Denitrification and phenol degradation in a contaminated aquifer

A natural groundwater system modified by pollutant phenols and agricultural nitrate has been modelled in the laboratory by a series of sacrificial microcosm experiments. Samples of aquifer sediment and groundwater from the margin of the phenol plume were used to inoculate anaerobic microcosms enriched in nitrate and pollutant phenols. Rapid degradation of phenol and p-cresol was observed over a 35-day period leading to the generation of inorganic carbon and a number of transient intermediates. O-cresol proved to be recalcitrant on the experimental time-scale. A mass balance calculation shows that, during degradation, carbon was conserved in the aqueous phase. Groundwater-sediment interactions were monitored using carbon stable isotope data. A mass balance for solution TIC indicates thatp-cresol degradation stimulated the dissolution of sedimentary carbonate phases due to the formation of carbonic acid. Compound-specific carbon isotope analysis (GC-IRMS) was used to search for 13C enrichment in residual p-cresol. A slight enrichment trend (epsilon = -2.5/1000) was tentatively identified. The potential of this fractionation effect for obtaining in situ degradation rates is discussed. Results from the microcosm experiments help to explain the observed distribution of nitrate and phenols within the polluted aquifer.     

Processes controlling the distribution and natural attenuation of dissolved phenolic compounds in a deep sandstone aquifer

Processes controlling the distribution and natural attenuation (NA) of phenol, cresols and xylenols released from a former coal-tar distillation plant in a deep Triassic sandstone aquifer are evaluated from vertical profiles along the plume centerline at 130 and 350 m from the site. Up to four groups of contaminants (phenols, mineral acids, NaOH, NaCl) form discrete and overlapping plumes in the aquifer. Their distribution reflects changing source history with releases of contaminants from different locations. Organic contaminant distribution in the aquifer is determined more by site source history than degradation. Contaminant degradation at total organic carbon (TOC) concentrations up to 6500 mg l(-1) (7500 mg l(-1) total phenolics) is occurring by aerobic respiration NO3-reduction, Mn(IV)-/Fe(III)-reduction, SO4-reduction, methanogenesis and fermentation, with the accumulation of inorganic carbon, organic metabolites (4-hydroxybenzaldehyde, 4-hydroxybenzoic acid), acetate, Mn(II), Fe(II), S(-II), CH4 and H2 in the plume. Aerobic and NO3-reducing processes are restricted to a 2-m-thick plume fringe but Mn(IV)-/Fe(II)-reduction, SO4-reduction, methanogenesis and fermentation occur concomitantly in the plume. Dissolved H2 concentrations in the plume vary from 0.7 to 110 nM and acetate concentrations reach 200 mg l(-1). The occurrence of a mixed redox system and concomitant terminal electron accepting processes (TEAPs) could be explained with a partial equilibrium model based on the potential in situ free energy (deltaGr) yield for oxidation of H2 by specific TEAPs. Respiratory processes rather than fermentation are rate limiting in determining the distribution of H2 and TEAPs and H2 dynamics in this system. Most (min. 90%) contaminant degradation has occurred by aerobic and NO3-reducing processes at the plume fringe. This potential is determined by the supply of aqueous O2 and NO3 from uncontaminated groundwater, as controlled by transverse mixing, which is limited in this aquifer by low dispersion. Consumption to date of mineral oxides and SO4 is, respectively, <0.15% and 0.4% of the available aquifer capacity, and degradation using these oxidants is <10%. Fermentation is a significant process in contaminant turnover, accounting for 21% of degradation products present in the plume, and indicating that microbial respiration rates are slow in comparison with fermentation. Under present conditions, the potential for degradation in the plume is very low due to inhibitory effects of the contaminant matrix. Degradation products correspond to <22% mass loss over the life of the plume, providing a first-order plume scale half-life >140 years. The phenolic compounds are biodegradable under the range of redox conditions in the aquifer and the aquifer is not oxidant limited, but the plume is likely to be long-lived and to expand. Degradation is likely to increase only after contaminant concentrations are reduced and aqueous oxidant inputs are increased by dispersion of the plume. The results imply that transport processes may exert a greater control on the natural attenuation of this plume than aquifer oxidant availability.     

