Synthesis and analytical follow-up of the mineralization of a new fluorosurfactant prototype

Fluorinated surfactants have become essential in numerous technical applications due to their unparalleled effectiveness and efficiency. The environmental persistence of the non-biodegradable perfluorinated alkyl moiety has become a matter of concern. Therefore, it was searched for new molecules with chemically stable fluorinated end groups which can be microbially transformed into labile fluorinated substances. One prototype substance, 10-(trifluoromethoxy)decane-1-sulfonate, has shown biomineralization. Monitoring the formation of metabolites over time elucidated the mechanism of biotransformation. Analysis was performed utilizing liquid chromatography-single quadrupole mass spectrometry (LC-MS) and quadrupole-time of flight tandem mass spectrometry (QqTOF-MS). It was possible to distinguish between two major degradation pathways of the fluorinated alkylsulfonate derivative: (i) a desulfonation and subsequent oxidation and degradation of the alkyl chain being predominant and (ii) an insertion of oxygen with a subsequent cleavage and degradation of the molecule. The utilized trifluoromethoxy-endgroup resulted in instable trifluoromethanol after degradation of the alkyl chain, which led to a high degree of mineralization of the molecule.     

Bottom sediments of the Arabian Gulf--II. TPH and TOC contents as indicators of oil pollution and implications for the effect and fate of the Kuwait oil slick

Measurements of total petroleum hydrocarbon (TPH) concentrations in 77 core samples collected in 1992 from the bottom sediments of the Arabian Gulf were used to delineate oil pollution levels and their distribution in the region. Seven chronic moderately (TPH 50-89 microg g(-1)) and heavily (TPH 266-1448 microg g(-1)) polluted areas were identified; three in the northern part of the region and four in the southern part. Oil pollution in these areas was attributed to natural oil seepage, accidental damage to pipelines, accidental spillage from tankers, the Nowruz oil slick, and tanker deballasting. Present-day intermediate (TPH 50-114 microg g(-1)) and high (TPH 200-1122 microg g(-1)) pollution levels were identified in 10 areas. Of these, three polluted areas in the northeastern corner, offshore Saudi Arabia and offshore Bahrain, Qatar and United Arab Emirates are probably directly affected by the Kuwait oil slick. A new scenario is suggested for the movement and fate of the oil slick, in which additional large oil discharges from northern sources, as well as substantial quantities of eroded oiled sediments and oil floating from heavily impacted tidal flats along the Saudi Arabian coastline, serve as sources of oil pollution. A definite relationship exists between the grain-size distribution and the TPH content of bottom sediments, with the highest TPH concentrations in the muddy sediments, suggesting that adsorption onto muds is the primary mechanism of oil pollutant accumulation in the Arabian Gulf. Total organic carbon measurements do not correlate positively with the grain-size distribution and TPH contents of the sediments, and hence cannot be used as indicators for petroleum hydrocarbon pollution in the Arabian Gulf.     

Transport of Sr2+ and SrEDTA2- in partially-saturated and heterogeneous sediments

Strontium-90 has migrated deep into the unsaturated subsurface beneath leaking storage tanks in the Waste Management Areas (WMA) at the U.S. Department of Energy's (DOE) Hanford Reservation. Faster than expected transport of contaminants in the vadose zone is typically attributed to either physical hydrologic processes such as development of preferential flow pathways, or to geochemical processes such as the formation of stable, anionic complexes with organic chelates, e.g., ethylenediaminetetraacetic acid (EDTA). The goal of this paper is to determine whether hydrological processes in the Hanford sediments can influence the geochemistry of the system and hence control transport of Sr(2+) and SrEDTA(2-). The study used batch isotherms, saturated packed column experiments, and an unsaturated transport experiment in an undisturbed core. Isotherms and repacked column experiments suggested that the SrEDTA(2-) complex was unstable in the presence of Hanford sediments, resulting in dissociation and transport of Sr(2+) as a divalent cation. A decrease in sorption with increasing solid:solution ratio for Sr(2+) and SrEDTA(2-) suggested mineral dissolution resulted in competition for sorption sites and the formation of stable aqueous complexes. This was confirmed by detection of MgEDTA(2-), MnEDTA(2-), PbEDTA(2-), and unidentified Sr and Ca complexes. Displacement of Sr(2+) through a partially-saturated undisturbed core resulted in less retardation and more irreversible sorption than was observed in the saturated repacked columns, and model results suggested a significant reservoir (49%) of immobile water was present during transport through the heterogeneous layered sediments. The undisturbed core was subsequently disassembled along distinct bedding planes and subjected to sequential extractions. Strontium was unequally distributed between carbonates (49%), ion exchange sites (37%), and the oxide (14%) fraction. An inverse relationship between mass wetness and Sr suggested that sandy sediments of low water content constituted the immobile flow regime. Our results suggested that the sequestration of Sr(2+) in partially-saturated, heterogeneous sediments was most likely due to the formation of immobile water in drier regions having low hydraulic conductivities.     

Wastewater disinfection by peracetic acid: assessment of models for tracking residual measurements and inactivation.

