Influence of the operation conditions on CO2 capture by CaO-derived sorbents prepared from synthetic CaCO3

In this work, a statistical experimental design is performed in order to prepare CaCO₃ materials for use as CaO-based CO₂ sorbent precursors. The influence of different operational parameters such as synthesis temperature (ST), stirring rate (SR) and surfactant percent (SP) on CO₂ capture is studied by applying Response Surface Methodology (RSM). The samples were characterized using different analytical techniques including X-ray diffraction, N₂ adsorption isotherm analysis and Scanning Electron Microscopy–X-ray Energy Dispersive Spectroscopy (SEM-EDX). CO₂ capture capacity was determined by means of a thermogravimetric analyzer which recorded the mass uptake of the samples when these were exposed to a gas stream containing diluted (15%) CO₂. The statistical approach used in this work provides a rapid way of predicting and optimizing the main preparation variables of CaO-derived sorbents for CO₂ sorption. The results obtained clearly indicate that four parameters statistically influence CO₂ uptake: SR, the square of SR, its interaction with SP and the square of SP.     

Emission Factors for High-Emitting Vehicles Based on On-Road Measurements of Individual Vehicle Exhaust with a Mobile Measurement Platform

ABSTRACT

Fuel-based emission factors for 143 light-duty gasoline vehicles (LDGVs) and 93 heavy-duty diesel trucks (HDDTs) were measured in Wilmington, CA using a zero-emission mobile measurement platform (MMP). The frequency distributions of emission factors of carbon monoxide (CO), nitrogen oxides (NO_x), and particle mass with aerodynamic diameter below 2.5 μm (PM_2.5) varied widely, whereas the average of the individual vehicle emission factors were comparable to those reported in previous tunnel and remote sensing studies as well as the predictions by Emission Factors (EMFAC) 2007 mobile source emission model for Los Angeles County. Variation in emissions due to different driving modes (idle, low- and high-speed acceleration, low- and high-speed cruise) was found to be relatively small in comparison to intervehicle variability and did not appear to interfere with the identification of high emitters, defined as the vehicles whose emissions were more than 5 times the fleet-average values. Using this definition, approximately 5% of the LDGVs and HDDTs measured were high emitters. Among the 143 LDGVs, the average emission factors of NO_x, black carbon (BC), PM_2.5, and ultrafine particle (UFP) would be reduced by 34%, 39%, 44%, and 31%, respectively, by removing the highest 5% of emitting vehicles, whereas CO emission factor would be reduced by 50%. The emission distributions of the 93 HDDTs measured were even more skewed: approximately half of the NO_x and CO fleet-average emission factors and more than 60% of PM_2.5, UFP, and BC fleet-average emission factors would be reduced by eliminating the highest-emitting 5% HDDTs. Furthermore, high emissions of BC, PM_2.5, and NO_x tended to cluster among the same vehicles.

IMPLICATIONS This study presents the characterization of on-road vehicle emissions in Wilmington, CA, by sampling individual vehicle plumes. Approximately 5% of the vehicles were high emitters, whose emissions were more than 5 times the fleet-average values. These high emitters were responsible for 30% and more than 50% of the average emission factors of LDGVs and HDDVs, respectively. It is likely that as the overall fleet becomes cleaner due to more stringent regulations, a small fraction of the fleet may contribute a growing and disproportionate share of the overall emissions. Therefore, long-term changes in on-road emissions need to be monitored.     

Behavior of fenhexamid in soil and water

A study was conducted to investigate fenhexamid (FEX) behavior in soil and in water. FEX proved to be rather stable at acid pH but showed slight degradation at neutral and alkaline pH. After 101 days of FEX spiking of a soil sample, 94% at pH 4, 12% at pH 7 and 23% at pH 9 of the active ingredient was still present. In natural water the rate of FEX disappearance appeared to be slow which may be due to abiotic rather than biotic processes. The soil degradation tests showed low persistence of the active ingredient if a good microflora activity is guaranteed (DT₅₀ about 1 day). Moreover, in absence of microorganisms, FEX proved to be stable. Humidities of 25 and 50% of Water Holding Capacity (WHC) influenced in equal measure the rate of degradation. From the same soil, a bacterium was isolated and identified as Bacillus megaterium, which was able to metabolize FEX with the hydroxylation of the cyclohexane ring. Moreover, FEX showed an elevated affinity for humic acid (73%), smectite (31%), and ferrihydrite(20%) and low affinity for vermiculite (11%) and kaolinite (7%).     

Aqueous solubility, effects of salts on aqueous solubility, and partitioning behavior of hexafluorobenzene: experimental results and COSMO-RS predictions

The aqueous solubility of hexafluorobenzene has been determined, at 298.15 K, using a shake-flask method with a spectrophotometric quantification technique. Furthermore, the solubility of hexafluorobenzene in saline aqueous solutions, at distinct salt concentrations, has been measured. Both salting-in and salting-out effects were observed and found to be dependent on the nature of the cationic/anionic composition of the salt. COSMO-RS, the Conductor-like Screening Model for Real Solvents, has been used to predict the corresponding aqueous solubilities at conditions similar to those used experimentally. The prediction results showed that the COSMO-RS approach is suitable for the prediction of salting-in/-out effects. The salting-in/-out phenomena have been rationalized with the support of COSMO-RS σ-profiles. The prediction potential of COSMO-RS regarding aqueous solubilities and octanol-water partition coefficients has been compared with typically used QSPR-based methods. Up to now, the absence of accurate solubility data for hexafluorobenzene hampered the calculation of the respective partition coefficients. Combining available accurate vapor pressure data with the experimentally determined water solubility, a novel air-water partition coefficient has been derived.     

