Apportionment of ambient primary and secondary fine particulate matter during a 2001 summer intensive study at the CMU Supersite and NETL Pittsburgh site

Gaseous and particulate pollutant concentrations associated with five samples per day collected during a July 2001 summer intensive study at the Pittsburgh Carnegie Mellon University (CMU) Supersite were used to apportion fine particulate matter (PM2.5) into primary and secondary contributions using PMF2. Input to the PMF2 analysis included the concentrations of PM2.5 nonvolatile and semivolatile organic material, elemental carbon (EC), ammonium sulfate, trace element components, gas-phase organic material, and NO(x), NO2, and O3 concentrations. A total of 10 factors were identified. These factors are associated with emissions from various sources and facilities including crustal material, gasoline combustion, diesel combustion, and three nearby sources high in trace metals. In addition, four secondary sources were identified, three of which were associated with secondary products of local emissions and were dominated by organic material and one of which was dominated by secondary ammonium sulfate transported to the CMU site from the west and southwest. The three largest contributors to PM2.5 were secondary transported material (dominated by ammonium sulfate) from the west and southwest (49%), secondary material formed during midday photochemical processes (24%), and gasoline combustion emissions (11%). The other seven sources accounted for the remaining 16% of the PM2.5. Results obtained at the CMU site were comparable to results previously reported at the National Energy Technology Laboratory (NETL), located approximately 18 km south of downtown Pittsburgh. The major contributor at both sites was material transported from the west and southwest. Some difference in nearby sources could be attributed to meteorology as evaluated by HYSPLIT model back-trajectory calculations. These findings are consistent with the majority of the secondary ammonium sulfate in the Pittsburgh area being the result of contributions from distant transport, and thus decoupled from local activity involving organic pollutants in the metropolitan area. In contrast, the major local secondary sources were dominated by organic material.     

Variations in speciated emissions from spark-ignition and compression-ignition motor vehicles in California's south coast air basin

The U.S. Department of Energy Gasoline/Diesel PM Split Study examined the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the contributions of spark-ignition (SI) and compression-ignition (CI) engine exhaust to ambient fine particulate matter (PM2.5). This paper presents the chemical composition profiles of SI and CI engine exhaust from the vehicle-testing portion of the study. Chemical analysis of source samples consisted of gravimetric mass, elements, ions, organic carbon (OC), and elemental carbon (EC) by the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Speciation Trends Network (STN) thermal/optical methods, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, alkanes, and polar organic compounds. More than half of the mass of carbonaceous particles emitted by heavy-duty diesel trucks was EC (IMPROVE) and emissions from SI vehicles contained predominantly OC. Although total carbon (TC) by the IMPROVE and STN protocols agreed well for all of the samples, the STN/IMPROVE ratios for EC from SI exhaust decreased with decreasing sample loading. SI vehicles, whether low or high emitters, emitted greater amounts of high-molecular-weight particulate PAHs (benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene) than did CI vehicles. Diesel emissions contained higher abundances of two- to four-ring semivolatile PAHs. Diacids were emitted by CI vehicles but are also prevalent in secondary organic aerosols, so they cannot be considered unique tracers. Hopanes and steranes were present in lubricating oil with similar composition for both gasoline and diesel vehicles and were negligible in gasoline or diesel fuels. CI vehicles emitted greater total amounts of hopanes and steranes on a mass per mile basis, but abundances were comparable to SI exhaust normalized to TC emissions within measurement uncertainty. The combustion-produced high-molecular-weight PAHs were found in used gasoline motor oil but not in fresh oil and are negligible in used diesel engine oil. The contributions of lubrication oils to abundances of these PAHs in the exhaust were large in some cases and were variable with the age and consumption rate of the oil. These factors contributed to the observed variations in their abundances to total carbon or PM2.5 among the SI composition profiles.     

