Feasibility of Soil Dust Source Apportionment by the Pyrolysis-Gas Chromatography/Mass Spectrometry Method

Abstract

This study tested the feasibility of using pyrolysis (Py)-gas chromatography (GC)/mass spectrometry (MS) to obtain organic chemical species data suitable for source apportionment modeling of soil-derived coarse particulate matter (PM₁₀) dust on ambient filters. A laboratory resuspension apparatus was used with known soils to generate simulated receptor filter samples loaded with ～0.4 mg of PM₁₀ dust, which is within the range of mass loading on ambient filters. Py-GC/MS at 740 °C generated five times more resolvable compounds than were obtained with thermal desorption GC/MS at 315 °C. The identified compounds were consistent with literature from Py experiments using larger samples of bulk soils. A subset of 91 organic species out of the 178 identified Py products was used as input to CMB8 software in a demonstration of source apportionment using laboratory-generated mixtures simulating ambient filter samples. The 178 quantified organic species obtained by Py of soil samples is an improvement compared with the 38 organic species obtained by thermal desorption of soils and the four functionally defined organic fractions reported by thermal/optical reflectance. Significant differences in the concentration of specific species were seen between samples from different sites, both geographically distant and close, using analysis of variance and cluster analysis. This feasibility study showed that Py-GC/MS can generate useful source profile data for receptor modeling and justifies continued method development.     

Biodiversity Conservation in a Changing Climate: A Review of Threats and Implications for Conservation Planning in Myanmar

High levels of species richness and endemism make Myanmar a regional priority for conservation. However, decades of economic and political sanctions have resulted in low conservation investment to effectively tackle threats to biodiversity. Recent sweeping political reforms have placed Myanmar on the fast track to economic development—the expectation is increased economic investments focused on the exploitation of the country’s rich, and relatively intact, natural resources. Within a context of weak regulatory capacity and inadequate environmental safeguards, rapid economic development is likely to have far-reaching negative implications for already threatened biodiversity and natural-resource-dependent human communities. Climate change will further exacerbate prevailing threats given Myanmar’s high exposure and vulnerability. The aim of this review is to examine the implications of increased economic growth and a changing climate within the larger context of biodiversity conservation in Myanmar. We summarize conservation challenges, assess direct climatological impacts on biodiversity and conclude with recommendations for long-term adaptation approaches for biodiversity conservation.     

Size-differentiated chemical characteristics of Asian paleo dust: records from aeolian deposition on Chinese Loess Plateau

The Chinese Loess Plateau (CLP) receives and potentially contributes to Asian dust storms that affect particulate matter (PM) concentrations, visibility, and climate. Loess on the CLP has experienced little weathering effect and is regarded as an ideal record to represent geochemical characteristics of Asian paleo dust. Samples were taken from 2-, 9-, and 15-m depths (representing deposition periods from approximately 12,000 to approximately 200,000 yr ago) in the Xi Feng loess profile on the CLP. The samples were resuspended and then sampled through total suspended particulates (TSP), PM10, PM2.5, and PM1 (PM with aerodynamic diameters < approximately 30, 10, 2.5, and 1 microm, respectively) inlets onto filters for mass, elemental, ionic, and carbon analyses using a Desert Research Institute resuspension chamber. The elements Si, Ca, Al, Fe, K, Mg, water-soluble Ca (Ca2+), organic carbon, and carbonate carbon are the major constituents (> 1%) in loess among the four PM fractions (i.e., TSP, PM10, PM2.5, and PM1). Much of Ca is water soluble and corresponds with measures of carbonate, indicating that most of the calcium is in the form of calcium carbonate rather than other calcium minerals. Most of the K is insoluble, indicating that loess can be separated from biomass burning contributions when K+ is measured. The loess has elemental abundances similar to those of the upper continental crust (UCC) for Mg, Fe, Ti, Mn, V, Cr, and Ni, but substantially different ratios for other elements such as Ca, Co, Cu, As, and Pb. These suggest that the use of UCC as a reference to represent pure or paleo Asian dust needs to be further evaluated. The aerosol samples from the source regions have similar ratios to loess for crustal elements, but substantially different ratios for species from anthropogenic sources (e.g., K, P, V, Cr, Cu, Zn, Ni, and Pb), indicating that the aerosol samples from the geological-source-dominated environment are not a "pure" soil product as compared with loess.     

