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1.
Methyl tertiary hexyl ether (MtHxE) and methyl tertiary octyl ether (MtOcE) are currently being developed as replacement oxygenates for methyl tertiary butyl ether (MtBE) in gasoline. As was the case with MtBE, the introduction of these ethers into fuel supplies guarantees their introduction into the environment as well. In this study, a screening-level risk assessment was performed by comparing predicted environmental concentrations (PEC) of these ethers to concentrations that might cause adverse effects to humans or ecosystems. A simple box model that has successfully estimated urban air concentrations of MtBE was adapted to predict atmospheric concentrations of MtHxE and MtOcE. Expected atmospheric concentrations of these ethers were also estimated using the European Union System for the Evaluation of Substances (EUSES) multimedia fate model, which simultaneously calculates PECs in the various environmental compartments of air, water, soil, and sediment. Because little or no data are available on the physicochemical, environmental, and toxicological properties of MtHxE and MtOcE, estimation methods were used in conjunction with EUSES to predict both the PECs and the concentrations at which these ethers might pose a threat. The results suggest that these ethers would contaminate the air of a moderately sized U.S. city (Boston, MA) at levels similar to those found previously for MtBE. The risk assessment module in EUSES predicted risk characterization ratios of 10(-3) and 10(-2) for MtHxE and MtOcE, respectively, in Boston, and 10(-2) and 10(-1) in very large urban centers, suggesting that these ethers pose only a minimal threat to ecosystems at the anticipated environmental concentrations. The assessment also indicates that these compounds are possible human carcinogens and that they may be present in urban air at concentrations that pose an unacceptable cancer risk. Therefore, testing of the toxicological properties of these compounds is recommended before they replace MtBE in gasoline.  相似文献   

2.
Abstract

Expected urban air concentrations of the gasoline additive methyl tertiary butyl ether (MTBE) were calculated using volatile emissions estimates and screening transport models, and these predictions were compared with Boston, MA, area urban air measurements. The total volatile flux of MTBE into the Boston primary metropolitan statistical area (PMSA) airshed was calculated based on estimated automobile nontailpipe emissions and the Universal Quasi-Chemical Functional-Group Activity Coefficient computed abundance of MTBE in gasoline vapor. The fate of MTBE in the Boston PMSA was assessed using both the European Union System for the Evaluation of Substances, which is a steady-state multimedia box model, and a simple airshed box model. Both models were parameterized based on the meteorological conditions observed during air sampling in the Boston area. Measured average urban air concentrations of 0.1 and 1 [H9262]g/m3 MTBE during February and September of 2000, respectively, were comparable to corresponding model predictions of 0.3 and 1 μg/m3 and could be essentially explained from estimated temperature-dependent volatile emissions rates, observed average wind speed (the airshed flushing rate), and reaction with ambient tropospheric hydroxyl radical (.OH), within model uncertainty. These findings support the proposition that one can estimate gasoline component source fluxes and use simple multimedia models to screen the potential impact of future proposed gasoline additives on urban airsheds.  相似文献   

3.
《Environmental Forensics》2013,14(4):239-243
Groundwater contaminated by the gasoline additive methyl tertiary butyl ether (MtBE) is also frequently impacted by tertiary butyl alcohol (tBA). The USEPA recently sponsored a study that discusses the possibility of hydrolysis of MtBE to form tBA during analytical procedures. This finding is important because it suggests that existing tBA data may not accurately depict tBA or MtBE concentrations in groundwater. This article discusses the mechanism and kinetics of MtBE hydrolysis, then presents three case studies of analytical results from sites in California, USA. Although these case studies are limited in scope, the data do not support the occurrence of the hydrolysis of MtBE to form tBA due to acid preservation of groundwater samples. At a minimum, this suggests that MtBE hydrolysis may not be as pervasive a problem as suggested in USEPA's study; therefore, concerns about the validity of historical tBA data may not be warranted. The reason for this result may be simple: there are two necessary factors that promote hydrolysis: low pH and high temperature (above 40°C). Although the static headspace analysis method used to obtain the data in the White et al. study may require heating to achieve adequate sensitivity, many laboratories perform purge-and-trap analyses without heating. Under those conditions, hydrolysis may not occur. However, it may be prudent to preserve samples with alkaline preservatives, to eschew high temperatures during the analysis of groundwater samples, or to neutralize the sample pH before heating.  相似文献   

