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.     

Rotary Kiln Incineration III. An Indepth Study—Kiln Exit/Afterburner/Stack Train and Kiln Exit Pattern Factor Measurements During Liquid CCl4 Processing

Temperature and stable species concentration data are presented from various locations within a full-scale rotary kiln incinerator firing natural gas/carbon tetrachloride/air. The data are being collected as part of a cooperative program involving university, industry and government participation. The overall goal of the program is to develop a more sophisticated understanding of and a predictive capability for rotary kiln and afterburner performance as influenced by basic design and operational parameters. Non-uniformities in stable species and temperature exist for this particular kiln, at the kiln exit, under certain operating conditions. Flow perturbations from within the kiln were found to persist into the afterburner, but not into the stack. High destruction and removal efficiencies (DRE’s) were achieved under the operating conditions of these tests through adequate secondary combustion processing.     

Rotary Kiln Incineration IV. An Indepth Study— Kiln Exit,Transition and Afterburner Sampling During Liquid CCl4 Processing

Detailed temperature and stable species concentration data are presented from the kiln exit, transition section and afterburner of a full-scale incinerator facility firing natural gas/carbon tetrachloride/air. The data are collected as part of a cooperative program involving university, industry and government participation. The overall goal of the program is to develop an understanding and predictive capability for rotary kiln and afterburner performance as influenced by basic design and operational parameters. The data demonstrate that nonuniformities in stable species and temperature exist, under certain operating conditions, at the kiln exit in the vertical direction only. Measurements from the transition section indicate that non-uniformities may exist within this region under certain operating conditions. Flow perturbations from within the kiln can persist into the afterburner, although the degree of nonuniformity is substantially reduced compared to either the kiln or transition sections. High destruction and removal efficiencies were achieved under all operating conditions of these tests through a combination of kiln and secondary combustion processing.     

Variability in the content and composition of alkaloid found in Canadian ergot. iii. triticale and barley∗

Abstract

The total alkaloid content and individual alkaloid composition were determined by colorimetry and high performance liquid chromatography, respectively, for Canadian triticale and barley ergot (Claviceps purpurea). The total alkaloid content was highly variable between individual sclerotia from the same or different sources and ranged from 0.042 to 0.752% for triticale and from 0.082 to 1.04% for barley; average values were 0.239% for Ottawa triticale, 0.289% for Prairie triticale, and 0.264% for barley. Ergocristine and its isomer ergocristinine were the major constituents in both grains. On average, Canadian ergot pooled from rye, wheat, triticale, and barley consists of ergocristine (31%), ergocristinine (13%), ergocristinine (13%), ergotamine (17%), ergotaminine (8%), ergocryptine (5%), ergocryptinine (3%), ergo‐metrine (5%), ergometrinine (2%), ergosine (4%), ergosinine (2%), ergocornine (4%), ergocorninine (2%), and unidentified alkaloids (3%) and an average total alkaloid content of 0.236%. With the exception of rye and barley ergot from the maritime regions, Canadian rye, wheat, triticale, and barley ergot is fairly uniform in individual alkaloid composition.     

Speciation of organotins in polyvinyl chloride pipe via X-ray absorption spectroscopy and in leachates using GC-PFPD after derivatisation

Three different polyvinyl chloride (PVC) pipe types were subjected to de-ionized water exposures over the course of at least 180 days. Water exposed to the pipe was analyzed for organotin speciation and concentration. Organotin concentrations were the highest during the first 1-5 days. The species and concentrations of organotins leached varied by pipe type. Data were normalized by surface area in order to compare laboratory results with results from a residential pipe system. For one pipe type, the lowest non-zero concentrations from the laboratory tests overestimated organotin concentrations in solution when compared with water samples from the same pipe type in a residence. For organotin exposure estimates, a range of 0.1 ng m(-2) to 10 ng m(-2) could be used for mature pipes (e.g. in use for 1 year). These estimates should be refined with more field study, however, due to the high variation in organotin species and concentrations leached as a function of pipe type, accuracy within an order of magnitude may be optimal as, in many instances, the type of pipe installed or buried may be unknown. X-ray absorption spectroscopy (XAS) was used to identify organic and inorganic tin species in reference materials and the PVC samples. Monobutyl tin was identified as the primary organotin species in the pipes. Results from the XAS analyses also indicate that the technique shows promise for distinguishing between inorganic tin and organotins. Furthermore, organotins may be distinguished between mono-, di-, and tri-ligand species using XAS.     