Winter and summer characteristics of airborne particles inside emperor Qin's Terra-Cotta Museum, China: a study by scanning electron microscopy-energy dispersive X-ray spectrometry

Day- and nighttime total suspended particulate matter was collected inside and outside Emperor Qin's Terra-Cotta Museum in winter and summer 2008. The purpose was to characterize the winter and summer differences of indoor airborne particles in two display halls with different architectural and ventilation conditions, namely the Exhibition Hall and Pit No. 1. The morphology and elemental composition of two season samples were investigated using scanning electron microscopy and energy dispersive X-ray spectrometry. It is found that the particle size, particle mass concentration, and particle type were associated with the visitor numbers in the Exhibition Hall and with the natural ventilation in Pit No. 1 in both winter and summer. Evident winter and summer changes in the composition and physicochemical properties of the indoor suspended particulate matters were related to the source emission and the meteorological conditions. Particle mass concentrations in both halls were higher in winter than in summer. In winter, the size of the most abundant particles at the three sites were all between 0.5 and 1.0 microm, whereas in summer the peaks were all located at less than 0.5 microm. The fraction of sulfur-containing particles was 2-7 times higher in winter than in summer. In addition to the potential soiling hazard, the formation and deposition of sulfur-containing particles in winter may lead to the chemical and physical weathering of the surfaces of the terra-cotta statues.     

Regional source identification using Lagrangian stochastic particle dispersion and HYSPLIT backward-trajectory models

The main objective of this study was to investigate the capabilities of the receptor-oriented inverse mode Lagrangian Stochastic Particle Dispersion Model (LSPDM) with the 12-km resolution Mesoscale Model 5 (MM5) wind field input for the assessment of source identification from seven regions impacting two receptors located in the eastern United States. The LSPDM analysis was compared with a standard version of the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) single-particle backward-trajectory analysis using inputs from MM5 and the Eta Data Assimilation System (EDAS) with horizontal grid resolutions of 12 and 80 km, respectively. The analysis included four 7-day summertime events in 2002; residence times in the modeling domain were computed from the inverse LSPDM runs and HYPSLIT-simulated backward trajectories started from receptor-source heights of 100, 500, 1000, 1500, and 3000 m. Statistics were derived using normalized values of LSPDM- and HYSPLIT-predicted residence times versus Community Multiscale Air Quality model-predicted sulfate concentrations used as baseline information. From 40 cases considered, the LSPDM identified first- and second-ranked emission region influences in 37 cases, whereas HYSPLIT-MM5 (HYSPLIT-EDAS) identified the sources in 21 (16) cases. The LSPDM produced a higher overall correlation coefficient (0.89) compared with HYSPLIT (0.55-0.62). The improvement of using the LSPDM is also seen in the overall normalized root mean square error values of 0.17 for LSPDM compared with 0.30-0.32 for HYSPLIT. The HYSPLIT backward trajectories generally tend to underestimate near-receptor sources because of a lack of stochastic dispersion of the backward trajectories and to overestimate distant sources because of a lack of treatment of dispersion. Additionally, the HYSPLIT backward trajectories showed a lack of consistency in the results obtained from different single vertical levels for starting the backward trajectories. To alleviate problems due to selection of a backward-trajectory starting level within a large complex set of 3-dimensional winds, turbulence, and dispersion, results were averaged from all heights, which yielded uniform improvement against all individual cases.     

The IMPROVE_A temperature protocol for thermal/optical carbon analysis: maintaining consistency with a long-term database

Thermally derived carbon fractions including organic carbon (OC) and elemental carbon (EC) have been reported for the U.S. Interagency Monitoring of PROtected Visual Environments (IMPROVE) network since 1987 and have been found useful in source apportionment studies and to evaluate quartz-fiber filter adsorption of organic vapors. The IMPROVE_A temperature protocol defines temperature plateaus for thermally derived carbon fractions of 140 degrees C for OC1, 280 degrees C for OC2, 480 degrees C for OC3, and 580 degrees C for OC4 in a helium (He) carrier gas and 580 degrees C for EC1, 740 degrees C for EC2, and 840 degrees C for EC3 in a 98% He/2% oxygen (O2) carrier gas. These temperatures differ from those used previously because new hardware used for the IMPROVE thermal/optical reflectance (IMPROVE_TOR) protocol better represents the sample temperature than did the old hardware. A newly developed temperature calibration method demonstrates that these temperatures better represent sample temperatures in the older units used to quantify IMPROVE carbon fractions from 1987 through 2004. Only the thermal fractions are affected by changes in temperature. The OC and EC by TOR are insensitive to the change in temperature protocol, and therefore the long-term consistency of the IMPROVE database is conserved. A method to detect small quantities of O2 in the pure He carrier gas shows that O2 levels above 100 ppmv also affect the comparability of thermal carbon fractions but have little effect on the IMPROVE_TOR split between OC and EC.     

