A critical compilation of Henry's law constant temperature dependence relations for organic compounds in dilute aqueous solutions

A comprehensive compilation of published studies reporting directly measured experimental determinations of Henry's law constant (HLC) temperature dependence relationships for organic compounds in dilute, non-saline aqueous solutions under ambient conditions was conducted. From this effort, 55 such studies (covering 204 organic compounds) were identified, critically reviewed, summarized and discussed. Of the 204 compounds, 57 were studied in more than one investigation. For the 57 'multi-studied' compounds, relatively good agreement (averaging within 20-30%) was found between the results from different investigations. Given such results, a 'consensus' relationship (i.e., an average temperature dependence relation) was generated for each of the multi-studied compounds. Overall, considering relations established for 197 of the 204 compounds investigated (the results for the other 7 compounds being excluded due to poor correlation coefficients), the average slope of the temperature dependence line was found to correspond to an increase in HLC values by a factor of 1.88 (i.e., an 88% increase) per 10 degrees C rise in temperature (thermodynamically equivalent to an average enthalpy of volatilization of 47 kJ/mole). The associated range found for the temperature dependence slope corresponds to an increase in HLC values by a factor ranging from 1.12 to 3.55 (i.e., a 12-255% increase) per 10 degrees C rise (equivalent enthalpy of volatilization range: 8-93 kJ/mole). The wide range of slope values found indicates that serious errors may result if one applies the commonly cited 'rule of thumb' that HLC values double per 10 degrees C rise in temperature to a specific compound. In light of this finding, when faced with a lack of data, a prudent course for practitioners to take appears to be conducting a laboratory study to determine the exact temperature dependence for the compound(s) of interest.     

Evaluation of the digital opacity compliance system in high mountain desert environments

The digital opacity compliance system (DOCS) has been proposed as an alternative to the U.S. Environmental Protection Agency Reference Method 9 (Visual Determination of the Opacity of Emissions for Stationary Sources). The DOCS, which employs standard digital photography to estimate the opacity of visible emissions, was evaluated in a high mountain desert environment located in Weber County, UT. The DOCS recorded an average opacity deviation of 5.28% when applied to black smoke plumes having true opacities in the range of 0-100%, an error rate that was found to be significantly less than 7.5% (allowable error rate for attaining certification under Method 9). In contrast, results from estimating the opacity of white smoke plumes indicated that the accuracy of the DOCS was less than the Method 9 error rate only in the opacity range of 0-60%, over which the DOCS average opacity deviation was determined to be 6.7%. For the 0-40% opacity range, the DOCS recorded an average opacity deviation of 5.44% and 5.9% for black and white plumes, respectively. Results from the present study suggest that the DOCS has the potential to quantify visible opacity with an error rate that is significantly less than the Method 9 permissible error rate. Although encouraging, it is unclear to what extent the DOCS is affected by climatic conditions other than those encountered in a dry desert environment. Future studies should focus on evaluating the performance of the DOCS under variable weather conditions.     

Air quality modeling and decisions for ozone reduction strategies

Despite the widespread application of photochemical air quality models (AQMs) in U.S. state implementation planning (SIP) for attainment of the ambient ozone standard, documentation for the reliability of projections has remained highly subjective. An "idealized" evaluation framework is proposed that provides a means for assessing reliability. Applied to 18 cases of regulatory modeling in the early 1990s in North America, a comparative review of these applications is reported. The intercomparisons suggest that more than two thirds of these AQM applications suffered from having inadequate air quality and meteorological databases. Emissions representations often were unreliable; uncertainties were too high. More than two thirds of the performance evaluation efforts were judged to be substandard compared with idealized goals. Meteorological conditions chosen according regulatory guidelines were limited to one or two cases and tended to be similar, thus limiting the extent to which public policy makers could be confident that the emission controls adopted would yield attainment for a broad range of adverse atmospheric conditions. More than half of the studies reviewed did not give sufficient attention to addressing the potential for compensating errors. Corroborative analyses were conducted in only one of the 18 studies reviewed. Insufficient attention was given to the estimation of model and/or input database errors, uncertainties, or variability in all of the cases examined. However, recent SIP and policy-related regional modeling provides evidence of substantial improvements in the underlying science and available modeling systems used for regulatory decision making. Nevertheless, the availability of suitable databases to support increasingly sophisticated modeling continues to be a concern for many locations. Thus, AQM results may still be subject to significant uncertainties. The evaluative process used here provides a framework for modelers and public policy makers to assess the adequacy of contemporary and future modeling work.     

