A photochemical reactor for studies of atmospheric chemistry

A photochemical reactor for studies of atmospheric kinetics and spectroscopy has been built at the Copenhagen Center for Atmospheric Research. The reactor consists of a vacuum FTIR spectrometer coupled to a 100 L quartz cylinder by multipass optics mounted on electropolished stainless steel end flanges, surrounded by UV-A, UV-C and broadband sun lamps in a temperature-controlled housing. The combination of a quartz vessel and UV-C lamps allows higher concentrations of O(¹D) and OH than can be generated by similar chambers. The reactor is able to produce radical concentrations of ca. 8 × 10¹¹ cm^?3 for OH, 3 × 10⁶ cm^?3 for O(¹D), 3.3 × 10¹⁰ cm^?3 for O(³P) and 1.6 × 10¹² cm^?3 for Cl. The reactor can be operated at pressures from 10^?3 to 10³ mbar and temperatures from 240 to 330 K. As a test of the system we have studied the reaction CHCl₃ + Cl using the relative rate technique and find k_CHCl3+Cl/k_CH4+Cl = 1.03 ± 0.11, in good agreement with the accepted value.     

Microenvironmental characteristics important for personal exposures to aldehydes in Sacramento,CA, and Milwaukee,WI

Oxygenated additives in gasoline are designed to decrease the ozone-forming hydrocarbons and total air toxics, yet they can increase the emissions of aldehydes and thus increase human exposure to these toxic compounds. This paper describes a study conducted to characterize targeted aldehydes in microenvironments in Sacramento, CA, and Milwaukee, WI, and to improve our understanding of the impact of the urban environment on human exposure to air toxics. Data were obtained from microenvironmental concentration measurements, integrated, 24-h personal measurements, indoor and outdoor pollutant monitors at the participants' residences, from ambient pollutant monitors at fixed-site locations in each city, and from real-time diaries and questionnaires completed by the technicians and participants. As part of this study, a model to predict personal exposures based on individual time/activity data was developed for comparison to measured concentrations. Predicted concentrations were generally within 25% of the measured concentrations. The microenvironments that people encounter daily provide for widely varying exposures to aldehydes. The activities that occur in those microenvironments can modulate the aldehyde concentrations dramatically, especially for environments such as “indoor at home.” By considering personal activity, location (microenvironment), duration in the microenvironment, and a knowledge of the general concentrations of aldehydes in the various microenvironments, a simple model can do a reasonably good job of predicting the time-averaged personal exposures to aldehydes, even in the absence of monitoring data. Although concentrations of aldehydes measured indoors at the participants' homes tracked well with personal exposure, there were instances where personal exposures and indoor concentrations differed significantly. Key to the ability to predict exposure based on time/activity data is the quality and completeness of the microenvironmental characterizations for the chemicals of interest. Consistent with many earlier studies, personal exposures are difficult to predict using data from regional outdoor monitors.     

Climate Change, Coral Reef Ecosystems, and Management Options for Marine Protected Areas

Marine protected areas (MPAs) provide place-based management of marine ecosystems through various degrees and types of protective actions. Habitats such as coral reefs are especially susceptible to degradation resulting from climate change, as evidenced by mass bleaching events over the past two decades. Marine ecosystems are being altered by direct effects of climate change including ocean warming, ocean acidification, rising sea level, changing circulation patterns, increasing severity of storms, and changing freshwater influxes. As impacts of climate change strengthen they may exacerbate effects of existing stressors and require new or modified management approaches; MPA networks are generally accepted as an improvement over individual MPAs to address multiple threats to the marine environment. While MPA networks are considered a potentially effective management approach for conserving marine biodiversity, they should be established in conjunction with other management strategies, such as fisheries regulations and reductions of nutrients and other forms of land-based pollution. Information about interactions between climate change and more “traditional” stressors is limited. MPA managers are faced with high levels of uncertainty about likely outcomes of management actions because climate change impacts have strong interactions with existing stressors, such as land-based sources of pollution, overfishing and destructive fishing practices, invasive species, and diseases. Management options include ameliorating existing stressors, protecting potentially resilient areas, developing networks of MPAs, and integrating climate change into MPA planning, management, and evaluation.     

