Characterization of Major Chemical Components of Fine Particulate Matter in North Carolina

Abstract

This paper presents measurements of daily sampling of fine particulate matter (PM_2.5) and its major chemical components at three urban and one rural locations in North Carolina during 2002. At both urban and rural sites, the major insoluble component of PM_2.5 is organic matter, and the major soluble components are sulfate (SO₄ ^2?), ammonium (NH₄ ⁺), and nitrate (NO₃ ^?). NH₄ ⁺ is neutralized mainly by SO₄ ^2? rather than by NO₃ ^?, except in winter when SO₄ ^2? concentration is relatively low, whereas NO₃ ^? concentration is high. The equivalent ratio of NH₄ ⁺ to the sum of SO₄ ^2? and NO₃ ^? is <1, suggesting that SO₄ ^2?and NO₃ ^?are not completely neutralized by NH₄ ⁺. At both rural and urban sites, SO₄ ^2?concentration displays a maximum in summer and a minimum in winter, whereas NO₃ ^?displays an opposite seasonal trend. Mass ratio of NO₃ ^? to SO₄ ^2?is consistently <1 at all sites, suggesting that stationary source emissions may play an important role in PM_2.5 formation in those areas. Organic carbon and elemental carbon are well correlated at three urban sites although they are poorly correlated at the agriculture site. Other than the daily samples, hourly samples were measured at one urban site. PM_2.5 mass concen trations display a peak in early morning, and a second peak in late afternoon. Back trajectory analysis shows that air masses with lower PM_2.5 mass content mainly originate from the marine environment or from a continental environment but with a strong subsidence from the upper troposphere. Air masses with high PM_2.5 mass concentrations are largely from continental sources. Our study of fine particulate matter and its chemical composition in North Carolina provides crucial information that may be used to determine the efficacy of the new National Ambient Air Quality Standard (NAAQS) for PM fine. Moreover, the gas-to-particle conversion processes provide improved prediction of long-range transport of pollutants and air quality.     

Photocatalytic mineralization of glyphosate in a small-scale plug flow simulation reactor by UV/TiO2

The present work involves the photocatalytic mineralization of glyphosate on a plug flow reactor by UV/TiO₂. The effect of catalyst loading shows an optimal value (0.4 g L^?1) which is necessary to mineralize glyphosate. The kinetic rate of glyphosate mineralization decreases with the increasing initial concentration of glyphosate, and the data can be described using the first-order model. An alkaline environment is conducive to glyphosate mineralization. The mineralization efficiency increases with elevated flow rate to 114 mL min^?1, which is followed by a decrease with a further increase in flow rate due to the reduction of the residence time. The presence of external oxidants (K₂S₂O₈, H₂O₂ and KBrO₃) and photosencitizer (humic acid) can significantly enhance glyphosate mineralization. Photocatalysis oxidation ability of the three studied oxidants decrease in the order of: S₂O₈ ^2? > BrO₃ ^? > H₂O₂. Finally, the Langmuir–Hinshelwood (L-H) model was used to rationalize the mechanisms of reactions occurring on TiO₂ surfaces and L-H model constants were also determined.     

Effects of cyclodextrin on the stereoselectivity inhibition of acetylcholinesterase by isomalathion

ABSTRACT

In attempt to evaluate the effects of cyclodextrins (CDs) on enantioselectivity of chiral pesticides toxicity, this study investigated effects of three kinds of cyclodextrins including α-CD, β-CD and randomly methylated β-CD (RAMEB) on toxicity of four enantiomers of isomalathion including (1R, 3R)-isomalathion, (1S, 3S)-isomalathion, (1S, 3R)-isomalathion and (1R, 3S)-isomalathion. Generally, the addition of α-CD and RAMEB (1.5 g/L to 3.5 g/L concentration) could lead to reduction of isomalathion toxicity in most cases, while the presence of β-CD (0.3 g/L to 1.5 g/L concentration) enhanced the toxicity of isomalathion. It was speculated that higher electronic cloud density and lower water solubility of β-CD than α-CD and RAMEB might favor to combination between acetylcholinesterase (AChE) and isomalathion included by β-CD. With respect for α-CD and RAMEB, isomalathion included by them could be easily dissolved in water because of high water solubility of the two CDs. Therefore, α-CD and RAMEB can be used as remediation regent for the pollution of isomalathion, and β-CD can act as an additive in improving bioactivity of such pesticides. In addition, the presence of CDs can alter enantioselectivity of chiral pesticides. The differences on the extent of enantioselectivity variation of isomalathion induced by α-CD, RAMEB and β-CD might be ascribe to the different cavity, electron cloud density and solubility among the three CDs. In conclusion, the above results gave researchers a possibility to change enantioselectivity of chiral pesticides from undesirable outcomes to desirable ones.     

