PM2.5 source apportionment with organic markers in the Southeastern Aerosol Research and Characterization (SEARCH) study

Positive matrix factorization (PMF) and effective variance (EV) solutions to the chemical mass balance (CMB) were applied to PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) mass and chemically speciated measurements for samples taken from 2008 to 2010 at the Atlanta, Georgia, and Birmingham, Alabama, sites. Commonly measured PM_2.5 mass, elemental, ionic, and thermal carbon fraction concentrations were supplemented with detailed nonpolar organic speciation by thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS). Source contribution estimates were calculated for motor vehicle exhaust, biomass burning, cooking, coal-fired power plants, road dust, vegetative detritus, and secondary sulfates and nitrates for Atlanta. Similar sources were found for Birmingham, with the addition of an industrial source and the separation of biomass burning into open burning and residential wood combustion. EV-CMB results based on conventional species were qualitatively similar to those estimated by PMF-CMB. Secondary ammonium sulfate was the largest contributor, accounting for 27–38% of PM_2.5, followed by biomass burning (21–24%) and motor vehicle exhaust (9–24%) at both sites, with 4–6% of PM_2.5 attributed to coal-fired power plants by EV-CMB. Including organic compounds in the EV-CMB reduced the motor vehicle exhaust and biomass burning contributions at both sites, with a 13–23% deficit for PM_2.5 mass. The PMF-CMB solution showed mixing of sources within the derived factors, both with and without the addition of speciated organics, as is often the case with complex source mixtures such as those at these urban-scale sites. The nonpolar TD-GC/MS compounds can be obtained from existing filter samples and are a useful complement to the elements, ions, and carbon fractions. However, they should be supplemented with other methods, such as TD-GC/MS on derivitized samples, to obtain a wider range of polar compounds such as sterols, sugars, and organic acids. The PMF and EV solutions to the CMB equations are complementary to, rather than replacements for, each other, as comparisons of their results reveal uncertainties that are not otherwise evident.

Implications:?Organic markers can be measured on currently acquired PM_2.5 filter samples by thermal methods. These markers can complement element, ion, and carbon fraction measurements from long-term speciation networks. Applying the positive matrix factorization and effective variance solutions for the chemical mass balance equations provides useful information on the accuracy of the source contribution estimates. Nonpolar compounds need to be complemented with polar compounds to better apportion cooking and secondary organic aerosol contributors.     

Low-disturbance manure incorporation effects on ammonia and nitrate loss

Low-disturbance manure application methods can provide the benefits of manure incorporation, including reducing ammonia (NH3) emissions, in production systems where tillage is not possible. However, incorporation can exacerbate nitrate (NO3?) leaching. We sought to assess the trade-offs in NH3 and NO3? losses caused by alternative manure application methods. Dairy slurry (2006-2007) and liquid swine manure (2008-2009) were applied to no-till corn by (i) shallow (<10 cm) disk injection, (ii) surface banding with soil aeration, (iii) broadcasting, and (iv) broadcasting with tillage incorporation. Ammonia emissions were monitored for 72 h after application using ventilated chambers and passive diffusion samplers, and NO3? leaching to 80 cm was monitored with buried column lysimeters. The greatest NH3 emissions occurred with broadcasting (35-63 kg NH3-N ha?), and the lowest emissions were from unamended soil (<1 kg NH-N ha?1). Injection decreased NH-N emissions by 91 to 99% compared with broadcasting and resulted in lower emissions than tillage incorporation 1 h after broadcasting. Ammonia-nitrogen emissions from banding manure with aeration were inconsistent between years, averaging 0 to 71% that of broadcasting. Annual NO3? leaching losses were small (<25 kg NO3-N ha?1) and similar between treatments, except for the first winter when NO3? leaching was fivefold greater with injection. Because NO3? leaching with injection was substantially lower over subsequent seasons, we hypothesize that the elevated losses during the first winter were through preferential flow paths inadvertently created during lysimeter installation. Overall, shallow disk injection yielded the lowest NH3 emissions without consistently increasing NO3? leaching, whereas manure banding with soil aeration conserved inconsistent amounts of N.     

