Treatment technologies for aqueous perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA)

Fluorochemicals (FCs) are oxidatively recalcitrant, environmentally persistent, and resistant to most conventional treatment technologies. FCs have unique physiochemical properties derived from fluorine which is the most electronegative element. Perfluorooctanesulfonate (PFOS), and perfluorooctanoate (PFOA) have been detected globally in the hydrosphere, atmosphere and biosphere. Reducing treatment technologies such as reverses osmosis, nano-filtration and activated carbon can remove FCs from water. However, incineration of the concentrated waste is required for complete FC destruction. Recently, a number of alternative technologies for FC decomposition have been reported. The FC degradation technologies span a wide range of chemical processes including direct photolysis, photocatalytic oxidation, photochemical oxidation, photochemical reduction, thermally-induced reduction, and sonochemical pyrolysis. This paper reviews these FC degradation technologies in terms of kinetics, mechanism, energetic cost, and applicability. The optimal PFOS/PFOA treatment method is strongly dependent upon the FC concentration, background organic and metal concentration, and available degradation time.     

Radiocesium storage in soil microbial biomass of undisturbed alpine meadow soils and its relation to 137Cs soil-plant transfer

This study focuses on radiocesium storage in soil microbial biomass of undisturbed alpine meadow sites and its relation to the soil-to-plant transfer. Soil and plant samples were taken in August 1999 from an altitude transect (800-1600m.a.s.l.) at Gastein valley, Austria. Soil samples were subdivided into 3-cm layers for analyses of total, K(2)SO(4)-extractable and microbially stored (137)Cs. Microbial biomass was measured by the fumigation extraction method, and fungal biomass was quantified using ergosterol as biomarker molecule. In general, the quantity of (137)Cs stored in the living soil microbial biomass was relatively small. At the high-altitude meadows, showing high amounts of fungal biomass, microbially stored (137)Cs amounted to 0.64+/-0.14kBqm(-2) which corresponds to about 1.2-2.7% of the total (137)Cs soil inventory. At lower altitudes, microbial (137)Cs content was distinctly smaller and in most cases not measurable at all using the fumigation extraction method. However, a positive correlation between the observed soil-to-plant aggregated transfer factor, microbially stored (137)Cs and fungal biomass was found, which indicates a possible role of fungal biomass in the storage and turnover of (137)Cs in soils and in the (137)Cs uptake by plants.     

Characterization and source identification of polycyclic aromatic hydrocarbons (PAHs) in river bank soils

Elevated PAH concentrations were detected in bank soils along the Mosel and Saar Rivers in Germany. Information on the identification of PAH sources in this area however remains unclear. This study was able to characterize the PAH sources by application of several approaches, including consideration of the distribution patterns of 45 PAHs (including 16 EPA PAHs and some alkyl PAHs), specific PAH ratios, distribution patterns of n-alkanes and principal component analysis (PCA). In addition, the efficiency of the tested approaches was assessed. The results from the application of the various source identification methods showed that pyrogenic PAHs dominate soil samples collected upstream of the confluence of the Mosel and Saar Rivers, and petrogenic and pyrogenic PAHs dominate samples downstream of the confluence. Based on the analysis of reference materials and organic petrography, the petrogenic input was found to be dominated by coal particles. More detailed information on the petrogenic sources was provided by the n-alkane analyses. The current study concludes that to accurately determine the origin of PAHs, several identification methods must be applied.     

Impact of alternative metrics on estimates of extent of occurrence for extinction risk assessment

In International Union for Conservation of Nature (IUCN) Red List assessments, extent of occurrence (EOO) is a key measure of extinction risk. However, the way assessors estimate EOO from maps of species’ distributions is inconsistent among assessments of different species and among major taxonomic groups. Assessors often estimate EOO from the area of mapped distribution, but these maps often exclude areas that are not habitat in idiosyncratic ways and are not created at the same spatial resolutions. We assessed the impact on extinction risk categories of applying different methods (minimum convex polygon, alpha hull) for estimating EOO for 21,763 species of mammals, birds, and amphibians. Overall, the percentage of threatened species requiring down listing to a lower category of threat (taking into account other Red List criteria under which they qualified) spanned 11–13% for all species combined (14–15% for mammals, 7–8% for birds, and 12–15% for amphibians). These down listings resulted from larger estimates of EOO and depended on the EOO calculation method. Using birds as an example, we found that 14% of threatened and near threatened species could require down listing based on the minimum convex polygon (MCP) approach, an approach that is now recommended by IUCN. Other metrics (such as alpha hull) had marginally smaller impacts. Our results suggest that uniformly applying the MCP approach may lead to a one‐time down listing of hundreds of species but ultimately ensure consistency across assessments and realign the calculation of EOO with the theoretical basis on which the metric was founded.     

