Investigating the chemical nature of humic-like substances (HULIS) in North American atmospheric aerosols by liquid chromatography tandem mass spectrometry

The high-molecular weight water-soluble organic compounds present in atmospheric aerosols underwent functional-group characterization using liquid chromatography tandem mass spectrometry (LC-MS/MS), with a focus on understanding the chemical structure and origins of humic-like substances (HULIS) in the atmosphere. Aerosol samples were obtained from several locations in North America at times when primary sources contributing to organic aerosol were well-characterized: Riverside, CA, Fresno, CA, urban and peripheral Mexico City, Atlanta, GA, and Bondville, IL. Chemical analysis targeted identification and quantification of functional groups, such as aliphatic, aromatic, and bulk carboxylic acids, organosulfates, and carbohydrate-like substances that comprise species with molecular weights (MW) 200–600 amu. Measured high-MW functional groups were compared to modeled primary sources with the purpose of identifying associations between aerosol sources, high-MW aerosol species, and HULIS. Mobile source emissions were linked to high-molecular weight carboxylic acids, especially aromatic acids, biomass burning was associated with carboxylic acids and carbohydrate-like substances, and secondary organic aerosol (SOA) correlated well with the total amount of HULIS measured, whereas organosulfates showed no correlation with aerosol sources and exhibited unique spatial trends. These results suggested the importance of motor vehicles, biomass burning, and SOA as important sources of precursors to HULIS. Structural characteristics of atmospheric HULIS were compared to terrestrial humic and fulvic acids and revealed striking similarities in chemical structure, with the exception of organosulfates which were unique to atmospheric HULIS.     

A global assessment of chromium pollution using sperm whales (Physeter macrocephalus) as an indicator species

Chromium (Cr) is a well-known human carcinogen and a potential reproductive toxicant, but its contribution to ocean pollution is poorly understood. The aim of this study was to provide a global baseline for Cr as a marine pollutant using the sperm whale (Physeter macrocephalus) as an indicator species. Biopsies were collected from free-ranging whales around the globe during the voyage of the research vessel The Odyssey. Total Cr levels were measured in 361 sperm whales collected from 16 regions around the globe detectable levels ranged from 0.9 to 122.6 μg Cr g tissue⁻¹ with a global mean of 8.8 ± 0.9 μg g⁻¹. Two whales had undetectable levels. The highest levels were found in sperm whales sampled in the waters near the Islands of Kiribati in the Pacific (mean = 44.3 ± 14.4) and the Seychelles in the Indian Ocean (mean = 19.5 ± 5.4 μg g⁻¹). The lowest mean levels were found in whales near the Canary Islands (mean = 3.7 ± 0.8 μg g⁻¹) and off of the coast of Sri Lanka (mean = 3.3 ± 0.4 μg g⁻¹). The global mean Cr level in whale skin was 28-times higher than mean Cr skin levels in humans without occupational exposure. The whale levels were more similar to levels only observed previously in human lung tissue from workers who died of Cr-induced lung cancer. We conclude that Cr pollution in the marine environment is significant and that further study is urgently needed.     

Ultraviolet absorbance as a proxy for total dissolved mercury in streams

Stream water samples were collected over a range of hydrologic and seasonal conditions at three forested watersheds in the northeastern USA. Samples were analyzed for dissolved total mercury (THg_d), DOC concentration and DOC composition, and UV₂₅₄ absorbance across the three sites over different seasons and flow conditions. Pooling data from all sites, we found a strong positive correlation of THg_d to DOC (r² = 0.87), but progressively stronger correlations of THg_d with the hydrophobic acid fraction (HPOA) of DOC (r² = 0.91) and with UV₂₅₄ absorbance (r² = 0.92). The strength of the UV₂₅₄ absorbance-THg_d relationship suggests that optical properties associated with dissolved organic matter may be excellent proxies for THg_d concentration in these streams. Ease of sample collection and analysis, the potential application of in-situ optical sensors, and the possibility for intensive monitoring over the hydrograph make this an effective, inexpensive approach to estimate THg_d flux in drainage waters.     