4.
Expected urban air concentrations of the gasoline additive methyl tertiary butyl ether (MTBE) were calculated using volatile emissions estimates and screening transport models, and these predictions were compared with Boston, MA, area urban air measurements. The total volatile flux of MTBE into the Boston primary metropolitan statistical area (PMSA) airshed was calculated based on estimated automobile nontailpipe emissions and the Universal Quasi-Chemical Functional-Group Activity Coefficient computed abundance of MTBE in gasoline vapor. The fate of MTBE in the Boston PMSA was assessed using both the European Union System for the Evaluation of Substances, which is a steady-state multimedia box model, and a simple airshed box model. Both models were parameterized based on the meteorological conditions observed during air sampling in the Boston area. Measured average urban air concentrations of 0.1 and 1 microg/m3 MTBE during February and September of 2000, respectively, were comparable to corresponding model predictions of 0.3 and 1 microg/m3 and could be essentially explained from estimated temperature-dependent volatile emissions rates, observed average wind speed (the airshed flushing rate), and reaction with ambient tropospheric hydroxyl radical (*OH), within model uncertainty. These findings support the proposition that one can estimate gasoline component source fluxes and use simple multimedia models to screen the potential impact of future proposed gasoline additives on urban airsheds.  相似文献   

5.
Wind T 《Chemosphere》2004,54(8):1145-1153
The aim of this study was the comparison between predicted environmental concentrations (PEC) derived using a generic aspacial model, European Union System for the Evaluation of Substances (EUSES), and a geo-referenced model, the Geo-referenced Regional Environmental Assessment Tool for European Rivers (GREAT-ER). The PECs of some consumer-product ingredients (boron, LAS) and professional uses (EDTA, NTA and Triclosan) were calculated for the river catchment of the Itter, a small tributary to the river Rhine. The PEClocal and PECregional for the water compartment generated by EUSES (default scenario) were subsequently refined with data that realistically reflects the region of North Rhine-Westphalia (NRW scenario) and the Itter catchment (Itter scenario). The results of the three scenarios were then compared with the PECinitial and PECcatchment calculated by GREAT-ER, that was designed as a higher-tiered exposure assessment tool, and with concrete concentrations in the Itter, measured as 24-h composite samples. While the PECregional of all scenarios was close to the lower end of the measured concentrations, the geo-referenced PECs described equally well the real spacial situation. The measured environmental concentrations confirmed the built-in conservatism of the PEClocal calculations by EUSES showing for all investigated chemicals an unrealistically high PEClocal (default). The refinement in the more realistic scenarios could not provide a straight forward general improvement of the PEClocal. In conclusion, when the EUSES prognosis is refined using more detailed substance and regional specific data, it may provide a fairly accurate modelling especially of substances that are not eliminated in the environment. However, in the case of eliminable substances, it does not match the accuracy of higher-tiered geo-referenced exposure models like GREAT-ER.  相似文献   

6.
7.
In this paper the results of a thorough evaluation of the environmental fate and effects of azilsartan are presented. Azilsartan medoxomil is administered as a pro-drug for the treatment of patients with essential hypertension. The pro-drug is converted by hydrolysis to the active pharmaceutical ingredient azilsartan. Laboratory tests to evaluate the environmental fate and effects of azilsartan medoxomil were conducted with azilsartan and performed in accordance with OECD test guidelines. The predicted environmental concentration (PEC) in surface water was estimated at 0.32 μg L−1 (above the action limit of 0.01 μg L−1), triggering a Phase II assessment. Azilsartan is not readily biodegradable. Results of the water sediment study demonstrated significant shifting of azilsartan metabolites to sediment. Based on the equilibrium partitioning method, metabolites are unlikely to pose a risk to sediment-dwelling organisms. Ratios of the predicted environmental concentrations (PECs) to the predicted-no-effect concentrations (PNECs) did not exceed the relevant triggers, and the risk to aquatic, sewage treatment plant (STP), groundwater and sediment compartments was concluded acceptable. A terrestrial assessment was not triggered. Azilsartan poses an acceptable risk to the environment.  相似文献   

