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.     

New measurements of cyanobacterial toxins in natural waters using high performance liquid chromatography coupled to tandem mass spectrometry

The presence and levels of the cyanobacterial toxins microcystin-LR, anatoxin-a, and cylindrospermopsin were measured in various Wisconsin waters where algal nuisance or bloom conditions were noted. Out of 74 samples analyzed, 36 had detectable levels of microcystin-LR (49%), and four had detectable levels of anatoxin-a (5%). Cylindrospermopsin, the toxin produced by Cylindrospermopsis (a warm water species that has been moving its range northward, including to Wisconsin), was not detected in the field samples tested. Concentrations of microcystin-LR ranged from 1.2 to 7600 microg L(-1). Anatoxin-a ranged from 0.68 to 1750 microg L(-1), which is the highest concentration reported from around the world. Cyanobacterial toxins, because of their high potency, deserve continued scrutiny by resource managers and public health officials responsible for recreational waters.     

Insights into the nature of secondary organic aerosol in Mexico City during the MILAGRO experiment 2006

This study targets understanding the secondary sources of organic aerosol in Mexico City during the Megacities Impact on Regional and Global Environment (MIRAGE) 2006 field campaign. Ambient PM_2.5 was collected daily at urban and peripheral locations. Particle-phase secondary organic aerosol (SOA) products of anthropogenic and biogenic precursor gases were measured by gas chromatography mass spectrometry. Ambient concentrations of SOA tracers were used to estimate organic carbon (OC) from secondary origins (SOC). Anthropogenic SOC was estimated as 20–25% of ambient OC at both sites, while biogenic SOC was less abundant, but was relatively twice as important at the peripheral site. The OC that was not attributed secondary sources or to primary sources in a previous study showed temporal consistency with biomass-burning events, suggesting the importance of secondary processing of biomass-burning emissions in the region. The best estimate of biomass-burning-related SOC was in the range of 20–30% of ambient OC during peak biomass burning events. Low-molecular weight (MW) alkanoic and alkenoic dicarboxylic acids (C₂–C₅) were also measured, of which oxalic acid was the most abundant. The spatial and temporal trends of oxalic acid differed from tracers for primary and secondary sources, suggesting that it had different and/or multiple sources in the atmosphere.     

Pharmaceuticals and personal care products found in the Great Lakes above concentrations of environmental concern

The monitoring of pharmaceuticals and personal care products (PPCPs) has focused on the distribution in rivers and small lakes, but data regarding their occurrence and effects in large lake systems, such as the Great Lakes, are sparse. Wastewater treatment processes have not been optimized to remove influent PPCPs and are a major source of PPCPs in the environment. Furthermore, PPCPs are not currently regulated in wastewater effluent. In this experiment we evaluated the concentration, and corresponding risk, of PPCPs from a wastewater effluent source at varying distances in Lake Michigan. Fifty-four PPCPs and hormones were assessed on six different dates over a two-year period from surface water and sediment samples up to 3.2 km from a wastewater treatment plant and at two sites within a harbor. Thirty-two PPCPs were detected in Lake Michigan and 30 were detected in the sediment, with numerous PPCPs being detected up to 3.2 km away from the shoreline. The most frequently detected PPCPs in Lake Michigan were metformin, caffeine, sulfamethoxazole, and triclosan. To determine the ecological risk, the maximum measured environmental concentrations were compared to the predicted no-effect concentration and 14 PPCPs were found to be of medium or high ecological risk. The environmental risk of PPCPs in large lake systems, such as the Great Lakes, has been questioned due to high dilution; however, the concentrations found in this study, and their corresponding risk quotient, indicate a significant threat by PPCPs to the health of the Great Lakes, particularly near shore organisms.     

Creating markets for combined heat and power and clean distributed generation in New York State

Combined heat and power (CHP) is the simultaneous production of electrical or mechanical power and thermal energy from in a single process. Because thermal output from the generation of electricity is captured and utilized onsite, CHP systems can achieve efficiencies from 60% to as high as 90%. In contrast generation of electric power at sites remote from the loads served often results in efficiencies of 33% or less due to losses in generation and transmission and distribution of the power to ultimate end users. A well designed CHP system is the essence of energy efficiency. It may also provide significant environmental benefits. However, the full promise of CHP for improving the efficiency and productivity of businesses and the quality of the environment is unlikely to be realized given the current market structure and regulatory environment in which CHP projects are forced to compete. This paper examines the market structure and regulatory obstacles that hinder the development of more robust markets for CHP in New York State.     

