24 h diffusive sampling of toxic VOCs in air onto Carbopack X solid adsorbent followed by thermal desorption/GC/MS analysis-laboratory studies

Diffusive sampling of a mixture of 42 volatile organic compounds (VOCs) in humidified, purified air onto the solid adsorbent Carbopack X was evaluated under controlled laboratory conditions. The evaluation included variations in sample air temperature, relative humidity and ozone concentration. Linearity of samples with loading was examined both for a constant concentration with time varied up to 24 h and for different concentrations over 24 h. Reverse diffusion and its increase with accumulation of sample were determined for all compounds. Tubes were examined for blank levels, change of blanks with storage time, and variability of blanks. Method detection limits were determined based on seven replicate samples. Based on this evaluation, 27 VOCs were selected for quantitative monitoring in the concentration range from approximately 0.1 to 4 ppbv. Comparison results of active and diffusive samples taken over 24 h and under the same simulated ambient conditions at a constant 2 ppbv were interpreted to estimate the effective diffusive sampling rates (ml min(-1)) and their uncertainties and to calculate the corresponding diffusive uptake rates (ng ppmv(-1) min(-1)).     

Measurement of atmospheric concentrations of common household pesticides: A pilot study

Air concentrations of 28 of the most commonly used household pesticides were measured inside nine homes in Jacksonville, Florida, and compared with corresponding outdoor levels. The households selected were sorted into three categories according to the degree of pesticide indoor usage. Personal air monitoring was also performed on one resident of each household by means of a portable sampler, which was kept with the person at all times. Five of the pesticides were found in the air inside of the majority of the homes at concentrations as high as 15 gm^–3 (average concentrations, 12 ngm^–3 to 2.4 gm^–3). Indoor levels were generally one to two ordrrs of magnitude higher than surrounding outdoor air levels and personal air measurements were within ± 50% of corresponding indoor values. All samples were collected over 24-hr periods on polyurethane foam and analyzed by capillary colum gas chromatography with mass spectrometric and/or electron capture detection.     

DEVELOPMENT AND TESTING OF BIOINDICATORS FOR MONITORING THE CONDITION OF ESTUARINE ECOSYSTEMS

As part of the Environmental Monitoring and Assessment Programin 1991, the field efficacy of six research indicators wasexamined in the estuarine systems of the Gulf of Mexico. Theutility of these indicators was tested by examining thoseresponses at both ends of multiple environmental gradients;namely, under minimally impacted conditions (reference) andheavily impacted conditions (by hypoxia, industrialdischarges, agricultural runoff). In addition, the geographiceffects of location (east and west of the Mississippi River)were examined. Numbers and frequencies of pathologies,abundance of splenic macrophage aggregates, and vertebralabnormalities showed response patterns that suggest widerfield testing along full gradients rather than simply theextremes of the gradient are warranted. Selected bloodproteins showed some promise but logistical constraints inestuarine environments may limit its utility. Concentrationsof selected organic compounds in bile showed no differences inthis study between references and contaminated sites.Molecular bioindicators are discussed with regard to theirpotential utility as indicators of ecosystem conditions. Ofthese potential indicators, the use of vitellogenin assays asa measure of reproductive impairment and frequency of shelldisease in selected crustaceans as an indicator ofimmunological aberrations deserve further examination.     

Method to assess component contribution to toxicity of complex mixtures: Assessment of puberty acquisition in rats exposed to disinfection byproducts

A method based on regression modeling was developed to discern the contribution of component chemicals to the toxicity of highly complex, environmentally realistic mixtures of disinfection byproducts(DBPs). Chemical disinfection of drinking water forms DBP mixtures.Because of concerns about possible reproductive and developmental toxicity, a whole mixture(WM) of DBPs produced by chlorination of a water concentrate was administered as drinking water to Sprague–Dawley(S–D) rats in a multigenerational study. Age of puberty acquisition,i.e., preputial separation(PPS) and vaginal opening(VO), was examined in male and female offspring, respectively. When compared to controls, a slight, but statistically significant delay in puberty acquisition was observed in females but not in males. WM-induced differences in the age at puberty acquisition were compared to those reported in S–D rats administered either a defined mixture(DM) of nine regulated DBPs or individual DBPs. Regression models were developed using individual animal data on age at PPS or VO from the DM study. Puberty acquisition data reported in the WM and individual DBP studies were then compared with the DM models. The delay in puberty acquisition observed in the WM-treated female rats could not be distinguished from delays predicted by the DM regression model, suggesting that the nine regulated DBPs in the DM might account for much of the delay observed in the WM. This method is applicable to mixtures of other types of chemicals and other endpoints.     

