Improvements in the two-dimensional nuclear magnetic resonance spectroscopy of humic substances

Understanding pollutant sorption, bioremediation of these pollutants, and their interactions with humic substances requires knowledge of molecular-level processes. New developments with nuclear magnetic resonance (NMR) experiments and labeled compounds have improved the overall understanding of these mechanisms. The advancements made with two-dimensional NMR show great promise, as structural information and hydrogen-carbon bond connectivity can be discerned. This communication presents the application of improved two-dimensional NMR methods, the double quantum filtered (DQF) correlation spectroscopy (COSY) and echo/anti-echo heteronuclear single quantum coherence (HSQC) experiments, for use in structural studies of humic substances. Both experiments were found to produce significant improvements over the conventional COSY and heteronuclear multiple quantum coherence (HMQC) experiments that have been previously employed in similar studies. The more sensitive echo/anti-echo HSQC experiment produced more cross-peaks with higher resolution when compared with the HMQC spectra. The DQF-COSY significantly suppressed the diagonal signals and allowed numerous signals previously hidden in the standard COSY experiment to be observed. These improvements will aid current characterization strategies of humic substances from soils, sediments, and water and their subsequent reactions with pollutants and microorganisms.     

Simulating endosulfan transport in runoff from cotton fields in Australia with the GLEAMS model

Endosulfan (6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9methano-2,4,3-benzodioxathiepin 3-oxide), a pesticide that is highly toxic to aquatic organisms, is widely used in the cotton (Gossypium hirsutum L.) industry in Australia and is a risk to the downstream riverine environment. We used the GLEAMS model to evaluate the effectiveness of a range of management scenarios aimed at minimizing endosulfan transport in runoff at the field scale. The field management scenarios simulated were (i) Conventional, bare soil at the beginning of the cotton season and seven irrigations per season; (ii) Improved Irrigation, irrigation amounts reduced and frequency increased to reduce runoff from excess irrigation; (iii) Dryland, no irrigation; (iv) Stubble Retained, increased soil cover created by retaining residue from the previous crop or a specially planted winter cover crop; and (v) Reduced Sprays, a fewer number of sprays. Stubble Retained was the most effective scenario for minimizing endosulfan transport because infiltration was increased and erosion reduced, and the stubble intercepted and neutralized a proportion of the applied endosulfan. Reducing excess irrigation reduced annual export rates by 80 to 90%, but transport in larger storm events was still high. Reducing the number of pesticide applications only reduced transport when three or fewer sprays were applied. We conclude that endosulfan transport from cotton farms can be minimized with a combination of field management practices that reduce excess irrigation and concentration of pesticide on the soil at any point in time; however, discharges, probably with endosulfan concentrations exceeding guideline values, will still occur in storm events.     

Recovery of benthic communities at Macquarie Island (sub-Antarctic) following a small oil spill

Intertidal communities at Macquarie Island (sub-Antarctic) were re-evaluated seven years after a small oil spill resulting from the grounding of the “Nella Dan”, and six years after the first assessment of biological impact. Sampling was conducted to evaluate community structure in three zones of the exposed rocky shore (upper red, kelp, and lower red) and in samples of Durvillaea antarctica holdfasts. There were no significant differences between the community structure in oiled and control locations in any of the three shore zones, but holdfast macrofaunal communities at oiled sites still showed evidence of impact. Holdfast community-structure in samples from heavily oiled sites showed moderate levels of recovery, with increased abundances of species which were considered sensitive to the oiling in the first post-impact studies and decreased abundances of opportunistic polychaete and oligochaete worms. In contrast, samples collected from the moderately oiled location at Secluded Bay showed little evidence of recovery. Holdfasts at this site were filled with sediment containing traces of diesel oil, and the macrofaunal community was dominated by opportunistic worms. This study clearly indicates that even small incidents of anthropogenic perturbation can have long-lasting consequences for marine communities at Macquarie Island. Received: 23 July 1997 / Accepted: 5 February 1998     

Nutrient transfer functions: the site of integration between feeding behaviour and nutritional physiology

Summary. We describe and extend a graphical approach to quantitative nutrition that focuses on the interplay between behavioural and physiological components of nutritional regulation. The site of integration is the nutrient transfer function, which is the function describing the time course of nutrient transfer between serially connected nutritional compartments (e.g., from the gut to the blood). The relationship between the shape of the nutrient transfer function and the temporal patterns of feeding determines the values of two key quantitative parameters of nutrition: the rate ('power') and the efficiency of nutrient acquisition. The approach can be extended to consider, in addition to the short-term behavioural and physiological decisions made by animals, some ecological determinants and longer-term, life history consequences of such decisions. Most importantly, this category of models can provide insights into the interplay among the various nutrients in an animal's diet. We illustrate this using hypothetical examples, and also present preliminary data for the power-efficiency relationships of protein and digestible carbohydrates in locusts. Finally, we consider existing evidence for the various means available to these and other insects for regulating such relationships. Received 24 September 1997; accepted 9 December 1997.     