Effects of environmentally relevant concentrations of the xeno-androgen, methyldihydrotestosterone, on male and female mating behavior in Xenopus laevis

Endocrine disrupting compounds (EDCs) are well known to interfere with the hormone system of aquatic vertebrates and to affect their reproductive biology. 17α-Methyldihydrotestosterone (MDHT) is a widely used model compound for the assessment of androgenic EDCs, because it binds with high affinity to nuclear androgen receptors. It was previously shown to affect various aspects of reproductive biology in aquatic vertebrates, however, evidence for MDHT affecting mating behavior of aquatic vertebrate species is lacking. In order to test the assumption that MDHT affects reproductive behavior of aquatic vertebrates, we exposed male and female Xenopuslaevis to three environmentally relevant concentrations of MDHT (30.45 ng L⁻¹, 3.05 μg L⁻¹ and 30.45 μg L⁻¹). In males, MDHT at all concentrations led to enhanced levels of advertisement calling and decreased the relative proportions of rasping, a call type characterizing a sexually unaroused state of the male, indicating an increase in sexual arousal of MDHT exposed males. Temporal and spectral parameters of the advertisement call itself, however, were not affected by MDHT exposure. In females, MDHT (30.45 ng L⁻¹) did not have any effects, while MDHT at 3.05 μg L⁻¹ increased female receptivity, increased the duration of time females spent close to the speaker playing male advertisement calls and reduced their latency to respond. MDHT at 30.45 μg L⁻¹, on the other hand, decreased female receptivity and increased their latency to respond. In summary, this study illustrates that exposure to environmentally relevant concentrations of the androgenic EDC MDHT affects male and female mating behavior of X. laevis. Hence, we suggest that nonaromatizable androgens might play a direct and predominant role in the physiology and regulation of reproduction not only in male but also in female frogs.     

Kinetics of microwave-enhanced oxidation of phenol by hydrogen peroxide

Aqueous solutions of phenol were oxidized by hydrogen peroxide assisted by microwave (MW) irradiation. A simple kinetic model for the overall degradation of phenol in the presence of excess H₂O₂ is proposed in which the degradation rate of phenol is expressed as a linear function of the concentrations of phenol and H₂O₂. A detailed parametric study showed that the degradation rate of phenol increased with increasing [H₂O₂] until saturation was observed. Phenol degradation followed apparent zero-order kinetics under MW radiation or H₂O₂ oxidation. However, after 90 min of irradiation, the observed kinetics shifted to pseudo first order. The overall reaction rates were significantly enhanced in the combined MW/H₂O₂ system, mainly because microwave could accelerate H₂O₂ to generate hydroxyl radical (·OH) and other reactive oxygen intermediates. The observed synergetic effects of the MW/H₂O₂ process resulted in an increased in the net reaction rate by a factor of 5.75. When hydrogen peroxide is present in a large stoichiometric excess, the time required to achieve complete mineralization is reduced significantly.     

Chromosomal mosaicism: Origins and clinical implications in preimplantation and prenatal diagnosis

The diagnosis of chromosomal mosaicism in the preimplantation and prenatal stage is fraught with uncertainty and multiple factors need to be considered in order to gauge the likely impact. The clinical effects of chromosomal mosaicism are directly linked to the type of the imbalance (size, gene content, and copy number), the timing of the initial event leading to mosaicism during embryogenesis/fetal development, the distribution of the abnormal cells throughout the various tissues within the body as well as the ratio of normal/abnormal cells within each of those tissues. Additional factors such as assay noise and culture artifacts also have an impact on the significance and management of mosaic cases. Genetic counseling is an important part of educating patients about the likelihood of having a liveborn with a chromosome abnormality and these risks differ according to the time of ascertainment and the tissue where the mosaic cells were initially discovered. Each situation needs to be assessed on a case-by-case basis and counseled accordingly. This review will discuss the clinical impact of finding mosaicism through: embryo biopsy, chorionic villus sampling, amniocentesis, and noninvasive prenatal testing using cell-free DNA.     

Use of a novel biomarker,botryococcane, to monitor biodegradation of two lacustrine‐sourced crude oils

Bioremediation is a proven alternative for remediating petroleum‐impacted soils at exploration and production (E&P) sites. Monitoring remediation performance can involve detection and quantification of biodegradation resistant compounds such as C₃₀17α(H),21β(H)‐hopane, which requires the use of gas chromatography with mass spectrometry detection (GC/MS). Due to the remoteness of many E&P sites, this technology is not always available, and alternative methods are needed to provide reliable quantitative measurements of petroleum remediation efficiency. This study provides a detailed chemical characterization of lacustrine‐sourced crude oils and a technical basis for measuring the effectiveness of bioremediation efforts for soil impacted by those crudes. We show that the novel isoprenoid hydrocarbon botryococcane is relatively stable in lacustrine‐sourced crude oils compared with C₃₀17α(H),21β(H)‐hopane under moderate biodegradation conditions generally observed in field samples. We have also demonstrated that, due to the stability and relatively elevated concentration of botryococcane in lacustrine oils, it can be reliably measured using the more cost‐effective and available GC/FID methodology, and thereby be used to monitor the progress of ongoing soil bioremediation activities at remote sites.