The Effect of Coal Combustion Flue Gas Components on Low-Level Chlorine Speciation Using EPA Method 26A

ABSTRACT

U.S. Environmental Protection Agency (EPA) Method 26A is the recommended procedure for capturing and speci-ating halogen (X₂) and hydrogen halide (HX) stack emissions from combustion sources. Previous evaluation studies of Method 26A have focused primarily on hydrogen chloride (HCl) speciation. Capture efficiency, bias, and the potential interference of Cl₂ at high levels (>20 ppm [u,g/m³]) and NH₄Cl in the flue gas stream have been investigated. It has been suggested that precise Cl₂ measurement and accuracy in quantifying HX or X₂ using Method 26A are difficult to achieve at Cl₂ concentrations <5 ppm; however, no performance data exist to support this. Coal contains low levels of Cl, in the range of 5-2000 ppmw, which results in the presence of HCl and Cl₂ in the products of combustion. HCl is the predominant Cl compound formed in the high-temperature combustion process, and it persists in the gas as the products of combustion cool. Concentrations of Cl₂ in coal combustion flue gas at stack temperatures typically do not exceed 5 ppm. For this research, bench-scale experiments using simulated combustion flue gas were designed to validate the ability of Method 26A to speci-ate low levels of Cl₂ accurately. This paper presents the results of the bench-scale tests. The effect of various flue gas components is discussed. The results indicate that SO₂ is the only component in coal combustion flue gas that has an appreciable effect on Cl₂ distribution in Method 26A impingers, and that Method 26A cannot accurately speciate HCl and Cl₂ in coal combustion flue gas without modification.     

Windblown Dust Contributes to High PM25 Concentrations

ABSTRACT

The revised National Ambient Air Quality Standards for PM include fine particulate standards based upon mass measurements of PM₂₅. It is possible in arid and semi-arid regions to observe significant coarse mode intrusion in the PM_2.5 measurement. In this work, continuous PM₁₀, PM_2.5, and PM_1.0 were measured during several windblown dust events in Spokane, WA. PM_{2 5} constituted ~30% of the PM₁₀ during the dust event days, compared with ~48% on the non-dusty days preceding the dust events. Both PM₁₀ and PM_2.5 were enhanced during the dust events. However, PM_1.0 was not enhanced during dust storms that originated within the state of Washington. During a dust storm that originated in Asia and impacted Spokane, PM_1.0 was also enhanced, although the Asian dust reached Washington during a period of stagnation and poor dispersion, so that local sources were also contributing to high particulate levels. The “intermodal” region of PM, defined as particles ranging in aerodynamic size from 1.0 to 2.5 um, was found to represent a significant fraction of PM₂₅ (~51%) during windblown dust events, compared with 28% during the non-dusty days before the dust events.     

A novel pretreatment approach for fast determination of organochlorine pesticides in biotic samples

Recent studies have focused on enantiomeric behaviors of chiral organochlorine pesticides (OCPs) in biotic matrix because they provide insights into the biotransformation processes of chiral OCPs. In the present paper, a double in-line column chromatographic method was developed to effectively remove the lipid impurity in different biotic samples for clean-up of OCPs. After an initial Soxhlet extraction of OCPs from the biotic samples by a mixture of acetone and dichloromethane (DCM), dimethyl sulfoxide (DMSO) was directly added to the extract, and low boiling point solvents (acetone and DCM) were then evaporated. OCPs remained in DMSO were eluted via column 1 filled with silicon gel, and subsequently passed through column 2 packed with 15% deactivated florisil. This novel method was characterized by significant time and solvent savings. The recovery rates of α -HCH (hexachlorocyclohexane), β -HCH, γ -HCH and δ -HCH were 78.5 ± 3.1%, 72.4 ± 7.7%, 72 ± 4.0% and 70.0 ± 8.7%, respectively, and 92.5 ± 3.8%, 79.7 ± 6.7% and 83.4 ± 6.5% for 1,1-dichloro-2-(2-chlorophenyl)-2-(4- chlorophenyl) ethylene (o,p′-DDE), 1,1-dichloro-2-(2-chlorophenyl)-2-(4-chloro phenyl)ethane (o,p′-DDD) and 1,1,1-trichloro-2-(2-chlorophenyl)-2-(4-chlorophenyl) ethane (o,p′-DDT), separately. In addition, the separation efficiencies of the target compounds by both achiral and chiral gas chromatographic columns were satisfactory using the established method. Therefore, the double in-line column chromatography was a useful alternative method for pretreatment of OCPs in different biotic samples.     

