Modeling tracer diffusion in fractured and unfractured, unsaturated, porous media

A proposed tracer diffusion test for the Exploratory Shaft Facility at Yucca Mountain, NV, is modeled. For the proposed test, a solution containing conservative tracers will be introduced into a borehole in the geologic medium of interest. The tracers will diffuse and advect from the saturated source region into the unsaturated matrix in the surrounding tuff. After some time, the borehole is to be overcored, and tracer concentrations in the fluid will be measured in the core as a function of distance from emplacement. The data will be used to evaluate diffusive behavior and to derive effective diffusion coefficients for the tracers in the specific tuff. Numerical simulations are used to study the effects of effective diffusion coefficient, porosity, saturation, and fracturing on tracer transport. Results are reported for numerical simulations of tests in the Topopah Spring Member and the Tuff of Calico Hills, which have significantly different porosities and saturations. The simulations make the following predictions: The spread of tracer during the test will be sensitive to the effective diffusion coefficient of the tracer. Tracer will diffuse farther in the Topopah Spring Member than in the Tuff of Calico Hills because of the former's lower porosity and saturation. Tracer transport by advection into the Topopah Spring Member will be greater than that into the Tuff of Calico Hills because of capillary effects. While advection will be a significant mechanism for tracer penetration into the Topopah Spring tuff, it will be less significant for tracer penetration into the Calico Hills tuff. The proximity of a single vertical fracture to the source region determines its effects on tracer transport, especially if the fracture diverts fluid flowing from the source region into the matrix.     

Estimated hourly personal exposures to ambient and nonambient particulate matter among sensitive populations in Seattle, Washington

Epidemiological studies of particulate matter (PM) routinely use concentrations measured with stationary outdoor monitors as surrogates for personal exposure. Despite the frequently reported poor correlations between ambient concentrations and total personal exposure, the epidemiologic associations between ambient concentrations and health effects depend on the correlation between ambient concentrations and personal exposure to ambient-generated PM. This paper separates personal PM exposure into ambient and nonambient components and estimates the outdoor contribution to personal PM exposures with continuous light scattering data collected from 38 subjects in Seattle, WA. Across all subjects, the average exposure encountered indoors at home was lower than in all other microenvironments. Cooking and being at school were associated with elevated levels of exposure. Previously published estimates of particle infiltration (Finf) were combined with time-location data to estimate an ambient contribution fraction (alpha, mean = 0.66+/-0.21) for each subject. The mean alpha was significantly lower for subjects monitored during the heating season (0.55+/-0.16) than for those monitored during the nonheating season (0.80+/-0.17). Our modeled alpha estimates agreed well with those estimated with the sulfur-tracer method (slope = 1.08; R2 = 0.67). We modeled exposure to ambient and nonambient PM with both continuous light scattering and 24-hr gravimetric data and found good agreement between the two methods. On average, ambient particles accounted for 48% of total personal exposure (range = 21-80%). The personal activity exposure was highly influenced by time spent away from monitored microenvironments. The median hourly longitudinal correlation between central site concentrations and personal exposures was 0.30. Although both alpha and the nonambient sources influence the personal-central relationship, the latter seems to dominate. Thus, total personal exposure may be poorly predicted by stationary outdoor monitors, particularly among persons whose PM exposure is dominated by nonambient exposures, for example, those living in tightly sealed homes, those who cook, and children.     

Variation in the response of the invasive species Potamopyrgus antipodarum (Smith) to natural (cyanobacterial toxin) and anthropogenic (herbicide atrazine) stressors

In the context of increasing freshwater pollution, the impact on life-traits (survival, growth and fecundity) and locomotion of Potamopyrgus antipodarum of a 5-week field-concentration exposure to the cyanobacterial toxin microcystin-LR and the triazine herbicide, atrazine was studied. Whatever the age of exposed snails (juveniles, subadults, adults), microcystin-LR induced a decrease in survival, growth and fecundity but had no effect on locomotion. Atrazine induced a decrease in locomotory activity but had no significant effect on the life-traits. These results are discussed in terms of consequences to field populations.     