Models for waste life cycle assessment: Review of technical assumptions

A number of waste life cycle assessment (LCA) models have been gradually developed since the early 1990s, in a number of countries, usually independently from each other. Large discrepancies in results have been observed among different waste LCA models, although it has also been shown that results from different LCA studies can be consistent. This paper is an attempt to identify, review and analyse methodologies and technical assumptions used in various parts of selected waste LCA models. Several criteria were identified, which could have significant impacts on the results, such as the functional unit, system boundaries, waste composition and energy modelling. The modelling assumptions of waste management processes, ranging from collection, transportation, intermediate facilities, recycling, thermal treatment, biological treatment, and landfilling, are obviously critical when comparing waste LCA models.This review infers that some of the differences in waste LCA models are inherent to the time they were developed. It is expected that models developed later, benefit from past modelling assumptions and knowledge and issues. Models developed in different countries furthermore rely on geographic specificities that have an impact on the results of waste LCA models. The review concludes that more effort should be employed to harmonise and validate non-geographic assumptions to strengthen waste LCA modelling.     

A performance evaluation of the National Air Quality Forecast Capability for the summer of 2007

This paper provides a performance evaluation of the real-time, CONUS-scale National Air Quality Forecast Capability (NAQFC) that supported, in part, its transition into operational status. This evaluation focuses primarily on discrete forecasts for the maximum 8-h O₃ concentrations covering the 4-month period, June through September, 2007, using measurements obtained from EPA's AIRNow network. Results indicate that the 2007 NAQFC performed as well or better than previous configurations, despite the expansion of the forecast domain into the western half of the nation that is dominated by complex terrain. The mean, domain-wide, season-long correlation was 0.70. When examined over time, the domain-wide correlations exhibit a fairly consistent nature, with values exceeding 0.60 (0.70) over 90% (55%) of the days. The NAQFC systematically over-predicted the 8-h O₃ concentrations, continuing a trend established by earlier NAQFC configurations, though to a lesser degree. The summer-long mean forecast value of 53.2 ppb was 4.2 ppb higher than the observed value, resulting in a domain-wide Normalized Mean Bias (NMB) of 8.7%. Most of the over-prediction is associated with observed concentrations less than 50 ppb. In fact the model tends to under-predict when concentrations exceed 70 ppb. As with the bias, the error associated with the latest configuration was also lower. The summer-long Root Mean Square Error of 13.0 ppb (Normalized Mean Error (NME) = 20.4%) represented marked improvements over earlier forecasts. Examination of the spatial distribution of both the NMB and NME reveals that the NAQFC was generally within 25% for the NME and 25% for the NMB over a majority of the domain. Several areas of poorer performance, where the NMB and NME often exceed 25% and in some cases 50%, were noted. These areas include southern California, where the NAQFC tended to under-predict concentrations (especially on weekends) and the southeast Atlantic and Gulf coasts regions, where the model over-predicted. Subsequent analysis revealed that the incorrect temporal allocation of precursor emissions was likely the source of the under-prediction in southern California, while inaccurate simulation of PBL heights likely contributed to the over-prediction in the coastal regions.     

Natural emissions for regional modeling of background ozone and particulate matter and impacts on emissions control strategies

Natural emissions adopted in current regional air quality modeling are updated to better describe natural background ozone and PM concentrations for North America. The revised natural emissions include organosulfur from the ocean, NO from lightning, sea salt, biogenic secondary organic aerosol (SOA) precursors, and pre-industrial levels of background methane. The model algorithm for SOA formation was also revised. Natural background ozone concentrations increase by up to 4 ppb in annual average over the southeastern US and Gulf of Mexico due to added NO from lightning while the revised biogenic emissions produced less ozone in the central and western US. Natural PM_2.5 concentrations generally increased with the revised natural emissions. Future year (2018) simulations were conducted for several anthropogenic emission reduction scenarios to assess the impact of the revised natural emissions on anthropogenic emission control strategies. Overall, the revised natural emissions did not significantly alter the ozone responses to the emissions reductions in 2018. With revised natural emissions, ozone concentrations were slightly less sensitive to reducing NOx in the southeastern US than with the current natural emissions due to higher NO from lightning. The revised natural emissions have little impact on modeled PM_2.5 responses to anthropogenic emission reductions. However, there are substantial uncertainties in current representations of natural sources in air quality models and we recommend that further study is needed to refine these representations.     

