The Formation of Mg3Ca(S04)4 during the Sulfation Reaction of Dolomite

Abstract

Inspection and maintenance programs for motor vehicles in the United States increasingly use loaded mode mass emissions testing (IM240). A method was developed to predict mass emission rates and mass emission changes, particularly from repair benefits, using a low-cost, portable four-gas non-dispersive infrared (NDIR) vehicle exhaust gas analyzer. A single vehicle was tested several times with the analyzer while on the dynamometer and undergoing successive repairs. Excellent correlations for CO and HC were observed. Five vehicles were measured using an on-road driving loop before and after emissions-related repairs, while another three vehicles were tested with no repairs performed. The on-road concentration data used to guide the repair process were converted to grams per gallon; when divided by estimated miles per gallon, this gave grams per mile emissions for comparison to IM240. Correlation coefficients (r²) of 0.87 for CO and 0.76 for HC were achieved for the 13 tests. The linear correlations between IM240 and emissions measured by this method would allow repair facilities to perform a relatively inexpensive test for diagnostic purposes and to estimate repair effectiveness without the need for a dynamometer.     

Measurement of Volatile Organics at Part per Billion Concentrations Using a Cold Trap Inlet and High Speed Gas Chromatography

Direct inlet gas chromatography (GC) is becoming one of the most frequently used techniques for measurement of volatile organics in air. Although GC is an effective tool, its usefulness as a field method can be limited by retention times of several minutes or more, and by the limits of detection. In order to address these issues, a high speed GC system featuring a capillary cold trap inlet and variable speed electrometeramplifier was developed and tested.

The gas cooled inlet was used to collect and focus organic vapors from injection volumes of up to 1 ml. Resistance heating of the metal cold trap produced a narrow injection band that allowed simple separations to be completed in 5 to 20 seconds. Use of a variable speed electrometer-amplifier allowed the response time and noise suppression characteristics to be adjusted to the needs of the specific analysis.

Simple mixtures of organics including aromatics, alkanes and chlorinated hydrocarbons were separated in 20 seconds or less. The limits of detection for 13 test compounds ranged from less than 1 part per billion by volume (ppbv) to about 50 ppbv. Data presented here indicate that high speed GC using a cold trap inlet may be a feasible approach for near real-time measurement of volatile organics in ambient air.     

Some Effects of Atmospheric Fluoride on Plant Metabolism

Leaves of Tendergreen bean plants exposed to atmospheric fluoride concentrations in the range 1.7 to 7.6 μg/m³ showed increased levels of enolase and catalase activity and decreased levels of pyruvate and α-ketoglutarate. Phosphoenolpyruvate carboxylase activity and oxalacetate were not affected. The leaves of Milo maize plants exposed to 5.0 μg F/m³ showed increased levels of enolase and pyruvate kinase activity and a decreased level of pyruvate. Oxalacetate and α-ketoglutarate levels were not affected. Catalase activity was increased, then decreased by IIF fumigation. The changes induced by HF were greatest six to 10 days after the start of fumigation and disappeared or decreased in magnitude during the post-fumigation period.     

Uptake of metals by food plants grown on soils 10 years after biosolids application

Potentially hazardous trace elements such as Cd, Cu, Cr, Ni and Zn are expected to accumulate in biosolids–amended soil and remain in the soil for a long period of time. In this research, uptake of metals by food plants including cabbage, carrot, lettuce and tomato grown on soils 10 years after biosolids application was studied. All the five metals were significantly accumulated in the biosolids-amended soils. The accumulation of metal in soil did not result in significant increase in concentrations of Cu, Cr and Ni in the edible plant tissues. However, the Cd and Zn concentrations of the edible tissues of plants harvested from the biosolids receiving soils were significantly enhanced in comparison with those of the unaffected soils. The plant uptake under Greenfield sandy loam soil was generally higher than those under the Domino clayey loam soil. The metal concentration of edible plant tissue exhibited increasing trends with respect to the concentrations of the ambulated metals. The extents of the increases were plant species dependent. The indigenous soil metals were absorbed by the plants in much higher rates than those of the biosolids–receiving soils. It appeared that the plant uptake of the indigenous soil-borne metal and the added biosolids-borne metals are independent of one another and mathematically are additive.     

δ 13C and δ 15N variations in organic matter pools, Mytilus spp. and Macoma balthica along the European Atlantic coast

Stable carbon (δ ¹³C) and nitrogen (δ ¹⁵N) isotope (SI) values of sedimentary organic matter (SOM), seston and two dominant bivalves, Mytilus spp. and Macoma balthica, were studied at 18 stations along the European coast in spring and autumn 2004. Three main regions, the Baltic Sea (BS), the North Sea and English Channel (NS), and the Bay of Biscay (BB), were tested for possible geographic (latitudinal) differences in the SI values. In spring, only BS showed lower δ ¹³C values of seston and Mytilus spp., and higher δ ¹⁵N values of SOM, than NS and BB. No significant differences between the 3 regions were found in autumn. Irrespective of season and regions, Mytilus spp. was more ¹³C-depleted than M. balthica. δ ¹³C values of M. balthica, but not those of Mytilus spp., were significantly correlated with SOM. These results are consistent with differences in feeding behavior of Mytilus spp. and M. balthica, as the two species are known as obligatory-suspension and facultative-deposit feeders, respectively. In contrast, no differences in the δ ¹⁵N values of Mytilus spp. and M. balthica were found at individual stations, indicating the same trophic level of the two bivalves within the food webs. At some stations, irrespective of geographic location, both bivalves showed δ ¹⁵N values up to 18–20 ‰. These were two trophic levels higher than those found at the other stations, indicating local and/or episodic eutrophic conditions, probably due to waste water discharge, and the effectiveness of both Mytilus spp. and M. balthica as bio-indicators of anthropogenic eutrophication. Overall, our results suggest that pathways of energy flow from OM pools to dominant bivalves is more related to local environmental conditions than to geographic regions across the European coastline. This has implications for food web studies along the Atlantic coast because most of the values are consistent over a large area and show no significant differences. Therefore, the present study can be used twofold for the determination of trophic baselines and for the correction of the trophic position of consumers higher up in the food web in the case of differences in waste water discharge.     