Skier and Snowboarder Motivations and Knowledge Related to Voluntary Environmental Programs at an Alpine Ski Area

Many alpine ski areas have recently adopted voluntary environmental programs (VEPs) such as using recycling, renewable energy, and biofuels to help reduce their environmental impacts. Studies have addressed the performance of these VEPs in mitigating environmental impacts of this industry, but little is known about visitor awareness and perceptions of these programs. This article addresses this knowledge gap by exploring skier and snowboarder knowledge of VEPs at a ski area and the influence of these programs on their motivations to visit this area currently and behavioral intentions to visit again in the future. Data were obtained from an onsite survey at the Mt. Bachelor ski area in Oregon, USA (n = 429, 89.7% response rate). Few skiers and snowboarders were knowledgeable of VEPs at this area and fewer than 20% were motivated to visit on their current trip because of these programs. Other attributes such as scenery, snow conditions, and access were more important for influencing visitation. Up to 38% of skiers and snowboarders, however, intend to visit this ski area more often if it adopts and promotes more VEPs. Managers can use these results to inform communication and marketing of their environmental programs and performance to visitors. Additional implications for management and future research are discussed.     

Assessing conservation opportunity on private land: socio-economic, behavioral, and spatial dimensions

This study presents a method for assessing conservation opportunity on private land based on landholders' socio-economic, behavioral, and farm characteristics. These characteristics include age, gender, education, level of off-farm income, farm size, proportion of remnant native vegetation on-farm, and ecological value of native vegetation on-farm. A sample of landholders who own greater than 2 ha of land in the South Australian Murray-Darling Basin region were sent a mail-based survey about their values and preferences for environmental management (N = 659, 52% response). Cross-tabulations and ANOVA statistical analysis techniques were used to compare the socio-economic attributes across three landholder classes: disengaged, moderately engaged, and highly engaged in native vegetation planting. Results indicate that highly engaged landholders were more likely to be female, formally educated, hobby farmers who managed small parcels of land and have high off-farm incomes, whereas disengaged landholders held significantly stronger farming connections (more farming experience, family have lived on the farm for more generations). Spatial analysis revealed area-specific differences in conservation opportunity and conservation priority. In some areas, properties of high ecological value were managed by highly engaged landholders, but nearby properties of high value were managed by moderately engaged or disengaged landholders. Environmental managers therefore cannot assume areas of high conservation priority will be areas of high conservation opportunity. At the regional scale, the potential for revegetation seems most promising within the moderately engaged landholder group considering the vast amount of land managed by this group in areas of high ecological value, particularly within the less represented Mallee and Coorong and Rangelands sub-regions. We suggest that incentive schemes which purchase conservation need to be targeted at disengaged landholders; mentoring schemes led by commercial farmers highly engaged in native vegetation planting should be directed at moderately engaged landholders, and; awards programs which acknowledge conservation successes should be targeted at highly engaged landholders.     

Ecosystems emerging. 5: Constraints

Ecosystem constraints are both ontic and epistemic. They limit activity, and as problems to be solved they drive organization, which is our hypothesis:

The driver of organization is constraint.

