Methods for sampling and analysis of tropospheric ethanol in gaseous and aqueous phases

In this paper, we report on techniques for sampling and measuring ethanol in both the gas and aqueous phases of the lower troposphere. In the gas phase, the best sampling conditions were ensured by adsorption on Hayesep Q with a Chromosorb W AW coated with LiCl dryer (method 1) or by cryogenic trapping (method 2). An intercomparison campaign showed good agreement between both methods under various conditions. Method 1 (adsorption on Hayesep Q with dryer) is easier to set up and to carry away from the laboratory. Method 2 (cryogenic trapping) requires longer sampling time (up to 60 min while method 1 requires only 10-15 min). Method 1 is adapted to high concentrations of ethanol (>20 ppb) and low relative humidity (<30%). Method 2 gives more accurate results than method 1 for low ethanol concentrations (1-20 ppb). Comparing these results to previous studies, it is clear that sampling with appropriate solid adsorbents or with stainless steel canisters (with appropriate humidified air and short storage time) is adapted to urban or industrial environments where ethanol concentrations are high. Cryogenic sampling must be preferred for remote places where ethanol concentrations are low. Three techniques were tested for sampling ethanol in the liquid phase, namely solid phase microextraction, purge and trap injection, and direct injection. Among those, the latter was chosen for field measurements of ethanol in rain samples at an urban location. These first ever results at an urban location show concentrations ranging from <1 to 5 microM in rains, which agree with the expected range of concentrations. However, the purge and trap method showed detection limits that were 50 times lower and should be preferred for liquid phase ethanol measurements in rural and remote locations. Combining cryogenic trapping for the gas phase (method 2) and direct injection for the liquid phase is convenient and well adapted for a multiphase study of ethanol in the atmosphere, where simultaneous measurements in both phases are needed.     

Does the Harvard/U.S. Environmental Protection Agency Ambient Particle Concentrator change the toxic potential of particles?

Inhalation exposure to urban air particles is known to increase morbidity in humans and animals. Our group utilizes the Harvard/U.S. Environmental Protection Agency Ambient Particle Concentrator (HAPC) to generate concentrated aerosols of outdoor air particles for experimental exposures. We have reported increased pathologic responses to inhalation of concentrated urban air particles and identified silicon (as silicate) as an element associated with many of these responses. Using silicate-rich Mt. St. Helen's volcanic ash (MSHA), we exposed three groups of Sprague-Dawley rats by inhalation for 6 hr to filtered air, MSHA, or MSHA passed though the HAPC. Twenty-four hours following exposure, bronchoalveolar lavage was performed to assess total cell count, differential cell count, protein, lactate dehydrogenase, and n-beta-glucosaminidase levels. Peripheral blood was examined for packed cell volume, total protein, total white cells, and differential cell count. Morphologic studies localized particles in the lung and assessed pulmonary vasculature. No significant differences were observed among any of the groups in any parameter measured including morphometric analysis of pulmonary vasoconstriction. Scanning electron microscopy and X-ray analysis identified particles as silicates typical of MSHA throughout the lung. These findings suggest that particles passing through the HAPC have no change in their toxic potential in an exposure setting where particle deposition in the lung has occurred.     

Modeling recovery of Swedish ecosystems from acidification

Dynamic models complement existing time series of observations and static critical load calculations by simulating past and future development of chemistry in forest and lake ecosystems. They are used for dynamic assessment of the acidification and to produce target load functions, that describe what combinations of nitrogen and sulfur emission reductions are needed to achieve a chemical or biological criterion in a given target year. The Swedish approach has been to apply the dynamic acidification models MAGIC, to 133 lakes unaffected by agriculture and SAFE, to 645 productive forest sites. While the long-term goal is to protect 95% of the area, implementation of the Gothenburg protocol will protect approximately 75% of forest soils in the long term. After 2030, recovery will be very slow and involve only a limited geographical area. If there had been no emission reductions after 1980, 87% of the forest area would have unwanted soil status in the long term. In 1990, approximately 17% of all Swedish lakes unaffected by agriculture received an acidifying deposition above critical load. This fraction will decrease to 10% in 2010 after implementation of the Gothenburg protocol. The acidified lakes of Sweden will recover faster than the soils. According to the MAGIC model the median pre-industrial ANC of 107 microeq L(-1) in acid sensitive lakes decreased to about 60 microeq L(-1) at the peak of the acidification (1975-1990) and increases to 80 microeq L(-1) by 2010. Further increases were small, only 2 microeq L(-1) between 2010 and 2040. Protecting 95% of the lakes will require further emission reductions below the Gothenburg protocol levels. More than 7000 lakes are limed regularly in Sweden and it is unlikely that this practice can be discontinued in the near future without adverse effects on lake chemistry and biology.     