The ecological effects of trichloroacetic acid in the environment

Trichloroacetic acid (TCAA) is a member of the family of compounds known as chloroacetic acids, which includes mono-, di- and trichloroacetic acid. The significant property these compounds share is that they are all phytotoxic. TCAA once was widely used as a potent herbicide. However, long after TCAA's use as a herbicide was discontinued, its presence is still detected in the environment in various compartments. Methods for quantifying TCAA in aqueous and solid samples are summarized. Concentrations in various environmental compartments are presented, with a discussion of the possible formation of TCAA through natural processes. Concentrations of TCAA found to be toxic to aquatic and terrestrial organisms in laboratory and field studies were compiled and used to estimate risk quotients for soil and surface waters. TCAA levels in most water bodies not directly affected by point sources appear to be well below toxicity levels for the most sensitive aquatic organisms. Given the phytotoxicity of TCAA, aquatic plants and phytoplankton would be the aquatic species to monitor for potential effects. Given the concentrations of TCAA measured in various soils, there appears to be a risk to terrestrial organisms. Soil uptake of TCAA by plants has been shown to be rapid. Also, combined uptake of TCAA from soil and directly from the atmosphere has been shown. Therefore, risk quotients derived from soil exposure may underestimate the risk TCAA poses to plants. Moreover, TCE and TCA have been shown to be taken up by plants and converted to TCAA, thus leading to an additional exposure route. Mono- and di-chloroacetic acids can co-occur with TCAA in the atmosphere and soil and are more phytotoxic than TCAA. The cumulative effects of TCAA and compounds with similar toxic effects found in air and soil must be considered in subsequent terrestrial ecosystem risk assessments.     

Using air pollution based community clusters to explore air pollution health effects in children

To study respiratory health effects of long-term exposure to ambient air pollutant mixture, we observed 7058 school children 5-16 years of age living in the four Chinese cities of Lanzhou, Chongqing, Wuhan, and Guangzhou. These children were enrolled from elementary schools located in eight districts, one urban district and one suburban district in each of the above cities. Ambient levels of PM(2.5), PM(10-2.5), total suspended particles (TSP), SO(2), and NO(x) were measured in these districts from 1993 to 1996. Based on a cluster analysis of arithmetic mean concentrations of PM(2.5), PM(10-2.5), (TSP-PM(10)), SO(2), and NO(x), we classified these children into four ordinal categories of exposure to ambient air pollutant mixtures. We tested for exposure-response relationships using logistic regression models, controlling for relevant covariates. We observed monotonic, positive relationships of exposure to the pollutant mixture with prevalence rates of cough with phlegm and wheeze. Other outcomes were not associated with the exposure in a monotonic exposure-response pattern. Even so, odds ratios for cough, phlegm, bronchitis, and asthma in the higher exposure district clusters were all higher than in the lowest exposure district cluster. We found evidence that exposure to the pollutant mixtures had adverse effects on children living in the four Chinese cities.     

Modeling of dispersion near roadways based on the vehicle-induced turbulence concept

A mathematical model is developed for dispersion near roadways by incorporating vehicle-induced turbulence (VIT) into Gaussian dispersion modeling using computational fluid dynamics (CFD). The model is based on the Gaussian plume equation in which roadway is regarded as a series of point sources. The Gaussian dispersion parameters are modified by simulation of the roadway using CFD in order to evaluate turbulent kinetic energy (TKE) as a measure of VIT. The model was evaluated against experimental carbon monoxide concentrations downwind of two major freeways reported in the literature. Good agreements were achieved between model results and the literature data. A significant difference was observed between the model results with and without considering VIT. The difference is rather high for data very close to the freeways. This model, after evaluation with additional data, may be used as a framework for predicting dispersion and deposition from any roadway for different traffic (vehicle type and speed) conditions.