Solid-phase extraction using hierarchical organosilicates for enhanced detection of nitroenergetic targets

A novel porous organosilicate material was evaluated for application as a solid phase extraction sorbent for preconcentration of nitroenergetic targets from aqueous solution prior to HPLC analysis. The performance of the sorbent in spiked deionized water, groundwater, and surface water was evaluated. Targets considered included 2,4,6-trinitrotoluene, 2,4-dinitrotoluene, RDX, HMX, and nitroglycerin. The sorbent was shown to provide improved performance over Sep-Pak RDX. The impact of complex matrices on target preconcentration by the sorbent was also found to be less dramatic than that observed for LiChrolut EN. The impact of changes in pH on target preconcentration was considered. Aqueous soil extracts generated from samples collected at sites of ordnance testing were also used to evaluate the materials. The results presented here demonstrate the potential of this novel sorbent for application as a solid phase extraction material for the preconcentration of nitroenergetic targets from aqueous solutions.     

Bottom-up effects of plant genotype on aphids, ants, and predators

Theory predicts that bottom-up ecological forces can affect community dynamics, but whether this extends to the effects of heritable plant variation on tritrophic communities is poorly understood. In a field experiment, I contrasted the effects of plant genotype (28 genotypes; 1064 plants), aphid density, and the presence/absence of mutualistic ants in affecting the per capita population growth of a specialist aphid herbivore, as well as the effects of plant genotype on the third trophic level. Plant genotype strongly affected aphid population growth rate, explaining 29% of the total variation in growth rate, whereas aphid density and ant-aphid interactions explained substantially less variation (< 2%) in aphid population growth rate. Plant genotype also had direct and indirect effects on the third trophic level, affecting the abundance of aphid-tending ants and the richness of predators. Multiple regression identified several heritable plant traits that explained 49% of the variation in aphid growth rate and 30% of the variation in ant abundance among plant genotypes. These bottom-up effects of plant genotype on tritrophic interactions were independent of the effects of either initial aphid density or the presence/absence of mutualistic ants. This study shows that plant genotype can be one of the most important ecological factors shaping tritrophic communities.     

Continuous-time correlated random walk model for animal telemetry data

We propose a continuous-time version of the correlated random walk model for animal telemetry data. The continuous-time formulation allows data that have been nonuniformly collected over time to be modeled without subsampling, interpolation, or aggregation to obtain a set of locations uniformly spaced in time. The model is derived from a continuous-time Ornstein-Uhlenbeck velocity process that is integrated to form a location process. The continuous-time model was placed into a state-space framework to allow parameter estimation and location predictions from observed animal locations. Two previously unpublished marine mammal telemetry data sets were analyzed to illustrate use of the model, by-products available from the analysis, and different modifications which are possible. A harbor seal data set was analyzed with a model that incorporates the proportion of each hour spent on land. Also, a northern fur seal pup data set was analyzed with a random drift component to account for directed travel and ocean currents.     

Festering food: chytridiomycete pathogen reduces quality of Daphnia host as a food resource

When parasitic infections are severe or highly prevalent among prey, a significant component of the predator's diet may consist of parasitized hosts. However, despite the ubiquity of parasites in most food webs, comparisons of the nutritional quality of prey as a function of infection status are largely absent. We measured the nutritional consequences of chytridiomycete infections in Daphnia, which achieve high prevalence in lake ecosystems (>80%), and tested the hypothesis that Daphnia pulicaria infected with Polycaryum laeve are diminished in food quality relative to uninfected hosts. Compared with uninfected adults, infected individuals were smaller, contained less nitrogen and phosphorus, and were lower in several important fatty acids. Infected zooplankton had significantly shorter carapace lengths (8%) and lower mass (8-20%) than uninfected individuals. Parasitized animals contained significantly less phosphorus (16-18% less by dry mass) and nitrogen (4-6% less) than did healthy individuals. Infected individuals also contained 26-34% less saturated fatty acid and 31-42% less docosahexaenoic acid, an essential fatty acid that is typically low in cladocera, but critical to fish growth. Our results suggest that naturally occurring levels of chytrid infections in D. pulicaria populations reduce the quality of food available to secondary consumers, including planktivorous fishes, with potentially important effects for lake food webs.     