Dilution-based emissions sampling from stationary sources: Part 2--Gas-fired combustors compared with other fuel-fired systems

With the recent focus on fine particle matter (PM2.5), new, self-consistent data are needed to characterize emissions from combustion sources. Such data are necessary for health assessment and air quality modeling. To address this need, emissions data for gas-fired combustors are presented here, using dilution sampling as the reference. The dilution method allows for collection of emitted particles under conditions simulating cooling and dilution during entry from the stack into the air. The sampling and analysis of the collected particles in the presence of precursor gases, SO2 nitrogen oxide, volatile organic compound, and NH3 is discussed; the results include data from eight gas fired units, including a dual-fuel institutional boiler and a diesel engine powered electricity generator. These data are compared with results in the literature for heavy-duty diesel vehicles and stationary sources using coal or wood as fuels. The results show that the gas-fired combustors have very low PM2.5 mass emission rates in the range of approximately 10(-4) lb/million Btu (MMBTU) compared with the diesel backup generator with particle filter, with approximately 5 x 10(-3) lb/MMBTU. Even higher mass emission rates are found in coal-fired systems, with rates of approximately 0.07 lb/MMBTU for a bag-filter-controlled pilot unit burning eastern bituminous coal. The characterization of PM2.5 chemical composition from the gas-fired units indicates that much of the measured primary particle mass in PM2.5 samples is organic or elemental carbon and, to a much less extent, sulfate. Metal emissions are quite low compared with the diesel engines and the coal- or wood-fueled combustors. The metals found in the gas-fired combustor particles are low in concentration, similar in concentration to ambient particles. The interpretation of the particulate carbon emissions is complicated by the fact that an approximately equal amount of particulate carbon (mainly organic carbon) is found on the particle collector and a backup filter. It is likely that measurement artifacts, mostly adsorption of volatile organic compounds on quartz filters, are positively biasing "true" particulate carbon emission results.     

Testing the limits of social resilience in ant colonies

Social resilience is the ability of Leptothorax ant colonies to re-assemble after dissociation, as caused, for example, by an emigration to a new nest site. Through social resilience individual workers re-adopt their spatial positions relative to one another and resume their tasks without any time being wasted in worker respecialisation. Social resilience can explain how an efficient division of labour can be maintained throughout the trials and tribulations of colony ontogeny including the, often substantial, period after the queen dies when the ability to conserve worker social relationships may be essential for efficiency to be maintained. The mechanism underlying social resilience is, therefore, expected to be robust even in the absence of many of the colony’s components, such as the queen, the brood and even a large proportion of the workers. Such losses are likely, given the ecology of this genus. Using sociotomy experiments, we found that social resilience can occur in the absence of the queen. Furthermore, the spatial component of social resilience can occur even when the queen, the brood, as well as a large proportion of the workers, are all absent simultaneously and hence many of the tasks are missing. We conclude, therefore, that social resilience is indeed robust. This does not, however, preclude worker flexibility in response to changes in task supply and demand. We propose a possible sorting mechanism based on worker mobility levels which might explain the robustness underlying this phenomenon. Received: 25 October 1999 / Accepted: 1 April 2000     

Gaps and opportunities for the World Heritage Convention to contribute to global wilderness conservation

Wilderness areas are ecologically intact landscapes predominantly free of human uses, especially industrial‐scale activities that result in substantial biophysical disturbance. This definition does not exclude land and resource use by local communities who depend on such areas for subsistence and bio‐cultural connections. Wilderness areas are important for biodiversity conservation and sustain key ecological processes and ecosystem services that underpin planetary life‐support systems. Despite these widely recognized benefits and values of wilderness, they are insufficiently protected and are consequently being rapidly eroded. There are increasing calls for multilateral environmental agreements to make a greater and more systematic contribution to wilderness conservation before it is too late. We created a global map of remaining terrestrial wilderness following the established last‐of‐the‐wild method, which identifies the 10% of areas with the lowest human pressure within each of Earth's 62 biogeographic realms and identifies the 10 largest contiguous areas and all contiguous areas >10,000 km². We used our map to assess wilderness coverage by the World Heritage Convention and to identify gaps in coverage. We then identified large nationally designated protected areas with good wilderness coverage within these gaps. One‐quarter of natural and mixed (i.e., sites of both natural and cultural value) World Heritage Sites (WHS) contained wilderness (total of 545,307 km²), which is approximately 1.8% of the world's wilderness extent. Many WHS had excellent wilderness coverage, for example, the Okavango Delta in Botswana (11,914 km²) and the Central Suriname Nature Reserve (16,029 km²). However, 22 (35%) of the world's terrestrial biorealms had no wilderness representation within WHS. We identified 840 protected areas of >500 km² that were predominantly wilderness (>50% of their area) and represented 18 of the 22 missing biorealms. These areas offer a starting point for assessing the potential for the designation of new WHSs that could help increase wilderness representation on the World Heritage list. We urge the World Heritage Convention to ensure that the ecological integrity and outstanding universal value of existing WHS with wilderness values are preserved.