Kinetic aspects and identification of by-products during the ozonation of bitertanol in agricultural wastewaters

The degradation of bitertanol by ozone treatment is investigated. Solutions of bitertanol (8.4 μg mL^?1) were prepared either by dissolution of the standard or by dilution of Gaucho Blé seed loading solution and then ozonated under different conditions. Evolution of the concentrations of bitertanol and its ozonation by-products in both solutions was monitored by HPLC–UV as a function of the treatment time for a concentration of 100 g m^?3 of ozone in the inlet gas. Bitertanol degradation was found to follow a pseudo-first order reaction in both cases. However, the rate of the reaction in diluted seed loading solution was much lower (0.19 vs. 0.27 min^?1 in standard solution) and was close to the reaction rate observed in the presence of a radical scavenger, tert-butanol (0.11 min^?1). Thus, it may be suggested that additives present in the seed loading solution may play the role of radical scavengers. Study of ozone concentration in the inlet gas (from 25 to 100 g m^?3) showed that ozone degradation is also a first-order reaction with respect to ozone. Four ozonation by-products were highlighted, collected and identified by HPLC coupled with an ion trap mass spectrometer using positive electrospray ionization mode. A degradation pathway of bitertanol was finally proposed.     

Comparison of Emission of Dioxins and Furans from Gasohol- and Ethanol-Powered Vehicles

ABSTRACT

The exhaust emissions of 17 polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) were investigated in two spark-ignition light-duty vehicles, one gasohol-fueled and a flexible-fuel one fueled with hydrated ethanol. Gasohol is a mixture of gasoline and 22% ethanol. The influence of fuel type and quality, lubricant oil type, and use of fuel additives on the formation of these compounds was tested using standardized U.S. Federal Test Procedure (FTP)-75 cycle tests. The sampling of the PCDD/Fs followed the recommendations of a modified U.S. Environmental Protection Agency (EPA) Method 23 (http://www.epa.gov/ttn/emc/promgate/m-23.pdf) and the analysis basically followed the U.S. EPA Method 8290 (http://www.epa.gov/osw/hazard/testmethods/sw846/pdfs/8290a.pdf). Results showed that emission factors of PCDD/Fs for the gasohol vehicle varied from undetected to 0.068 pg international toxic equivalency (I-TEQ) km^?1 (average of 0.0294 pg I-TEQ km^?1), whereas in the ethanol vehicle they varied from 0.004 to 0.157 pg (I-TEQ) km^?1 (average of 0.031 pg I-TEQ km^?1). In the gasohol-powered vehicle, the use of fuel additive diminished the emission of Octachlorodibenzo-p-dioxin (OCDD) significantly, whereas in the ethanol vehicle no significant associations were observed between the investigated variables and the emissions.

IMPLICATIONS The objective of this work was to analyze differences in emissions from a traditional fossil fuel (gasoline) and an alternative renewable fuel (ethanol from sugarcane), and the influence of fuel additives and lubricant oils on the formation of chlorinated dioxins and furans in spark-ignition light-duty gasohol and ethanol vehicles. Renewable fuels are very important in terms of climate change but the risk to the population's health must not increase. Thus the results of this work could help in the development of environmental impact studies as well as orienting policy-makers in formulating strategies for air pollution control.     

Development of a livestock odor dispersion model: part II. Evaluation and validation

A livestock odor dispersion model (LODM) was developed to predict odor concentration and odor frequency using routine hourly meteorological data input. The odor concentrations predicted by the LODM were compared with the results obtained from other commercial models (Industrial Source Complex Short-Term model, version 3, CALPUFF) to evaluate its appropriateness. Two sets of field odor plume measurement data were used to validate the model. The model-predicted mean odor concentrations and odor frequencies were compared with those measured. Results show that this model has good performance for predicting odor concentrations and odor frequencies.     

Observed chemical characteristics of long-range transported particles at a marine background site in Korea

