Residence time effects on phase transformation of nanosilver in reduced soils

Residence time effects on phase transformation of silver nanoparticles (AgNPs) (15–50 nm, with and without polyvinylpyrrolidone (PVP) coating) were investigated in reducing soils using experimental geochemistry and synchrotron-based x-ray techniques. After 30 days of anaerobic incubation, a substantial fraction of PVP-coated AgNPs (15 nm) were transformed into Ag₂S and or humic acid (HA) complexed Ag(I), whereas only the HA fraction was dominant in uncoated AgNPs (50 nm). Several investigations recently reported that sulfidation of AgNPs to Ag₂S was the predominant mechanism controlling the fate of AgNP in soil–water environments. However, this investigation showed each AgNP underwent particle-specific chemical transformations to different end compounds after 30 days. Considering the small contribution of Ag(I) dissolution from all AgNPs (less than 5 %), we concluded that changes in solid-state chemical speciation of sorbed AgNPs was promoted by particle-specific interactions of NPs in soil chemical constituents, suggesting a critical role of soil absorbents in predicting the fate of AgNPs in terrestrial environments.     

Resource allocation in Mytilus edulis on the shore and in suspended culture

The annual cycle of carbon and nitrogen content of the flesh of wild and cultivated mussels (Mytilus edulis L.) in Killary Harbour, Ireland, was measured over two years, starting in February, 1980 and ending in November, 1981. The carbon and nitrogen contents of mussel gametes were determined and the allometry of growth of wild and cultured mussel shells was examined with respect to length, weight and organic content. The carbon and nitrogen contents of the organic fraction of the shell were determined. These data were combined with those we had previously published on growth rate, gametogenesis and the annual cycle of ash-free dry weight (AFDW) of mussels in the same locality. Estimates were made of fecundity, reproductive effort and the partitioning of carbon and nitrogen between soma, gametes and shell. In suspended culture, cumulative production after eighteen months is equal to cumulative production after six to seven years on the shore. For comparison, partitioning of carbon and nitrogen resources between soma, shell and gonad is estimated when total cumulative production by wild and cultivated mussels is approximately equal. Differences in resource allocation are considerable. Wild mussels allocate some 57% of their carbon budget and 52% of their nitrogen budget to gamete output. In culture, mussels allocate only 22% of their carbon budget and 19% of their nitrogen budget to gamete output. It is concluded that in response to a higher production rate, cultivated mussels increase allocation of resources to somatic growth.     

Evaluating Experience with Renewables Portfolio Standards in the United States

Increased use of renewable energy is one of several promising methods for reducing emissions of local, regional, and global air pollutants, including greenhouse gas emissions associated with fossil-fuel based electricity production. Among the available options for encouraging renewable electricity generation, the renewables portfolio standard (RPS) has become especially popular in recent years. The RPS is a newly established policy mechanism, however, and experience with its use has not been widely documented and evaluated. This paper describes and evaluates the design, impacts, and early experience of 13 U.S. state RPS policies. These 13 policies share a common goal of encouraging renewable energy supply, but each specific RPS is designed differently. Our evaluation shows both successes and failures with this policy mechanism; some state RPS policies are positively impacting renewable energy development, while others have been poorly designed and will do little to advance renewable energy markets.We emphasize the importance of policy design details, and specifically highlight critical design pitfalls that have been commonly experienced. Though experience with the RPS is still limited, we have now gained some knowledge of the conditions and design features necessary to make an RPS policy work. An important objective of this article is therefore to identify and describe broad policy design principles and specific best practice design elements that might be used to guide the design of future renewables portfolio standards.     

Inclusion of 13C12-labelled mono-, di-, and tri-chlorinated dibenzo-p-dioxin and dibenzofuran standards in US EPA methods 0023A/8290

13C12-Labelled mono-, di-, and tri-chlorinated dibenzo-p-dioxin (CDD) and chlorinated dibenzofuran (CDF) standards have been tested for their applicability to standard EPA sampling and analytical Methods 0023A/8290. These methods target for analysis only the tetra- through octa-CDD/CDF homologues. Extension of the isotope dilution method to include those lower chlorinated homologues is important toward obtaining reliable species concentration data on the complete, mono- to octa-chlorinated homologue profile. These data will improve our ability to model poly-CDD/CDF concentrations through understanding mechanisms of poly-CDD/CDF formation, chlorination, and dechlorination.     

