Verification of diffusive and pumped samplers for volatile organic compounds using a controlled atmosphere test facility

There is a requirement to verify the performance of sorbent-based passive or active samplers and to extend their use, where possible, to monitor volatile organic compounds (VOCs) that are known to be photochemical ozone pre-cursors or are relevant to the activities of the petrochemical industry. We report measurements of the 14-day diffusive uptake rates for the VOCs: i-butane (2-methyl propane), n-butane, i-pentane (2-methyl butane), n-pentane, n-hexane, benzene, toluene, and m-xylene (at environmental level concentrations) for industry standard axial samplers (Perkin–Elmer-type samplers) containing the sorbents Carbopack-X, -Z, -B or Tenax-TA. We also present data on back-diffusion, blank levels, and storage for the above sorbents, and describe the simultaneous use of the sorbent Carbopack-X for pumped sampling of certain VOCs. The results were obtained by dosing samplers in a controlled atmosphere test facility (CATFAC) operating under well-defined conditions of concentration, nominal temperature of 20 °C, wind speed of 0.5 m s^?1, and relative humidities of 0% and 80%. Field measurements were also obtained to provide supplementary data to support the laboratory study. Results are compared to existing published data, where these are available.     

Stewardship among lifestyle oriented rural landowners

Changes in landownership associated with amenity migration are affecting the demographic, cadastral and ecological conditions of rural landscapes. These changes and concerns about their impacts on natural resource management, including ecological conservation, relate to both the structural consequences of landownership change, land subdivision and to the motivations, management ability and attitudes of lifestyle oriented rural landowners. Based on an Australian case study near Sydney, NSW, this paper examines the motivations and practices of such landowners, assesses potential consequences for vegetation and characterises the landowners according to three stewardship types.     

Volatile Organic Compounds from Coal Tar and Soil Vapor Samples at MGP Sites

This study characterized organic compounds found in New York State manufactured gas plant (MGP) coal tar vapors using controlled laboratory experiments from four separate MGP sites. In addition, a limited number of deep (0.3–1.2 m above coal tar) and shallow (1.2–2.4 m above coal tar) soil vapor samples were collected above the in situ coal tar source at three of these sites. A total of 29 compounds were consistently detected in the laboratory-generated coal tar vapors at 50°C, whereas 24 compounds were detected at 10°C. The compounds detected in the field sample results were inconsistent with the compounds found in the laboratory-generated samples. Concentrations of compounds in the shallow soil vapor sample were either non-detectable or substantially lower than those found in deeper samples, suggesting attenuation in the vadose zone. Laboratory-generated data at 50°C compared the (% non-aromatic)/(% aromatic) ratio and indicated that this ratio may provide good discrimination between coal tar vapor and common petroleum distillates.     

Reducing Interference Effects in the Chemiluminescent Measurement of Nitric Oxides from Combustion Systems

Experiments were carried out to determine the relative chemiluminescence quenching efficiencies as a function of third body concentration for each of the common combustion products, H₂O, CO₂, CO, H₂, O₂ and Ar. These results are compared with those of other investigators. The effect of reaction chamber pressure on analyzer response and the development of an analyzer design which incorporates an adjustable sample capillary inlet capable of maintaining a constant molar flow rate of sample gas to the reaction chamber are discussed. The effect of carbon monoxide interference on chemiluminescent NO_x measurement has been isolated and found to be significant. A means of correcting NO, measurements for these CO interference effects is described. Quantification of NO and NO₂ absorption in liquid water in NO_x sampling systems has been made. Recommendations for sample system designs to handle the presence of water in the sample gas are made.     

Comparison of Short-Term Variations (15-Minute Averages) in Outdoor and Indoor PM2.5 Concentrations

ABSTRACT

Measurements of 15-min average PM_2.5 concentrations were made with a real-time light-scattering instrument at both outdoor (central monitoring sites in three communities) and indoor (residential) locations over two seasons in the Minneapolis-St. Paul metropolitan area. These data are used to examine within-day variability of PM_2.5 concentrations indoors and outdoors, as well as matched indoor-to-outdoor (I/O) ratios. Concurrent gravimetric measurements of 24-hr average PM_2.5 concentrations were also obtained as a way to compare real-time measures with this more traditional metric. Results indicate that (1) within-day variability for both indoor and outdoor 15-min average PM_2.5 concentrations was substantial and comparable in magnitude to day-to-day variability for 24hr average concentrations; (2) some residences exhibited substantial variability in indoor aerosol characteristics from one day to the next; (3) peak values for indoor short-term (15-min) average PM_2.5 concentrations routinely exceeded 24-hr average outdoor values by factors of 3-4; and (4) relatively strong correlations existed between indoor and outdoor PM_2.5 concentrations for both 24-hr and 15-min averages.     