An Application of the T‐TEL Assessment Method to Evaluate Connectivity in a Lake‐Dominated Watershed after Drought

Lakes are landscape features that influence connectivity of mass and energy by being foci for the reception, mixing, and provision of water and material. Where lake fractions are high, they influence hydrological connectivity. This behavior was exemplified in the Baker Creek watershed in Canada's Northwest Territories during a two‐year drought in which many lake levels declined below outlet elevations. This study evaluated how lakes controlled surface runoff connectivity reestablishment following the drought using a new assessment method, T‐TEL (time scales — thresholds, excesses, losses). Analysis of daily data showed that during a summer period following the drought, connectivity occurred between 0% and 41% of the time. The size of run‐of‐the‐river lakes relative to their upstream watershed area, and the upstream lake fraction, are two factors for connectivity. These terms represent a lake's ability to control the size of storage deficits relative to rainfall, and evaporation and storage losses along pathways. The connectivity magnitude–duration curve only aligned with the watershed flow duration curve during high‐water conditions, implying lakes functioned as individuals rather than as part of a perennial watercourse during much of the study. The T‐TEL method can be used to quantify consistent metrics of hydrologic connectivity that can be used for regionalization exercises and understanding hydrologic controls on material transport.     

Infrared Measurement of Fluorocarbons,Carbon Tetrachloride,Carbonyl Sulfide,And Other Atmospheric Trace Gases

A cryogenic procedure for concentrating trace gases in the atmosphere has been developed and applied to the ambient air at Research Triangle Park, NC, Atlantic Beach, NC, and New York City. The concentrated gases have been analyzed by long path infrared absorption spectroscopy, with a detectability down to partial pressures of 10^?11 atmospheres. Carbonyl sulfide has been detected at partial pressures in the range 1 × 10^?10 atm. to 3 × 10^?10 atm. Carbon tetrachloride was always detected with a rather narrow partial pressure range of 0.7 × 10^?10 atm. to 1.1 × 10^?10 atm. Fluorocarbon-11 values ranged from about 1.3 × 10^?10 atm. at Research Triangle Park to 8 × 10^?10 atm. at New York City. Fluo-rocarbon-12 covered the range 1.8 × 10^?10 atm. to 1.0 × 10^?9 atm. Hydrocarbon pollutants varied widely in concentration, but were always detected, even in the clean rural air.     

A comparison of hourly with annual air pollutant emissions: Implications for estimating acute exposure and public health risk

Health risks from air pollutants are evaluated by comparing chronic (i.e., an average over 1 yr or greater) or acute (typically 1-hr) exposure estimates with chemical- and duration-specific reference values or standards. When estimating long-term pollutant concentrations via exposure modeling, facility-level annual average emission rates are readily available as model inputs for most air pollutants. In contrast, there are far fewer facility-level hour-by-hour emission rates available for many of these same pollutants. In this report, we first analyze hour-by-hour emission rates for total reduced sulfur (TRS) compounds from eight kraft pulp mill operations. This data set is used to demonstrate discrepancies between estimating exposure based on a single TRS emission rate that has been calculated as the mean of all operating hours of the year, as opposed to reported hourly emission rates. A similar analysis is then performed using reported hourly emission rates for sulfur dioxide (SO₂) and oxides of nitrogen (NO_x) from three power generating units from a U.S. power plant. Results demonstrate greater variability at kraft pulp mill operations, with ratios of reported hourly to average hourly TRS emissions ranging from less than 1 to greater than 160 during routine facility operations. Thus, if fluctuations in hourly emission rates are not accounted for, over- or underestimates of hourly exposure, and thus acute health risk, may occur. In addition to this analysis, we also demonstrate an additional challenge when assessing health risk based on hourly exposures: the lack of human health reference values based on 1-hr exposures.

Implications: Largely due to the lack of reported hourly emission rate data for many air pollutants, an hourly average emission rate (calculated from an annual emission rate) is often used when modeling the potential for acute health risk. We calculated ratios between reported hourly and hourly average emission rates from pulp and paper mills and a U.S. power plant to demonstrate that if not considered, hourly fluctuations in emissions could result in an over- or underestimation of exposure and risk. We also demonstrate the lack of 1-hr human health reference values meant to be protective of the general population, including children.     

INTERACTIVE COMPUTER-AIDED HYDRAULIC DESIGN: CULVERTS1

ABSTRACT: Regular use of interactive computer programs in hydraulic design can materially increase the productivity of designers without sacrificing accuracy. This article considers the hydraulic design of culverts by interactive use of a computer program; this approach most profitably combines the speed and accuracy of the computer with the experience of the designer.     