Variation of dioxins and furans in human tissues

A number of chlorinated dibenzo-p-dioxins (PCDDs) and chlorinated dibenzofurans (PCDFs) occur in human adipose tissue at levels from 5 pg/g for 2, 3, 7, 8-TCDD to approximately 1000 pg/g for octachlorodibenzo-p-dioxin (OCDD). The variation of these compounds in tissues has been studied with respect to age, sex, tissue type, and country. A sampling of 46 adipose tissues from Canada in 1976 has shown a positive correlation of 2,3,7,8-TCDD level of detectable samples with age but not sex. This relationship is supported by the analysis for the first time of tissue from a 6 month old infant and the demonstration of little or no measurable levels of PCDDs/PCDFs. Three additional tissue types, pancreas, brain, and testis, from two autopsies were assayed for PCDDs/PCDFs for the first time but little or none were found even though the first two tissues had up to 10% lipid. A small sampling of adipose tissue from the general population in Japan in 1984 contained generally the same types and concentrations of PCDDs/PCDFs as are found in tissues from other industrialized countries.     

Colloid transport in a geochemically heterogeneous porous medium: aquifer tank experiment and modeling

To examine colloid transport in geochemically heterogeneous porous media at a scale comparable to field experiments, we monitored the migration of silica-coated zirconia colloids in a two-dimensional layered porous media containing sand coated to three different extents by ferric oxyhydroxides. Transport of the colloids was measured over 1.65 m and 95 days. Colloid transport was modeled by an advection-dispersion-deposition equation incorporating geochemical heterogeneity and colloid deposition dynamics (blocking). Geochemical heterogeneity was represented as favorable (ferric oxyhydroxide-coated) and unfavorable (uncoated sand) deposition surface areas. Blocking was modeled as random sequential adsorption (RSA). Release of deposited colloids was negligible. The time to colloid breakthrough after the onset of blocking increased with increasing ferric oxyhydroxide-coated surface area. As the ferric oxyhydroxide surface area increased, the concentration of colloids in the breakthrough decreased. Model-fits to the experimental data were made by inverse solutions to determine the fraction of surface area favorable for deposition and the deposition rate coefficients for the favorable (ferric oxyhydroxide-coated) and unfavorable sites. The favorable deposition rate coefficient was also calculated by colloid filtration theory. The model described the time to colloid breakthrough and the blocking effect reasonably well and estimated the favorable surface area fraction very well for the two layers with more than 1% ferric oxyhydroxide coating. If mica edges in the uncoated sand were considered as favorable surface area in addition to the ferric oxyhydroxide coatings, the model predicted the favorable surface area fraction accurately for the layer with less than 1% ferric oxyhydroxide coating.     

The formation of polychlorinated dibenzo-p-dioxins/dibenzofurans from carbon model mixtures containing ferrous chloride

The potential to form polychlorinated dibenzo-p-dioxins/furans (PCDD/F) was investigated in carbon model systems containing ferrous chloride tetrahydrate and a matrix representative of that found in particle emission from the catalytic extraction process (CEP) for wastes. Various types of carbons were used resulting in different PCDD/F yields but, with one exception, similar homologue distributions. Due to the similarity between the turbostratic structure of the carbon in the representative CEP dusts and the carbon blacks used in the model system, experiments were performed using two carbon blacks (termed CBA and CBB). On a mass basis, CBB was more reactive over the temperature range of 275-325 degrees C and reaction times of 20-60 min in the formation of PCDD/F; as well as more adsorptive in terms of the desorption of PCDD/F. On a volume basis, the reactivities and adsorptivities were similar. A maximum in PCDD/F formation occurred at an oxygen concentration of 2% in nitrogen.     

