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.     

Effects of pig manure compost and nonionic-surfactant Tween 80 on phenanthrene and pyrene removal from soil vegetated with Agropyron elongatum

This paper evaluates the effects of pig manure compost (PMC) and Tween 80 on the removal of phenanthrene (PHE) and pyrene (PYR) from soil cultivated with Agropyron elongatum. Soils spiked with about 300mgkg(-1) of PHE and PYR were individually amended with 0%, 2.5%, 5% and 7.5% (dry wt) of PMC or 0, 20 and 100mgkg(-1) of Tween 80. Unplanted and sterile microcosms were prepared as the controls. PAH concentration, total organic matter (TOM), dissolved organic carbon (DOC), total heterotrophic and PAH degrading microbial populations in soil were quantified before and after 60d period. The results indicated that A. elongatum could significantly enhance PYR removal (from 46% to 61%) but had less impact on PHE removal (from 96% to 97%). Plant uptake of the PAHs was insignificant. Biodegradation was the key mechanism of PAH removals (<3% losses in the sterile control). Increase in PMC or Tween 80 levels increased the removal of PYR but not of PHE. Maximal PYR removal of 79% and 92% were observed in vegetated soil receiving 100mgkg(-1) Tween 80 and 7.5% PMC, respectively. Enhanced PYR removal in soil receiving PMC could be explained by the elevated levels of DOC, TOM and microbial populations as suggested by Pearson correlation test. While the positive effect of Tween 80 on PYR removal could probably due to its capacities to enhance PYR bioavailability in soil. This paper suggests that the addition of either PMC or nonionic-surfactant Tween 80 could facilitate phytoremediation of PAH contaminated soil.     

Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of gamma- to alpha-HBCD isomerization

Hexabromocyclododecanes (HBCDs) are high production volume chemicals (>20000 ty(-1)) used as flame retardants for plastics and textiles. Lately, we reported on the stereoselective isomerization of beta-HBCDs. Herein we present insights into the mechanism and kinetics of (+)gamma- to (+)alpha- and of (-)gamma- to (-)alpha-HBCD isomerization. Only two of the six bromine atoms migrated, indicating that rearrangements of gamma- to alpha-HBCDs are regio- and stereoselective as well. The apparent first-order isomerization rate constants increased from 0.0013 to 0.0031 to 0.0070 min(-1) at 120, 130, and 140 degrees C, respectively, corresponding to half-lives of 540, 230, and 99 min. Thus, a thermal treatment of materials containing gamma-HBCDs at temperatures >100 degrees C may induce the formation of alpha-HBCDs and, hence, may alter the diastereomeric ratio of a HBCD mixture. The inversion of vicinal dibromides in like-configurations (RR/SS) prevailed, whereas unlike-configurations (RS/SR) were not affected. An intramolecular, stereoselective migration of neighboring bromine atoms via a four-center transition state would explain the observed stereoisomer pattern and first-order kinetics. Despite the fact that vicinal dibromides in HBCDs prefer synclinal (gauche) conformations, antiperiplanar (staggered) conformations are assumed to facilitate concerted 1.2-shifts of both bromine atoms. A conformation analysis revealed that under kinetic control, only those bromine atoms in the more flexible part of the molecules are migrating, whereas those in the conserved triple-turn motive were not affected. Thus, this structural motive, common to all alpha-, beta-, and gamma-HBCDs, is more rigid and less reactive than the flexible part, containing the reacting dibromides in like-configurations.     

Fungal bioremediation of the creosote-contaminated soil: influence of Pleurotus ostreatus and Irpex lacteus on polycyclic aromatic hydrocarbons removal and soil microbial community composition in the laboratory-scale study

