Determination of Levoglucosan in Atmospheric Fine Particulate Matter

Abstract

A microanalytical method suitable for the quantitative determination of the sugar anhydride levoglucosan in low-volume samples of atmospheric fine particulate matter (PM) has been developed and validated. The method incorporates two sugar anhydrides as quality control standards. The recovery standard sedoheptulosan (2,7-anhydro-β-D-altro-heptulopyranose) in 20 μL solvent is added onto samples of the atmospheric fine PM and aged for 1 hr before ultrasonic extraction with ethylacetate/ triethylamine. The extract is reduced in volume, an internal standard is added (1,5-anhydro-D-mannitol), and a portion of the extract is derivatized with 10% by volume N-trimethylsilylimidazole. The derivatized extract is analyzed by gas chromatography/mass spectrometry (GC/MS). The recovery of levoglucosan using this procedure was 69 ± 6% from five filters amended with 2 μg levoglu-cosan, and the reproducibility of the assay is 9%. The limit of detection is ～0.1 μg/mL, which is equivalent to ～3.5 ng/m³ for a 10 L/min sampler or ～8.7 ng/m³ for a 4 L/min personal sampler (assuming 24-hr integrated samples). We demonstrated that levoglucosan concentrations in collocated samples (expressed as ng/m³) were identical irrespective of whether samples were collected by PM with aerodynamic diameter ≤2.5 μm or PM with aerodynamic diameter ≤10 μm impactors. It was also demonstrated that X-ray fluorescence analysis of samples of atmospheric PM, before levoglucosan determinations, did not alter the levels of levoglucosan.     

An Environmental Decision-Making Tool for Evaluating Ground-Level Ozone-Related Health Effects

Abstract

A computer model called the Ozone Risk Assessment Model (ORAM) was developed to evaluate the health effects caused by ground-level ozone (O₃) exposure. ORAM was coupled with the U.S. Environmental Protection Agency’s (EPA) Third-Generation Community Multiscale Air Quality model (Models-3/CMAQ), the state-of-the-art air quality model that predicts O₃ concentration and allows the examination of various scenarios in which emission rates of O₃ precursors (basically, oxides of nitrogen [NO_x] and volatile organic compounds) are varied. The principal analyses in ORAM are exposure model performance evaluation, health-effects calculations (expected number of respiratory hospital admissions), economic valuation, and sensitivity and uncertainty analysis through a Monte Carlo simulation. As a demonstration of the system, ORAM was applied to the eastern Tennessee region, and the entire O₃ season was simulated for a base case (typical emissions) and three different emission scenarios. The results indicated that a synergism occurs when reductions in NO_x emissions from mobile and point sources were applied simultaneously. A 12.9% reduction in asthma hospital admissions is expected when both mobile and point source NO_x emissions are reduced (50 and 70%, respectively) versus a 5.8% reduction caused by mobile source and a 3.5% reduction caused by point sources when these emission sources are reduced individually.     

Critique of “Precipitation in Light Extinction Reconstruction” by P.A. Ryan

Abstract

The goal of the Regional Haze Rule (RHR) is to return visibility in class I areas (CIAs) to natural levels, excluding weather-related events, by 2064. Whereas visibility, the seeing of scenic vistas, is a near instantaneous and sight-path-dependent phenomenon, reasonable progress toward the RHR goal is assessed by tracking the incremental changes in 5-yr average visibility. Visibility is assessed using a haze metric estimated from 24-hr average aerosol measurements that are made at one location representative of the CIA. It is assumed that, over the 5-yr average, the aerosol loadings and relative humidity along all of the site paths are the same and can be estimated from the 24-hr measurements. It is further assumed that any time a site path may be obscured by weather (e.g., clouds and precipitation), there are other site paths within the CIA that are not. Therefore, when calculating the haze metric, sampling days are not filtered for weather conditions. This assumption was tested by examining precipitation data from multiple monitors for four CIAs. It is shown that, in general, precipitation did not concurrently occur at all monitors for a CIA, and precipitation typically occurred 3-8 hr or less in a day. In a recent paper in this journal, Ryan asserts that the haze metric should include contributions from precipitation and conducted a quantitative assessment incorrectly based on the assumption that the Optec NGN-2 nephelometer measurements include the effects of precipitation. However, these instruments are programmed to shut down during rain events, and any data logged are in error. He further assumes that precipitation occurs as often on the haziest days as the clearest days and that precipitation light scattering (bprecip) is independent of geographic location and applied an average bprecip derived for Great Smoky Mountains to diverse locations including the Grand Canyon. Both of these assumptions are shown to be in error.     