Field sampling of soil pore water to evaluate trace element mobility and associated environmental risk

Monitoring soil pollution is a key aspect in sustainable management of contaminated land but there is often debate over what should be monitored to assess ecological risk. Soil pore water, containing the most labile pollutant fraction in soils, can be easily collected in situ offering a routine way to monitor this risk. We present a compilation of data on concentration of trace elements (As, Cd, Cu, Pb, and Zn) in soil pore water collected in field conditions from a range of polluted and non-polluted soils in Spain and the UK during single and repeated monitoring, and propose a simple eco-toxicity test using this media. Sufficient pore water could be extracted for analysis both under semi-arid and temperate conditions, and eco-toxicity comparisons could be effectively made between polluted and non-polluted soils. We propose that in-situ pore water extraction could enhance the realism of risk assessment at some contaminated sites.     

Phytostabilization of semiarid soils residually contaminated with trace elements using by-products: sustainability and risks

We investigated the efficiency of various by-products (sugarbeet lime, biosolid compost and leonardite), based on single or repeated applications to field plots, on the establishment of a vegetation cover compatible with a stabilization strategy on a multi-element (As, Cd, Cu, Pb and Zn) contaminated soil 4-6 years after initial amendment applications. Results indicate that the need for re-treatment is amendment- and element-dependent; in some cases, a single application may reduce trace element concentrations in above-ground biomass and enhance the establishment of a healthy vegetation cover. Amendment performance as evaluated by % cover, biomass and number of colonizing taxa differs; however, changes in plant community composition are not necessarily amendment-specific. Although the translocation of trace elements to the plant biotic compartment is greater in re-vegetated areas, overall loss of trace elements due to soil erosion and plant uptake is usually smaller compared to that in bare soil.     

Novel mesoporous microspheres of Al and Ni doped LMO spinels and their performance as cathodes in secondary lithium ion batteries

A facile, scalable, and solution-based technique is used to fabricate Al and Ni-doped (LiAl_0.1Mn_1.9O₄ and LiAl_0.1Ni_0.1Mn_1.8O₄) microspheres of lithium manganese oxide (LMO) spinels for use as reversible cathode materials for lithium ion batteries (LIBs). The spheres of the two samples exhibit different porosities. Cells with these LMO-based cathodes are then cycled between 4.5 V and 2 V to study their stabilities while simultaneously being subjected to the undesirable Jahn-Teller distortion that occurs around the ~3 V regime. The LiAl_0.1Mn_1.9O₄ (LAMO) and the LiAl_0.1Ni_0.1Mn_1.8O₄ (LANMO) cells exhibit comparable open circuit voltages (OCV) of 2.94 V and 2.97 V, respectively. During cell cycling, the LAMO cell exhibits a maximum specific capacity of 122.51 mAh g^?1 with a capacity fade of 65.35% after 75 cycles. The LiAl_0.1Ni_0.1Mn_1.8O₄ (LAMO) sample fares better and exhibits a maximum of 140.49 mAh g^?1 and a capacity drop of 52.59%. Detailed structural studies indicate that Ni doping and the greater degree of porosity of the LANMO sample to be a stabilizing factor. This is further confirmed by cyclic voltammetry (CV) and AC impedance spectra analysis.     

Using air quality modeling to study source–receptor relationships between nitrogen oxides emissions and ozone exposures over the United States

Human exposure to ambient ozone (O₃) has been linked to a variety of adverse health effects. The ozone level at a location is contributed by local production, regional transport, and background ozone. This study combines detailed emission inventory, air quality modeling, and census data to investigate the source–receptor relationships between nitrogen oxides (NO_x) emissions and population exposure to ambient O₃ in 48 states over the continental United States. By removing NO_x emissions from each state one at a time, we calculate the change in O₃ exposures by examining the difference between the base and the sensitivity simulations. Based on the 49 simulations, we construct state-level and census region-level source–receptor matrices describing the relationships among these states/regions. We find that, for 43 receptor states, cumulative NO_x emissions from upwind states contribute more to O₃ exposures than the state's own emissions. In-state emissions are responsible for less than 15% of O₃ exposures in 90% of U.S. states. A state's NO_x emissions can influence 2 to 40 downwind states by at least a 0.1 ppbv change in population-averaged O₃ exposure. The results suggest that the U.S. generally needs a regional strategy to effectively reduce O₃ exposures. But the current regional emission control program in the U.S. is a cap-and-trade program that assumes the marginal damage of every ton of NO_x is equal. In this study, the average O₃ exposures caused by one ton of NO_x emissions ranges from ? 2.0 to 2.3 ppm-people-hours depending on the state. The actual damage caused by one ton of NO_x emissions varies considerably over space.