Economic assessment of the negative impacts of ozone on crop yields and forest production. A case study of the estate Ostads Säteri in southwestern Sweden

Ground level ozone concentrations, in combination with the prevailing climate, at the estate Ostads S?teri in southwestern Sweden were estimated to reduce the yield of wheat and potato ranging between 5% and 10%. Occasionally, in years with the highest ozone concentrations and/or climatic conditions favoring high rates of ozone uptake to the leaves, yield loss levels above 10% may occur. Based on simple extrapolation, these ozone-induced reductions of crop yields at Ostads S?teri represent a potential total annual yield loss in Sweden in the range of 24.5 million Euro for wheat and 7.3 million Euro for potato, respectively. A simulation of forest growth at Ostad S?teri predicted that prevailing mean ozone exposure during 1993-2003 had the potential to reduce forest growth by 2.2% and the economic return of forest production by 2.6%. Using this value for extrapolation to the national level, the potential annual economic loss for Sweden due to negative impacts of ozone on forest production would be in the range of 56 million Euro (2004 prices).     

Dissolved oxygen and dietary phosphorus modulate utilization and effluent partitioning of phosphorus in rainbow trout (Oncorhynchus mykiss) aquaculture

Phosphorus (P) is the limiting nutrient in freshwater primary production, and excessive levels cause premature eutrophication. P levels in aquaculture effluents are now tightly regulated. Increasing our understanding of waste P partitioning into soluble, particulate, and settleable fractions is important in the management of effluent P. When water supply is limited, dissolved oxygen concentration (DO) decreases below the optimum levels. Therefore, we studied effects of DO (6 and 10mg/L) and dietary P (0.7 and 1.0% P) on rainbow trout growth, P utilization, and effluent P partitioning. Biomass increased by 40% after 3 weeks. DO at 10mg/L significantly increased fish growth and feed efficiency, and increased the amount of P in the soluble fraction of the effluent. Soluble effluent P was greater in fish fed 1.0% P. DO increases fish growth and modulates P partitioning in aquaculture effluent.     

Comparison of PM2.5 carbon measurement methods in Hong Kong, China

Samples from Hong Kong, China, were analyzed for organic carbon (OC), elemental carbon (EC), and total carbon (TC) by three thermal protocols (low-temperature IMPROVE and high-temperature STN and NIOSH) and two optical monitoring methods: reflectance and transmittance. Good agreement (+/-10%) for TC among the three protocols was observed for sample loadings of 1-55 microg m(-3). The two protocols using a reflectance pyrolysis correction showed best agreement for EC, with <20% differences found for approximately 80% of the samples. Hong Kong has a large diesel fleet, and for some heavily loaded samples the light transmittance was too low for quantitative detection, resulting in large uncertainties in the OC/EC split based on transmittance. Hong Kong experienced OC levels similar to those at US sites, but has much higher EC concentrations. OC/EC ratios range from 2 to 5 at two US sites and from 0.2 to 1.2 at three Hong Kong sites.     

Use of hydrophilic and hydrophobic microfiltration membranes to remove microorganisms and organic pollutants from primary effluents.

Primary-effluent wastewater from the Allegheny County Sanitary Authority (Pennsylvania) was used as a surrogate for combined-sewer-overflow waters contained in the sewershed. Pathogens contained in combined-primary-effluent wastewaters or combined-sewer overflows (CSOs) may pose a human-health threat to those coming in contact with such receiving waters. Polymeric ultra- and nano-membranes can be used to capture these microorganisms from CSOs. This research investigates the ability of polymeric hydrophobic and hydrophilic membranes, ranging in pore size from 0.2 to 0.8 microm, to remove pathogen-indicator organisms (Escherichia coli, enterococcus, and fecal coliforms). Membranes, with pore size 0.45 microm and smaller, were able to reduce the bacteria levels to nondetectable levels, with the sole exception of one membrane with pore size 0.3 microm.     

Generation pattern of sulfur containing gases from anaerobically digested sludge cakes.

Eleven dewatered sludge cakes collected from anaerobic digesters at different treatment plants were evaluated for the amount, type, and pattern of odorous gas production. All but one of the sludge cakes were from mesophilic anaerobic digesters. One was from a thermophilic digester. The pattern and quantities of sulfur gases were found to be unique for each of the samples with regard to the products produced, magnitude, and subsequent decline. The main odor-causing chemicals were volatile sulfur compounds, which included hydrogen sulfide, methanethiol, and dimethyl sulfide. Volatile sulfur compound production peaked in 3 to 8 days and then declined. The decline was a result of conversion of organic sulfur compounds to sulfide. In one side-by-side test, a high-solids centrifuge cake generated more odorous compounds than the low-solids centrifuge cake. The data show that anaerobic digestion does not eliminate the odor potential of anaerobically digested dewatered cakes.