Lanthanum cobaltite perovskite supported onto mesoporous zirconium dioxide: nature of active sites of VOC oxidation

Novel catalytic nano-sized materials based on LaCoO(x) perovskite nanoparticles incapsulated in the mesoporous matrix of zirconia were prepared, characterized by physicochemical methods and tested in complete methanol oxidation. LaCoO(x) nanoparticles were prepared inside the mesopores of ZrO(2) by decomposition of bimetallic La-Co glycine precursor complexes. The catalysts have been studied by diffuse-reflectance FTIR-spectroscopy using such probe molecules as CO, CD(3)CN and CDCl(3) to test low-coordinated metal ions. At low temperatures of decomposition of complexes (up to 400°C), low-coordinated Co(3+) ions predominate in the LaCoO(x) nanoparticles, whereas basically Co(2+) ions are found upon increasing the decomposition temperature to 600°C. The novel nano-sized perovskite catalysts exhibit a very high catalytic activity in the abatement of volatile organic compounds present in air, like methanol and light hydrocarbons.     

Levels of household particulate matter and environmental tobacco smoke exposure in the first year of life for a cohort at risk for asthma in urban Syracuse, NY

The Syracuse, NY, AUDIT (Assessment of Urban Dwellings for Indoor Toxics) study was designed to quantify asthma agent levels in the inner-city homes of a birth cohort whose mothers had a diagnosis of asthma. Risk of exposure to particulate matter (PM), particle number and tobacco smoke was assessed in 103 infants' homes. Repeat measurements were made in 44% of the homes. Infants also were examined on a quarterly basis during the first year of life to monitor their respiratory health and urine cotinine levels. Overall geometric mean (GM) values for PM(2.5) of 21.2 μg/m(3) and for PM(10) of 31.8 μg/m(3) were recorded in homes at visit 1. GM values for PM(2.5) and PM(10) in smoking homes were higher at 26.3 and 37.7 μg/m(3), while values in non-smoking homes were 12.7 and 21.2 μg/m(3) respectively. Fifty-four percent of mothers (55/103) smoked at some point in pregnancy (39% smoked throughout pregnancy). Environmental tobacco smoke (ETS) exposure occurred in 68% of homes during the infants' first year. Significant to this study was the size- and time-resolved monitoring of PM at 140 home visits and the classification of PM count data. PM number counts ranged from continuously low levels (little indoor activity) to continuously high counts (constant indoor activity), and recorded apparent instances of prolonged repeated cigarette smoking. Wheezing in the first year of life was recorded for 38% of the infants (39/103). Adjusted logistic regression modeling demonstrated that elevated levels of indoor PM(2.5) (≥ 15 μg/m(3)) were a significant risk factor for infant wheezing after controlling for infant gender, mothers' age and education level, season of home visit and presence of carpeting (OR 4.21; 95% CI 1.36-13.03; p=0.013). An elevated level of the nicotine metabolite cotinine in infant urine also was associated with infant wheezing after adjusting for infant gender, mothers' age and education level (OR 5.10; 95% CI 0.96-27.24; p=0.057). ETS exposure was pervasive in the AUDIT cohort and a risk for developing infants in this urban population.     

A temporal trend study (1972-2008) of perfluorooctanesulfonate, perfluorohexanesulfonate, and perfluorooctanoate in pooled human milk samples from Stockholm, Sweden

The widespread presence of perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and perfluorohexanesulfonate (PFHxS) in human general populations and their slow elimination profiles have led to renewed interest in understanding the potential human neonatal exposures of perfluoroalkyls (PFAs) from consumption of human milk. The objective of this study was to evaluate the concentrations of PFOS, PFHxS, and PFOA in pooled human milk samples obtained in Sweden between 1972 and 2008 (a period representing the most significant period of PFA production) and to see whether the time trend of these analytes parallels that indicated in human serum. Chemical analysis of PFOS, PFHxS, and PFOA was performed on pooled Swedish human milk samples from 1972 to 2008 after methodological refinements. The 20 samples which formed the 2007 pool were also analyzed individually to evaluate sample variations. Analyses were performed by HPLC-MS/MS. Due to the complexities of the human milk matrix and the requirement to accurately quantitate low pg/mL concentrations, meticulous attention must be paid to background contamination if accurate results are to be obtained. PFOS was the predominant analyte present in the pools and all three analytes showed statistically significant increasing trends from 1972 to 2000, with concentrations reaching a plateau in the 1990s. PFOA and PFOS showed statistically significant decreasing trends during 2001-2008. At the end of the study, in 2008, the measured concentrations of PFOS, PFHxS, and PFOA in pooled human milk were 75 pg/mL, 14 pg/mL, and 74 pg/mL, respectively. The temporal concentration trends of PFOS, PFHxS, and PFOA observed in human milk are parallel to those reported in the general population serum concentrations.     

