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.     

Combined PCDD/F Destruction and Particulate Control in a Baghouse: Experience with a Catalytic Filter System at a Medical Waste Incineration Plant

ABSTRACT

Phoenix Services, Inc., owns and operates the Baltimore Regional Medical Waste Incinerator in Baltimore, MD. New regulations for dioxins and furans imposed a limit that was considerably below historical emission levels. To determine a method to comply with the new dioxin/furan regulations, Phoenix Services performed trials with powdered activated carbon (PAC). Although the results with carbon were acceptable, Phoenix Services decided to replace their woven fiberglass filter bags with catalytic filters that simultaneously destroy dioxins and furans and collect particulate matter (PM). The catalytic filter system offered several advantages to Phoenix Services, including destruction of dioxins and furans instead of adsorption on carbon. The catalytic filters also offered a passive solution that did not require new carbon injection equipment. In January 2000, a campaign to measure dioxins/furans and PM was undertaken.     

Role of black carbon in the distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans in aged field-contaminated soils

Floodplain soils containing elevated levels of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were collected from several locations along the Tittabawassee River (Michigan, USA). The PCDD/F profiles of these soils exhibited distinct congener patterns consistent with byproducts from either chloralkali manufacturing or chlorophenols productions. Black carbon (BC) particles were isolated for the first time from floodplain soil impacted by PCDD/Fs. Petrographic analysis showed that BC particles, including coal, oxidized coal, metallurgical coke, depositional carbon, coal tar/pitch, cenosphere, and charcoal, comprised approximately 30% by volume of the organic fraction with size range of 250 μm-2000 μm from a typical floodplain soil. The BC particles with anthropogenic origin such as pitch and coke associated with the chloralkali production process served as both the source and subsequent transporter for the highly hydrophobic PCDD/Fs. These anthropogenic BC particles were enriched with high levels of PCDFs, containing approximately 1000-fold the concentration found in the bulk soil. The strong association of PCDD/Fs with anthropogenic BC directly impacts the physicochemical and biological availability thus the risk associated with these hydrophobic organochlorines in soils and sediments.     

Beyond depletion: Daily self-control motivation as an explanation of self-control failure at work

The organizational self-control literature usually applies resource perspectives that explain self-control failure at work by depletion of self-control resources. However, these perspectives neglect the role of self-control motivation. On a daily level, we examine several self-control aspects (resources, motivation, demands, and effort) as predictors of a manifestation of self-control failure at work, namely, daily counterproductive work behavior toward the organization (CWB-O). Additionally, we investigate self-control effort as a mechanism predicting the depletion of self-control resources throughout the day. We analyzed data from 155 employees in a 2-week diary study with 2 daily measurement points. Multilevel path modeling showed that self-control motivation and self-control demands, but not self-control resource depletion, predicted self-control effort. There was an indirect effect from self-control motivation on CWB-O via self-control effort but no indirect effect from self-control demands on self-control resource depletion throughout the day via self-control effort. Findings suggest that self-control motivation is a crucial factor explaining self-control failure at work and cast further doubt on the idea that exerted self-control effort is the only mechanism leading to self-control resource depletion.     

Practical Perspectives of 1,4‐Dioxane Investigation and Remediation

1,4‐Dioxane (dioxane) is a contaminant of emerging concern that is classified by the U.S. Environmental Protection Agency as a likely human carcinogen. Dioxane has been used as a minor or major ingredient in many applications, and is also generated as an unwanted by‐product of industrial processes associated with the manufacturing of polyethylene, nonionic surfactants, and many consumer products (cosmetics, laundry detergents, shampoos, etc.). Dioxane is also a known stabilizer of chlorinated solvents, particularly 1,1,1‐trichloroethane, and has been commonly found comingled with chlorinated solvent plumes. Dioxane plumes at chlorinated solvent sites can complicate site closure strategies, which to date have not typically focused on dioxane. Aggressive treatment technologies have greatly advanced and are clearly capable of achieving lower parts per billion cleanup criteria using ex situ advanced oxidation processes and sorption media. In situ chemical oxidation has also been demonstrated to effectively remediate dioxane and chlorinated solvents. Other in situ remedies, such as enhanced bioremediation, phytoremediation, and monitored natural attenuation, have been studied; however, their ability to achieve cleanup levels is still somewhat questionable and is limited by co‐occurring contaminants. This article summarizes and provides practical perspectives on dioxane analysis, plume stability relative to other contaminants, and the development of investigation tools and treatment technologies.     

PCDD/Fs in ambient air collected in Zagreb, Croatia

Levels of PCDD/Fs were measured at four different sites in Zagreb, capital of Croatia. Also one sample was taken during spontaneously initiated open fire on a landfill and one sample where garden waste of unknown content was burnt. Over period 1997–2000, 28 samples were collected and levels ranged between 9 and 306 fg I-TEQ m⁻³, except in the sample collected during landfill fire. Air PCDD/F levels in Zagreb at four sites were different and the highest levels were observed in industrial area. Seasonal variation of levels is also evident with higher levels in winter than in summer. Our results show that PCDD/F levels in ambient air collected in Zagreb are at lower end of the published data range. In general, homologue profiles were quite similar for all locations, the concentration of PCDD homologues increased while the concentration of PCDF homologues decreased with increasing degree of chlorination. PCDD/F levels in the landfill fire sample was 13 200 fg I-TEQ m⁻³ which are much higher than levels in garden waste burning sample or in sample collected at industrial site. During landfill fire, the concentration of 2,3,7,8-TCDF becomes even higher than the concentration of OCDF and is equal to the concentration of 1,2,3,4,6,7,8-HpCDF.     