Dialdehyde starch and zein plastic: Mechanical properties and biodegradability

Dialdehyde starch (DAS) and zein, a hydrophobic corn protein, were investigated to produce biodegradable plastics with improved water resistance and mechanical properties. In the study, dialdehyde starch and zein ratio, plasticizers, and degree of starch oxidation were examined. Increased molding temperature and level of starch oxidation decreased water absorption of the plastic. Tensile strength and Young's modulus increased with starch oxidation. The biodegradation of starting materials and ground plastic specimens was studied in aerobic soil reactors maintained at 25°C for 180 days. Biodegradation of corn starch, zein, and dialdehyde starch for 180 days produced CO₂ equivalent to 64, 63, and 10% of theoretical carbon, respectively. Specimens of molded DAS and zein (3 : 1) plastic showed accelerated CO₂ evolution compared to DAS and other raw materials alone. By 180 days, specimens made with starch of low oxidation (1 and 5% oxidized) demonstrated a 60% biodegradation, and specimens with highly oxidized starch (90% oxidized) achieved 37% biodegradation.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.Journal Paper J-15927 of the Iowa Agriculture and Home Economics Experiment Station, Ames, Project No. 3258.     

A Multilevel Modeling Approach to Assessing Regional and Local Landscape Features for Lake Classification and Assessment of Fish Growth Rates

The ecoregion and watershed frameworks are landscape-based classifications that have been used to group waterbodies with respect to measures of community structure; however, they have yet to be evaluated for grouping lakes for demographic characteristics of fish populations. We used a multilevel modeling approach to determine if variability in mean fish length at age could be partitioned by ecoregions and watersheds. For the ecoregions analysis, we then examined if within-ecoregion variability could be explained by local water quality and lake morphometry characteristics. We used data from agency surveys conducted during 1974-1984 for age 2 and 3 fish of seven common warm and coolwater fish species. Variance in mean length at age between ecoregions for all species was not significant, and between-watershed variance estimates were only significant in 3 out of 14 analyses; however, the total amount of variation between watersheds was very small (ranging from 1.8% to 3.7% of the total variance), indicating that ecoregions and watersheds were ineffective in partitioning variability in mean length at age. Within ecoregions, water quality and lake morphometric characteristics accounted for 2%-23% of the variation in mean length at age. Measures of lake productivity were the most common significant covariates, with mean length at age increasing with increasing lake productivity. Much of the variability in mean length at age was not accounted for, suggesting that other local factors such as biotic interactions, fish density, and exploitation are important. The results indicate that the development of an effective regional framework for managing inland lakes will require a substantial effort to understand sources of demographic variability and that managers should not rely solely on ecoregions or watersheds for grouping lakes with similar growth rates.     

Assessment of the bioavailability of cadmium in Jamaican soils

Extraordinary geogenic concentrations of cadmium (Cd) have been reported for some Jamaican soils. However, the bioavailability of the metal in these soils remains unknown. Here, the bioavailability of Cd in selected Jamaican soils was investigated through the determination of total and sequentially extractable concentrations in paired soil–plant (yam; Dioscorea sp.) samples (n?=?24), using neutron activation analysis and atomic absorption spectroscopy as primary analytical techniques. Our results indicate that total soil Cd varied widely (2.2–148.7 mg kg^?1), and on average, total extractable Cd accounted for ~55 % of the total soil Cd. The exchangeable and oxidizable species averaged 1.5 and 6.4 % of the total Cd, respectively, and, based on Spearman analysis, are the best predictors of yam Cd. There is also good evidence to suggest that variation in the bioavailability of the metal is in part controlled by the geochemical characteristics of the soils analyzed and is best explained by pH, cation exchange capacity (CEC) and organic matter content (% LOI).     

The impact of non‐performance information on ratings of job performance: A policy‐capturing approach

Researchers have suggested that rater motives and the organizational context should be considered as sources of performance appraisal inaccuracies. A review of the performance appraisal literature revealed three primary non‐performance factors that managers consider when rating employee performance: (a) Potential negative consequences of ratings, (b) organizational norms, and (c) the opportunity to advance self‐interests. Using a policy‐capturing methodology, the current study investigated if these three non‐performance factors, as well as individual rater differences (e.g., conscientiousness, agreeableness, and performance appraisal experience), influence performance ratings. A sample of 303 experienced managers rated the performance of a fictitious employee, featured in a series of hypothetical scenarios, in which the above information was manipulated. Using hierarchical linear modeling, the results revealed that each of the three non‐performance related considerations accounted for variance incremental to objective employee performance. Managers' performance appraisal experience also predicted ratings, such that more experience was associated with lower ratings. These results provide support for the view that non‐performance factors can be a substantive component of performance ratings. Copyright © 2009 John Wiley & Sons, Ltd.