8.
Glycol ethers are a class of semi-volatile substances used as solvents in a variety of consumer products like cleaning agents, paints, cosmetics as well as chemical intermediates.We determined 11 metabolites of ethylene and propylene glycol ethers in 44 urine samples of German residents (background level study) and in urine samples of individuals after exposure to glycol ethers during cleaning activities (exposure study).In the study on the background exposure, methoxyacetic acid and phenoxyacetic acid (PhAA) could be detected in each urine sample with median (95th percentile) values of 0.11 mg L?1 (0.30 mg L?1) and 0.80 mg L?1 (23.6 mg L?1), respectively. The other metabolites were found in a limited number of samples or in none.In the exposure study, 5–8 rooms were cleaned with a cleaner containing ethylene glycol monobutyl ether (EGBE), propylene glycol monobutyl ether (PGBE), or ethylene glycol monopropyl ether (EGPE). During cleaning the mean levels in the indoor air were 7.5 mg m?3 (EGBE), 3.0 mg m?3 (PGBE), and 3.3 mg m?3 (EGPE), respectively. The related metabolite levels analysed in the urine of the residents of the rooms at the day of cleaning were 2.4 mg L?1 for butoxyacetic acid, 0.06 mg L?1 for 2-butoxypropionic acid, and 2.3 mg L?1 for n-propoxyacetic acid.Overall, our study indicates that the exposure of the population to glycol ethers is generally low, with the exception of PhAA. Moreover, the results of the cleaning scenarios demonstrate that the use of indoor cleaning agents containing glycol ethers can lead to a detectable internal exposure of residents.  相似文献   

9.
Methyl ethers of halogenated phenols have been identified in marine air samples from the North and South Hemispheres. The compounds are tribromoanisole, pentachloroanisole and tetrachlorohydroquinone dimethyl ether. The concentrations of these compounds are in the pg m−3 range, and they are among the more abundant high-molecular weight halocarbons in the remote marine troposphere. A probable source of these compounds is the microbial methylation of the biocide pentachlorophenol and tribromophenol of either pollutant or natural origin.  相似文献   

10.
Concentrations of metals in household dust samples from rural, semi-urban and urban zones of the Niger Delta in Nigeria were measured during both 2009 and 2014 with the aim of providing information on changes in the concentrations, distribution patterns, sources and risks of metals in these zones. The concentrations of metals in the dust samples were quantified by using inductively coupled plasma atomic emission spectrophotometry (ICP-AES) after digestion with aqua regia. The measured concentrations (mg kg?1) of metals in the three zones within the study periods were as follows: <LOQ–21.2; <LOQ–182; 7.90–265; <LOQ–117; <LOQ–471; 3.37–2310; 0.35–7.9; 4.25–365; 6.78–61,600; 219–37,700; and 1180–18,000 for Cd, Pb, Ba, Cr, Ni, Cu, Co, Mn, Zn, Fe and Al, respectively. The results from the two periods indicate significant changes in the concentrations, distribution patterns and risk factors which reflects a deterioration of the quality of the household environment over this time span. The hazard index (HI) values calculated for children were greater than 1 indicating significant non-cancer risks for these subjects in these areas. The HI values for adults were less than 1 and consequently do not pose a significant risk. The carcinogenic risk levels for exposure to metals for both adults and children in these zones were below the range specified as safe by the US EPA (×10?6 and ×10?4) thereby indicating a low cancer risk. The sources of metals in household dust from these zones include emissions from industries, traffic, artisanal workshops and releases from household furniture, metal-based fittings, metal roofing and pesticides.  相似文献   