Determination of bromacil transport as a function of water and carbon content in soils

This study was conducted to determine the significance of bromacil transport as a function of water and carbon content in soils and to explore the implications of neglecting sorption when making assessments of travel time of bromacil through the vadose zone. Equilibrium batch sorption tests were performed for loamy sand and sandy soil added with four different levels of powdered activated carbon (PAC) content (0, 0.01, 0.05, and 0.1%). Column experiments were also conducted at various water and carbon contents under steady-state flow conditions. The first set of column experiments was conducted in loamy sand containing 1.5% organic carbon under three different water contents (0.23, 0.32, and 0.41) to measure breakthrough curves (BTCs) of bromide and bromacil injected as a square pulse. In the second set of column experiments, BTCs of bromide and bromacil injected as a front were measured in saturated sandy columns at the four different PAC levels given above. Column breakthrough data were analyzed with both equilibrium and nonequilibrium (two-site) convection-dispersion equation (CDE) models to determine transport and sorption parameters under various water and carbon contents. Analysis with batch data indicated that neglect of the partition-related term in the calculation of solute velocity may lead to erroneous estimation of travel time of bromacil, i.e. an overestimation of the solute velocity by a factor of R. The column experiments showed that arrival time of the bromacil peak was larger than that of the bromide peak in soils, indicating that transport of bromacil was retarded relative to bromide in the observed conditions. Extent of bromacil retardation (R) increased with decreasing water content and increasing PAC content, supporting the importance of retardation in the estimation of travel time of bromacil even at small amounts of organic carbon for soils with lower water content.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine approximately amitrole approximately simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K(ow)) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.     

Rapid determination of ETS markers with a prototype field-portable GC employing a microsensor array detector

The adaptation of a portable gas chromatograph (GC) prototype with several unique design features to the determination of vapor-phase markers of environmental tobacco smoke (ETS) is described. This instrument employs a dual-stage adsorbent preconcentrator, two series-coupled separation columns that can be independently temperature programmed, and a detector consisting of an array of nanoparticle-coated chemiresistors, whose response patterns are used together with retention times for vapor recognition. An adsorbent pre-trap was developed to remove semi-volatile organics from the sample stream. Conditions were established to quantitatively capture two ETS markers, 2,5-dimethylfuran (2,5-DMF) and 4-ethenylpyridine (4-EP, as a surrogate for 3-EP), and to separate them from the 34 most prominent co-contaminants present in ETS using ambient air as the carrier gas. A complete analysis can be performed every 15 min. Projected detection limits are 0.58 and 0.08 ppb for 2,5-DMF and 4-EP, respectively, assuming a 1 L sample volume, which are sufficiently low to determine these markers in typical smoking-permitted environments.     

Modeling Runoff Response to Land Cover and Rainfall Spatial Variability in Semi-Arid Watersheds

Hydrologic response is an integrated indicator of watershed condition, and significant changes in land cover may affect the overall health and function of a watershed. This paper describes a procedure for evaluating the effects of land cover change and rainfall spatial variability on watershed response. Two hydrologic models were applied on a small semi-arid watershed; one model is event-based with a one-minute time step (KINEROS), and the second is a continuous model with a daily time step (SWAT). The inputs to the models were derived from Geographic Information System (GIS) theme layers of USGS digital elevation models, the State Soil Geographic Database (STATSGO) and the Landsat-based North American Landscape Characterization classification (NALC) in conjunction with available literature and look up tables. Rainfall data from a network of 10 raingauges and historical stream flow data were used to calibrate runoff depth using the continuous hydrologic model from 1966 to 1974. No calibration was carried out for the event-based model, in which six storms from the same period were used in the calculation of runoff depth and peak runoff. The assumption on which much of this study is based is that land cover change and rainfall spatial variability affect the rainfall-runoff relationships on the watershed. To validate this assumption, simulations were carried out wherein the entire watershed was transformed from the 1972 NALC land cover, which consisted of a mixture of desertscrub and grassland, to a single uniform land cover type such as riparian, forest, oak woodland, mesquite woodland, desertscrub, grassland, urban, agriculture, and barren. This study demonstrates the feasibility of using widely available data sets for parameterizing hydrologic simulation models. The simulation results show that both models were able to characterize the runoff response of the watershed due to changes of land cover.     