Organic aerosol characterization by complementary measurements of chemical bonds and molecular fragments

Organic aerosol chemical markers from normalized concentrations of independent measurements of mass fragments (using Aerosol Mass Spectrometry, AMS) are compared to bond-based functional groups (from Fourier Transform Infrared spectroscopy, FTIR) during eight field projects in the western hemisphere. Several field projects show weak correlations between alcohol group fractions and m/z 60 fractions, consistent with the organic hydroxyl groups and the fragmentation of saccharides, but the weakness of the correlations indicate chemical differences among the relationships for ambient aerosols in different regions. Carboxylic acid group fractions and m/z 44 fractions are correlated weakly for three projects, with correlations expected for aerosols dominated by di-acid compounds since their fragmentation is typically dominated by m/z 44. Despite differences for three projects with ratios of m/z 44 to m/z 57 fragments less than 10, five projects showed a linear trend between the project-average m/z 44 to m/z 57 ratio and the ratio of acid and alkane functional groups. While this correlation explains only a fraction of the fragment and bond variability measured, the consistency of this relationship at multiple sites indicates a general agreement with the interpretation of the relative amount of m/z 44 as a carboxylic acid group marker and m/z 57 as an alkane group marker.     

Population dynamics and the economics of invasive species management: the greenhouse whitefly in California-grown strawberries

In agriculture, relatively few efficacious control measures may be available for an invasive pest. In the case of a new insect pest, insecticide use decisions are affected by regulations associated with its registration, insect population dynamics, and seasonal market price cycles. We assess the costs and benefits of environmental regulations designed to regulate insecticide applications on an invasive species. We construct a bioeconomic model, based on detailed scientific data, of management decisions for a specific invasion: greenhouse whiteflies in California-grown strawberries. The empirical model integrates whitefly population dynamics, the effect of whitefly feeding on strawberry yields, and weekly strawberry price. We use the model to assess the optimality of alternative treatment programs on a simulated greenhouse whitefly population. Our results show that regulations may lead growers to "under-spray" when placed in an economic context, and provide some general lessons about the design of optimal invasive species control policies.     

Challenges to liberalism: The case of Australian energy policy

This paper considers liberal and nationalist economic policy approaches to the ownership and development of Australian energy resources (oil, gas, coal and uranium). In the two decades prior to 1983, Australia pursued economic policies in relation to its energy resources which could broadly be described as ‘nationalist’. Governments of the day intervened in development decisions in an effort to enhance the ‘national interest’. From 1983, along with the deregulation of the Australian economy as a whole, policy relating to energy resources was liberalised. Development of energy reserves henceforth occurred according to the dictates of the market. This paper argues that recent Australian energy policy initiatives reflect an increase in nationalist influences and a retreat from the liberalisation agenda that dominated energy policy making in the 1980s and 1990s. Three examples are discussed where policy has been influenced by a nationalist framework: (1) the domestic gas reservation policy in Western Australia; (2) Australian government efforts to promote a ‘value adding’ nuclear processing industry and (3) Australian Labor Party policy giving preferential financial incentives for gas to liquids projects. The re-emergence of nationalism in Australia is occurring either because policy makers now favour it as a path to energy security or in some cases because they believe that appeals to nationalism will generate political support.     

Efficiency of perchlorate consumption in road flares, propellants and explosives

When an explosive detonates or a propellant or flare burns, consumption of the energetic filler should be complete but rarely is, especially in the presence of large amounts of non-combustible materials. Herein we examine three types of perchlorate-containing devices to estimate their potential as sources of contamination in their normal mode of functioning. Road flares, rocket propellants and ammonium nitrate (AN) emulsion explosives are potentially significant anthropogenic sources of perchlorate contamination. This laboratory evaluated perchlorate residue from burning of flares and propellants as well as detonations of ammonium nitrate emulsion explosives. Residual perchlorate in commercial products ranged from 0.094 mg perchlorate per gram material (flares) to 0.012 mg perchlorate per gram material (AN emulsion explosives). The rocket propellant formulations, prepared in this laboratory, generated 0.014 mg of perchlorate residue per gram of material.     