Interactive effects of CO2 and O3 on a ponderosa pine plant/litter/soil mesocosm.

To study individual and combined impacts of two important atmospheric trace gases, CO2 and O3, on C and N cycling in forest ecosystems; a multi-year experiment using a small-scale ponderosa pine (Pinus ponderosa Laws.) seedling/soil/litter system was initiated in April 1998. The experiment was conducted in outdoor, sun-lit chambers where aboveground and belowground ecological processes could be studied in detail. This paper describes the approach and methodology used, and presents preliminary data for the first two growing seasons. CO2 treatments were ambient and elevated (ambient + 280 ppm). O3 treatments were elevated (hourly averages to 159 ppb, cumulative exposure > 60 ppb O3, SUM 06 approximately 10.37 ppm h), and a low control level (nearly all hourly averages <40 ppb. SUM 06 approximately 0.07 ppm h). Significant (P < 0.05) individual and interactive effects occurred with elevated CO2 and elevated O3. Elevated CO2 increased needle-level net photosynthetic rates over both seasons. Following the first season, the highest photosynthetic rates were for trees which had previously received elevated O3 in addition to elevated CO2. Elevated CO2 increased seedling stem diameters, with the greatest increase at low O3. Elevated CO2 decreased current year needle % N in the summer. For 1-year-old needles measured in the fall there was a decrease in % N with elevated CO2 at low O3, but an increase in % N with elevated CO2 at elevated O3. Nitrogen fixation (measured by acetylene reduction) was low in ponderosa pine litter and there were no significant CO2 or O3 effects. Neither elevated CO2 nor elevated O3 affected standing root biomass or root length density. Elevated O3 decreased the % N in coarse-fine (1-2 mm diameter) but not in fine (< 1 mm diameter) roots. Both elevated CO2 and elevated O3 tended to increase the number of fungal colony forming units (CFUs) in the AC soil horizon, and elevated O3 tended to decrease bacterial CFUs in the C soil horizon. Thus, after two growing seasons we showed interactive effects of O3 and CO2 in combination, in addition to responses to CO2 or O3 alone for a ponderosa pine plant/litter/soil system.     

Full‐scale in‐situ biobarrier demonstration for containment and treatment of MTBE

The Naval Facilities Engineering Service Center (NFESC), Arizona State University, and Equilon Enterprises LLC are partners in an innovative Environmental Security Technology Certification Program cleanup technology demonstration designed to contain dissolved MTBE groundwater plumes. This full‐scale demonstration is being performed to test the use of an oxygenated biobarrier at Naval Base Ventura County, in Port Hueneme, California. Surprisingly, few cost‐effective in‐situ remedies are known for the cleanup of MTBE‐impacted aquifers, and remediation by engineered in‐situ biodegradation was thought to be an unlikely candidate just a few years ago. This project demonstrates that MTBE‐impacted groundwater can be remediated in‐situ through engineered aerobic biodegradation under natural‐flow conditions. With respect to economics, the installation and operation costs associated with this innovative biobarrier system are at least 50 percent lower than those of a conventional pump and treat system. Furthermore, although it has been suggested that aerobic MTBE biodegradation will not occur in mixed MTBE‐BTEX dissolved plumes, this project demonstrates otherwise. The biobarrier system discussed in this article is the largest of its kind ever implemented, spanning a dissolved MTBE plume that is over 500 feet wide. This biobarrier system has achieved an in‐situ treatment efficiency of greater than 99.9 percent for dissolved MTBE and BTEX concentrations. Perhaps of greater importance is the fact that extensive performance data has been collected, which is being used to generate best‐practice design and cost information for this biobarrier technology. © 2001 John Wiley & Sons, Inc.     