Comparison of Stream Invertebrate Response Models for Bioassessment Metrics1

Waite, Ian R., Jonathan G. Kennen, Jason T. May, Larry R. Brown, Thomas F. Cuffney, Kimberly A. Jones, and James L. Orlando, 2012. Comparison of Stream Invertebrate Response Models for Bioassessment Metrics. Journal of the American Water Resources Association (JAWRA) 48(3): 570-583. DOI: 10.1111/j.1752-1688.2011.00632.x Abstract: We aggregated invertebrate data from various sources to assemble data for modeling in two ecoregions in Oregon and one in California. Our goal was to compare the performance of models developed using multiple linear regression (MLR) techniques with models developed using three relatively new techniques: classification and regression trees (CART), random forest (RF), and boosted regression trees (BRT). We used tolerance of taxa based on richness (RICHTOL) and ratio of observed to expected taxa (O/E) as response variables and land use/land cover as explanatory variables. Responses were generally linear; therefore, there was little improvement to the MLR models when compared to models using CART and RF. In general, the four modeling techniques (MLR, CART, RF, and BRT) consistently selected the same primary explanatory variables for each region. However, results from the BRT models showed significant improvement over the MLR models for each region; increases in R² from 0.09 to 0.20. The O/E metric that was derived from models specifically calibrated for Oregon consistently had lower R² values than RICHTOL for the two regions tested. Modeled O/E R² values were between 0.06 and 0.10 lower for each of the four modeling methods applied in the Willamette Valley and were between 0.19 and 0.36 points lower for the Blue Mountains. As a result, BRT models may indeed represent a good alternative to MLR for modeling species distribution relative to environmental variables.     

Responses of Hyalella azteca and phytoplankton to a simulated agricultural runoff event in a managed backwater wetland

We assessed the aqueous toxicity mitigation capacity of a hydrologically managed floodplain wetland following a synthetic runoff event amended with a mixture of sediments, nutrients (nitrogen and phosphorus), and pesticides (atrazine, S-metolachlor, and permethrin) using 48-h Hyalella azteca survival and phytoplankton pigment, chlorophyll a. The runoff event simulated a 1 h, 1.27 cm rainfall event from a 16 ha agricultural field. Water (1 L) was collected every 30 min within the first 4 h, every 4 h until 48 h, and on days 5, 7, 14, 21, and 28 post-amendment at distances of 0, 10, 40, 300 and 500 m from the amendment point for chlorophyll a, suspended sediment, nutrient, and pesticide analyses. H. azteca 48-h laboratory survival was assessed in water collected at each site at 0, 4, 24, 48 h, 5 d and 7 d. Greatest sediment, nutrient, and pesticide concentrations occurred within 3 h of amendment at 0 m, 10 m, 40 m, and 300 m downstream. Sediments and nutrients showed little variation at 500 m whereas pesticides peaked within 48 h but at <15% of upstream peak concentrations. After 28 d, all mixture components were near or below pre-amendment concentrations. H. azteca survival significantly decreased within 48 h of amendment up to 300 m in association with permethrin concentrations. Chlorophyll a decreased within the first 24 h of amendment up to 40 m primarily in conjunction with herbicide concentrations. Variations in chlorophyll a at 300 and 500 m were associated with nutrients. Managed floodplain wetlands can rapidly and effectively trap and process agricultural runoff during moderate rainfall events, mitigating impacts to aquatic invertebrates and algae in receiving aquatic systems.     

Urban transformation of a metropolis and its environmental impacts

Purpose

The aim of this paper is to understand the sustainability of urban spatial transformation in the process of rapid urbanization, and calls for future research on the demographic and economic dimensions of climate change. Shanghai towards its transformation to a metropolis has experienced vast socioeconomic and ecological change and calls for future research on the impacts of demographic and economic dimensions on climate change. We look at the major questions (1) to explore economic and demographic growth, land use and land-cover changes in the context of rapid economic and city growth, and (2) to analyze how the demography and economic growth have been associated with the local air temperature and vegetation.

Method

We examine urban growth, land use and land-cover changes in the context of rapid economic development and urbanization. We assess the impact of urban expansion on local air temperature and vegetation. The analysis is based on time series data of land use, normalized difference vegetation index (NDVI), and meteorological, demographic and economic data.

Results and discussion

The results indicate that urban growth has been driven by mass immigration; as a consequence of economic growth and urban expansion, a large amount of farmland has been converted to paved road and residential buildings. Furthermore, the difference between air temperature in urban and exurban areas has increased rapidly. The decrease of high mean annual NDVI has mainly occurred around the dense urban areas.     

