Source diagnostic and weathering indicators of tar balls utilizing acyclic, polycyclic and S-heterocyclic components

This study represents a forensic chemical analysis to define the liability for the coastal bitumens polluting the beaches of the Mediterranean city of Alexandria. Six tar balls collected from several locations along the coast of the city were analyzed for their acyclic and polycyclic hydrocarbons as well as sulfur heterocycles using GC/FID, GC/AED and gas chromatography/mass spectrometry techniques. The analysis of one Egyptian crude oil is also included as a possible source oil. The tar ball samples were at early stages of weathering. Based on the GC traces and biomarker signatures, the tar balls could be genetically different. One sample collected from the Eastern Harbor region appears to be a Bunker C type fuel produced from Egyptian crudes. The refining process has removed the low molecular weight components. On the other hand, the wide n-alkane distribution together with the absence of an unresolved complex mixture suggests that crude oils probably from tank washings, ballast discharges or accident spills from tankers could have contributed significantly to the other tar ball samples. The distribution of source specific hopane and sterane markers revealed that the tar samples probably originate from different oil fields.     

Prediction of the vertical profile of ozone based on ground-level ozone observations and cloud cover

A number of statistical techniques have been used to develop models to predict high-elevation ozone (O3) concentrations for each discrete hour of day as a function of elevation based on ground-level O3 observations. The analyses evaluated the effect of exclusion/inclusion of cloud cover as a variable. It was found that a simple model, using the current maximum ground-level O3 concentration and no effect of cloud cover provided a reasonable prediction of the vertical profile of O3, based on data analyzed from O3 sites located in North Carolina and Tennessee. The simple model provided an approach that estimates the concentration of O3 as a function of elevation (up to 1800 m) based on the statistical results with a +/- 13.5 ppb prediction error, an R2 of 0.56, and an index of agreement, d1, of 0.66. The inclusion of cloud cover resulted in a slight improvement in the model over the simple regression model. The developed models, which consist of two matrices of 24 equations (one for each hour of day for clear to partly cloudy conditions and one for cloudy conditions), can be used to estimate the vertical O3 profile based on the inputs of the current day's 1-hr maximum ground-level O3 concentration and the level of cloud cover.     

Electrochemical decolourisation of structurally different dyes

The electrochemical decolourisation of structurally different dyes (bromophenol blue, indigo, poly R-478, phenol red, methyl orange, fuchsin, methyl green and crystal violet) by means of the application of DC electric current was assessed. It was found that the electrochemical process allowed a colour removal of all dyes studied, although the decolourisation rate largely depended on the chemical structure of the different dyes. Nearly complete decolourisation was achieved for bromophenol blue followed by methyl orange and methyl green, whereas phenol red was hardly decolourised (30% in 60 min). In mixtures of two dyes, the decolourisation rate became similar for both dyes. However, the addition of a redox mediator, (Co(2+/3+)) clearly enhanced the degradation rate of all tested dyes, but the simplest dye molecules were attacked firstly, followed by dyes with more complex chemical structures. The results revealed the suitability of the process to effectively decolourise wastewaters from dyeing process.     

Occurrence and abatement of volatile sulfur compounds during biogas production

Volatile sulfur compounds (VSCs) in biogas originating from a biogas production plant and from a municipal sewage water treatment plant were identified. Samples were taken at various stages of the biogas-producing process, including upgrading the gas to vehicle-fuel quality. Solid-phase microextraction was used for preconcentration of the VSCs, which were subsequently analyzed using gas chromatography in combination with mass spectrometry. Other volatile organic compounds present also were identified. The most commonly occurring VSCs in the biogas were hydrogen sulfide, carbonyl sulfide, methanethiol, dimethyl sulfide, and dimethyl disulfide, and hydrogen sulfide was not always the most abundant sulfur (S) compound. Besides VSCs, oxygenated organic compounds were commonly present (e.g., ketones, alcohols, and esters). The effect of adding iron chloride to the biogas reactor on the occurrence of VSCs also was investigated. It was found that additions of 500-g/m3 substrate gave an optimal removal of VSCs. Also, the use of a prefermentation step could reduce the amount of VSCs formed in the biogas process. Moreover, in the carbon dioxide scrubber used for upgrading the gas, VSCs were removed efficiently, leaving traces (ppbv levels). The scrubber also removed other organic compounds.     