11.
Probabilistic material flow analysis and graph theory were combined to calculate predicted environmental concentrations (PECs) of engineered nanomaterials (ENMs) in Swiss rivers: 543 river sections were used to assess the geographical variability of nano-TiO2, nano-ZnO and nano-Ag, and flow measurements over a 20-year period at 21 locations served to evaluate temporal variation. A conservative scenario assuming no ENM removal and an optimistic scenario covering complete ENM transformation/deposition were considered. ENM concentrations varied by a factor 5 due to uncertain ENM emissions (15%-85% quantiles of ENM emissions) and up to a factor of 10 due to temporal river flow variations (15%-85% quantiles of flow). The results indicate highly variable local PECs and a location- and time-dependent risk evaluation. Nano-TiO2 median PECs ranged from 11 to 1′623 ng L−1 (conservative scenario) and from 2 to 1′618 ng L−1 (optimistic scenario). The equivalent values for nano-ZnO and nano-Ag were by factors of 14 and 240 smaller.  相似文献   

12.
Little information is available on the environmental occurrence and ecotoxicological effects of pharmaceutical gestagens released in the aquatic environment. Since eighteen different gestagens were found to be used in France, preliminary exposure and hazard assessment were done. Predicted environmental concentrations (PECs) suggest that if parent gestagens are expected to be found in the ng l−1 range, some active metabolites could be present at higher concentrations, although limited data on metabolism and environmental fate limit the relevance of PECs. The biological effects are not expected to be restricted to progestagenic activity. Both anti-androgenic activity (mainly for cyproterone acetate, chlormadinone acetate and their metabolites) and estrogenic activity (mainly for reduced metabolites of levonorgestrel and norethisterone) should also occur. All these molecules are likely to have a cumulative effect among themselves or with other xenoestrogens. Studies on occurrence, toxicity and degradation time are therefore needed for several of these compounds.  相似文献   

13.
Regional PECs (Potential Environmental Concentrations) calculated with the software EUSES were compared with measured values using different emission and environmental distribution scenarios. The environmental data set recommended in EUSES (default data set) represents a generic standard region. In different scenarios the parameters of the generic region are replaced by concrete values, and estimated parameters (emissions, degradation rates and partition coefficients) are substituted by measured or investigated values. Deviations with regard to the measured values can be up to three orders of magnitude. Despite the basically conservative approximations, underestimations can occur. However, these are usually due to poor monitoring data or inappropriate input values. The use of regional data instead of default parameters only slightly ameliorates the results. The use of real emission and degradation rates alone can improve the results significantly.  相似文献   

14.
Abstract

Methyl tertiary butyl ether (MTBE) is added to gasoline (15% by volume) in many areas of the U.S. to help control carbon monoxide emissions from motor vehicles. In this study we present a sampling and analytical methodology that can be used to assess consumers' exposures to MTBE that may result from routine vehicle refueling operations. The method is based on the collection of alveolar breath samples using evacuated one-liter stainless steel canisters and analysis using a gas chromatograph-mass spectrometer equipped with a patented "valveless" cryogenic preconcentrator.

To demonstrate the utility of this approach, a series of breath samples was collected from two individuals (the person pumping the fuel and a nearby observer) immediately before and for 64 min after a vehicle was refueled with premium grade gasoline. Results demonstrate low levels of MTBE in both subjects' breaths before refueling, and levels that increased by a factor of 35 to 100 after the exposure. Breath elimination models fitted to the post exposure measurements indicate that the half-life of MTBE in the first physiological compartment was between 1.3 and 2.9 min. Analysis of the resulting models suggests that breath elimination of MTBE during the 64 min monitoring period was approximately 115 jug for the refueling subject while it was only 30 ug for the nearby observer. This analysis also shows that the post exposure breath elimination of other gasoline constituents was consistent with previously published observations.