Chlorinated dibenzo-p-dioxin and dibenzofuran levels in human adipose tissue and milk samples from the north and south of Vietnam

Although 2,3,7,8-TCDD has been found to be extremely toxic to a variety of laboratory aminals, human epidemiology studies, where exposure to 2,3,7,8-TCDD has been less well characterized than in animal toxicologic studies, have been less conclusive in characterizing the extent of toxicity. In order to determine whether the newly refined techniques of human adipose tissue biopsy including isomer specific and sensitive measurement of PCDDs and PCDFs might be able to assist in finding populations within the same country with high and low levels of dioxins, adipose tissue samples were taken and levels analyzed from the north and south of Vietnam. It seemed reasonable, based on previous work, that high levels of 2,3,7,8-TCDD might still be found in adipose tissue in selected patients living in areas sprayed with Agent Orange and other 2,3,7,8-TCDD containing herbicides, and that lower levels should be found in patients not exposed to 2,3,7,8-TCDD from herbicides or other sources, such as persons who had always resided in the north of Vietnam. Of 9 specimens from patients hospitalized in Hanoi who had never been south, none had detectable adipose tissue levels of 2,3,7,8-TCDD at a detection limit of 2 or 3 ppt on a wet weight basis. Of 15 specimens from Ho Chi Minh City hospitalized patients the mean of positive specimens (12 of 15) was 28 on a lipid basis. The mean of the positive values from the south is about 2 to 3 times higher than found in the North American Continent control patients where the mean is about 6–10 ppt and much higher than in the north of Vietnam. In the northern specimens, the levels were non-detectable with a sensitivity of between 2 and 3 ppt. Other PCDD and PCDF isomers not found in Agent Orange, the penta- through octachlorinated dibenzo-dioxins and dibenzofurans, were similar in isomer type and quantity in the south of Vietnam to what we previously reported in North America. Adipose tissue from the north of Vietnam contained the lowest levels of four through eight chlorinated dioxins and furans thus far reported. The initial data suggests that populations exist in the south of Vietnam with elevated levels of 2,3,7,8-TCDD at the present time, fourteen years after the last known 2,3,7,8-TCDD (Agent Orange) application, superimposed on a preexisting body burden of dioxins and dibenzofurans from sources other than Agent Orange such as technical grade pentachlorophenol or products of incineration contaminated with higher chlorinated PCDDs or PCDFs. In light of the recent finding that unexpected levels of PCDDs and PCDFs exist in the general adult population of industrialized countries, ca. 1,000 to 1,200 ppt, wet weight of total dioxin and furan isomers in adipose tissues, it seems reasonable that the extent of human toxicity of dioxins may be more readily characterized in Vietnam than in industrialized countries. Because 2,3,7,8-TCDD was applied in 1962–1970, although not yet cleaned up, the levels of 2,3,7,8-TCDD in the environment, the food chain, and in humans, would be expected to decrease with time. Therefore, if studies are not initiated in a timely fashion, the opportunity to better characterize the extent of the toxicity of TCDD to humans as well as the persistence of TCDD in the environment in Vietnam may be lost.     

Plant uptake of non-ionic organic chemicals from soils

Methodologies utilizing simple properties of chemicals - half-life (T_1/2), log octanol-water partition coefficient (log K_ow) and Henery's Law constant (Hc) - are developed to screen organic chemicals for potential plant uptake.     

Seasonal anorexia in the male red-sided garter snake,<Emphasis Type="Italic"> Thamnophis sirtalis parietalis</Emphasis>

Many animals show seasonal shifts in behaviors that coincide with breeding, migration, or hibernation. These behavioral shifts provide ideal opportunities to study the regulation of behavior. The red-sided garter snake (Thamnophis sirtalis parietalis) spends 8 months of the year inactive in underground hibernacula, 1 month breeding, and 3 months feeding to build up enough energy stores to survive the following winter. Although they emerge from 8 months of hibernation with severely depleted energy reserves, they do not feed until weeks later, after the breeding season. We tested the hypothesis that this lack of feeding during the breeding season is due to a shift in behavior rather than the distribution of food and potential mates. Male garter snakes were given a series of choices between pursuing a breeding or feeding opportunity. The proportion of tests in which males selected feeding over breeding gradually increased throughout the study period, reaching almost 100% in the final tests. Males also were given opportunities to feed and court at the beginning and end of the study. Males initially refused food and courted females, but when retested at the end of the study they fed and did not court females. Thus aphagia during the breeding season is due at least in part to an endogenous shift in behavior.Communicated by P. Weatherhead