cereals, baby foods, party snacks, and chips, for the presence of this modified genetic material. In a survey of 63 products, the cry9C transgene was detected in 4 taco shells.

Bacillus thuringiensis Toxins↗

Practical considerations on the use of predictive models for regulatory purposes.

Interest in the use of quantitative structure-activity relationships (QSARs) for regulatory purposes has been growing steadily over the years, and many models have been evaluated under the guidance and acceptability criteria defined at the Setubal workshop held in March 2002. This work explores some of the practical issues related to the use of QSARs for regulatory purposes using results obtained from rat oral lethality and fish acute toxicity estimates generated from computational models (including TOPKAT, MCASE, OASIS, and ECOSAR). Using data submitted under the Environmental Protection Agency's (EPA's) High Production Volume (HPV) Challenge Program, the results on the quality of the estimations are compared using a standard statistical review and an additional classification approach in which the hazard predictions were grouped using well-defined regulatory criteria (those used in EPA's New Chemical Program). Our results indicate that an evaluation of a model's regulatory applicability and predictive power is ultimately dependent on the specific criteria used in the assessment process. This work also discusses the practical difficulties associated with defining the domain of a predictive model using the estimates of four different ready biodegradation models and experimental data submitted under the EPA's New Chemical program. Our results suggest that the method a model employs for its predictions is as important as the training set in determining its domain of applicability. Together, these results highlight the challenges associated with developing reliable and easily applied acceptability criteria for the regulatory use of QSAR models.

Biodegradation, Environmental↗