These results demonstrate that this new methodology can be used effectively in studies designed to assess exposures to MTBE. The method can be used to objectively demonstrate recent exposures, the relative magnitude of an exposure, and the approximate duration of the resulting bloodborne dose. Once a blood/breath partition coefficient for MTBE has been firmly established, the bloodborne concentration of the absorbed material can be determined using these techniques as well.  相似文献   

15.
Abstract

Ozone and several polar volatile organic compounds (VOCs) including organic acids and carbonyls (aldehydes and ketones) were measured over an approximately 24 hour period in four residences during the winter of 1993 and in nine residences during the summer of 1993. All residences were in the greater Boston, Massachusetts area. The relation of the polar VOCs to the ozone concentration was examined. Indoor carbonyl concentrations were similar between the summer and winter, with the total mean winter concentration being 31.7 ppb and the total mean summer concentration being 36.6 ppb. However, the average air exchange rate was 0.9 hr?1 during the winter and 2.6 hr?1 during the summer. Therefore, the estimated carbonyl emission rates were significantly higher during the summer. Indoor organic acid concentrations were about twice as high during the summer as during the winter. For formic acid, the indoor winter mean was 9.8 ppb, and the summer indoor mean was 17.8 ppb. For acetic acid, the indoor winter mean was 15.5 ppb, and the summer indoor mean was 28.7 ppb. The concentrations of the polar VOCs were found to be significantly correlated with one another. Also, the emission rates of the polar VOCs were found to be correlated with both the environmental variables such as temperature and relative humidity and the ozone removal rate; however, it was difficult to apportion the relative effects of the environmental variables and the ozone removal.  相似文献   

16.
There is global concern about the effects of decabromodiphenyl ether (BDE209) on environmental and public health. The molecular properties, biosorption, degradation, accumulation, and cellular metabolic effects of BDE209 were investigated in this study to identify the mechanisms involved in the aerobic biodegradation of BDE209. BDE209 is initially absorbed by wall teichoic acid and N-acetylglucosamine side chains in peptidoglycan, and then, BDE209 is transported and debrominated through three pathways, giving tri-, hepta-, octa-, and nona-bromodiphenyl ethers. The C–C bond energies decrease as the number of bromine atoms on the diphenyl decreases. Polybrominated diphenyl ethers (PBDEs) inhibit protein expression or accelerate protein degradation and increase membrane permeability and the release of Cl?, Na+, NH4 +, arabinose, proteins, acetic acid, and oxalic acid. However, PBDEs increase the amounts of K+, Mg2+, PO4 3?, SO4 2?, and NO3 ? assimilated. The biosorption, degradation, accumulation, and removal efficiencies when Brevibacillus brevis (1 g L?1) was exposed to BDE209 (0.5 mg L?1) for 7 days were 7.4, 69.5, 16.3, and 94.6 %, respectively.  相似文献   

17.
Currently, butter and margarine are food products attracting wide customer interest. Every day, consumers around the world buy these products for human consumption. Butter is obtained from milk fat, while margarine is derived from vegetable oils. The content of organochlorine pesticide (OCP) residues was examined in both types of these high fatty products. A gas chromatograph with MSD (HP 5973) detector was used for the determination of pesticides such as α-HCH, β-HCH, γ-HCH, DDT, DDD, DDE, aldrin, dieldrin, endrin, heptachlor and heptachlor epoxide. The examined products had diverse concentrations of the analyzed compounds. Visible was the division based on the origin of the product, which might be composed of animal or vegetable fats. The research has revealed the presence of OCP residues in all examined spreads. Quantities of organochlorine compounds did not pose an immediate danger to the consumers’ health. Human and environmental health risk assessment was carried out by the estimation of lifetime average daily dose (LADD) and non-carcinogenic health hazard quotient (HQ). Total estimated LADD ranged between 1.3 × 10?5 and 3.1 × 10?5 mg kg?1 d?1 for butter, and 1.9 × 10?6 and 4.6 × 10?6 mg kg?1 d?1 for margarine and mix spread. The HQ ranged between 1.1 × 10?4 and 3.7 × 10?4 for butter, and 1.4 × 10?5 and 9.0 × 10?6 for margarine and mix spread for adults. These estimated HQs were within the safe acceptable limits, indicating a negligible risk to the residents of the study area.  相似文献   