Deokjeok Island is located off the west coast of the Korean Peninsula and is a suitable place to monitor the long-range transport of air pollutants from the Asian continent. In addition to pollutants, Asian dust particles are also transported to the island during long-range transport events. Episodic transport of dust and secondary particles was observed during intensive measurements in the spring (March 31-April 11) and fall (October 13-26) of 2009. In this study, the chemical characteristics of long-range-transported particles were investigated based on highly time-resolved ionic measurements with a particle-into-liquid system coupled with an online ion chromatograph (PILS-IC) that simultaneously measures concentrations of cations (Li+, Na , NH4+, K+, Ca2+, Mg2+) and anions (F-, C1-, NO3-, SO42-). The aerosol optical thickness (AOT) distribution retrieved by the modified Bremen Aerosol Retrieval (M-BAER) algorithm from moderate resolution imaging spectroradiometer (MODIS) satellite data confirmed the presence of a thick aerosol plume coming from the Asian continent towards the Korean peninsula. Seven distinctive events involving the long-range transport (LRT) of aerosols were identified and studied, the chemical components of which were strongly related to sector sources. Enrichment of acidic secondary aerosols on mineral dust particles, and even of sea-salt components, during transport was observed in this study. Backward trajectory, chemical analyses, and satellite aerosol retrievals identified two distinct events: a distinctively high [Ca2++Mg2]/[Na+] ratio (>2.0), which was indicative of a preprocessed mineral dust transport event, and a low [Ca2++Mg2+]/[Na+] ratio (<2.0), which was indicative of severe aging of sea-salt components on the processed dust particles. Particulate C1- was depleted by up to 85% in spring and 50% in the fall. A consistent fraction of carbonate replacement (FCR) averaged 0.53 in spring and 0.55 in the fall. Supporting evidences of C1- enrichment on the marine boundary layer prior to a dust front were also found. Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of the Air & Waste Management Association for sector and air mass classifications of clean and LRT cases.     

Comparison of emission of dioxins and furans from gasohol- and ethanol-powered vehicles

The exhaust emissions of 17 polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) were investigated in two spark-ignition light-duty vehicles, one gasohol-fueled and a flexible-fuel one fueled with hydrated ethanol. Gasohol is a mixture of gasoline and 22% ethanol. The influence of fuel type and quality, lubricant oil type, and use of fuel additives on the formation of these compounds was tested using standardized U.S. Federal Test Procedure (FTP)-75 cycle tests. The sampling of the PCDD/Fs followed the recommendations of a modified U.S. Environmental Protection Agency (EPA) Method 23 (www.epa.gov/ttn/ emc/promgate/m-23.pdf) and the analysis basically followed the U.S. EPA Method 8290 (http://www.epa.gov/osw/ hazard/testmethods/sw846/pdfs/8290a.pdf). Results showed that emission factors of PCDD/Fs for the.gasohol vehicle varied from undetected to 0.068 pg international toxic equivalency (I-TEQ) km(-1) (average of 0.0294 pg I-TEQ km(-1)), whereas in the ethanol vehicle they varied from 0.004 to 0.157 pg (I-TEQ) km(-1) (average of 0.031 pg I-TEQ km(-1)). In the gasohol-powered vehicle, the use of fuel additive diminished the emission of Octachlorodibenzo-p-dioxin (OCDD) significantly, whereas in the ethanol vehicle no significant associations were observed between the investigated variables and the emissions.     

Environmental impact of APC residues from municipal solid waste incineration: reuse assessment based on soil and surface water protection criteria

Waste management and environmental protection are mandatory requirements of modern society. In our study, air pollution control (APC) residues from municipal solid waste incinerators (MSWI) were considered as a mixture of fly ash and fine particulate solids collected in scrubbers and fabric filters. These are hazardous wastes and require treatment before landfill. Although there are a number of treatment options, it is highly recommended to find practical applications rather than just dump them in landfill sites. In general, for using a construction material, beyond technical specifications also soil and surface water criteria may be used to ensure environmental protection. The Dutch Building Materials Decree (BMD) is a valuable tool in this respect and it was used to investigate which properties do not meet the threshold criteria so that APC residues can be further used as secondary building material. To this end, some scenarios were evaluated by considering release of inorganic species from unmoulded and moulded applications. The main conclusion is that the high amount of soluble salts makes the APC residues a building material prohibited in any of the conditions tested. In case of moulding materials, the limits of heavy metals are complied, and their use in Category 1 would be allowed. However, also in this case, the soluble salts lead to the classification of "building material not allowed". The treatments with phosphates or silicates are able to solve the problem of heavy metals, but difficulties with the soluble salts are still observed. This analysis suggests that for APC residues to comply with soil and surface water protection criteria to be further used as building material at least a pre-treating for removing soluble salts is absolutely required.     