Forecasting Alpine Vegetation Change Using Repeat Sampling and a Novel Modeling Approach

Global change affects alpine ecosystems by, among many effects, by altering plant distributions and community composition. However, forecasting alpine vegetation change is challenged by a scarcity of studies observing change in fixed plots spanning decadal-time scales. We present in this article a probabilistic modeling approach that forecasts vegetation change on Niwot Ridge, CO using plant abundance data collected from marked plots established in 1971 and resampled in 1991 and 2001. Assuming future change can be inferred from past change, we extrapolate change for 100 years from 1971 and correlate trends for each plant community with time series environmental data (1971–2001). Models predict a decreased extent of Snowbed vegetation and an increased extent of Shrub Tundra by 2071. Mean annual maximum temperature and nitrogen deposition were the primary a posteriori correlates of plant community change. This modeling effort is useful for generating hypotheses of future vegetation change that can be tested with future sampling efforts.     

Direct and indirect effects of ammonia, ammonium and nitrate on phosphatase activity and carbon fluxes from decomposing litter in peatland

Here we investigate the response of soils and litter to 5 years of experimental additions of ammonium (NH₄), nitrate (NO₃), and ammonia (NH₃) to an ombrotrophic peatland. We test the importance of direct (via soil) and indirect (via litter) effects on phosphatase activity and efflux of CO₂. We also determined how species representing different functional types responded to the nitrogen treatments. Our results demonstrate that additions of NO₃, NH₄ and NH₃ all stimulated phosphatase activity but the effects were dependent on species of litter and mechanism (direct or indirect). Deposition of NH₃ had no effect on efflux of CO₂ from Calluna vulgaris litter, despite it showing signs of stress in the field, whereas both NO₃ and NH₄ reduced CO₂ fluxes. Our results show that the collective impacts on peatlands of the three principal forms of nitrogen in atmospheric deposition are a result of differential effects and mechanisms on individual components.     

Characterization and identification of trends in average ambient ozone and fine particulate matter levels through trajectory cluster analysis in eastern Canada

In many locations in Eastern Canada, ambient levels of fine particulate matter (PM,25) and surface ozone (O3) depend on airflow direction and synoptic scale meteorological conditions. In this study, a cluster analysis was performed on 10 yr (1994-2003) of back-trajectory data for 11 locations in Eastern Canada, resulting in the identification of 10 unique back-trajectory clusters (or airflows) for each location. The airflows were then used to characterize and identify spatial and temporal trends in the daily maximum 8-hr average O3 (dmax 8-hr O3) and the daily average PM2.5 levels. Results showed that airflows from the southwest passing over Michigan and Southern Ontario were associated, on average, with the highest O3 levels at most locations in Eastern Canada. For PM2.5, the highest levels occurred with airflows from the Eastern Ohio River Valley. At major urban locations in Ontario and Quebec, the warm season mean (May to September) dmax 8-hr O3 and the annual mean PM2.5 were, on average, 12 parts per billion and 7.6 microg/m3 higher, respectively, than airflows from the north. Elevated levels of O3 and PM2.5 also occurred under light airflows, and, on average, the levels under light airflows were higher than their nonlight counterparts. At several locations in Canada, including Toronto, Montreal, Quebec City, and Kejimkujik, the annual warm season mean dmax 8-hr O3 experienced a statistically significant (95% confidence) increasing trend over the 10-yr period. When airflow direction was considered, a number of locations experienced statistically significant upward trends in O3 for airflow from the north and northwest. Several locations also showed significant upward trends associated with airflow from the southwest passing over Michigan and Southwestern Ontario. Although there are no statistically significant downward trends, airflows from the southwest have shown a reduction in O3 levels in Southwestern Ontario in more recent years.     

Use of the electrical aerosol detector as an indicator of the surface area of fine particles deposited in the lung

Because of recent concerns about the health effects of ultrafine particles and the indication that particle toxicity is related to surface area, we have been examining techniques for measuring parameters related to the surface area of fine particles, especially in the 0.003- to 0.5-microm size range. In an earlier study, we suggested that the charge attached to particles, as measured by a prototype of the Electrical Aerosol Detector (EAD, TSI Inc., Model 3070), was related to the 1.16 power of the mobility diameter. An inspection of the pattern of particle deposition in the lung as a function of particle size suggested that the EAD measurement might be a useful indicator of the surface area of particles deposited in the lung. In this study, we calculate the particle surface area (micrometer squared) deposited in the lung per cubic centimeter of air inhaled as a function of particle size using atmospheric particle size distributions measured in Minneapolis, MN, and East St. Louis, IL. The correlations of powers of the mobility diameter, Dx, were highest for X = 1.1-1.6 for the deposited surface area and for X = 1.25 with the EAD signal. This overlap suggested a correspondence between the EAD signal and the deposited surface area. The correlation coefficients of the EAD signal and particle surface area deposited in the alveolar and tracheobronchial regions of the lung for three breathing patterns are in the range of Pearson's r = 0.91-0.95 (coefficient of determination, R2 = 0.82-0.90). These statistical relationships suggest that the EAD could serve as a useful indicator of particle surface area deposited in the lung in exposure and epidemiologic studies of the human health effects of atmospheric particles and as a measure of the potential surface area dose for the characterization of occupational environments.     

