In situ bioreactors and deep drain-pipe installation to reduce nitrate losses in artificially drained fields

Nitrate in water removed from fields by subsurface drain ('tile') systems is often at concentrations exceeding the 10 mg N L(-1) maximum contaminant level (MCL) set by the USEPA for drinking water and has been implicated in contributing to the hypoxia problem within the northern Gulf of Mexico. Because previous research shows that N fertilizer management alone is not sufficient for reducing NO(3) concentrations in subsurface drainage below the MCL, additional approaches are needed. In this field study, we compared the NO(3) losses in tile drainage from a conventional drainage system (CN) consisting of a free-flowing pipe installed 1.2 m below the soil surface to losses in tile drainage from two alternative drainage designs. The alternative treatments were a deep tile (DT), where the tile drain was installed 0.6 m deeper than the conventional tile depth, but with the outlet maintained at 1.2 m, and a denitrification wall (DW), where trenches excavated parallel to the tile and filled with woodchips serve as additional carbon sources to increase denitrification. Four replicate 30.5- by 42.7-m field plots were installed for each treatment in 1999 and a corn-soybean rotation initiated in 2000. Over 5 yr (2001-2005) the tile flow from the DW treatment had annual average NO(3) concentrations significantly lower than the CN treatment (8.8 vs. 22.1 mg N L(-1)). This represented an annual reduction in NO(3) mass loss of 29 kg N ha(-1) or a 55% reduction in nitrate mass lost in tile drainage for the DW treatment. The DT treatment did not consistently lower NO(3) concentrations, nor reduce the annual NO(3) mass loss in drainage. The DT treatment did exhibit lower NO(3) concentrations in tile drainage than the CN treatment during late summer when tile flow rates were minimal. There was no difference in crop yields for any of the treatments. Thus, denitrification walls are able to substantially reduce NO(3) concentrations in tile drainage for at least 5 yr.     

Sexual dimorphism in house sparrow eggs

Recent evidence has revealed an apparently high degree of control by female birds over the physiological aspects of their reproduction and offspring sex allocation, consistent with adaptive hypotheses of sex allocation and differential investment in their offspring. In the house sparrow, we investigated possible mechanisms that may be used by females to enhance the fitness returns from a reproductive effort. Using molecular techniques, we demonstrate that house sparrow eggs containing male embryos are significantly larger than those containing female embryos. We also found that male embryos were laid randomly with respect to laying order. We speculate that this sexual dimorphism of eggs is adaptive, because male house sparrows show greater variance in condition-dependent reproductive success than females. More important, the result provides further evidence of the ability of females to detect or control ovulation of either male or female ova and to differentially invest in one sex over the other. Received: 19 January 2000 / Revised: 29 June 2000 / Accepted 20 July 2000     

Designing for interaction in research environments: A case study

Graduate researchers are an essential part of higher education (HE) in terms of its contribution to knowledge and the wider economy, but how the work environment influences behaviour and productivity in this work domain is poorly understood. Nevertheless, building programmes continue with a detectable trend towards more open office designs. Beyond issues of cost-efficiency, this reflects a popular belief in the significance of face-to-face interaction to research productivity. Using a combination of subjective and quantitative methods, this case study investigates the validity of this claim and how a redesigned environment impacts upon work practices and collaboration within a community of researchers. Although the new environment was judged favourably by occupants and managers, analysis suggests a less positive behavioural response. Contrary to expectation, we conclude that providing open plan environments is not sufficient to produce more collaborative practices in HE. We argue that this would require changes in the organisational structure, the reward structure for individual and team-driven tasks, and the firm policing of the management of change.     

Can varying concepts of susceptibility in risk assessment affect particulate matter standards?

The Clean Air Act mandates that sensitive subpopulations be considered in setting standards to protect the public's health. The purposes of this paper are to point out different conceptualizations of susceptibility, examine how it is approached in risk-related processes, and recommend ways it may be more explicitly framed for risk assessment and management purposes. We studied the traditional risk assessment paradigm, the U.S. Environmental Protection Agency (EPA) guidelines and revised PM standard, discussions from recent interdisciplinary meetings, and peer-reviewed literature. Areas of controversy include what factors intrinsic and extrinsic to the host should be incorporated in susceptibility, what health endpoints are of concern, whether susceptibility is deterministic or stochastic, and whether it should be defined on an individual or population scale. Recent discussions about susceptibility applied to PM indicate that it needs to be more clearly defined and evaluated for scientific and policy purposes. We conclude that varying concepts of susceptibility can affect risk-related processes such as PM standard setting. We recommend that susceptibility be clearly defined in the problem statement of risk assessments and be addressed in a specific subsection of risk characterization, integrating all susceptibility findings from the prior three steps in the risk assessment paradigm.     