Survey of waste comminglers' VOC exposures

Twelve U.S. universities performing hazardous waste solvent commingling operations were surveyed for waste handler exposures to 45 U.S. Environmental Protection Agency (EPA)-designated volatile organic compounds (VOCs). Personal exposures (n = 33) and area concentrations (n = 30) were determined using gas chromatography/ mass spectrometry (GC/MS) analysis of passively collected samples. Air monitoring data were used to determine the veracity of laboratory-generated reports of waste container contents. Participants completed a questionnaire concerning the use of personal protective equipment, ventilation, and other appropriate safety equipment for their specific commingling operation. Follow-up telephone interviews were conducted to elucidate safeguards in place. Results showed that personal exposures exceeded area concentrations in 70% of operations. For the contaminant concentrations reported, 17% of personal samples exceeded Occupational Safety & Health Administration (OSHA) time-weighted average or ceiling limit values. Methylene chloride was a frequently seen airborne contaminant not listed on drum inventory sheets. When airborne constituents were compared with container content tags, 44% of the chemicals detected in air were omitted from the waste tags. This study concluded that the most frequently necessary safeguard is respiratory protection, preferably a supplied-air-type. The use of local exhaust ventilation systems rather than dilution or natural systems and facility operation in a totally explosion-safe manner are also recommended.     

The validation of a passive sampler for indoor and outdoor concentrations of volatile organic compounds

Volatile organics compounds (VOCs) are ubiquitous in the air we breathe. The use of passive samplers to measure these concentrations can be an effective technique. When exposed for long durations, a passive sampler may be a good tool for investigating chronic exposures to chemicals in the environment. A passive sampler that was designed for occupational exposures can be used as such a tool. Laboratory validation under as many conditions as possible needs to be accomplished so as to characterize the sampler with known parameters. This paper describes the methods and results of an investigation into the validity of using a passive monitor to sample VOCs for a three-week period. Two concentration levels, two relative humidities, and five VOCs were studied. Results indicate that the samplers work best under conditions of high concentration with low relative humidity and low concentration with high relative humidity. For the passive sampler, excluding chloroform, percent deviations from the predicted values varied between -41 and +22 percent; while the values between the passive and the active samplers varied between -27 and +24 percent. Benzene, heptane, and perchloroethylene were sampled with equal precision and accuracy.     

Environmental photooxidation of dibenzothiophenes following the Amoco Cadiz oil spill

Photooxidation products of dibenzothiophenes (sulfur containing petroleum heteroaromatic hydrocarbons) were characterized in an oil slick sample obtained from a field location following the AMOCO CADIZ oil spill. The same oxidation products were formed in the laboratory by the photooxidation of a medium Arabian crude oil which contained the identical precursor hydrocarbons. Analytical techniques included fractionation by liquid/solid chromatography and characterization using high resolution gas chromatography-mass spectrometry. To the best of the author's knowledge, this represents the first reported instance for the formation of photooxidation products following an actual oil spill. A comparison of the quantities of various oxidation products was carried out by quantitative mass spectrometry using extracted ion current profiles of dibenzothiophenes and their corresponding sulfoxides. The geochemical and physiological implications of such photooxidation processes are also discussed.     

Female cannibalism and male courtship tactics in threespine sticklebacks

Summary Female threespine sticklebacks (Gasterosteus aculeatus) frequently raid male nests and eat all the eggs therein. We tested the hypothesis of Vickery et al. (1988) that females prefer to raid nests containing large numbers of eggs than ones with smaller numbers of eggs. This hypothesis is based on the finding that females spawning in nests containing many eggs will have reduced hatching success because of egg crowding. By consuming the male's eggs and forcing him to rebuild his nest, raiding females might obtain a new opportunity to spawn under better conditions. Our results were consistent with the first prediction of this hypothesis that females were more likely to spawn in nests containing fewer eggs than in nests with many eggs. However, this may be the result of males becoming less receptive to females as the number of eggs in their nests increases. Prediction 2 was that females should raid those nests containing the most eggs. Contrary to this prediction, males defending only one clutch were as likely to have their nests raided by groups of females as males defending several clutches of eggs. Female cannibalism is therefore unlikely to have evolved as a means of gaining access to a male defending a small number of eggs. We also examined the tactics used by males to counter female raids. Most raids occur when the male is courting, and nests are more vulnerable to shoals of females than to single females. Therefore, we hypothesized that males with eggs preferentially court a single female rather than large groups of females, and that males without eggs court both groups indiscriminately. We also predicted that males restrict the number of females they mate with when risk of having their nest raided is high. Our results indicate that: (1) both males with eggs and those without eggs minimize the risk of female cannibalism by courting solitary females rather than groups of females and (2) males limit the number of females that lay eggs in their nest when several potentially raiding females are present. Offprint requests to: G.J. FitzGerald     

