Air pollutant concentrations near three Texas roadways, part II: Chemical characterization and transformation of pollutants

Spatial gradients of vehicular emitted air pollutants were measured in the vicinity of three roadways in the Austin, Texas area: (1) State Highway 71 (SH-71), a heavily traveled arterial highway dominated by passenger vehicles; (2) Interstate 35 (I-35), a limited access highway north of Austin in Georgetown; and (3) Farm to Market Road 973 (FM-973), a heavily traveled surface roadway with significant truck traffic. A mobile monitoring platform was used to characterize the gradients of CO and NO_x concentrations with increased distance from each roadway, while concentrations of carbonyls in the gas-phase and fine particulate matter mass and composition were measured at stationary sites upwind and at one (I-35 and FM-973) or two (SH-71) downwind sites. Regardless of roadway type or wind direction, concentrations of carbon monoxide (CO), nitric oxide (NO), and oxides of nitrogen (NO_x) returned to background levels within a few hundred meters of the roadway. Under perpendicular wind conditions, CO, NO and NO_x concentrations decreased exponentially with increasing distance perpendicular to the roadways. The decay rate for NO was more than a factor of two greater than for CO, and it comprised a larger fraction of NO_x closer to the roadways than further downwind suggesting the potential significance of near roadway chemical processing as well as atmospheric dilution. Concentrations of most carbonyl species decreased with distance downwind of SH-71. However, concentrations of acetaldehyde and acrolein increased farther downwind of SH-71, suggesting chemical generation from the oxidation of primary vehicular emissions. The behavior of particle-bound organic species was complex and further investigation of the size-segregated chemical composition of particulate matter (PM) at increasing downwind distances from roadways is warranted. Fine particulate matter (PM_2.5) mass concentrations, polycyclic aromatic hydrocarbons (PAHs), hopanes, and elemental carbon (EC) concentrations generally exhibited concentrations that decreased with distance downwind of SH-71. Concentrations of organic carbon (OC) increased from upwind concentrations immediately downwind of SH-71 and continued to increase further downwind from the roadway. This behavior may have primarily resulted from condensation of semi-volatile organic species emitted from vehicle sources with transport downwind of the roadway.     

Air pollutant concentrations near three Texas roadways,Part I: Ultrafine particles

Vehicular emitted air pollutant concentrations were studied near three types of roadways in Austin, Texas: (1) State Highway 71 (SH-71), a heavily traveled arterial highway dominated by passenger vehicles; (2) Interstate 35 (I-35), a limited access highway north of Austin in Georgetown; and (3) Farm to Market Road 973 (FM-973), a heavily traveled surface roadway dominated by truck traffic. Air pollutants examined include carbon monoxide (CO), oxides of nitrogen (NO_x), and carbonyl species in the gas-phase. In the particle phase, ultrafine particle (UFP) concentrations (diameter < 100 nm), fine particulate matter (PM_2.5, diameter < 2.5 μm) mass and carbon content and several particle-bound organics were examined. All roadways had an upwind stationary sampling location, one or two fixed downwind sample locations and a mobile monitoring platform that characterized pollutant concentrations fall-off with increased distance from the roadways. Data reported in this paper focus on UFP while other pollutants and near-roadway chemical processes are examined in a companion paper. Traffic volume, especially heavy-duty traffic, wind speed, and proximity to the road were found to be the most important factors determining UFP concentrations near the roadways. Since wind directions were not consistent during the sampling periods, distances along wind trajectories from the roadway to the sampling points were used to study the decay characteristics of UFPs. Under perpendicular wind conditions, for all studied roadway types, particle number concentrations increased dramatically moving from the upwind side to the downwind side. The elevated particle number concentrations decay exponentially with increasing distances from the roadway with sharp concentration gradients observed within 100–150 m, similar to previously reported studies. A single exponential decay curve was found to fit the data collected from all three roadways very well under perpendicular wind conditions. No consistent pattern was observed for UFPs under parallel wind conditions. However, regardless of wind conditions, particle concentrations returned to background levels within a few hundred meters of the roadway. Within measured UFP size ranges, smaller particles (6–25 nm) decayed faster than larger ones (100–300 nm). Similar decay rates were observed among UFP number, surface, and volume.     

Dissolved antimony concentrations in contrasted watersheds: the importance of lithogenic origin

A large series of data on dissolved antimony concentrations (900 values) from the hydrological network of Canton Geneva, Switzerland, has been statistically analysed. Data were collected from 90 sampling sites over 12 years. The watercourses surveyed (178 km) accounted for 73% of the total network. Previous studies have classified these rivers as belonging to three clearly-differentiated lithogenic zones: Alps (rivers draining crystalline regions), Jura (rivers draining carbonate-rich zones) and Plain (rivers draining molasses derived from the Alps). Antimony concentrations in the different river waters have been found to be significantly dependent on the geological characteristics of the drainage basins (median values: 0.13, 0.08 and 0.16 microg L(-1) for Alps, Jura and Plain, respectively). For antimony, it is thus possible to define background levels of the element adapted to the lithogenic characteristics for a system of interest. Since establishing background levels is an unavoidable preliminary step in any study aiming to identify and evaluate the various sources of pollution, the behaviour described here has undeniable implications for environmental surveys.     