Feasibility of a tandem photocatalytic oxidation–adsorption system for removal of monoaromatic compounds at concentrations in the sub-ppm-range

Unlike previous photocatalytic oxidation (PCO) studies incorporated with adsorption, this study investigates the feasibility of applying a tandem PCO-adsorption hybrid technique regarding low-level monoaromatic compound removal. The PCO efficiencies decreased as the hydraulic diameter (HD) increased. A PCO reactor of a medium HD size was selected for further experiments. Under conditions relevant to the use of the PCO system, the CO level measured during the PCO process was minimal in comparison to indoor CO levels. Trace level formations of formaldehyde and acetaldehyde were observed during the photocatalytic process, but these compounds were undetectable at the activated carbon unit outlet. The degradation efficiencies, obtained from the PCO unit, exhibited a dependence on both the inlet concentration (IC) and relative humidity (RH), whereas those from the PCO-adsorption hybrid system did not. Under specific conditions, the PCO unit presented a high degradation efficiency of close to, or exceeding 90%, in regards to ethyl benzene, o-xylene, and m,p-xylene. However, the benzene air concentrations, after being treated by the PCO unit, substantially exceeded the USEPA inhalation reference concentration guideline of 30 μg m⁻³ (corresponding to 0.01 ppm). In contrast, the PCO-adsorption hybrid system presented a high removal efficiency of close to 100% regarding all compounds, regardless of the IC or RH range. Consequently, it is suggested that the PCO-adsorption hybrid system has a synergistic advantage of photocatalysis and adsorption in regards to the BTEX elimination process.     

The anthropogenic atmospheric elements fraction: A new interpretation of elemental deposits on tree barks

The superficial deposit on the bark surface of several trees (mainly Fraxinus excelsior L.) was sampled in the experimental station of the university campus in Grenoble (France). Its composition was studied by scanning electron microscopy–energy dispersive X-ray emission (SEM–EDX) and, after digestion, by inductively coupled plasma-mass spectrometry (ICP-MS). The deposit was composed of 81.3% ± 7.4 organic matter, 9.4% ± 4.9 of geogenic minerals issued from the atmosphere (atmospheric geogenic fraction: AGF) and 9.3% ± 2.7 of a mixture of elements which was called anthropogenic atmospheric elements fraction (AAEF). The SEM–EDX analysis showed the presence of particles of geogenic compounds such as different types of silicates, phosphates, carbonates, sulphates, oxides and also particles of metals such as iron or of alloys of Fe–Zn, Fe–Ni, Ni–Cr and Ca sulphates or phosphates. Typical spheres of “fly ashes” composed of pure iron or Al-silicates were detected. Using the SEM–EDX analysis of the deposit and the average local soil composition, an empiric formula for the AGF (without polluting elements) was chosen, which presented a clear analogy with the global formula of the upper continental crust. In the same way, a formula for the pure organic matter fraction was chosen. Withdrawing the elements corresponding to these two fractions allows a tentative estimation of the content of the AAEF which was supposed to better represent the elemental anthropogenic contamination issued from the atmosphere. In the station, most of Sb, Cd, Sn, Pb, Cu, V and Zn were found in the AAEF. This AAEF composition was compared to that of the deposit in a highway tunnel where Pb and Cu were at a very high level. The meaning and the limits of the AAEF concept were critically discussed.     

Monitoring and assessing processes of organic chemicals removal in constructed wetlands

Physical, chemical and biological processes interact and work in concert during attenuation of organic chemicals in wetland systems. This review summarizes the recent progress made towards understanding how the various mechanisms attributed to organic chemicals removal interact to form a functioning wetland. We also discuss the main degradation pathways for different groups of contaminants and examine some of the key characteristics of constructed wetlands that control the removal of organic chemicals. Furthermore, we address possible comprehensive approaches and recent techniques to follow up in situ processes within the system, especially those involved in the biodegradation processes.     

Differential global profiling as a new analytical strategy for revealing micropollutant treatment by-products: application to ethinylestradiol and chlorination water treatment

The detection and structural elucidation of micropollutants treatment by-products are major issues to estimate efficiencies of the processes employed for drinking water production versus endocrine disruptive compounds contamination. This issue was mainly investigated at the laboratory scale and in high concentration conditions. However, potential by-products generated after chlorination can be influenced by the dilution factor employed in real conditions. The present study proposes a new methodology borrowed to the metabolomic science, using liquid chromatography coupled to high-resolution mass spectrometry, in order to reveal potential chlorination by-products of ethinylestradiol in spiked real water samples at the part-per-billion level (5 μg L⁻¹). Conventional targeted measurements first demonstrated that chlorination with sodium hypochlorite (0.8 mg L⁻¹) led to removals of ethinylestradiol over 97%. Then, the developed differential global profiling approach permitted to reveal eight chlorination by-products of EE2, six of them being described for the first time. Among these eight halogenated compounds, five have been structurally identified, demonstrating the potential capabilities of this new methodology applied to environmental samples.