Evaluation of groundwater flow patterns around a dual-screened groundwater circulation well

Dual-screened groundwater circulation wells (GCWs) can be used to remove contaminant mass and to mix reagents in situ. GCWs are so named because they force water in a circular pattern between injection and extraction screens. The radial extent, flux and direction of the effective flow of this circulation cell are difficult to measure or predict. The objective of this study is to develop a robust protocol for assessing GCW performance. To accomplish this, groundwater flow patterns surrounding a GCW are assessed using a suite of tools and data, including: hydraulic head, in situ flow velocity, measured hydraulic conductivity data from core samples, chemical tracer tests, contaminant distribution data, and numerical flow and transport models. The hydraulic head data show patterns that are consistent with pumping on a dual-screened well, however, many of the observed changes are smaller than expected. In situ thermal perturbation flow sensors successfully measured horizontal flow, but vertical flow could not be determined with sufficient accuracy to be useful in mapping flow patterns. Two types of chemical tracer tests were utilized at the site and showed that much of the flow occurs within a few meters of the GCW. Flow patterns were also assessed based on changes in contaminant (trichloroethylene, TCE) concentrations over time. The TCE data clearly showed treated water moving away from the GCW at shallow and intermediate depths, but the circulation of that water back to the well, except very close to the well, was less clear. Detailed vertical and horizontal hydraulic conductivities were measured on 0.3 m-long sections from a continuous core from the GCW installation borehole. The measured vertical and horizontal hydraulic conductivity data were used to construct numerical flow and transport models, the results of which were compared to the head, velocity and concentration data. Taken together, the field data and modeling present a fairly consistent picture of flow and transport around the GCW. However, the time and expense associated with conducting all of those tests would be prohibitive for most sites. As a consequence, a sequential protocol for GCW characterization is presented here in which the number of tools used can be adjusted to meet the needs of individual sites. While not perfect, we believe that this approach represents the most efficient means for evaluating GCW performance.     

Contaminant exposure in outmigrant juvenile salmon from Pacific Northwest estuaries of the United States

To better understand the dynamics of contaminant uptake in outmigrant juvenile salmon in the Pacific Northwest, concentrations of polychlorinated biphenyls (PCBs), DDTs, polycylic aromatic hydrocarbons (PAHs) and organochlorine pesticides were measured in tissues and prey of juvenile chinook and coho salmon from several estuaries and hatcheries in the US Pacific Northwest. PCBs, DDTs, and PAHs were found in tissues (whole bodies or bile) and stomach contents of chinook and coho salmon sampled from all estuaries, as well as in chinook salmon from hatcheries. Organochlorine pesticides were detected less frequently. Of the two species sampled, chinook salmon had the highest whole body contaminant concentrations, typically 2--5 times higher than coho salmon from the same sites. In comparison to estuarine chinook salmon, body burdens of PCBs and DDTs in hatchery chinook were relatively high, in part because of the high lipid content of the hatchery fish. Concentrations of PCBs were highest in chinook salmon from the Duwamish Estuary, the Columbia River and Yaquina Bay, exceeding the NOAA Fisheries' estimated threshold for adverse health effects of 2400 ng/g lipid. Concentrations of DDTs were especially high in juvenile chinook salmon from the Columbia River and Nisqually Estuary; concentrations of PAH metabolites in bile were highest in chinook salmon from the Duwamish Estuary and Grays Harbor. Juvenile chinook salmon are likely absorbing some contaminants during estuarine residence through their prey, as PCBs, PAHs, and DDTs were consistently present in stomach contents, at concentrations significantly correlated with contaminant body burdens in fish from the same sites.     

What difference might sewage treatment performance make to endocrine disruption in rivers?

An assessment of the steroid estrogen removing performance of 23 different sewage treatment plants (STPs) was performed. The assessment relied on a model to estimate influent concentrations, and completed questionnaires on the STP treatment details from the relevant water companies. This information was compared with observed effluent 17beta-estradiol (E2) and estrone (E1) concentrations. The 10 biological filter plants (BFP) in the study performed poorly with only 30% (SD 31) removal on average for E1. This reduced E1 removal performance of the BFPs compared to all the other STP types in the survey was statistically significant (p<0.001). Scenarios of all the STPs as activated sludge types, and one as all BFP types were modelled using the GREAT-ER model set up for the Aire/Calder catchment in the UK. This difference was shown to have an important effect on predicted river E1 concentrations and consequent risk classifications.