18.
Ponds play an important role in urban areas. However, cyanobacterial blooms counteract the societal need for a good water quality and pose serious health risks for citizens and pets. To provide insight into the extent and possible causes of cyanobacterial problems in urban ponds, we conducted a survey on cyanobacterial blooms and studied three ponds in detail. Among 3,500 urban ponds in the urbanized Dutch province of North Brabant, 125 showed cyanobacterial blooms in the period 2009–2012. This covered 79 % of all locations registered for cyanobacterial blooms, despite the fact that urban ponds comprise only 11 % of the area of surface water in North Brabant. Dominant bloom-forming genera in urban ponds were Microcystis, Anabaena and Planktothrix. In the three ponds selected for further study, the microcystin concentration of the water peaked at 77 μg l?1 and in scums at 64,000 μg l?1, which is considered highly toxic. Microcystin-RR and microcystin-LR were the most prevalent variants in these waters and in scums. Cyanobacterial chlorophyll-a peaked in August with concentrations up to 962 μg l?1 outside of scums. The ponds were highly eutrophic with mean total phosphorus concentrations between 0.16 and 0.44 mg l?1, and the sediments were rich in potential releasable phosphorus. High fish stocks dominated by carp lead to bioturbation, which also favours blooms. As urban ponds in North Brabant, and likely in other regions, regularly suffer from cyanobacterial blooms and citizens may easily have contact with the water and may ingest cyanobacterial material during recreational activities, particularly swimming, control of health risk is of importance. Monitoring of cyanobacteria and cyanobacterial toxins in urban ponds is a first step to control health risks. Mitigation strategies should focus on external sources of eutrophication and consider the effect of sediment P release and bioturbation by fish.  相似文献   

19.
A three-part study was conducted to quantify the impact of landscaped vegetation on air quality in a rapidly expanding urban area in the arid southeastern United States. The study combines in situ, plant-level measurements, a spatial emissions inventory, and a photochemical box model. Maximum plant-level basal emission rates were moderate: 18.1 μgC gdw?1 h?1 (Washingtonia spp., palms) for isoprene and 9.56 μgC gdw?1 h?1 (Fraxinus velutina, Arizona ash) for monoterpenes. Sesquiterpene emission rates were low for plant species selected in this study, with no measurement exceeding 0.1 μgC gdw?1 h?1. The high ambient temperatures combined with moderate plant-level emission factors resulted in landscape emission factors that were low (250–640 μgC m?2 h?1) compared to more mesic environments (e.g., the southeastern United States). The Regional Atmospheric Chemistry Mechanism (RACM) was modified to include a new reaction pathway for ocimene. Using measured concentrations of anthropogenic hydrocarbons and other reactive air pollutants (NOx, ozone), the box model employing the RACM mechanism revealed that these modest emissions could have a significant impact on air quality. For a suburban location that was downwind of the urban core (high NOx; low anthropogenic hydrocarbons), biogenic terpenes increased time-dependent ozone production rates by a factor of 50. Our study demonstrates that low-biomass density landscapes emit sufficient biogenic terpenes to have a significant impact on regional air quality.  相似文献   

20.
Abstract

The purpose of this study was to characterize and measure indoor air quality in public facilities and office buildings. The pollutants of interest were particulate matter smaller than 2.5 μm in diameter, PM-2.5, and environmental tobacco smoke (ETS). Integrated PM- 2.5 samples were taken on Teflon membrane filters using Harvard Aerosol Impactors as a pre-size selector. Filters were analyzed by gravimetric analysis. Nicotine, which was used as a marker for ETS, was collected on sodium-bisulfate-impregnated, glass-fiber filters and was analyzed by gas chromatography. Twenty-one structures were monitored in Metropolitan Boston. Measured particle concentrations ranged from 6.0 μg/m3 to about 550 μg/m3. Nicotine concentrations were as high as 26 μg/m3 in a designated smoking room. Real-time measurements were also taken using two types of nephelometers; a Handheld Aerosol Monitor (HAM) and a Miniature Real-Time Aerosol Monitor (MINIRAM). Short-term field measurements with these instruments correlated better with the integrated PM-2.5 concentrations in smoking locations than with concentrations in non-smoking areas.  相似文献   

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