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.     

Fundamentals of Successful Monitoring,Reporting, and Verification under a Cap-and-Trade Program

Abstract

The U.S. Environmental Protection Agency (EPA) developed and implemented the Acid Rain Program (ARP), and NO_x Budget Trading Programs (NBTP) using several fundamental monitoring, reporting, and verification (MRV) elements: (1) compliance assurance through incentives and automatic penalties; (2) strong quality assurance (QA); (3) collaborative approach with a petition process; (4) standardized electronic reporting; (5) compliance flexibility for low-emitting sources; (6) complete emissions data record required; (7) centralized administration; (8) level playing field; (9) publicly available data; (10) performance-based approach; and (11) reducing conflicts of interest. Each of these elements is discussed in the context of the authors’ experience under two U.S. cap-and-trade programs and their potential application to other capand-trade programs.

The U.S. Office of Management and Budget found that the Acid Rain Program has accounted for the largest quantified human health benefits of any federal regulatory program implemented in the last 10 yr, with annual benefits exceeding costs by >40 to 1. The authors believe that the elements described in this paper greatly contributed to this success. EPA has used the ARP fundamental elements as a model for other cap-and-trade programs, including the NBTP, which went into effect in 2003, and the recently published Clean Air Interstate Rule and Clean Air Mercury Rule. The authors believe that using these fundamental elements to develop and implement the MRV portion of their cap-and-trade programs has resulted in public confidence in the programs, highly accurate and complete emissions data, and a high compliance rate (>99% overall).     

Fingerprinting of High Boiling Hydrocarbon Fuels,Asphalts and Lubricants

Fingerprinting of hydrocarbon products requires high resolution differentiation of individual hydrocarbon compounds in any mixture. This requires the applications of various measuring techniques. In this paper, we have chosen the heavy hydrocarbons in fuels, lubricants and paving material as examples to discuss the methods for chemical characterization and differentiation. In the category most frequently termed "semi-volatile hydrocarbons" with boiling points from about 500°F to 1200°F or higher, there are several families of hydrocarbons, both natural and refined that are not easily distinguished by conventional EPA tests. Among the groups which we will use as examples are asphalts, hydraulic fluid, transmission oil, motor lubricating oils, heating oils, crude oil and coal. These hydrocarbon families are best studied using combined gas chromatography-mass spectrometry in full scan mode and characterizing various homologous series of hydrocarbons at known fragment ions. The hydrocarbon series providing the best information are: (1) N -alkanes; (2) iso-alkanes; (3) steranes; (4) terpanes; (5) polynuclear aromatic hydrocarbons; (6) aromatic steranes; and (7) specific polycyclic compounds.     

Seawater Intrusion and Sustainable Yield of Basal Aquifers1

Liu, Clark C.K. and John J. Dai, 2012. Seawater Intrusion and Sustainable Yield of Basal Aquifers. Journal of the American Water Resources Association (JAWRA) 48(5): 861‐870. DOI: 10.1111/j.1752‐1688.2012.00659.x Abstract: Basal aquifers, in which freshwater floats on top of saltwater, are the major freshwater supply for the Hawaiian Islands, as well as many other coastal regions around the world. Under unexploited or natural conditions, freshwater and the underlying seawater are separated by a relatively sharp interface located below mean sea level at a depth of about 40 times the hydraulic head. With forced draft, the hydraulic head of a basal aquifer would decline and the sharp interface would move up. It is a serious problem of seawater intrusion as huge amounts of freshwater storage is replaced by saltwater. Also, with forced draft, the sharp interface is replaced by a transition zone in which the salinity increases downward from freshwater to saltwater. As pumping continues, the transition zone expands. The desirable source‐water salinity in Hawaii is about 2% of the seawater salinity. Therefore, the transition zone expansion is another serious problem of seawater intrusion. In this study, a robust analytical groundwater flow and salinity transport model (RAM2) was developed. RAM2 has a simple mathematical structure and its model parameters can be determined satisfactorily with the available field monitoring data. The usefulness of RAM2 as a viable management tool for coastal ground water management is demonstrated by applying it to determine the sustainable yield of the Pearl Harbor aquifer, a principal water supply source in Hawaii.     

System Dynamics to Sustainable Water Resources Management in the Eastern Snake Plain Aquifer Under Water Supply Uncertainty1

Abstract: Water supply uncertainty continues to threaten the reliability of regional water resources in the western United States. Climate variability and water dispute potentials induce water managers to develop proactive adaptive management strategies to mitigate future hydroclimate impacts. The Eastern Snake Plain Aquifer in the state of Idaho is also facing these challenges in the sense that population growth and economic development strongly depend on reliable water resources from underground storage. Drought and subsequent water conflict often drive scientific research and political agendas because water resources availability and aquifer management for a sustainable rural economy are of great interest. In this study, a system dynamics approach is applied to address dynamically complex problems with management of the aquifer and associated surface‐water and groundwater interactions. Recharge and discharge dynamics within the aquifer system are coded in an environmental modeling framework to identify long‐term behavior of aquifer responses to uncertain future hydrological variability. The research shows that the system dynamics approach is a promising modeling tool to develop sustainable water resources planning and management in a collaborative decision‐making framework and also to provide useful insights and alternative opportunities for operational management, policy support, and participatory strategic planning to mitigate future hydroclimate impacts in human dimensions.     