Comparing computing formulas for estimating concentration ratios

The purpose of this paper is to provide guidance on the choice of computing formulas (estimators) for estimating average concentration ratios and other ratio-type measures of radionuclides and other environmental contaminant transfers between ecosystem components. Mathematical expressions for the expected value of three commonly used estimators (arithmetic mean of ratios, geometric mean of ratios, and the ratio of means) are obtained when the multivariate lognormal distribution is assumed. These expressions are used to explain why these estimators will not in general give the same estimate of the average concentration ratio. They illustrate that the magnitude of the discrepancies depends on the magnitude of measurement biases, and on the variance and correlations associated with spatial heterogeneity and measurement errors. This paper also reports on a computer simulation study that compares the accuracy of eight computing formulas for estimating a ratio relationship that is constant over time and/or space. Statistical models appropriate for both controlled spiking experiments and observational field studies for either normal or lognormal distributions are considered. Our results indicate that for either type of study the geometric mean is generally preferred if the lognormal distribution applies. However, the geometric mean has the disadvantage that its expected value depends on n, the number of measurements taken. Ricker's estimator, $\text{R}\text{?}{}_{\mathrm{rt}}$, appears to perform worse than the other estimators studied when the observations are lognormal. All eight estimators appear to be equally accurate for the controlled spiking study when data are normally distributed. For observational field studies when data are normally distributed the ratio of means or slight modifications thereof are preferred to other estimators investigated. Before one chooses a computing formula for estimating a concentration ratio, thought should be given to what target value needs to be estimated to satisfy study objectives, and to whether the normal or lognormal distribution is a more realistic model. The geometric mean performs well for lognormal distributions, but comparison of geometric means or of a geometric mean with environmental limits can be misleading if n is small. The arithmetic mean of ratios is a conservative choice in that it will always give a larger estimate than will the geometric mean. It may also be severely biased when data are lognormal and the variances of measurement errors are large. The ratio of the means is a reasonable choice if the distribution is normal. The median of the observed ratios, $\text{R}\text{?}{}_{\mathrm{<mtext>md</mtext>}}$, is useful estimate since it is easily obtained and has an easily understood interpretation as the point above which and below which 50% of the observed ratios lie. Also, it is appropriate no matter what the distribution of the observed ratios may be. Confidence limits on the median are also easily obtained. Finally, while this paper emphasizes applications in radionuclide research, our results should be applicable to a wide range of environmental contaminants since many contaminants have approximately lognormal distributions.     

Determination of Levoglucosan in Atmospheric Fine Particulate Matter

Abstract

A microanalytical method suitable for the quantitative determination of the sugar anhydride levoglucosan in low-volume samples of atmospheric fine particulate matter (PM) has been developed and validated. The method incorporates two sugar anhydrides as quality control standards. The recovery standard sedoheptulosan (2,7-anhydro-β-D-altro-heptulopyranose) in 20 μL solvent is added onto samples of the atmospheric fine PM and aged for 1 hr before ultrasonic extraction with ethylacetate/ triethylamine. The extract is reduced in volume, an internal standard is added (1,5-anhydro-D-mannitol), and a portion of the extract is derivatized with 10% by volume N-trimethylsilylimidazole. The derivatized extract is analyzed by gas chromatography/mass spectrometry (GC/MS). The recovery of levoglucosan using this procedure was 69 ± 6% from five filters amended with 2 μg levoglu-cosan, and the reproducibility of the assay is 9%. The limit of detection is ～0.1 μg/mL, which is equivalent to ～3.5 ng/m³ for a 10 L/min sampler or ～8.7 ng/m³ for a 4 L/min personal sampler (assuming 24-hr integrated samples). We demonstrated that levoglucosan concentrations in collocated samples (expressed as ng/m³) were identical irrespective of whether samples were collected by PM with aerodynamic diameter ≤2.5 μm or PM with aerodynamic diameter ≤10 μm impactors. It was also demonstrated that X-ray fluorescence analysis of samples of atmospheric PM, before levoglucosan determinations, did not alter the levels of levoglucosan.