Emissions from small-scale energy production using co-combustion of biofuel and the dry fraction of household waste

In sparsely populated rural areas, recycling of household waste might not always be the most environmentally advantageous solution due to the total amount of transport involved. In this study, an alternative approach to recycling has been tested using efficient small-scale biofuel boilers for co-combustion of biofuel and high-energy waste. The dry combustible fraction of source-sorted household waste was mixed with the energy crop reed canary-grass (Phalaris Arundinacea L.), and combusted in both a 5-kW pilot scale reactor and a biofuel boiler with 140-180 kW output capacity, in the form of pellets and briquettes, respectively. The chlorine content of the waste fraction was 0.2%, most of which originated from plastics. The HCl emissions exceeded levels stipulated in new EU-directives, but levels of equal magnitude were also generated from combustion of the pure biofuel. Addition of waste to the biofuel did not give any apparent increase in emissions of organic compounds. Dioxin levels were close to stipulated limits. With further refinement of combustion equipment, small-scale co-combustion systems have the potential to comply with emission regulations.     

Impact of climate change and seasonal trends on the fate of Arctic oil spills

We investigated the effects of a warmer climate, and seasonal trends, on the fate of oil spilled in the Arctic. Three well blowout scenarios, two shipping accidents and a pipeline rupture were considered. We used ensembles of numerical simulations, using the OSCAR oil spill model, with environmental data for the periods 2009–2012 and 2050–2053 (representing a warmer future) as inputs to the model. Future atmospheric forcing was based on the IPCC’s A1B scenario, with the ocean data generated by the hydrodynamic model SINMOD. We found differences in “typical” outcome of a spill in a warmer future compared to the present, mainly due to a longer season of open water. We have demonstrated that ice cover is extremely important for predicting the fate of an Arctic oil spill, and find that oil spills in a warming climate will in some cases result in greater areal coverage and shoreline exposure.     

Air quality impacts of distributed energy resources implemented in the northeastern United States

Emissions from the potential installation of distributed energy resources (DER) in the place of current utility-scale power generators have been introduced into an emissions inventory of the northeastern United States. A methodology for predicting future market penetration of DER that considers economics and emission factors was used to estimate the most likely implementation of DER. The methodology results in spatially and temporally resolved emission profiles of criteria pollutants that are subsequently introduced into a detailed atmospheric chemistry and transport model of the region. The DER technology determined by the methodology includes 62% reciprocating engines, 34% gas turbines, and 4% fuel cells and other emerging technologies. The introduction of DER leads to retirement of 2625 MW of existing power plants for which emissions are removed from the inventory. The air quality model predicts maximum differences in air pollutant concentrations that are located downwind from the central power plants that were removed from the domain. Maximum decreases in hourly peak ozone concentrations due to DER use are 10 ppb and are located over the state of New Jersey. Maximum decreases in 24-hr average fine particulate matter (PM2.5) concentrations reach 3 microg/m3 and are located off the coast of New Jersey and New York. The main contribution to decreased PM2.5 is the reduction of sulfate levels due to significant reductions in direct emissions of sulfur oxides (SO(x)) from the DER compared with the central power plants removed. The scenario presented here represents an accelerated DER penetration case with aggressive emission reductions due to removal of highly emitting power plants. Such scenario provides an upper bound for air quality benefits of DER implementation scenarios.     

Stress on and off the job as related to sex and occupational status in white-collar workers

Sixty healthy non-smoking white collar employees, aged 30–50, from a large corporation in Sweden participated in the study. There were four groups: 15 male and 15 female middle managers, 15 male and 15 female clerical workers. Each participant was examined individually with regard to cardiovascular and neuroendocrine functions and self-reports for 12 consecutive hours under each of two conditions: (1) a normal day at work (9 a.m.–5 p.m.) and after work (6–9 p.m.), and (2) for the same time period during work-free conditions at home. In addition, everyone was given a videotaped type A-interview and a general health check-up including blood-lipid determination. Attitudes towards work, total workload (including responsibilities outside the paid work) and sex role identity were examined by questionnaires. As expected, all groups showed a moderate increase in cardiovascular and neuroendocrine activity during the day at work. After work, however, interesting group differences emerged, suggesting slower unwinding in female managers. Differences related to occupational level and/ or sex were found for autonomy and social support at work, competitiveness, sex role and reported conflict between demands from paid work and other responsibilities. The stress profile of the female managers was considered in terms of possible long-term health risks.