Blowing Smoke in Yellowstone: Air Quality Impacts of Oversnow Motorized Recreation in the Park

Snowmobile use in Yellowstone National Park has been shown to impact air quality, with implications for the safety and welfare of Park staff and other Park resource values. Localized impacts have been documented at several high-use sites in the Park, but the broader spatial variability of snowmobile emissions and air quality was not understood. Measurements of 87 volatile organic compounds (VOCs) were made for ambient air sampled across the Park and West Yellowstone, Montana, during 2 days of the 2002–2003 winter use season, 1 year before the implementation of a new snowmobile policy. The data were compared with similar data from pristine West Coast sites at similar latitudes. Backward trajectories of local air masses, alkyl nitrate-parent alkane ratios, and atmospheric soundings were used to identify the VOC sources and assess their impact. Different oversnow vehicle types used in the Park were sampled to determine their relative influence on air mass pollutant composition. VOCs were of local origin and demonstrated strong spatiotemporal variability that is primarily influenced by levels of snowmobile traffic on given road segments at different times of day. High levels of snowmobile traffic in and around West Yellowstone produced consistently high levels of benzene, toluene, and carbon monoxide.     

Characterizing Storm Hydrograph Rise and Fall Dynamics With Stream Stage Data1

Abstract: Storm‐flow transients (i.e., hydrograph rise and fall dynamics) may represent an important aspect of understanding streamflow dynamics. However, little is known about how temporal resolution of transient data and climate variability may color these potential indicators of hydrologic pattern or condition. Warm‐season stream stage and rainfall were monitored continuously (5 min) during the 2002 water year in eight tributaries of the Little Miami River (Ohio), which drain 17‐58 km² catchments. Rise rates generated using 5‐min data were different than those generated with mean daily data [calculated with the Indicators of Hydrologic Alteration (IHA) software], though fall rates were similar for fine and coarse temporal data. This result suggests that data with low temporal resolution may not be adequate to fully represent the dynamics of storm rise rates. Conversely, fall rates based on daily stage data (via IHA) were similar to those based on the 5‐min data, and so daily mean data may be appropriate for characterizing fall rates. We next analyzed the possible correlations between rainfall variability and storm‐flow stage dynamics. We derived rise and recession rates from storm stage hydrographs by assuming exponential rise and decay of a runoff peak. We found that raw rise rates (R_raw) were correlated with both the maximum rainfall rate and the time to the centroid of a rain event. We subsequently removed the trend based on these rainfall characteristics, which yielded new representations of rise rates abbreviated as R_rate and R_tcent, respectively, and that had lower variability than the uncorrected (raw) data. Fall rates were found to be independent of rainfall characteristics. Due to the predominant influence of stream hydrology upon aquatic biota and nutrient fluxes, our work suggests that these stage data analysis protocols can refine or otherwise reduce variability in these indices by accounting for relevant factors such as rainfall forcing. These protocols for derivation of transient indices should be tested for their potential to improve correlations between stream hydrology and temporally aligned biotic data and dissolved nutrient fluxes in streams.     

Evaluation of post-Katrina flooded soils for contaminants and toxicity to the soil invertebrates Eisenia fetida and Caenorhabditis elegans

This research evaluated soil samples from a New Orleans neighborhood in the Chalmette, Saint Bernard Parish, that had been inundated by flooding associated with Hurricane Katrina. The goal was to determine if ecological risks persisted from flood waters that had come in contact with hazardous surface chemicals before inundating this low-lying neighborhood for a prolonged period. Research objectives were to establish the presence or absence of volatile organic and heavy metal contaminants, and then asses the toxicity of this soil to Eisenia fetida in a soil exposure assay and Caenorhabditis elegans in a simulated porewater exposure assay. Soil analysis revealed detectable levels of metals and organics in the surface soil at each location. No contaminant was detected in concentrations above human health screening values. Chromium and mercury were detected at levels in excess of typical ecological risk values. Soil extracts revealed concentrations of nitrate, sulfate, and chloride above those from an unflooded background sample. Toxicity testing resulted in no acute effects to either test species, but did show bioaccumulation of arsenic, cadmium, and lead in E. fetida exposed to several samples. The combination of mercury and sulfate provide the potential for mercury methylation should flooding and prolonged inundation occur again.     