A case study characterizing animal fecal sources in surface water using a mitochondrial DNA marker

Water quality impairment by fecal waste in coastal watersheds is a public health issue. The present study provided evidence for the use of a mitochondrial (mtDNA) marker to detect animal fecal sources in surface water. The accurate identification of fecal pollution is based on the notion that fecal microorganisms preferentially inhabit a host animal’s gut environment. In contrast, mtDNA host-specific markers are inherent to eukaryotic host cells, which offers the advantage by detecting DNA from the host rather than its fecal bacteria. The present study focused on sampling water presumably from non-point sources (NPS), which can increase bacterial and nitrogen concentrations to receiving water bodies. Stream sampling sites located within the Piscataqua River Watershed (PRW), New Hampshire, USA, were sampled from a range of sites that experienced nitrogen inputs such as sewer and septic systems and suburban runoff. Three mitochondrial (mtDNA) gene marker assays (human, bovine, and canine) were tested from surface water. Nineteen sites were sampled during an 18-month period. Analyses of the combined single and multiplex assay results showed that the proportion of occurrence was highest for bovine (15.6%; n = 77) compared to canine (5.6%; n = 70) and human (5.7%; n = 107) mtDNA gene markers. For the human mtDNA marker, there was a statistically significant relationship between presence vs. absence and land use (Fisher’s test p = 0.0031). This result was evident particularly for rural suburban septic, which showed the highest proportion of presence (19.2%) compared to the urban sewered (3.3%), suburban sewered (0%), and agricultural (0%) as well as forested septic (0%) sites. Although further testing across varied land use is needed, our study provides evidence for using the mtDNA marker in large watersheds.     

How far are biodiversity loss and climate change similar as policy issues?

Climate change and biodiversity loss have a central position in policy debate about global environmental change; however, of the two, climate change has a higher profile. This paper explores the similarities and difference between the two issues. Climate change is better defined and better understood as a policy issue, it is underpinned by a strong scientific consensus and practical units of measurement (CO₂ and financial impacts), and mitigation involves a key economic sector in energy. Biodiversity loss is less easily understood, more diffuse and less tangible, and policy responses do not engage major economic sectors. We argue that these differences contribute to the higher public and policy profile of climate change and can inform attempts to enhance responses to the problem of biodiversity loss.     

Comparative sorption,desorption and leaching potential of aminocyclopyrachlor and picloram

Sorption and desorption of aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropylpyrimidine-4-carboxylic acid) were compared to that of the structurally similar herbicide picloram (4-amino-3,5,6-trichloro-2-pyridinecarboxylic acid) in three soils of differing origin and composition to determine if picloram data is representative of aminocyclopyrachlor behavior in soil. Aminocyclopyrachlor and picloram batch sorption data fit the Freundlich equation and was independent of concentration for aminocyclopyrachlor (1/n = 1), but not for picloram (1/n = 0.80–0.90). Freundlich sorption coefficients (K _f) for aminocyclopyrachlor were lowest in the eroded and depositional Minnesota soils (0.04 and 0.12 μmol ^(1–1/n) L^1/n kg^?1) and the highest in Molokai soil (0.31 μmol ^(1–1/n) L^1/n kg^?1). For picloram, K _f was lower in the eroded (0.28 μmol ^(1–1/n) L^1/n kg^?1) as compared to the depositional Minnesota soil (0.75 μmol ^(1–1/n) L^1/n kg^?1). Comparing soil to soil, K _f for picloram was consistently higher than those found for aminocyclopyrachlor. Desorption of aminocyclopyrachlor and picloram was hysteretic on all three soils. With regard to the theoretical leaching potential based on groundwater ubiquity score (GUS), leaching potential of both herbicides was considered to be similar. Aminocyclopyrachlor would be ranked as leacher in all three soils if t_1/2 was > 12.7 days. To be ranked as non-leacher in all three soils, aminocyclopyrachlor t_1/2 would have to be <3.3 days. Calculated half-life that would rank picloram as leacher was calculated to be ～15.6 d. Using the current information for aminocycloprachlor, or using picloram data as representative of aminocycloprachlor behavior, scientists can now more accurately predict the potential for offsite transport of aminocycloprachlor.