Solutions proliferate further constraints in an unending spiral of problem (constraint) generation and solution. As constraints proliferate, behavior narrows, and species diversify to compensate (paradox of constraint). Resource enrichment reduces constraints, releases behavior, and reduction of challenges decreases diversity (paradox of enrichment)—high diversity is expressed in low-resource environments and low diversity in high-resource environments. A three-part model of constraints is formulated for non-living systems, and also for goal-directed, problem-solving biota. Mode 1: dynamical means behavior is co-determined by internal states and external inputs. Mode 2: cybernetic employs negative feedback to keep dynamics within goal-oriented operating limits. Mode 3: model-making entails ability to represent (model) physical reality and respond to both phenomenal (modeled) and physical inputs; this property distinguishes living from nonliving systems. Principal sections of the paper elaborate dynamical constraints (three classes), boundary constraints (expressed in edge effects and trophic dynamics), physical constraints (space, time, temperature), chemical constraints (environment fitness, ecological stoichiometry, chemical evolution, limiting factors), coding constraints (environmental vs. genetic coding), network and pathway constraints (connectivity), and natural selection constraints (fitting to the biosphere). Consideration of how the world would look without constraints suggests how fundamental these are in ecosystem emergence, and how the next property in this series, differentiation, would be unmotivated without them. We conclude that constraints as a category are under-studied in ecology, poorly understood in ecological phenomenology, and (our hypothesis) comprise a ubiquitous organizing force in nature.     

The role of canopy structural complexity in wood net primary production of a maturing northern deciduous forest

The even-aged northern hardwood forests of the Upper Great Lakes Region are undergoing an ecological transition during which structural and biotic complexity is increasing. Early-successional aspen (Populus spp.) and birch (Betula papyrifera) are senescing at an accelerating rate and are being replaced by middle-successional species including northern red oak (Quercus rubra), red maple (Acer rubrum), and white pine (Pinus strobus). Canopy structural complexity may increase due to forest age, canopy disturbances, and changing species diversity. More structurally complex canopies may enhance carbon (C) sequestration in old forests. We hypothesize that these biotic and structural alterations will result in increased structural complexity of the maturing canopy with implications for forest C uptake. At the University of Michigan Biological Station (UMBS), we combined a decade of observations of net primary productivity (NPP), leaf area index (LAI), site index, canopy tree-species diversity, and stand age with canopy structure measurements made with portable canopy lidar (PCL) in 30 forested plots. We then evaluated the relative impact of stand characteristics on productivity through succession using data collected over a nine-year period. We found that effects of canopy structural complexity on wood NPP (NPPw) were similar in magnitude to the effects of total leaf area and site quality. Furthermore, our results suggest that the effect of stand age on NPPw is mediated primarily through its effect on canopy structural complexity. Stand-level diversity of canopy-tree species was not significantly related to either canopy structure or NPPw. We conclude that increasing canopy structural complexity provides a mechanism for the potential maintenance of productivity in aging forests.     

Uptake of some selected aquatic pollutants in semipermeable membrane devices (SPMDs) and the polar organic chemical integrative sampler (POCIS)

The uptake characteristics of semipermeable membrane devices (SPMDs) and polar organic chemical integrative samplers (POCISs) were examined for mono, di and tributyltin, triphenyltin, pyrene, benzo[a]pyrene, 4-tert-butylphenol, 4-n-nonylphenol, PCBs 77 and 153, PBDE 47, lindane, triclosan and DDT. Exposure in a flow through system continued for 28 days with samplers removed every 7 days in order to study the relevant uptake kinetics. Uptake remained linear for POCISs with sampling rates (Rs) of up to 0.2 L d(-1). For SPMDs uptake varied from linear to approaching equilibrium with Rs values of up to 14 L d(-1). 7 out of 9 results for SPMDs could be explained by an empirical model (nonylphenol and lindane were exceptions). None of the four organo-tin compounds studied were detected in POCISs and only tributyltin was accumulated significantly by SPMDs. The establishment of these sampling rates allows the calculation of time weighted water concentrations for several important contaminants. Using presented methods, sampling rates and exposure conditions, theoretical detection limits for selected compounds by SPMDs were between 11-68 pg L(-1), which is well below the environment quality standard proposed for those compounds that are included in the European Water Framework Directive.