Biomonitoring the genotoxic effects of pollutants on <Emphasis Type="Italic">Tradescantia pallida</Emphasis> (Rose) D.R. Hunt in Dourados,Brazil

Purpose  

This study aimed to associate the intensity of vehicular traffic in the city of Dourados (Mato Grosso do Sul State, Brazil) with mutagenic effects and alterations in leaf physiology as measured by the quantity of micronuclei and the leaf surface parameters of Tradescantia pallida.     

The adsorption and degradation of chlorpyriphos-methyl, pendimethalin and metalaxyl in solid urban waste compost

To evaluate the feasibility of using compost to prepare substrates for the disposal of pesticide residues, adsorption and degradation studies were carried out on three widely used agricultural pesticides: chlorpyriphos-methyl, pendimethalin and metalaxyl. Obtained from solid urban waste, this compost has been shown to be able to adsorb high levels of chlorpyriphos-methyl and pendimethalin (85%, 100%) whereas metalaxyl was only adsorbed at a level of 37%. However, adding smectite to the compost increased the adsorption of metalaxyl by 117%. Chlorpyriphos-methyl and pendimethalin degraded quickly with half-lives of 1.7 and 14.5 days, respectively, whereas metalaxyl proved more persistent (a half-life of 84 days). Adding ammonium nitrate to the compost accelerated metalaxyl degradation to a half-life of 15 days.     

Physico-chemical analysis and calorific values of poultry manure

Spain is one of the major producers of broilers and laying hens in the European Union, with an overall market share of around 12%. The poultry manure that is produced is usually employed as fertilizer on cropland, either directly or after a composting process. In some cases, however, this waste is transported over 120 km to be used as fertilizer, with the resulting high transport costs. In other countries, poultry manure is used as an alternative natural fuel source for power generation. In this study, poultry manure from all the laying hen farms in Asturias was characterized with a view to its possible use as an energy source. The Higher Heating Values on a dry basis (experimental) varies between 12,052 and 13,882 kJ/kg. Lower Heating Values (LHVs) on a wet basis range are much lower (mean values of 2664 kJ/kg) due to the high moisture content of poultry manure. Accordingly, the co-combustion of this waste with other types of waste such as forest and wood waste (LHV on a wet basis of 8044 and 15,830 kJ/kg, respectively) or municipal solid waste (LHV on a wet basis of 10,725 kJ/kg) should be considered as an alternative energy source. Chlorine and sulphur contents in dry matter vary around mean values of 0.64% and 0.11%, respectively. The waste also presents high amounts of Ca (4.84%) and K (2.38%).     

Behavior of fenhexamid in soil and water

A study was conducted to investigate fenhexamid (FEX) behavior in soil and in water. FEX proved to be rather stable at acid pH but showed slight degradation at neutral and alkaline pH. After 101 days of FEX spiking of a soil sample, 94% at pH 4, 12% at pH 7 and 23% at pH 9 of the active ingredient was still present. In natural water the rate of FEX disappearance appeared to be slow which may be due to abiotic rather than biotic processes. The soil degradation tests showed low persistence of the active ingredient if a good microflora activity is guaranteed (DT(50) about 1 day). Moreover, in absence of microorganisms, FEX proved to be stable. Humidities of 25 and 50% of Water Holding Capacity (WHC) influenced in equal measure the rate of degradation. From the same soil, a bacterium was isolated and identified as Bacillus megaterium, which was able to metabolize FEX with the hydroxylation of the cyclohexane ring. Moreover, FEX showed an elevated affinity for humic acid (73%), smectite (31%), and ferrihydrite(20%) and low affinity for vermiculite (11%) and kaolinite (7%).     

A wide area of air pollutant impact downwind of a freeway during pre-sunrise hours

We have observed a wide area of air pollutant impact downwind of a freeway during pre-sunrise hours in both winter and summer seasons. In contrast, previous studies have shown much sharper air pollutant gradients downwind of freeways, with levels above background concentrations extending only 300 m downwind of roadways during the day and up to 500 m at night. In this study, real-time air pollutant concentrations were measured along a 3600 m transect normal to an elevated freeway 1–2 h before sunrise using an electric vehicle mobile platform equipped with fast-response instruments. In winter pre-sunrise hours, the peak ultrafine particle (UFP) concentration (～95 000 cm^?3) occurred immediately downwind of the freeway. However, downwind UFP concentrations as high as ～40 000 cm^?3 extended at least 1200 m from the freeway, and did not reach background levels (～15 000 cm^?3) until a distance of about 2600 m. UFP concentrations were also elevated over background levels up to 600 m upwind of the freeway. Other pollutants, such as NO and particle-bound polycyclic aromatic hydrocarbons, exhibited similar long-distance downwind concentration gradients. In contrast, air pollutant concentrations measured on the same route after sunrise, in the morning and afternoon, exhibited the typical daytime downwind decrease to background levels within ～300 m as found in earlier studies. Although pre-sunrise traffic volumes on the freeway were much lower than daytime congestion peaks, downwind UFP concentrations were significantly higher during pre-sunrise hours than during the daytime. UFP and NO concentrations were also strongly correlated with traffic counts on the freeway. We associate these elevated pre-sunrise concentrations over a wide area with a nocturnal surface temperature inversion, low wind speeds, and high relative humidity. Observation of such wide air pollutant impact area downwind of a major roadway prior to sunrise has important exposure assessment implications since it demonstrates extensive roadway impacts on residential areas during pre-sunrise hours, when most people are at home.