Summary of the Federal Emissions Trading Policy Statement

This paper is directed to those concerned with using emissions trading to achieve greater flexibility and reduce the costs of complying with air pollution emission standards.     

Evaluating the capabilities of Aerosol-to-Liquid Particle Extraction System (ALPXS)/ICP-MS for monitoring trace metals in indoor air

This study investigates the application of the Aerosol-to-Liquid Particle Extraction System (ALPXS), which uses wet electrostatic precipitation to collect airborne particles, for multi-element indoor stationary monitoring. Optimum conditions are determined for capturing airborne particles for metal determination by inductively coupled plasma–mass spectrometry (ICP-MS), for measuring field blanks, and for calculating limits of detection (LOD) and quantification (LOQ). Due to the relatively high flow rate (300 L min^?1), a sampling duration of 1 hr to 2 hr was adequate to capture airborne particle-bound metals under the investigated experimental conditions. The performance of the ALPXS during a building renovation demonstrated signal-to-noise ratios appropriate for sampling airborne particles in environments with elevated metal concentrations, such as workplace settings. The ALPXS shows promise as a research tool for providing useful information on short-term variations (transient signals) and for trapping particles into aqueous solutions where needed for subsequent characterization. As the ALPXS does not provide size-specific samples, and its efficiency at different flow rates has yet to be quantified, the ALPXS would not replace standard filter-based protocols accepted for regulatory applications (e.g., exposure measurements), but rather would provide additional information if used in conjunction with filter based methods.

ImplicationsThis study investigates the capability of the Aerosol-to-Liquid Particle Extraction System (ALPXS) for stationary sampling of airborne metals in indoor workplace environments, with subsequent analysis by ICP-MS. The high flow rate (300 L/min) permits a short sampling duration (< 2 hr). Results indicated that the ALPXS was capable of monitoring short-term changes in metal emissions during a renovation activity. This portable instrument may prove to be advantageous in occupational settings as a qualitative indicator of elevated concentrations of airborne metals at short time scales.     

Dealing with disjunct concentration measurements in eddy covariance applications: A comparison of available approaches

Using proton transfer reaction mass spectrometry equipped with a quadrupol mass analyser to quantify the biosphere-atmosphere exchange of volatile organic compounds (VOC), concentrations of different VOC are measured sequentially. Depending on how many VOC species are targeted and their respective integration times, each VOC is measured at repeat rates on the order of a few seconds. This represents an order of magnitude longer sample interval compared to the standard eddy covariance (EC) method (5–20 Hz sampling rates). Here we simulate the effect of disjunct sampling on EC flux estimates by decreasing the time resolution of CO₂ and H₂O concentrations measured at 20 Hz above a temperate mountain grassland in the Austrian Alps. Fluxes for one month are calculated with the standard EC method and compared to fluxes calculated based on the disjunct data (1, 3 and 5 s sampling rates) using the following approaches: i) imputation of missing concentrations based on the nearest neighbouring samples (iDEC_nn), ii) imputation by linear interpolation (iDEC_li), and iii) virtual disjunct EC (vDEC), i.e. flux calculation based solely on the disjunct concentrations. It is shown that the two imputation methods result in additional low-pass filtering, longer lag times (as determined with the maximum cross-correlation method) and a flux loss of 3–30% as compared to the standard EC method. A novel procedure, based on a transfer function approach, which specifically corrects for the effect of data treatment, was developed, resulting in improved correspondence (to within 2%). The vDEC method yields fluxes which approximate the true (20 Hz) fluxes to within 3–7% and it is this approach we recommend because it involves no additional empirical corrections. The only drawback of the vDEC method is the noisy nature of the cross-correlations, which poses problems with lag determination – practical approaches to overcome this limitation are discussed.     

Degradation of paracetamol by advance oxidation processes using modified reticulated vitreous carbon electrodes with TiO2 and CuO/TiO2/Al2O3

The degradation of paracetamol in aqueous solutions in the presence of hydrogen peroxide was carried out by photochemistry, electrolysis and photoelectrolysis using modified 100 pores per inch reticulated vitreous carbon electrodes. The electrodes were coated with catalysts such as TiO₂ and CuO/TiO₂/Al₂O₃ by electrophoresis followed by heat treatment. The results of the electrolysis with bare reticulated vitreous carbon electrodes show that 90% paracetamol degradation occurs in 4 h at 1.3 V vs. SCE, forming intermediates such as benzoquinone and carboxylic acids followed by their complete mineralisation. When the electrolysis was carried out with the modified electrodes such as TiO₂/RVC, 90% degradation was achieved in 2 h while with CuO/TiO₂/Al₂O₃/RVC, 98% degradation took only 1 h. The degradation was also carried out in the presence of UV reaching 95% degradation with TiO₂/RVC/UV and 99% with CuO/TiO₂/Al₂O₃/RVC/UV in 1 h. The reactions were followed by spectroscopy UV-Vis, HPLC and total organic carbon analysis. These studies show that the degradation of paracetamol follows a pseudo-first order reaction kinetics.