Elimination of endocrine disrupting chemicals nonylphenol and bisphenol A and personal care product ingredient triclosan using enzyme preparation from the white rot fungus Coriolopsis polyzona

The biocatalytic elimination of the endocrine disrupting chemicals (EDC) nonylphenol (NP) and bisphenol A (BPA) and the personal care product ingredient triclosan (TCS) by the enzyme preparation from the white rot fungus Coriolopsis polyzona was investigated. Analysis of variance methodology showed that the pH and the temperature are statistically significant factors in the removal of NP, BPA and TCS. The elimination of NP and TCS was best at a temperature of 50 degrees C and the disappearance of BPA at 40 degrees C, whereas the most suitable pH for all three micropollutants was 5. After a 4-h treatment of the three target compounds at concentrations of 5 mg l(-1) all of the NP and BPA were eliminated. In the case of TCS, 65% was removed after either a 4 or an 8-h treatment. The utilisation of 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) in the laccase/mediator system significantly increased the efficiency of the enzymatic treatment. The elimination of NP and BPA was directly associated with the disappearance of the estrogenic activity. Mass spectrometry analysis showed that the enzymatic treatment produced high molecular weight metabolites through a radical polymerization mechanism of NP, BPA and TCS. These oligomers were produced through the formation of C-C or C-O bonds. The polymerization of NP produced dimers, trimers, tetramers and pentamers which had molecular weights of 438, 656, 874 and 1092 amu respectively. The polymerization of BPA produced dimers, trimers and tetramers which had molecular weights of 454, 680 and 906 amu. Finally, the polymerization of TCS produced dimers, trimers and tetramers which had molecular weights of 574, 859 and 1146 amu.     

Soil distribution of fipronil and its metabolites originating from a seed-coated formulation

Seed-coating with the insecticide fipronil has been intensively used in sunflower cultivation to control soil pests such as wireworms. A research project was undertaken to determine the soil distribution of fipronil and of its main phenylpyrazole metabolites. Under agronomic conditions, the quantity of fipronil in the seed-coat (437 microg/seed) decreased continuously during the cultivation period (3.9 microg day(-1) during the first two months; 0.3 microg day(-1) during the next four months). At the end of the cultivation period, 42% of all phenylpyrazole compounds remained in the seed-coat. Fipro nil was poorly mobile in soil, and at the end of the cultivation period it was mostly concentrated in the soil layer close to the seed (3240 microg kg(-1) soil). Starting from the seed-coating, a fipronil concentration gradient was measured in the soil, up to a distance of 11 cm from the seed. Degradation in the soil occurred at a moderate rate, probably due to the fact that water solubilization of the solid active ingredient present in the seed coating was rate limiting. Indeed, after 6 months of cultivation, only 51% of the fipronil seed-coating was found in the soil, about 7% having been absorbed by the sunflower plant, and 42% remaining in the seed coat. The predominant metabolites produced in the soil were sulfone-fipronil, sulfide-fipronil and amide-fipronil, which were produced at average rates of 5 microg kg(-1) soil day(-1), 3 microg kg(-1) soil day(-1), and 0.4 microg kg(-1) soil day(-1), respectively. In contrast, the photoproduct, desulfinyl-fipronil, was barely detected. All phenylpyrazole compounds were poorly mobile, except for the amide derivative, which is devoid of insecticidal activity in marked contrast to the other metabolites. Furthermore, detectable soil contamination was limited to a zone of about 11 cm around the seed.     

Study of the toxicity of diuron and its metabolites formed in aqueous medium during application of the electrochemical advanced oxidation process "electro-Fenton"

