Theoretical versus observed gas-particle partitioning of carbonyl emissions from motor vehicles

A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120-580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.     

Evaluating Conservation Program Success with Landsat and SWAT

In the United States, many state and federally funded conservation programs are required to quantify the water quality benefits resulting from their efforts. The objective of this research was to evaluate the impact of conservation practices subsidized by the Oklahoma Conservation Commission on phosphorus and sediment loads to Lake Wister. Conservation practices designed to increase vegetative cover in grazed pastures were evaluated using Landsat imagery and the Soil and Water Assessment Tool (SWAT). Several vegetative indices were derived from Landsat imagery captured before and after the implementation of conservation practices. Collectively, these indicators provided an estimate of the change in vegetative soil cover attributable to conservation practices in treated fields. Field characteristics, management, and changes in vegetative cover were used in the SWAT model to simulate sediment and phosphorus losses before and after practice implementation. Overall, these conservation practices yielded a 1.9% improvement in vegetative cover and a predicted sediment load reduction of 3.5%. Changes in phosphorus load ranged from a 1.0% improvement to a 3.5% increase, depending upon initial vegetative conditions. The use of fertilizers containing phosphorus as a conservation practice in low-productivity pastures was predicted by SWAT to increase net phosphorus losses despite any improvement in vegetative cover. This combination of vegetative cover analysis and hydrologic simulation was a useful tool for evaluating the effects of conservation practices at the basin scale and may provide guidance for the selection of conservation measures subsidized in future conservation programs.     

Reply to Discussion1 - by George Ice,George Brown,John Gravelle,C. Rhett Jackson,Jeff Light,Timothy Link,Douglas Martin,Dale McGreer,and Arne Skaugset2 “Stream Temperature Relationships to Forest Harvest in Western Washington”3

Pollock, Michael M. and Timothy J. Beechie, 2010. Reply to Discussion –“Stream Temperature Relationships to Forest Harvest in Western Washington” by George Ice, George Brown, John Gravelle, C. Rhett Jackson, Jeff Light, Timothy Link, Douglas Martin, Dale McGreer, and Arne Skaugset. Journal of the American Water Resources Association (JAWRA) 46(4): 843-847. DOI: 10.1111/j.1752-1688.2010.00456.x     

Comparison of selected nutrients and bacteria from common contiguous soils inside and outside swine lagoon effluent spray fields after long-term use

Swine (Sus scofa domestica) lagoon effluent is a valuable resource. In the U.S. Mid-South it is applied from April to September to fertilize grass hay in spray-irrigated fields. Lagoon levels of nutrients and bacteria, and soil levels of nutrients have been documented, but little was known of effluent bacterial levels in soil. The present study examined levels of selected effluent bacteria and nutrients in soils inside and outside spray fields after >15 yr of effluent irrigation. Samples were collected February to March 2009 from contiguous soils spanning adjacent irrigated and nonirrigated areas. Separate soil cores for bacterial and nutrient tests were collected in pairs <10 cm apart. Five cores each were collected at 15-m intervals and combined, respectively, to comprise inside and outside samples from each of 20 soils (four each from five farms/spray fields). Analyses of data combined across all soils showed higher pH and Mehlich-3-extracrable (M3-) P, Mg, K, Na, Cu, and Zn inside than outside spray fields, while total N, total C, M3-Ca, and M3-Mn did not differ. Bacterial levels were higher inside than outside spray fields for heterotrophic plate counts, thermotolerant coliforms, Staphylococcus spp., and Clostridium perfringens, but levels of Escherichia coli and Enterococcus spp. were not different. Cultural presence/absence tests for three pathogens (Listeria spp., Campylobacter spp., and Salmonella spp.) detected only Listeria spp., which did not differ inside (23% positive samples) and outside (28% positive). Molecular tests detected all three pathogens at low levels that were not different inside and outside. We found no evidence of cumulative buildup of Campylobacter spp., Listeria spp., or Salmonela s. in spray field soils.     

An ecological perspective on nanomaterial impacts in the environment

Growing concerns over the potential for unintended, adverse consequences of engineered nanoparticles (ENPs) in the environment have generated new research initiatives focused on understanding the ecological effects of ENPs. Almost nothing is currently known about the fate and transport of ENPs in environmental waters, soils, and sediments or about the biological impacts of ENPs in natural environments, and the bulk of modern nanotoxicogical research is focused on highly controlled laboratory studies with single species in simple media. In this paper, we provide an ecological perspective on the current state of knowledge regarding the likely environmental impacts of nanomaterials and propose a strategy for making rapid progress in new research in ecological nanoscience.     