Effective synthesis of sulfate metabolites of chlorinated phenols

Chlorophenols are an important class of persistent environmental contaminants and have been implicated in a range of adverse health effects, including cancer. They are readily conjugated and excreted as the corresponding glucuronides and sulfates in the urine of humans and other species. Here we report the synthesis and characterization of a series of ten chlorophenol sulfates by sulfation of the corresponding chlorophenols with 2,2,2-trichloroethyl (TCE) chlorosulfate using N,N-dimethylaminopyridine (DMAP) as base. Deprotection of the chlorophenol diesters with zinc powder/ammonium formate yielded the respective chlorophenol sulfate ammonium salts in good yield. The molecular structure of three TCE-protected chlorophenol sulfate diesters and one chlorophenol sulfate monoester were confirmed by X-ray crystal structure analysis. The chlorophenol sulfates were stable for several months if stored at −20 °C and, thus, are useful for future toxicological, environmental and human biomonitoring studies.     

Seasonal leaching and biodegradation of dicamba in turfgrass

The leaching of surface-applied herbicides, such as dicamba (2methoxy-3,6-dichlorobenzoic acid), to ground water is an environmental concern. Seasonal changes in soil temperature and water content, affecting infiltration and biodegradation, may control leaching. The objectives of this study were to (i) investigate the leaching of dicamba applied to turfgrass, (ii) measure the degradation rate of dicamba in soil and thatch in the laboratory under simulated field conditions, and (iii) test the ability of the model EXPRES (containing LEACHM) to simulate the field transport and degradation processes. Four field lysimeters, packed with sandy loam soil and topped with Kentucky bluegrass (Poa pratensis L.) sod, were monitored after receiving three applications (May, September, November) of dicamba. Concentrations of dicamba greater than 1 mg L(-1) were detected in soil water. Although drying of the soil during the summer prevented deep transport, greater leaching occurred in late autumn due to increased infiltration. From the batch experiment, the degradation rate for dicamba in thatch was 5.9 to 8.4 times greater than for soil, with a calculated half-life as low as 5.5 d. Computer modeling indicated that the soil and climatic conditions would influence the effectiveness of greater degradation in thatch for reducing dicamba leaching. In general, EXPRES predictions were similar to observed concentration profiles, though peak dicamba concentrations at the 10-cm depth tended to be higher than predicted in May and November. Differences between predictions and observations are probably a result of minor inaccuracies in the water-flow simulation and the model's inability to modify degradation rates with changing climatic conditions.     

Absolute configuration of 2,2′,3,3′,6-pentachlorinatedbiphenyl (PCB 84) atropisomers

Nineteen polychlorinated biphenyl (PCB) congeners, such as 2,2′,3,3′,6-pentachlorobiphenyl (PCB 84), display axial chirality because they form stable rotational isomers, or atropisomers, that are non-superimposable mirror images of each other. Although chiral PCBs undergo atropselective biotransformation and atropselectively alter biological processes, the absolute structure of only a few PCB atropisomers has been determined experimentally. To help close this knowledge gap, pure PCB 84 atropisomers were obtained by semi-preparative liquid chromatography with two serially connected Nucleodex β-PM columns. The absolute configuration of both atropisomers was determined by X-ray single-crystal diffraction. The PCB 84 atropisomer eluting first and second on the Nucleodex β-PM column correspond to (aR)-(?)-PCB 84 and (aS)-(+)-PCB 84, respectively. Enantioselective gas chromatographic analysis with the β-cyclodextrin-based CP-Chirasil-Dex CB gas chromatography column showed the same elution order as the Nucleodex β-PM column. Based on earlier reports, the atropisomers eluting first and second on the BGB-172 gas chromatography column are (aR)-(?)-PCB 84 and (aS)-(+)-PCB 84, respectively. An inversion of the elution order is observed on the Cyclosil-B gas chromatography and Cellulose-3 liquid chromatography columns. These results advance the interpretation of environmental and human biomonitoring as well as toxicological studies.     

Effect of sampling frequency on estimates of cumulative nitrous oxide emissions

It is generally recognized that soil N(2)O emissions can exhibit pronounced day-to-day variations; however, measurements of soil N(2)O flux with soil chambers typically are done only at discrete points in time. This study evaluated the impact of sampling frequency on the precision of cumulative N(2)O flux estimates calculated from field measurements. Automated chambers were deployed in a corn/soybean field and used to measure soil N(2)O fluxes every 6 h from 25 Feb. 2006 through 11 Oct. 2006. The chambers were located in two positions relative to the fertilizer bands-directly over a band or between fertilizer bands. Sampling frequency effects on cumulative N(2)O-N flux estimation were assessed using a jackknife technique where populations of N(2)O fluxes were constructed from the average daily fluxes measured in each chamber. These test populations were generated by selecting measured flux values at regular time intervals ranging from 1 to 21 d. It was observed that as sampling interval increased from 7 to 21 d, variances associated with cumulative flux estimates increased. At relatively frequent sampling intensities (i.e., once every 3 d) N(2)O-N flux estimates were within +/-10% of the expected value at both sampling positions. As the time interval between sampling was increased, the deviation in estimated cumulative N(2)O flux increased, such that sampling once every 21 d yielded estimates within +60% and -40% of the actual cumulative N(2)O flux. The variance of potential fluxes associated with the between-band positions was less than the over-band position, indicating that the underlying temporal variability impacts the efficacy of a given sampling protocol.