The aim of this study was to determine the efficacy of selected basidiomycetes in the removing of polycyclic aromatic hydrocarbons (PAH) from the creosote-contaminated soil. Fungi Pleurotus ostreatus and Irpex lacteus were supplemented with creosote-contaminated (50-200 mg kg(-1) PAH) soil originating from a wood-preserving plant and incubated at 15 °C for 120 d. Either fungus degraded PAH with 4-6 aromatic rings more efficiently than the microbial community present initially in the soil. PAH removal was higher in P. ostreatus treatments (55-67%) than in I. lacteus treatments (27-36%) in general. P. ostreatus (respectively, I. lacteus) removed 86-96% (47-59%) of 2-rings PAH, 63-72% (33-45%) of 3-rings PAH, 32-49% (9-14%) of 4-rings PAH and 31-38% (11-13%) of 5-6-rings PAH. MIS (Microbial Identification System) Sherlock analysis of the bacterial community determined the presence of dominant Gram-negative bacteria (G-) Pseudomonas in the inoculated soil before the application of fungi. Complex soil microbial community was characterized by phospholipid fatty acids analysis followed by GC-MS/MS. Either fungus induced the decrease of bacterial biomass (G- bacteria in particular), but the soil microbial community was influenced by P. ostreatus in a different way than by I. lacteus. The bacterial community was stressed more by the presence of I. lacteus than P. ostreatus (as proved by the ratio of the fungal/bacterial markers and by the ratio of trans/cis mono-unsaturated fatty acids). Moreover, P. ostreatus stimulated the growth of Gram-positive bacteria (G+), especially actinobacteria and these results indicate the potential of the positive synergistic interaction of this fungus and actinobacteria in creosote biodegradation.     

NMR study of the humification process during sewage sludge treatment

Humic acids, extracted from sludge at the biologic-mechanical sewage treatment plant in Jastrzebie Zdroj, have been investigated by means of (1)H, (13)C and (31)P NMR spectroscopy. Sludge samples for studies were taken from the primary settling tank, the nitrification chamber, the digestion chamber and the sludge drying beds. The (1)H NMR analysis of humic acid extracted from sludge at various stages of sewage treatment confirmed the presence of the functional groups that are characteristic for humic substances, and the analysis showed changes in their relative intensities. The (13)C NMR indicated that the aromatisation of the humic acid increased during sewage treatment. Moreover, the analysis of the (31)P NMR spectra allowed us to observe the changes in the phosphorus groups of the studied humic acids.     

Solubility of toluene, benzene and TCE in high-microbial concentration systems

We report measurements of solubility limits for benzene, toluene, and TCE in systems that contain varying levels of biomass up to 0.13 g mL⁻¹ for TCE and 0.25 g mL⁻¹ for benzene and toluene. The solubility limit increased from 21 to 48 mM when biomass (in the form of yeast) was added to aqueous batch systems containing benzene. The toluene solubility limit increased from 4.9 to greater than 20 mM. For TCE, the solubility increased from 8 mM to more than 1000 mM. Solubility for TCE (trichloroethylene) was most heavily impacted by biomass levels, changing by two orders of magnitude as the microbial concentrations approach those in biofilms.     

Assessment of sediment contamination in Casco Bay, Maine, USA

The current status of contaminant concentrations in Casco Bay, decadal trends of these contaminants and changes in their geographical distribution are assessed using sediment samples collected approximately 10 years apart. In general, regulated contaminants appeared to be decreasing in concentration. Total PAH and dioxins/furans concentrations did not significantly change over this period. Total organochlorine pesticides, 4,4-DDE, 4,4-DDD, total DDT, PCB, tributyltin and total butyltin decreased in concentration. Trace element concentrations in sediments decreased at the majority of the sampling sites for chromium, nickel, and selenium while arsenic, cadmium, copper, lead, mercury, silver, and zinc remained relatively constant. None of the contaminants measured has increased by more than a factor of 2. Selected sites located in the Inner Bay, where concentrations are higher and new inputs were more likely, showed increased concentrations of contaminants. Most contaminants were not found at concentrations expected to adversely affect sediment biota based on ERL/ERM guidelines.     

Long-term survey of heavy-metal pollution, biofilm contamination and diatom community structure in the Riou Mort watershed, South-West France

In a metal-polluted stream in the Riou Mort watershed in SW France, periphytic biofilm was analyzed for diatom cell densities and taxonomic composition, dry weight and metal bio-accumulation (cadmium and zinc). Periphytic diatom communities were affected by the metal but displayed induced tolerance, seen through structural impact (dominance of small, adnate species) as well as morphological abnormalities particularly in the genera Ulnaria and Fragilaria. Species assemblages were characterized by taxa known to occur in metal-polluted environments, and shifts in the community structure expressed seasonal patterns: high numbers of Eolimna minima, Nitzschia palea and Pinnularia parvulissima were recorded in Summer and Autumn, whereas the species Surirella brebissonii, Achnanthidium minutissimum, Navicula lanceolata and Surirella angusta were dominant in Winter and Spring. Commonly used indices such as the Shannon diversity index and Specific Pollution Sensitivity Index reflected the level of pollution and suggest seasonal periodicity, the lowest diversities being observed in Summer.