South Pole Antarctica observations and modeling results: New insights on HOx radical and sulfur chemistry

Measurements of OH, H₂SO₄, and MSA at South Pole (SP) Antarctica were recorded as a part of the 2003 Antarctic Chemistry Investigation (ANTCI 2003). The time period 22 November, 2003–2 January, 2004 provided a unique opportunity to observe atmospheric chemistry at SP under both natural conditions as well as those uniquely defined by a solar eclipse event. Results under natural solar conditions generally confirmed those reported previously in the year 2000. In both years the major chemical driver leading to large scale fluctuations in OH was shifts in the concentration levels of NO. Like in 2000, however, the 2003 observational data were systematically lower than model predictions. This can be interpreted as indicating that the model mechanism is still missing a significant HO_x sink reaction(s); or, alternatively, that the OH calibration source may have problems. Still a final possibility could involve the integrity of the OH sampling scheme which involved a fixed building site. As expected, during the peak in the solar eclipse both NO and OH showed large decreases in their respective concentrations. Interestingly, the observational OH profile could only be approximated by the model mechanism upon adding an additional HO_x radical source in the form of snow emissions of CH₂O and/or H₂O₂. This would lead one to think that either CH₂O and/or H₂O₂ snow emissions represent a significant HO_x radical source under summertime conditions at SP. Observations of H₂SO₄ and MSA revealed both species to be present at very low concentrations (e.g., 5 × 10⁵ and 1 × 10⁵ molec cm^?3, respectively), but similar to those reported in 2000. The first measurements of SO₂ at SP demonstrated a close coupling with the oxidation product H₂SO₄. The observed low concentrations of MSA appear to be counter to the most recent thinking by glacio-chemists who have suggested that the plateau's lower atmosphere should have elevated levels of MSA. We speculate here that the absence of MSA may reflect efficient atmospheric removal mechanisms for this species involving either dynamical and/or chemical processes.     

An Objective Multiattribute Analysis Approach for Allocation of Scarce Irrigation Water Resources1

Zardari, Noor ul Hassan, Ian Cordery, and Ashish Sharma, 2010. An Objective Multiattribute Analysis Approach for Allocation of Scarce Irrigation Water Resources. Journal of the American Water Resources Association (JAWRA) 46(2):412-428. DOI: 10.1111/j.1752-1688.2009.00410.x Abstract: In this study, end user (farmer) and decision maker (water allocator) opinions were surveyed and a conjoint analysis (CA) based method was applied to the quantitative and qualitative data to assess the utility associated with each attribute that plays a role in forming the final thinking of the water users. The application of CA for estimating the utility for each attribute level is a novel approach, which helps provide a formal, objective basis for assigning relative scales for each attribute interval within a multiattribute decision-making model. The utilities (part-worths) obtained from the CA have a cardinal scale and were found to be comparable within and across the attributes. A farmers’ survey on five water allocation attributes was completed from 62 farmers and their opinions on the relative importance of attributes were elicited for a subarea of the Indus River Basin. The CA method was then applied to the survey data and the utilities for each attribute level were determined. This allowed, for instance, decisions to be made, which take account of the perceived value of the water and of the availability of local labor to work on the farm. Finally, these interval scales were used within the specification of the ELECTRE multiattribute decision-making method to provide a complete and objective ranking of nine irrigation districts so that the best decisions on water allocation could be made.     

Flux measurements of volatile organic compounds by the relaxed eddy accumulation method combined with a GC-FID system in urban Houston,Texas

A tall tower flux measurement setup was established in metropolitan Houston, Texas, to measure trace gas fluxes from emission sources in the urban surface layer. We describe a new relaxed eddy accumulation (REA) system combined with a dual-channel GC-FID used for VOC flux measurements, focusing on benzene, toluene, ethylbenzene and xylenes (BTEX) results. Ambient air sampled from 60 m above the ground next to a sonic anemometer was subsampled by a membrane pump and pushed into an REA valve system with two Teflon bag reservoirs, then transferred to two preconcentration units for thermal desorption. We discuss the performance of our system and the selected BTEX measurement results using approximately 8 weeks of data (May 22–July 22, 2008), presenting diurnal variations of concentrations and fluxes of these traffic tracers. The measured values exhibited diurnal cycles with dominant morning and midday peaks during weekdays related to rush hour traffic and additional weekday daytime toluene and xylenes emissions. Local evaporative emissions, likely from solvent usage, significantly contributed to the measured fluxes. We upscaled measured emissions to the county level using a high resolution land cover data set and compared the results with EPA’s National Emission Inventory (NEI).