Enhancement of the CO(2) retention capacity of X zeolites by Na- and Cs-treatments

Adsorption of carbon dioxide on alkaline modified X zeolites was investigated by temperature programmed desorption (TPD) analysis of these materials previously saturated with CO(2) at 50, 100 and 200 degrees C. Parent X zeolite (in its sodium form) was treated with different sodium and cesium aqueous solutions, using both carbonates and hydroxides as precursors. The resulting materials were characterised by nitrogen physisorption, XRD, and NH(3)-TPD, in order to determine their morphological, crystallographic and chemical properties. Slight desilication phenomena were observed using hydroxides as precursors, whereas the treatment with Cs salts lead to higher crystallinity losses. Several successive adsorption-desorption cycles were carried out in order to check the regenerability of the adsorbents. Cesium-treated zeolites present higher carbon dioxide retention capacities than the sodium treated and than the parent material. When working with these Cs-modified materials, the desorption takes place mainly at temperatures between 250 and 400 degrees C, results of great practical interest, since it allows the use these kinds of materials for adsorption-desorption cycles. The evolution of the retention capacity with temperature is also markedly more positive for Cs-treated zeolite, especially when carbonate is used as the precursor. These materials maintain high retention capacities at 100 degrees C (10mg g(-1)) and even at 200 degrees C (3mg g(-1)), temperatures at which the most of the adsorbents are inactive.     

Ozonation of oil sands process water removes naphthenic acids and toxicity

Naphthenic acids are naturally-occurring, aliphatic or alicyclic carboxylic acids found in petroleum. Water used to extract bitumen from the Athabasca oil sands becomes toxic to various organisms due to the presence of naphthenic acids released from the bitumen. Natural biodegradation was expected to be the most cost-effective method for reducing the toxicity of the oil sands process water (OSPW). However, naphthenic acids are poorly biodegraded in the holding ponds located on properties leased by the oil sands companies. In the present study, chemical oxidation using ozone was investigated as an option for mitigation of this toxicity. Ozonation of sediment-free OSPW was conducted using proprietary technology manufactured by Seair Diffusion Systems Inc. Ozonation for 50min generated a non-toxic effluent (based on the Microtox bioassay) and decreased the naphthenic acids concentration by approximately 70%. After 130min of ozonation, the residual naphthenic acids concentration was 2mgl(-1): <5% of the initial concentration in the filtered OSPW. Total organic carbon did not change with 130min of ozonation, whereas chemical oxygen demand decreased by approximately 50% and 5-d biochemical oxygen demand increased from an initial value of 2mgl(-1) to a final value of 15mgl(-1). GC-MS analysis showed that ozonation resulted in an overall decrease in the proportion of high molecular weight naphthenic acids (n> or = 22).     

An enzyme-linked immunosorbent assay for the determination of dioxins in contaminated sediment and soil samples

A 96-microwell enzyme-linked immunosorbent assay (ELISA) method was evaluated to determine PCDDs/PCDFs in sediment and soil samples from an EPA Superfund site. Samples were prepared and analyzed by both the ELISA and a gas chromatography/high resolution mass spectrometry (GC/HRMS) method. Comparable method precision, accuracy, and detection level (8 ng kg(-1)) were achieved by the ELISA method with respect to GC/HRMS. However, the extraction and cleanup method developed for the ELISA requires refinement for the soil type that yielded a waxy residue after sample processing. Four types of statistical analyses (Pearson correlation coefficient, paired t-test, nonparametric tests, and McNemar's test of association) were performed to determine whether the two methods produced statistically different results. The log-transformed ELISA-derived 2,3,7,8-tetrachlorodibenzo-p-dioxin values and log-transformed GC/HRMS-derived TEQ values were significantly correlated (r=0.79) at the 0.05 level. The median difference in values between ELISA and GC/HRMS was not significant at the 0.05 level. Low false negative and false positive rates (<10%) were observed for the ELISA when compared to the GC/HRMS at 1,000 ng TEQ kg(-1). The findings suggest that immunochemical technology could be a complementary monitoring tool for determining concentrations at the 1,000 ng TEQ kg(-1) action level for contaminated sediment and soil. The ELISA could also be used in an analytical triage approach to screen and rank samples prior to instrumental analysis.     