Fate, effects and potential environmental risks of ethylene glycol: a review

The fate, effects, and potential environmental risks of ethylene glycol (EG) in the environment were examined. EG undergoes rapid biodegradation in aerobic and anaerobic environments (approximately 100% removal of EG within 24 h to 28 days). In air, EG reacts with photo-chemically produced hydroxyl radicals with a resulting atmospheric half-life of 2 days. Acute toxicity values (LC(50)s and EC(50)s) were generally >10,000 mg/l for fish and aquatic invertebrates. The data collectively show that EG is not persistent in air, surface water, soil, or groundwater, is practically non-toxic to aquatic organisms, and does not bioaccumulate in aquatic organisms. Potential long-term, quasi-steady state regional concentrations of EG estimated with a multi-media model for air, water, soil, and sediment were all less than predicted no effect concentrations (PNECs).     

Contamination of fish by 2,3,7,8-tetrachlorodibenzo-P-dioxin: A survey of fish from major watersheds in the United States

A survey of contamination of fish from major watersheds in the United States by 2,3,7,8-TCDD has been conducted by the U.S. EPA. Bottom feeding and predator fish were collected at 90 statistically selected and 305 regionally selected sites and analyzed by GC/MS. It was found that 19% of the statistically sampled sites and 31% of the regionally selected sites were contaminated at or above a minimum level of detection varying from 0.5 to 2.0 pg/g. Ten percent of all samples were contaminated at levels greater than 5.0 pg/g. It was also observed that a subset of samples collected at sites near discharge from pulp/paper manufacture (N=28) had a higher frequency of TCDD contamination above 5.0 pg/g (38%). This subset of samples also contained the sample of the greatest level of TCDD contamination (85 pg/g).     

Effects of reduced return activated sludge flows and volume on anaerobic zone performance for a septic wastewater biological phosphorus removal system.

Enhanced biological phosphorous removal (EBPR) performance was found to be adequate with reduced return-activated sludge (RAS) flows (50% of available RAS) to the anaerobic tank and smaller-than-typical anaerobic zone volume (1.08 hours hydraulic retention time [HRT]). Three identical parallel biological nutrient removal pilot plants were fed with strong, highly fermented (160 mg/L volatile fatty acids [VFAs]), domestic and industrial wastewater from a full-scale wastewater treatment facility. The pilot plants were operated at 100, 50, 40, and 25% RAS (percent of available RAS) flows to the anaerobic tank, with the remaining RAS to the anoxic tank. In addition, varying anaerobic HRT (1.08 and 1.5 hours) and increased hydraulic loading (35% increase) were examined. The study was divided into four phases, and the effect of these process variations on EBPR were studied by having one different variable between two identical systems. The most significant conclusion was that returning part of the RAS to the anaerobic zone did not decrease EBPR performance; instead, it changed the location of phosphorous release and uptake. Bringing less RAS to the anaerobic and more to the anoxic tank decreased anaerobic phosphorus release and increased anoxic phosphorus release (or decreased anoxic phosphorus uptake). Equally important is that, with VFA-rich influent wastewater, excessive anaerobic volume was shown to hurt overall phosphorus removal, even when it resulted in increased anaerobic phosphorus release.     

Relative efficacy of intrinsic and extant parameters for modeling biodegradation of synthetic organic compounds in activated sludge: dynamic systems.

The utility of intrinsic and extant kinetic parameters for simulating the dynamic behavior of a biotreatment system coupled with a distributed, unstructured, balanced microbial growth model were evaluated against the observed response of test reactors to transient loads of synthetic organic compounds (SOCs). Biomass from a completely mixed activated-sludge (CMAS) system was tested in fed-batch reactors, while a sequencing batch reactor (SBR) was tested by measuring SOC concentrations during the fill and react period. Both the CMAS system and the SBR were acclimated to a feed containing biogenic substrates and several SOCs, and the transient loading tests were conducted with biogenic substrates along with one or more SOCs. Extant parameters more closely reflect the steady-state degradative capacity of activated-sludge biomass than intrinsic parameters and, hence, were expected to be better predictors of system performance. However, neither extant nor intrinsic parameters accurately predicted system response and neither parameter set was consistently superior to the other. Factors that may have contributed to the inability of the model to predict system response were identified and discussed. These factors included the role of abiotic processes in SOC removal, disparity in the bases used to evaluate parameter estimates (substrate mineralization) and reactor performance (substrate disappearance), inhibitory substrate interactions under the severe loading conditions of the SBR, changes in the physiological state of the biomass during the transient loading tests, and the presumed correlation between the competent biomass concentration and the influent SOC concentration.     