Calanoid copepod escape behavior in response to a visual predator

Calanoid copepods typically exhibit escape reactions to hydrodynamic stimuli such as those generated by the approach of a predator. During the summers of 2000, 2001 and 2004, two small calanoid species, Temora turbinata Dana, 1849 and Paracalanus parvus Claus, 1863 were exposed to a visual predatory fish, the blenny Acanthemblemaria spinosa Metzelaar, 1919, and their predator–prey interactions were recorded using both high-speed and standard videographic techniques. Copepod escape reaction components, including swimming pattern, reactive distance, turning rate, and jump kinetics, were quantified from individual predation events using motion analysis techniques. Among the observed escape reaction components, differences were noted between the species’ swimming patterns prior to attack and their response latencies. Temora turbinata was a continuous cruiser and P. parvus exhibited a hop-and-sink swimming pattern. During periods of sinking, P. parvus stopped beating its appendages, which presumably reduced any self-generated hydrodynamic signals and increased perceptual abilities to detect an approaching predator. Response latency was determined for each copepod species using a hydrodynamic stimulus produced by a 1 ms acoustic signal. Response latencies of T. turbinata were significantly longer than those of P. parvus. Despite some apparent perceptual advantages of P. parvus, the blenny successfully captured both species by modifying its attack behavior for the targeted prey.     

Kin discrimination in the spotted hyena (<Emphasis Type="Italic">Crocuta crocuta</Emphasis>): nepotism among siblings

We examined patterns of affiliation, association, and aggression to inquire whether spotted hyenas (Crocuta crocuta) can distinguish among various groups of maternal and paternal siblings. If so, and if these animals conform to predictions of kin selection theory, then behavioral interactions among hyenas should vary with relatedness. We also considered familiarity-based recognition and phenotype matching as mechanisms hyenas might use to recognize kin. Patterns of affiliative behavior indicated that hyenas favored full-sibling littermates over half-sibling littermates or any other group of half-siblings. Rates of dyadic aggression generally did not vary with kinship. Hyenas associated more closely with half-sibling littermates than with non-littermate half-siblings, and hyenas affiliated more with maternal half-siblings than with paternal half-siblings, suggesting that familiarity-based cues might mediate discrimination among these sibling classes. In addition, operation of a phenotype-matching mechanism was suggested by the preference hyenas demonstrated during affiliative interactions for full- over half-sibling littermates, and by their lack of preference in these interactions for half-sibling littermates over non-littermate half-siblings. Phenotype matching was also suggested by our observation that paternal half-siblings cooperated more, and fought less, than did non-kin. Our data indicate that hyenas can discriminate among various types of siblings, that their social behavior conforms to predictions of kin selection theory, and that they recognize kin using mechanisms of both familiarity and phenotype matching.Communicated by S. Alberts     

Reduction of Ag(I), Au(III), Cu(II), and Hg(II) by Fe(II)/Fe(III) hydroxysulfate green rust

Green rusts are mixed Fe(II)/Fe(III) hydroxides that are found in many suboxic environments where they are believed to play a central role in the biogeochemical cycling of iron. X-ray absorption fine structure analysis of hydroxysulfate green rust suspensions spiked with aqueous solutions of AgCH(3)COO, AuCl(n)(OH)(4-n), CuCl(2), or HgCl(2) showed that Ag(I), Au(III), Cu(II), and Hg(II) were readily reduced to Ag(0), Au(0), Cu(0), and Hg(0). Imaging of the resulting solids from the Ag(I)-, Au(III)-, and Cu(II)-amended green rust suspensions by transmission electron microscopy indicated the formation of submicron-sized particles of Ag(0), Au(0), and Cu(0). The facile reduction of Ag(I), Au(III), Cu(II), and Hg(II) to Ag(0), Au(0), Cu(0), and Hg(0), respectively, by green rust suggests that the presence of green rusts in suboxic soils and sediments can have a significant impact on the biogeochemistry of silver, gold, copper, and mercury, particularly with respect to their mobility.