Effects of concentrated drinking water injection on glutathione and glutathione-dependent enzymes in liver of Cyprinus carpio L

Two drinking water production plants located in North Italy, collecting water from the River Po (Plants 1 and 2) were chosen for this study. Water samples were collected before and after the disinfection process and at two points along the piping system. Water samples were concentrated by the solid-phase extraction system and injected intraperitoneally into specimens of Cyprinus carpio. The concentration of water samples was 3 l/equiv. In order to assess the effects of the water samples on carp liver, total glutathione and glutathione-dependent enzymes, such as glutathione S-transferase, glutathione peroxidase, glutathione reductase and glyoxalase I, were measured following this treatment for 6 days at two experimental times (3 and 6 days). Both water plant-treated carp showed a general increase of the enzymatic activities of glutathione S-transferase, and glutathione reductase which might be employed as potential biomarkers of oxidative stress induced by disinfected river water. Plant 1-treated carp showed higher glyoxalase I and glutathione levels and lower glutathione peroxidase activity. A depleted level of total glutathione and of glyoxalase I for specimens of water plant 2 (for both experimental times), without correlation with the distances in the pipeline, suggests that river plant water can also lead to potentially adverse effects on selected biochemical parameters in C. carpio.     

Removal and degradation of aromatic compounds from a highly polluted site by coupling soil washing with photocatalysis

The possible application of two environmental remediation technologies - soil washing and photocatalysis - to remove and decompose various aromatic pollutants present in excavated soils of a contaminated industrial site has been investigated. Aqueous solutions containing the non-ionic surfactant Brij 35 were used to extract the contaminants from the soil samples. The photocatalytic treatment of the obtained washing wastes, performed in the presence of TiO(2) suspensions irradiated with simulated sunlight, showed a slow abatement of the toxic compounds due to the relevant concentrations of organics in the waste. A neat improvement of the process performances, obtained by operating in the presence of added potassium peroxydisulfate, suggests a feasible treatment route.     

LogD: lipophilicity for ionisable compounds

The octanol/water partition coefficient (Kow) for organic compounds is widely used in predictive environmental studies. A significant proportion of contaminants of surface and ground water are ionisable (e.g. many pesticides, pharmaceuticals, metabolites). Such compounds may be partially ionised dependent on the pH. Since the neutral and ionic species exhibit different polarities, the Kow value of ionisable pesticides is pH dependent. It is therefore essential to determine Kow values over the full range of pH that occurs in the environment in order to get appropriate predictors. Numerous methods are available to measure lipophilicity but only a few are appropriate for ionisable pesticides (e.g. pH metric and filter probe methods). Parameters such as pH and ionic strength need to be carefully controlled when working with ionisable compounds. Variation of these factors probably explains why literature can yield Kow values that differ by more than one order of magnitude for some compounds. In this article, Kow values obtained for six acidic pesticides with three different methods are compared as well (data from the literature, measured by pH metric method and calculated with five computer programs). The values used in predictive regression equations needs to be either measured with a suitable method or selected from the literature with great care.     

Treatment of groundwater contaminated with gasoline components by an ozone/UV process

In this paper, the treatment of real groundwater samples contaminated with gasoline components, such as benzene, toluene, ethylbenzene, and xylene (BTEX), methyl tert-butyl ether (MTBE), tert-butyl alcohol (TBA), and other gasoline constituents in terms of total petroleum hydrocarbons as gasoline (TPHg) by an ozone/UV process was investigated. The treatment was conducted in a semi-batch reactor under different experimental conditions by varying ozone gas dosage and incident UV light intensity. The groundwater samples contained BTEX compounds, MTBE, TBA, and TPHg in the ranges of 5-10000, 3000-5500, 80-1400, and 2400-20000mugl(-1), respectively. The ozone/UV process was very effective compared to ozonation in the removal of the gasoline components from the groundwater samples. For the various gasoline constituents, more than 99% removal efficiency was achieved for the ozone/UV process and the removal efficiency for ozonation was as low as 27%. The net ozone consumed per mol of organic carbon (from BTEX, MTBE, and TBA) oxidized varied in the range of 5-60 for different types of groundwater samples treated by the ozone/UV process. In ozonation experiments, it was observed that the presence of sufficient amount of iron in groundwater samples improved the removal of BTEX, MTBE, TBA, and TPHg.