Efficacy of stable isotope ratios in assigning endangered migrants to breeding and wintering sites.

A primary constraint on effective conservation of migratory animals is our inability to track individuals through their annual cycle. One such animal is the endangered southwestern subspecies of the Willow Flycatcher, which is difficult to distinguish from conspecifics. Identifying wintering regions used by the endangered subspecies would be an important step in formulating an effective conservation strategy. Our objective was to use stable isotope ratios as a means of identifying wintering sites of Southwestern Willow Flycatchers. We analyzed stable isotope ratios of carbon, nitrogen, and hydrogen from feathers of breeding and wintering Willow Flycatchers. Based on winter samples, we document a positive trend in hydrogen isotope ratios across latitude. We also found that Willow Flycatchers use C4 food webs south of 8 degrees N latitude, but we found no evidence of use of C4 food webs farther north. Nitrogen stable isotope ratios of feathers showed no discernable geographic variation. Discriminant function analyses, based on stable isotope ratios of wintering Willow Flycatchers, were only useful (>50% accurate) for assigning individuals to winter regions if the regions were large and the threshold probability for assignment was relatively high. When using these discriminant functions, most breeding samples of Southwestern Willow Flycatchers were assigned to two wintering regions: central Mexico and Ecuador. We think that assignment of Southwestern Willow Flycatchers to Ecuador is unrealistic. Given the large percentages of samples that could not be classified with certainty, we are not confident that these two regions are truly more likely to harbor wintering Southwestern Willow Flycatchers than other winter regions. We think our inconclusive results are due primarily to weak and nonlinear gradients in isotope ratios across the winter range of Willow Flycatchers.     

Fluorides in groundwater and its impact on health

Fluoride is a naturally occurring toxic mineral present in drinking water and causes yellowing of teeth, tooth problems etc. Fluorspar, Cryolite and Fluorapatite are the naturally occurring minerals, from which fluoride finds its path to groundwater through infiltration. In the present study two groundwater samples, Station I and Station II at Hyderabad megacity, the capital of Andhra Pradesh were investigated for one year from January 2001 to December 2001. The average fluoride values were 1.37 mg/l at Station I and 0.91 mg/l at Station II. The permissible limit given by BIS (1983) 0.6-1.2 mg/l and WHO (1984) 1.5 mg/l for fluoride in drinking water. The groundwaters at Station I exceeded the limit while at Station II it was within the limits. The study indicated that fluoride content of 0.5 mg/l is sufficient to cause yellowing of teeth and dental problems.     

Occurrence and fate of pesticides in four contrasting agricultural settings in the United States

Occurrence and fate of 45 pesticides and 40 pesticide degradates were investigated in four contrasting agricultural settings--in Maryland, Nebraska, California, and Washington. Primary crops included corn at all sites, soybeans in Maryland, orchards in California and Washington, and vineyards in Washington. Pesticides and pesticide degradates detected in water samples from all four areas were predominantly from two classes of herbicides--triazines and chloroacetanilides; insecticides and fungicides were not present in the shallow ground water. In most samples, pesticide degradates greatly exceeded the concentrations of parent pesticide. In samples from Nebraska, the parent pesticide atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine] was about the same concentration as the degradate, but in samples from Maryland and California atrazine concentrations were substantially smaller than its degradate. Simazine [6-chloro-N,N'-diethyl-1,3,5-triazine-2,4-diamine], the second most detected triazine, was detected in ground water from Maryland, California, and Washington. Metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] rarely was detected without its degradates, and when they were detected in the same sample metolachlor always had smaller concentrations. The Root-Zone Water-Quality Model was used to examine the occurrence and fate of metolachlor at the Maryland site. Simulations accurately predicted which metolachlor degradate would be predominant in the unsaturated zone. In analyses of relations among redox indicators and pesticide variance, apparent age, concentrations of dissolved oxygen, and excess nitrogen gas (from denitrification) were important indicators of the presence and concentration of pesticides in these ground water systems.