Diuron (N'-[3,4-dichlorophenyl]-N,N-dimethylurea) is a herbicide belonging to the phenylurea family, widely used to destroy weeds on uncultivated surfaces. Because of its toxicity for aquatic organisms and suspicion of being carcinogenic for humans, diuron is the object of growing environmental concern. Therefore, we have developed the electro-Fenton method, an electrochemical advanced oxidation process (EAOP), to degrade diuron in aqueous medium, and we have studied the evolution of the toxicity of treated solution during the process. Indeed, the EAOPs catalytically generate hydroxyl radicals that oxidize the persistent organic pollutants, and can ultimately destroy and mineralize them. But, sometimes, relatively toxic organic metabolites are formed during the oxidation reaction. In this work, the evolution of toxicity of diuron aqueous solutions was studied at different initial concentrations, during treatment by the electro-Fenton method. Samples were collected at various electrolysis times and mineralization degrees during the treatment. The toxicity of the samples was measured using the bacteria Vibrio fischeri (Microtox) and the green alga Scenedesmus obliquus. Our results demonstrated that the toxicity of diuron aqueous solutions (concentrations=3.0-27.6 mg L(-1)) varied considerably with time. The formation and disappearance of several metabolites, having toxicity often stronger than that of the initial herbicide, were observed. To improve the efficiency of water decontamination, the electro-Fenton method should be applied during a time long enough (several hours) and at relatively high electrolysis current (I=250 mA) to reach a nearly complete mineralization of the herbicide in the aqueous medium.     

Statistical modeling of crystalline silica exposure by trade in the construction industry using a database compiled from the literature

A quantitative determinants-of-exposure analysis of respirable crystalline silica (RCS) levels in the construction industry was performed using a database compiled from an extensive literature review. Statistical models were developed to predict work-shift exposure levels by trade. Monte Carlo simulation was used to recreate exposures derived from summarized measurements which were combined with single measurements for analysis. Modeling was performed using Tobit models within a multimodel inference framework, with year, sampling duration, type of environment, project purpose, project type, sampling strategy and use of exposure controls as potential predictors. 1346 RCS measurements were included in the analysis, of which 318 were non-detects and 228 were simulated from summary statistics. The model containing all the variables explained 22% of total variability. Apart from trade, sampling duration, year and strategy were the most influential predictors of RCS levels. The use of exposure controls was associated with an average decrease of 19% in exposure levels compared to none, and increased concentrations were found for industrial, demolition and renovation projects. Predicted geometric means for year 1999 were the highest for drilling rig operators (0.238 mg m(-3)) and tunnel construction workers (0.224 mg m(-3)), while the estimated exceedance fraction of the ACGIH TLV by trade ranged from 47% to 91%. The predicted geometric means in this study indicated important overexposure compared to the TLV. However, the low proportion of variability explained by the models suggests that the construction trade is only a moderate predictor of work-shift exposure levels. The impact of the different tasks performed during a work shift should also be assessed to provide better management and control of RCS exposure levels on construction sites.     

Assessing the impact of chloroacetanilide herbicides and their metabolites on periphyton in the Leyre River (SW France) via short term growth inhibition tests on autochthonous diatoms

The Leyre River is the main tributary to the Bassin d'Arcachon lagoon. Herbicides belonging to the chloroacetanilide class have been found in the river (S-metolachlor and acetochlor) as well as some of their metabolites at higher concentrations. As the environmental toxicity of these molecules is not well known, ecotoxicological tests have been carried out on river periphyton at different levels of biological diversity: from the clone of one diatom species (Nitzschia nana) to the population of the same species (several clones) up to the multi-specific species community dominated by diatoms. Moreover, tests were performed on diatoms coming from an unpolluted upstream site and from a contaminated downstream site, in order to investigate possible tolerance acquisition to pollutants. The method consisted in measuring diatom growth inhibition at different doses of each substance from the increase of chlorophyll-a concentration after 4 days. It resulted that acetochlor was clearly more toxic than S-metolachlor at all levels of biological diversity. EC(50) values estimated from the tests suggest no effect of contaminants on diatom growth or biomass in the river. The toxicity of the metabolites appeared very low compared to that of their parent compounds. No difference in tolerance to the herbicides was demonstrated between summer diatom communities from the two sites in spite of different specific compositions. However, concerning the populations of N. nana isolated in winter following the highest herbicide concentrations in the river (about 0.5 μg L(-1)), the downstream population showed a higher tolerance to acetochlor but there was no co-tolerance to S-metolachlor. Thus, it appeared that acetochlor represents the highest toxic pressure on periphyton among the other contaminants in the Leyre River.     

Ecosystem Viable Yields

The World Summit on Sustainable Development (Johannesburg, 2002) encouraged the application of the ecosystem approach by 2010. However, at the same summit, the signatory States undertook to restore and exploit their stocks at maximum sustainable yield (MSY), a concept and practice without ecosystemic dimension, since MSY is computed species by species, on the basis of a monospecific model. Acknowledging this gap, we propose a definition of “ecosystem viable yields” (EVY) as yields compatible (a) with biological safety levels (over which biomasses can be maintained for all times) and (b) with an ecosystem dynamics. The difference from MSY is that this notion is not based on equilibrium but on viability theory, which offers advantages for robustness. For a generic class of multispecies models with harvesting, we provide explicit expressions for the EVY. We apply our approach to the anchovy–hake couple in the Peruvian upwelling ecosystem.