Feeding preferences and the relationships between food choice and assimilation efficiency in the herbivorous marine snail Lithopoma undosum (Turbinidae)

Preference rankings for 13 macrophytes were established for the subtidal herbivorous snail Lithopoma undosum using two-choice laboratory experiments and consumption rates. L. undosum did not discriminate among three kelp foods (Egregia menziesii, Eisenia arborea and Macrocystis pyrifera) but ate kelp preferentially and more rapidly over all but Ulva spp. among tested macrophytes. Secondary preferences were established for the red alga Pterocladiella capillacea, followed by the coralline Lithothrix aspergillum, whereas the brown seaweeds Zonaria farlowii and Halidrys dioica and the seagrass Phyllospadix torreyi were the least preferred macrophytes. Fastest consumption rates (1.91 g day⁻¹) were measured in trials consisting only of kelp foods. These results indicate that L. undosum exhibits clear feeding preferences even when given less-preferred, non-kelp macrophytes. Using an ash-marker technique, we determined total organic, carbon, and nitrogen assimilation efficiencies (AE%) for six macroalgae used in preference trials. Tested macrophytes were assimilated at different efficiencies but a pattern was not detected between AE (%) and a macrophyte’s position in L. undosum’s preference hierarchy. Highest total organic AEs were found for P. capillacea (61.2%) and H. dioica (59.4%); lowest AEs were detected for E. menziesii (34.9%), a preferred dietary item. Nitrogen was assimilated from red algae with higher efficiencies (74.9–84.3%) than from brown or green algae. These data suggest that the digestive capabilities of L. undosum are better suited for assimilating organic material and nitrogen from less-preferred, non-kelp foods. This supports the hypothesis that factors besides nutritional composition and digestive optimization have played a role in the evolution of feeding preferences in L. undosum and probably other herbivorous snails associated with northeastern Pacific kelp beds.     

Spatial and temporal distribution of butyltin compounds in a Northern Chesapeake Bay Marina and river system

This study was designed to: determine dibutyltin (DBT), tributyltin (TBT) and tetrabutyltin (TTBT) bi-weekly for a four month period (June-September 1986) in the Port Annapolis Marina, Mears Marina, Back Creek and Severn River area of Northern Chesapeake Bay; measure DBT, TBT and TTBT for five successive days (Thursday-Monday) to determine possible daily effects (weekday versus weekend) and determine DBT, TBT and TTBT every two hours for one full tidal cycle in the study area. Maximum concentrations of TBT were reported at both Port Annapolis Marina (1801 ng L^–1) and Mears Marina (1171 ng L^–1) during early June followed by significant reductions in TBT during late summer and early fall. All 4 Back Creek Stations also had highest concentrations of TBT in early June; significant reductions occurred during the next three months. The highest concentration of TBT reported in the Severn River (48 ng L^–1) occurred in September. The lowest TBT value (5 ng L^-1) at this station occurred in June. TTBT was not detected in any of the samples. The day of week sampled (Thursday-Monday) during the daily experiments was not found to significantly affect TBT concentrations. TBT evaluations every two hours during the tidal cycle demonstrated that values peaked at 1400 and 1600 hr time intervals. Peak concentrations of TBT occurred during a rising tide. The possible consequence of the measured TBT concentrations for aquatic biota are discussed.     

Modeling the Effects of Air Quality Policy Changes on Water Quality in Urban Areas

This paper describes the development and application of an integrated modeling framework composed of an urban air chemistry model, an urban runoff model, and a water-quality model. The models were linked to simulate the fate and transport of air emissions of nitrogen compounds in the air, urban watershed, surface water runoff, and in a coastal receiving-water body. The model linkage is demonstrated by evaluating the potential water quality implications of reducing NO _x emissions by 32%, volatile organic compound emissions by 51%, and ammonia emissions by 30%, representing changes from 1987 levels to proposed 2000 target levels in Los Angeles, California, USA. Simulations of the Los Angeles dry season during the summer of 1987 (June 1 to August 31) indicated that by reducing emissions from 1987 to proposed year 2000 levels, the dry deposition nitrogen loads to Santa Monica Bay and the Ballona Creek watershed were reduced 21.4% and 15.0%, respectively. Water quality modeling results indicated that dry season atmospheric load reductions to the Ballona Creek Estuary did not reduce chlorophyll-a levels or significantly raise nighttime dissolved oxygen levels because the magnitude of the reductions was negligible compared to non-atmospheric inputs of nitrogen compounds. Simulations of the time period from November 18, 1987 to December 4, 1987 during the Los Angeles wet season indicated that air emissions reductions produced an 18.6% reduction in the dry deposition nitrogen load to Santa Monica Bay, a 15.5% reduction in the dry deposition nitrogen load to the Ballona Creek watershed, a 16.8% reduction in the wet deposition nitrogen load to the Ballona Creek watershed, and a 16.1% reduction in the stormwater discharge load from the Ballona Creek watershed. Although the wet season load reductions are significant, modeling results of the ultimate effect on the Ballona Creek Estuary water quality were inconclusive.