Comparative statistical study of hourly precipitation determined by radar-based Stage IV and ground-based methods in the North Central United States

Detailed hourly precipitation data are required for long-range modeling of dispersion and wet deposition of particulate matter and water-soluble pollutants using the CALPUFF model. In sparsely populated areas such as the north central United States, ground-based precipitation measurement stations may be too widely spaced to offer a complete and accurate spatial representation of hourly precipitation within a modeling domain. The availability of remotely sensed precipitation data by satellite and the National Weather Service array of next-generation radars (NEXRAD) deployed nationally provide an opportunity to improve on the paucity of data for these areas. Before adopting a new method of precipitation estimation in a modeling protocol, it should be compared with the ground-based precipitation measurements, which are currently relied upon for modeling purposes. This paper presents a statistical comparison between hourly precipitation measurements for the years 2006 through 2008 at 25 ground-based stations in the north central United States and radar-based precipitation measurements available from the National Center for Environmental Predictions (NCEP) as Stage IV data at the nearest grid cell to each selected precipitation station. It was found that the statistical agreement between the two methods depends strongly on whether the ground-based hourly precipitation is measured to within 0.1 in/hr or to within 0.01 in/hr. The results of the statistical comparison indicate that it would be more accurate to use gridded Stage IV precipitation data in a gridded dispersion model for a long-range simulation, than to rely on precipitation data interpolated between widely scattered rain gauges.

Implications:

The current reliance on ground-based rain gauges for precipitation events and hourly data for modeling of dispersion and wet deposition of particulate matter and water-soluble pollutants results in potentially large discontinuity in data coverage and the need to extrapolate data between monitoring stations. The use of radar-based precipitation data, which is available for the entire continental United States and nearby areas, would resolve these data gaps and provide a complete and accurate spatial representation of hourly precipitation within a large modeling domain.     

Teleconnections,midlatitude cyclones and Aegean Sea turbulent heat flux variability on daily through decadal time scales

We analyze daily wintertime cyclone variability in the central and eastern Mediterranean during 1958–2001 and identify four distinct “cyclone states,” corresponding to the presence or absence of cyclones in each basin. Each cyclone state is associated with wind flows that induce characteristic patterns of cooling via turbulent (sensible and latent) heat fluxes in the eastern Mediterranean basin and Aegean Sea. The relative frequency of occurrence of each state determines the heat loss from the Aegean Sea during that winter, with largest heat losses occurring when there is a storm in the eastern but not central Mediterranean (eNOTc) and the smallest occurring when there is a storm in the central but not eastern Mediterranean (cNOTe). Time series of daily cyclone states for each winter allow us to infer Aegean Sea cooling for winters prior to 1985, the earliest year for which we have daily heat flux observations. We show that cyclone states conducive to Aegean Sea convection occurred in 1991/1992 and 1992/1993, the winters during which deepwater formation was observed in the Aegean Sea, and also during the mid-1970s and the winters of 1963/1964 and 1968/1969. We find that the eNOTc cyclone state is anticorrelated with the North Atlantic Oscillation (NAO) prior to 1977/1978. After 1977/1978, the cNOTe state is anticorrelated with both the NAO and the North Caspian Pattern, showing that the area of influence of large-scale atmospheric teleconnections on regional cyclone activity shifted from the eastern to the central Mediterranean during the late 1970s. A trend toward more frequent occurrence of the positive phase of the NAO produced less frequent cNOTe states since the late 1970s, increasing the number of days with strong cooling of the Aegean Sea surface waters.     

Multi-GCM projections of future drought and climate variability indicators for the Mediterranean region

Future climate conditions for the Mediterranean region based on an ensemble of 16 Global Climate Models are expressed and mapped using three approaches, giving special attention to the intermodel uncertainty. (1) The scenarios of mean seasonal temperature and precipitation agree with the projections published previously by other authors. The results show an increase in temperature in all seasons and for all parts of the Mediterranean with good intermodel agreement. Precipitation is projected to decrease in all parts and all seasons (most significantly in summer) except for the northernmost parts in winter. The intermodel agreement for the precipitation changes is lower than for temperature. (2) Changes in drought conditions are represented using the Palmer Drought Severity Index and its intermediate Z-index product. The results indicate a significant decrease in soil moisture in all seasons, with the most significant decrease occurring in summer. The displayed changes exhibit high intermodel agreement. (3) The climate change scenarios are defined in terms of the changes in parameters of the stochastic daily weather generator calibrated with the modeled daily data; the emphasis is put on the parameters, which affect the diurnal and interdiurnal variability in weather series. These scenarios indicate a trend toward more extreme weather in the Mediterranean. Temperature maxima will increase not only because of an overall rise in temperature means, but partly (in some areas) because of increases in temperature variability and daily temperature range. Increased mean daily precipitation sums on wet days occurring in some seasons, and some parts of the Mediterranean may imply higher daily precipitation extremes, and decreased probability of wet day occurrence will imply longer drought spells all across the Mediterranean.