Occurrence and distribution of organic trace substances in waters from the Three Gorges Reservoir, China

This study deals with the evaluation of water quality of the Three Gorges Reservoir (TGR) in order to assess its suitability as a raw water source for drinking water production. Therefore, water samples from (1) surface water, (2) tap water, and (3) wastewater treatment plant effluents were taken randomly by 2011–2012 in the area of the TGR and were analyzed for seven different organic contaminant groups (207 substances in total), applying nine different analytical methods. In the three sampled water sources, typical contaminant patterns were found, i.e., pesticides and polycyclic aromatic hydrocarbons (PAH) in surface water with concentrations of 0.020–3.5 μg/L and 0.004–0.12 μg/L, disinfection by-products in tap water with concentrations of 0.050–79 μg/L, and pharmaceuticals in wastewater treatment plant effluents with concentrations of 0.020–0.76 μg/L, respectively. The most frequently detected organic compounds in surface water (45 positives out of 57 samples) were the pyridine pesticides clopyralid and picloram. The concentrations might indicate that they are used on a regular basis and in conjunction in the area of the TGR. Three- and four-ring PAH were ubiquitously distributed, while the poorly soluble five- and six-ring members, perfluorinated compounds, polychlorinated biphenyls, and polybrominated diphenyl ethers, were below the detection limit. In general, the detected concentrations in TGR are in the same range or even lower compared to surface waters in western industrialized countries, although contaminant loads can still be high due to a high discharge. With the exception of the two pesticides, clopyralid and picloram, concentrations of the investigated organic pollutants in TGR meet the limits of the Chinese Standards for Drinking Water Quality GB 5749 (Ministry of Health of China and Standardization Administration of China 2006) and the European Union (EU) Council Directive 98/83/EC on the quality of water intended for human consumption (The Council of the European Union 1998), or rather, the EU Directive on environmental quality standards in the field of water policy (The European Parliament and The Council of the European Union 2008). Therefore, the suggested use of surface water from TGR for drinking water purposes is a valid option. Current treatment methods, however, do not seem to be efficient since organic pollutants were detected in significant concentrations in purified tap water.     

Retention time profiling of all 136 tetra- through octa- chlorinated dibenzo-p-dioxins and dibenzofurans on a variety of Si-Arylene gas chromatographic stationary phases

The applicability of three different Silphenylene Silicone co-polymer (Si-Arylene) GC stationary phases (J&W Scientific DB-5ms, Varian VF-5ms, and VF-Xms) has been evaluated for the separation of all 136 tetra- through the octa- chlorinated dibenzo-p-dioxins (PCDD) and chlorinated dibenzofurans (PCDF) from closely eluting isomers using gas chromatography/high resolution mass spectrometry (GC/HRMS). Their relative performance data are compared to the “conventional” 5% diphenyl 95% dimethylpolysiloxane GC column (Supelco Equity-5) and to each other based on absolute retention times, visualized mass chromatograms, and the separation of 2,3,7,8-substituted isomers. VF-Xms GC column was able to demonstrate a better performance towards separation of 2,3,7,8-substituted PCDD/PCDF compared to other Si-Arylene GC columns tested, where only 2,3,4,7,8-PnCDF can not be resolved from 1,2,3,6,9-PnCDF and 2,3,4,6,7,8-/1,2,3,6,8,9-HxCDF and 1,2,3,7,8,9-/1,2,3,4,8,9-HxCDF can be at least partially resolved. These data suggest that the development of a single GC column for the separation of all 17 2,3,7,8-substituted dioxins and furans is feasible, which therefore could be used as a standard tool for the PCDD/PCDF methods globally including USEPA methods 1613b, 8290A, 8280B, European Standard Method EN 1948, Canadian methods DFPCB-E3418, EPS 1/RM/19, Japanese methods JIS K0311 and JIS K0312. Having one specific GC column to separate all 2,3,7,8-substituted PCDD/PCDF will significantly improve the data quality, comparability by the various methods and assessment techniques while simultaneously leading to a more cost and time efficient operation.     

Body mass index and serum chlorinated dibenzo-p-dioxin and dibenzofuran levels

Several studies have found that current levels of 2,3,7,8 tetrachlorodibenzo-p-dioxin in serum lipids are related to age with older persons generally having higher levels. To account for this age pattern, reference ranges based on national samples have been established in order to allow determination of background levels for regional studies. In several studies, body mass index (BMI), has also been associated with current 2,3,7,8 tetrachlorodibenzo-p-dioxin levels with increasing body mass index related to increasing levels. We measured lipid-adjusted serum levels for all 2,3,7,8-substituted dioxins and furans in 62 chemical manufacturing workers with chlorophenol exposures and 36 workers without chlorophenol exposures employed at the same location. We then assessed the impact of age and BMI on the serum levels of all these compounds in the presence of other potential confounders. We found that both factors are important independent determinants of serum levels of 2,3,7,8-substituted dioxins and furans. Specifically, age and BMI are both important factors for assessing background levels of 2,3,7,8 tetrachlorodibenzo-p-dioxin, 1,2,3,7,8 pentachlorodibenzo-p-dioxin and the calculated total toxic equivalency. BMI, but not age, is important for assessing background levels of higher chlorinated dioxins and some hexachlorofurans. We conclude that age and BMI are both important considerations when comparing a potentially exposed group to a referent group, or to national norms. Further, age and BMI may also be important in epidemiology studies where back-extrapolation from current dioxin levels is used to assess historical chlorophenol exposure.