Antibiotic resistant bacteria/genes dissemination in lacustrine sediments highly increased following cultural eutrophication of Lake Geneva (Switzerland)

This study investigates faecal indicator bacteria (FIB), multiple antibiotic resistant (MAR), and antibiotic resistance genes (ARGs), of sediment profiles from different parts of Lake Geneva (Switzerland) over the last decades. MARs consist to expose culturable Escherichia coli (EC) and Enterococcus (ENT) to mixed five antibiotics including Ampicillin, Tetracycline, Amoxicillin, Chloramphenicol and Erythromycin. Culture-independent is performed to assess the distribution of ARGs responsible for, β-lactams (blaTEM; Amoxicillin/Ampicillin), Streptomycin/Spectinomycin (aadA), Tetracycline (tet) Chloramphenicol (cmlA) and Vancomycin (van). Bacterial cultures reveal that in the sediments deposited following eutrophication of Lake Geneva in the 1970s, the percentage of MARs to five antibiotics varied from 0.12% to 4.6% and 0.016% to 11.6% of total culturable EC and ENT, respectively. In these organic-rich bacteria-contaminated sediments, the blaTEM resistant of FIB varied from 22% to 48% and 16% to 37% for EC and ENT respectively, whereas the positive PCR assays responsible for tested ARGs were observed for EC, ENT, and total DNA from all samples. The aadA resistance gene was amplified for all the sediment samples, including those not influenced by WWTP effluent water. Our results demonstrate that bacteria MARs and ARGs highly increased in the sediments contaminated with WWTP effluent following the cultural eutrophication of Lake Geneva. Hence, the human-induced changing limnological conditions highly enhanced the sediment microbial activity, and therein the spreading of antibiotic resistant bacteria and genes in this aquatic environment used to supply drinking water in a highly populated area. Furthermore, the presence of the antibiotic resistance gene aadA in all the studied samples points out a regional dissemination of this emerging contaminant in freshwater sediments since at least the late nineteenth century.     

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in breast milk of first-time Irish mothers: impact of the 2008 dioxin incident in Ireland

The 2008 dioxin incident in Ireland resulted in elevated concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) in Irish pork and pork products, due to the consumption of contaminated animal feed by pigs. In order to investigate any resulting impact on the Irish population, these contaminants were measured in pooled breast milk samples from 109 first-time mothers, collected in 2010. A comparison of the results with similar data from 2002 revealed generally lower concentrations of PCDD/Fs and dioxin-like PCBs in the 2010 samples, confirming the declining trend reported by many authors. Contaminant concentration levels for both 2002 and 2010 were generally slightly lower than those reported internationally, with a mean combined PCDD/F and PCB WHO-TEQ of 9.66 pg g⁻¹ fat, for an overall pooled sample of milk from 2010. An apparent slight increase in PCDFs was observed between 2002 and 2010 (from 2.73 pg WHO-TEQ g⁻¹ fat to 3.21 pg WHO-TEQ g⁻¹ fat), with the main contributory congener being 2,3,4,7,8-PentaCDF. While it cannot be totally discounted that the slight increase in 2,3,4,7,8-PentaCDF and in the overall PCDF WHO-TEQ in breast milk could be attributable to consumption of Irish pork during the 2008 incident, we consider that it is more likely that this was due to other factors, including the predominantly urban/industrial sampling locations for the 2010 samples, compared to 2002.     

Agricultural pesticide residues of farm runoff in the Okanagan Valley, British Columbia, Canada

The objectives of this study were to determine environmental occurrence and concentrations of selected currently-used-pesticides and some transformation products in agricultural farms in the Okanagan Valley (OKV), and to conduct a simple risk assessment of environmental pesticides levels detected in OKV on non-target aquatic organisms. The OKV is the tree fruit country of the Province of British Columbia where considerable amount of pesticides are applied annually. Water, sediment and soil samples were collected at eleven sites in early June and late September following rainfall events and/or extended periods of irrigation from drainage ditches and/or from small streams. Undisturbed reference sites were also sampled. Study results showed that forty of the eighty chemicals analyzed, including organochlorine, nitrogen-containing and organophosphate pesticides commonly used for OKV crops, were detected in runoff and small stream water samples. Among which, endosulfan-sulfate was the most frequently detected chemical. Also, azinophos-methyl (0.699-25.5 ng/L), diazinon (0.088-214 ng/L) exceeded, and α-, β- endosulfan, endosulfan sulphate approached the guidelines for the protection of aquatic life.