Evidence for the "grasshopper" effect and fractionation during long-range atmospheric transport of organic contaminants

Although there is indisputable evidence that long-range atmospheric transport (LRAT) of organic contaminants occurs on a global scale, uncertainties remain about the detailed mechanism and extent of this phenomenon as well as the physical-chemical properties which facilitate LRAT. In this study, we discuss how mass balance models and monitoring data can contribute to a fuller understanding of the mechanism and extent of LRAT. Specifically we address the issues of "grasshopping" or "hopping" (the extent to which molecules are subject to multiple hops as distinct from a single emission-deposition event) and "global fractionation" (the differing behavior of chemicals as they are transported). It is shown that simple mass balance models can be used to assist the interpretation of monitoring data while also providing an instrument that can be used to assess the LRAT potential and the extent of hopping that organic substances may experience. The available evidence supports the notion that many persistent organic pollutants experience varying degrees of "hopping" during their environmental journey and as a consequence become fractionated with distance from source.     

Comparison of various advanced oxidation processes and chemical treatment methods for COD and color removal from a polyester and acetate fiber dyeing effluent

In this paper, a comparison of various advanced oxidation processes (O3, O3/UV, H2O2/UV, O3/H2O2/UV, Fe2+/H2O2) and chemical treatment methods using Al2(SO4)3.18H2O, FeCl3 and FeSO4 for the chemical oxygen demand (COD) and color removal from a polyester and acetate fiber dyeing effluent is undertaken. Advanced oxidation processes (AOPs) showed a superior performance compared to conventional chemical treatment, which maximum achievable color and COD removal for the textile effluent used in this study was 50% and 60%, respectively. Although O3/H2O2/UV combination among other AOPs methods studied in this paper was found to give the best result (99% removal for COD and 96% removal for color), use of Fe2+/H2O2 seems to show a satisfactory COD and color removal performance and to be economically more viable choice for the acetate and polyester fiber dyeing effluent on the basis of 90% removal.     

Effects of fluoxetine on the reproduction of two prosobranch mollusks: Potamopyrgus antipodarum and Valvata piscinalis

Fluoxetine is a widely used antidepressant, frequently found in aquatic ecosystems. We investigated its effects on two freshwater prosobranch gastropods: Valvata piscinalis (European valve snail) and Potamopyrgus antipodarum (New Zealand mudsnail), which have different reproductive modes. The fecundity of V. piscinalis (cumulate number of eggs at day 42) was not affected with an NOEC of 100 μg/L nominal concentration (69 μg/L measured concentration). The mudsnail P. antipodarum responded in a biphasic dose-effect curve at low concentrations. The cumulate number of neonates at day 42 had an LOEC of 100 μg/L (69 μg/L) and an NOEC of 33.3 μg/L (13 μg/L), whereas the embryos in the brood pouch at day 42 only showed an LOEC of 3.7 μg/L (1 μg/L). We also observed histological effects in P. antipodarum (gonadal thickness). Among the sexual steroids we measured only testosterone which varied, independent of reproduction. Moreover the use of two closely related species highlights the interspecific variability.     

Comparison of an assay for Dehalococcoides DNA and a microcosm study in predicting reductive dechlorination of chlorinated ethenes in the field

The study aims to compare the detection of 16S rRNA gene of Dehalococcoides species and the microcosm study for biotransformation in predicting reductive dechlorination of chlorinated ethenes in ground water at hazardous waste sites. A total of 72 ground water samples were collected from 12 PCE or TCE contaminated sites in the United States. The samples were analyzed and used to construct microcosms in the laboratory. The results showed that the presence of Dehalococcoides DNA was well associated with dechlorination to ethene in the field. Nearly half of the wells where Dehalococcoides DNA was detected had ethene as a dechlorination end product. In comparison, for ground water samples of 16 wells where ethene was detected, ethene was produced in 11 of the corresponding microcosms. For most microcosms, during two years of incubation, dechlorination was less extensive than that observed in the field.     

The function of dart behavior in the paper wasp, Polistes fuscatus

Dominance behavior in Polistes wasps is a composite trait consisting of various discrete behaviors such as darts, lunges, bites, and mounts. The majority of these behaviors are considered aggressive, and these aggressive behaviors are considered to form a continuum from mild (e.g., darts) to severe (e.g., falling fights). In this paper we focus on darts, the most common of the dominance behaviors, and investigate their function in un-manipulated post-emergent colonies of the primitively eusocial wasp P. fuscatus. Here we show that darts are correlated with the more severe dominance behaviors, and that dominance ranks do not change with the addition or exclusion of darts. We find no correlation, however, between receiving darts and receiving more severe dominance behaviors. This result suggests that darts are not indicative of aggressive reinforcement of dominance, but rather may serve a different function. Our data suggest that the function of darts is to regulate activity on nests. Both foundresses and workers dart inactive workers significantly more often than by chance, and workers respond to a foundresss (but not a workers) dart by becoming less inactive. We also found that active workers who receive a dart from either a foundress or worker respond mostly by switching from one activity to another. Thus, our data suggest that darts are not aggressive behaviors, that foundresses use this signal to initiate activity, and that foundresses and workers both use the signal to regulate worker activity.