With its potential for low (if any) disinfection byproduct formation and easy retrofit for chlorine contactors, peracetic acid (PAA) or use of PAA in combination with other disinfectant technologies may be an attractive alternative to chlorine-based disinfection. Examples of systems that might benefit from use of PAA are water reuse schemes or plants discharging to sensitive receiving water bodies. Though PAA is in use in numerous wastewater treatment plants in Europe, its chemical kinetics, microbial inactivation rates, and mode of action against microorganisms are not thoroughly understood. This paper presents results from experimental studies of PAA demand, PAA decay, and microbial inactivation, with a complementary modeling analysis. Model results are used to evaluate techniques for measurement of PAA concentration and to develop hypotheses regarding the mode of action of PAA in bacterial inactivation. Kinetic and microbial inactivation rate data were collected for typical wastewaters and may be useful for engineers in evaluating whether to convert from chlorine to PAA disinfection.     

An assessment of the chronic toxicity of the synthetic pyrethroid, fenvalerate, to Daphnia galeata mendotae, using life tables

The effects of chronic exposure to fenvalerate, a synthetic pyrethroid insecticide, on the cladoceran Daphnia galeata mendotae were evaluated under laboratory conditions. The daphnids were exposed for their entire life cycle to concentrations ranging from 0.005 to 0.1 microg fenvalerate litre(-1). The parameters used to determined toxicity were survival, time to first reproduction, reproductive frequency, number of young per brood, cumulative brood size, intrinsic rate of natural increase (r(m)), generation time (T) and net reproductive rate (R(0)). A concentration of 0.005 microg fenvalerate litre(-1) resulted in an increase in longevity but a decrease in production of young. Higher concentrations caused a decrease in survival. Studies of shorter duration than the complete life cycle of the organisms would not have detected toxicity at such low levels. The intrinsic rate of natural increase, r(m), was not affected by fenvalerate until concentration reached 0.05 microg litre(-1) and r(m) decreased to 0.113 from 0.238. A concentration of 0.01 microg litre(-1) caused the net reproductive rate, R(0), and the generation time, T, to decrease to 73.2 offspring per female and 17.3 days from 125.9 offspring per female and 20.3 days, respectively.     

Temporal variation of the concentration and biochemical composition of seston within the Humboldt Current System off northern Chile (21°S)

Seasonal differences in the concentration and biochemical composition of seston have been assessed for the first time in the Humboldt Current System off northern Chile (21°S). The study comprised four seasonal surveys in the Bay of Chipana, including the summer and winter of 2006 and 2007, when El Niño 2006 and La Niña 2007 developed. Protein, lipid, carbohydrate and biogenic silica contents were measured in samples collected at four selected depths. The highest protein, lipid and carbohydrate concentrations were found at the fluorescence maximum (between 10 and 15 m depth), whereas the highest biogenic silica concentration was found 1 m above the seabed. When El Niño started developing, every variable showed low values throughout the water column; however, the lowest values were found when La Niña conditions dominated, together with low oxygen concentrations. Samples collected within the oxygen minimum zone (65 m depth) showed the lowest values for the water column and the lowest seasonal variations. After the evident decline coincident with El Niño 2006, the abundance and biochemical quality (high protein and lipid contents) of seston recovered earlier in the surface layer (upper 15 m) than at other depths.     

The effect of selenium on fluoride — clay interactions: Possible environmental health implications

Previous epidemiological studies have shown that dental fluorosis is endemic in the lowland, dry zone of Sri Lanka, which is considered to be an area in which excessive quantities of fluorides are present in the drinking water supplies. It has been found that kaolinitic clay forms a suitable raw material in the defluoridation of water.It is shown that there is a noticeable effect of selenium and media pH on the reactions involved in the interaction of fluoride with clay. In this study, 1 mM fluoride solutions containing SeO ₃ ^2– (selenite) concentrations of 0 mM, 0.1 mM, 0.5 mM and 1 mM were used in the reactions with kaolinitic clay. The effect of pH was monitored in the range 4 to 8. It was observed that fluoride adsorption was maximum at a pH of 5.6 without either SeO ₃ ^2– or SeO ₄ ^2– , the adsorption capacity being 15.2 mol F^– g^–1 clay. However, when the SeO ₃ ^2– concentration was increased up to 0.5 mM at this optimum pH, the adsorption capacity reduced to 12.8 mol F^– g^–1 clay. Monitoring of the effect of SeO ₄ ^2– and media pH on fluoride adsorption showed that when the SeO ₄ ^2– concentration increases from zero to 0.1 mM, there is a reduction of fluoride adsorption capacity. However, when the SeO ₄ ^2– concentration is further increased from 0.1 mM to 1.0 mM, there was an increase in the fluoride adsorption capacity, indicating a more consistent effect of SeO ₃ ^2– on fluoride-kaolinitic clay interaction than SeO ₄ ^2– .Fluoride concentrations in drinking water supplies have a marked effect on dental health and the geochemistry of selenium appears to play an important role in the geochemical mobility of fluoride ions.