A literature review on the safety assessment of genetically modified plants

In recent years, there has been a notable concern on the safety of genetically modified (GM) foods/plants, an important and complex area of research, which demands rigorous standards. Diverse groups including consumers and environmental Non Governmental Organizations (NGO) have suggested that all GM foods/plants should be subjected to long-term animal feeding studies before approval for human consumption. In 2000 and 2006, we reviewed the information published in international scientific journals, noting that the number of references concerning human and animal toxicological/health risks studies on GM foods/plants was very limited. The main goal of the present review was to assess the current state-of-the-art regarding the potential adverse effects/safety assessment of GM plants for human consumption. The number of citations found in databases (PubMed and Scopus) has dramatically increased since 2006. However, new information on products such as potatoes, cucumber, peas or tomatoes, among others was not available. Corn/maize, rice, and soybeans were included in the present review. An equilibrium in the number research groups suggesting, on the basis of their studies, that a number of varieties of GM products (mainly maize and soybeans) are as safe and nutritious as the respective conventional non-GM plant, and those raising still serious concerns, was currently observed. Nevertheless, it should be noted that most of these studies have been conducted by biotechnology companies responsible of commercializing these GM plants. These findings suggest a notable advance in comparison with the lack of studies published in recent years in scientific journals by those companies. All this recent information is herein critically reviewed.     

Cs, Pu concentrations and the Pu/Pu atom ratio in a sediment core from the sub-aqueous delta of Yangtze River estuary

A sediment core collected from the sub-aqueous delta of the Yangtze River estuary was subjected to analyses of ¹³⁷Cs and plutonium (Pu) isotopes. The ¹³⁷Cs was measured using γ-spectrometry at the laboratories at the Nanjing University and Pu isotopes were determined with Accelerator Mass Spectrometry (AMS), measurements made at the Australian National University. The results show considerable structure in the depth concentration profiles of the ¹³⁷Cs and ^239+240Pu. The shape of the vertical ¹³⁷Cs distribution in the sediment core was similar to that of the Pu. The maximum ¹³⁷Cs and ^239+240Pu concentrations were 16.21 ± 0.95 mBq/g and 0.716 ± 0.030 mBq/g, respectively, and appear at same depth. The average ²⁴⁰Pu/²³⁹Pu atom ratio was 0.238 ± 0.007 in the sediment core, slightly higher than the average global fallout value. The changes in the ²⁴⁰Pu/²³⁹Pu atom ratios in the sediment core indicate the presence of at least two different Pu sources, i.e., global fallout and another source, most likely close-in fallout from the Pacific Proving Grounds (PPG) in the Marshall Islands, and suggest the possibility that Pu isotopes are useful as a geochronological tool for coastal sediment studies. The ¹³⁷Cs and ^239+240Pu inventories were estimated to be 7100 ± 1200 Bq/m² and 407 ± 27 Bq/m², respectively. Approximately 40% of the ^239+240Pu inventory originated from the PPG close-in fallout and about 50% has derived from land-origin global fallout transported to the estuary by the river. This study confirms that AMS is a useful tool to measure ²⁴⁰Pu/²³⁹Pu atom ratio and can provide valuable information on sedimentary processes in the coastal environment.     

A regulatory perspective on the radiological impact of NORM industries: the case of the Spanish phosphate industry

Radioactive and chemical risks coexist in NORM industries although they are usually addressed separately by regulations. The European Union (EU) has developed extensive legislation concerning both matters, which has been diversely reflected in national policies. We consider the case of the Spanish phosphate industry and analyse to which extent regulatory mandates have reduced the historical and ongoing radiological impact on the environment of phosphate facilities. Although no specific radiological constraints on effluent monitoring and release or on waste disposal have yet been imposed on NORM industries in Spain, other environmental regulations have achieved a substantial reduction on the phosphate industry impact. Nevertheless, a more efficient control could be established by eliminating the current conceptual and practical separation of chemical and radioactive risks in NORM industries. We highlight research needs to accomplish so and propose shorter-term measures that require active cooperation among the regulatory bodies involved.     

Phospholipid fatty acid biomarkers in a freshwater periphyton community exposed to uranium: discovery by non-linear statistical learning

Phospholipid fatty acids (PLFA) have been widely used to characterize environmental microbial communities, generating community profiles that can distinguish phylogenetic or functional groups within the community. The poor specificity of organism groups with fatty acid biomarkers in the classic PLFA-microorganism associations is a confounding factor in many of the statistical classification/clustering approaches traditionally used to interpret PLFA profiles. In this paper we demonstrate that non-linear statistical learning methods, such as a support vector machine (SVM), can more accurately find patterns related to uranyl nitrate exposure in a freshwater periphyton community than linear methods, such as partial least squares discriminant analysis. In addition, probabilistic models of exposure can be derived from the identified lipid biomarkers to demonstrate the potential model-based approach that could be used in remediation. The SVM probability model separates dose groups at accuracies of ∼87.0%, ∼71.4%, ∼87.5%, and 100% for the four groups; Control (non-amended system), low dose (amended at 10 μg U L⁻¹), medium dose (amended at 100 μg U L⁻¹), and high dose (500 μg U L⁻¹). The SVM model achieved an overall cross-validated classification accuracy of ∼87% in contrast to ∼59% for the best linear classifier.