Restored Riparian Buffers as Tools for Ecosystem Restoration in the MAIA; Processes, Endpoints, and Measures of Success for Water, Soil, Flora, and Fauna

Riparian buffer restorations are used as management tools to produce favorable water quality impacts, moreover among the many benefits riparian buffers may provide, their application as instruments for water quality restoration rests on a relatively firm foundation of research. However, the extent to which buffers can restore riparian ecosystems; their functionality and species composition, are essentially unknown. In light of the foregoing, two broad areas of research are indicated. First, data are needed to document the relative effectiveness of riparian buffers that differ according to width, length, and plant species composition. These questions, of managing buffer dimension and species composition for functionality, are of central importance even when attenuation of nutrient and sediment loads alone are considered. Second, where ecosystem restoration is the goal, effects to in-stream and terrestrial riparian biota need to be considered. Relatedly, the effects of the restoration on the landscape need to be considered. Particularly, at what rate do the effects of the riparian buffer on in-stream water quality, biota, and habitat diminish downstream from restored sites? Answers to these important questions are needed, for streams and watersheds of different size and for areas of differing soil type within watersheds. U.S. EPA-NRMRL has initiated as research project that will document the potential for buffers to restore riparian ecosystems; focusing on water quality effects, but also, importantly, documenting effects on biota. While substantial riparian buffer management initiatives are already underway, the extent of landscapes that influence riparian ecosystems in the eastern United States is large; leaving ample opportunity for this suggested research to provide improved buffer designs in the future. The ultimate goal of research projects developed under this paradigm of ecosystem restoration is to develop data that are needed to implement riparian buffer restorations in the mid-Atlantic and elsewhere, especially the eastern United States.     

Landscape Correlates of Breeding Bird Richness Across the United States Mid-Atlantic Region

Using a new set of landscape indicator data generated by the U.S.EPA, and a comprehensive breeding bird database from the National Breeding Bird Survey, we evaluated associations between breeding bird richness and landscape characteristics across the entire mid-Atlantic region of the United States. We evaluated how these relationships varied among different groupings (guilds) of birds based on functional, structural, and compositional aspects of individual species demographics. Forest edge was by far the most important landscape attribute affecting the richness of the lumped specialist and generalist guilds; specialist species richness was negatively associated with forest edge and generalist richness was positively associated with forest edge. Landscape variables (indicators) explained a greater proportion of specialist species richness than the generalist guild (46% and 31%, respectively). The lower value in generalists may reflect finer-scale distributions of open habitat that go undetected by the Landsat satellite, open habitats created by roads (the areas from which breeding bird data are obtained), and the lumping of a wide variety of species into the generalist category. A further breakdown of species into 16 guilds showed considerable variation in the response of breeding birds to landscape conditions; forest obligate species had the strongest association with landscape indicators measured in this study (55% of the total variation explained) and forest generalists and open ground nesters the lowest (17% of the total variation explained). The variable response of guild species richness to landscape pattern suggests that one must consider species' demographics when assessing the consequences of landscape change on breeding birds.     

An evaluation of selenium concentrations in water, sediment, invertebrates, and fish from the Solomon River Basin

The Solomon River Basin is located in north-central Kansas in an area underlain by marine geologic shales. Selenium is an indigenous constituent of these shales and is readily leached into the surrounding groundwater. Portions of the Basin are irrigated primarily through the pumping of selenium-contaminated groundwater from wells onto fields in agricultural production. Water, sediment, macroinvertebrates, and fish were collected from various sites in the Basin in 1998 and analyzed for selenium. Selenium concentrations were analyzed spatially and temporally and compared to reported selenium toxic effect thresholds for specific ecosystem components: water, sediments, food-chain organisms, and wholebody fish. A selenium aquatic hazard assessment for the Basin was determined based on protocol established by Lemly. Throughout the Basin, water, macroinvertebrate, and whole fish samples exceeded levels suspected of causing reproductive impairment in fish. Population structures of several fish species implied that successful reproduction was occurring; however, the influence of immigration of fish from low-selenium habitats could not be discounted. Site-specific fish reproduction studies are needed to determine the true impact of selenium on fishery resources in the Basin. The U.S. Government’s right to retain a non-exclusive, royalty free license in and to any copyright is acknowledged.