Uptake, translocation, and accumulation of manufactured iron oxide nanoparticles by pumpkin plants

Rapid development and application of nanomaterials and nanotechnology make assessment of their potential health and environmental impacts on humans, non-human biota, and ecosystems imperative. Here we show that pumpkin plants (Cucurbita maxima), grown in an aqueous medium containing magnetite (Fe3O4) nanoparticles, can absorb, translocate, and accumulate the particles in the plant tissues. These results suggest that plants, as an important component of the environmental and ecological systems, need to be included when evaluating the overall fate, transport and exposure pathways of nanoparticles in the environment.     

Comparative distribution of the scalp hair trace metal contents in the benign tumour patients and normal donors

The scalp hair samples of benign tumour patients (n = 77) and normal donors (n = 86) were analysed for selected trace metal contents using atomic absorption spectrophotometry. In the scalp hair of benign tumour patients, highest average levels were found for Ca (1,401 microg/g), followed by Na (476.9 microg/g), Mg (441.6 microg/g), Zn (438.3 microg/g), K (119.2 microg/g) and Fe (96.38 microg/g) while in comparison, the maximum mean levels in the scalp hair of normal donors were shown by Ca (556.5 microg/g), followed by Zn (154.2 microg/g), Mg (153.4 microg/g), Na (97.45 microg/g) and Fe (81.68 microg/g). Almost all metal levels revealed higher dispersion and asymmetry in the scalp hair of benign tumour patients compared with the normal donors. The average concentrations of Ca, Cd, Co, K, Mg, Mn, Na, Ni, Pb, Sb, Sr and Zn were significantly higher in the hair of benign tumour patients compared with the normal donors. Significant gender-based differences were also observed in the scalp hair metal contents of benign tumour patients. Strong positive correlations were found between Cd-Cr (0.547) and Cd-Co (0.507) in the hair of benign tumour patients whereas Ca-Mg, Mg-Sr, Co-Cd, Cr-Cd, Li-Cr, Li-Co, Li-Cd, Na-Cd, Na-Co and Na-Li exhibited strong relationships (r > 0.50) in the hair of normal donors. Cluster analysis (CA) and principal component analysis (PCA) were used for the source identification and apportionment of scalp hair trace metals in the two donor groups. The scalp hair of benign tumour patients and normal donors revealed six and five main clusters of trace metals, respectively. PCA extracted seven principal components of trace metals in the scalp hair of benign tumour patients while six principal components were observed in the case of normal donors. The study evidenced significantly different patterns of metal distribution in the hair of benign tumour patients in comparison with normal donors.     

Effects of environmental factors on the production and release of matrix-bound phosphine from lake sediments

Effects of pH, temperature, and oxygen on the production and release of phosphine in eutrophic lake sediments were investigated under laboratory tests. Results indicated that the elimination of matrix-bound phosphine was accelerated under initial pH 1 or 12. Phosphine levels could reach maximum under initial pH 10. The contents of phosphine increased with the addition of alkali under pH 4–12. The rates of phosphine production and release from lake sediments varied with temperature. 20°C was the most favorable temperature for the production of matrix-bound phosphine. Oxygen showed little effect on matrix-bound phosphine. Matrix-bound phosphine concentrations in lake sediments were concluded to be dependent on a balance of natural generation and depletion processes.     

安全控制论的理论基础和应用

用现代控制论原理,通过分析安全系统的结构及其特性,建立了安全系统状态方程和安全度的动态模型,探讨了安全系统的宏观预测及状态方程的参数辨识问题。运用本文所述方法,曾在几个工厂进行试点,取得良好效果。