Environmental behavior of the chiral acetamide pesticide metalaxyl: enantioselective degradation and chiral stability in soil

Racemic metalaxyl is currently being replaced in many countries by metalaxyl-M, the fungicide enantiomerically enriched with the biologically active R-enantiomer. This "chiral switch" is expected to reduce the amount of pesticide released into the environment as well as potential side-effects on nontarget organisms. Detailed knowledge of the environmental behavior of such chiral compounds should include information on the chiral stability (interconversion of enantiomers). In the present study, the degradation/ dissipation of metalaxyl and its primary carboxylic acid metabolite (MX-acid) in soil was investigated under laboratory conditions using enantioselective gas chromatography mass spectrometry (GC-MS). Racemic and the enantiopure R- and S-compounds were incubated in separate experiments. The degradation of metalaxyl was shown to be enantioselective with the fungicidally active R-enantiomer being faster degraded than the inactive S-enantiomer, resulting in residues enriched with S-metalaxyl when the racemic compound was incubated. The relatively high enantioselectivity suggests that degradation/dissipation was largely biological. The data indicated a conversion of 40-50% of metalaxyl to MX-acid, and the remaining metalaxyl being degraded via other pathways. The degradation of MX-acid was also enantioselective. Metalaxyl and MX-acid were both configurationally stable in soil, showing no interconversion of R- to S-enantiomers, and vice-versa. Furthermore, the conversion of metalaxyl to MX-acid proceeded with retention of configuration. Degradation followed approximate first-order kinetics but showed significant lag phases.     

Ohmic cooking of whole turkey meat – Effect of rapid ohmic heating on selected product parameters

Intact turkey meat was cooked using low temperature long time (LTLT) and high temperature short time (HTST) protocols in a combined ohmic/convection system and compared to conventional (CONV) steam cooking. Both ohmic protocols gave a significantly lighter (p < 0.05) and a more uniform colour vs. CONV, while no significant differences (p ? 0.05) were found in texture profile analysis attributes between LTLT and CONV though HTST showed significantly higher attributes (p < 0.05). Cook loss was significantly (p < 0.05) different between treatments (25.2%, 27.9% and 31.3% for LTLT, CONV and HTST). Sensory studies largely confirmed these observations. Cook values (p < 0.05) were lowest for LTLT (4.0) followed by HTST (5.4) and control (8.5). Lipid oxidation and sulphur-flavour-compound development (measured over 7 days) were higher for conventional than ohmic treatments. Overall, these results demonstrate considerable industrial potential for ohmic heating, yielding high quality products with an 8–15-fold reduction in cooking time.     

Temporal trends, congener patterns, and sources of octa-, nona-, and decabromodiphenyl ethers (PBDE) and hexabromocyclododecanes (HBCD) in Swiss lake sediments

With the recent ban of pentabromodiphenyl ether (technical PentaBDE) and octabromodiphenyl ether (technical OctaBDE) mixtures in the European Union (EU) and in parts of the United States, decabromodiphenyl ether (technical DecaBDE) remains as the only polybrominated diphenyl ether (PBDE) based flame retardant available, today. The EU risk assessment report for DecaBDE identified a high level of uncertainty associated with the suitability of the current risk assessment approach for secondary poisoning by debromination of DecaBDE to toxic lower brominated diphenylethers. Addressing this still open question, we investigated concentrations and temporal trends of DecaBDE, NonaBDE, and OctaBDE congeners in the sediments of Greifensee, a small lake located in an urban area close to Zürich, Switzerland. PBDE appeared first in sediment layers corresponding to the mid 1970s. While total Tri-HeptaBDE (BDE-28, -47, -99, -100, -153, -154 and -183) concentrations leveled off in the mid 1990s to about 1.6 ng/g dw (dry weight), DecaBDE levels increased steadily to 7.4 ng/g dw in 2001 with a doubling time of 9 years. Hexabromocyclododecanes (HBCD) appeared in Greifensee sediments in the mid 1980s. They are an important class of flame retardants that are being used in increasing amounts, today. As was observed for DecaBDE, HBCD concentrations were continuously increasing to reach 2.5 ng/g dw in 2001. Next to DecaBDE, all 3 NonaBDE congeners (BDE-208, BDE-207, and BDE-206) and at least 7 out of the 12 possible OctaBDE congeners (BDE-202, BDE-201, BDE-197/204, BDE-198/203, BDE-196/200, BDE-205, and BDE-194) were detected in the sediments of Greifensee. Highest concentrations were found in the surface sediments with 7.2, 0.26, 0.14, and 1.6 ng/g dw for Deca-, Nona-, Octa-, and the sum of Tri-HeptaBDE, respectively. While DecaBDE and NonaBDE were found to increase rapidly, the increase of OctaBDE was slower. Congener patterns of Octa- and NonaBDE present in sediments of Greifensee did not change with time. Consequently, there was no evidence for sediment mediated long-term transformation of PBDE within the observed time span of almost 30 years. Despite the high persistence of DecaBDE, environmental debromination occurs, as shown by the detection of a shift in congener patterns of Octa- and NonaBDE in sediments, compared to the respective congener patterns in technical PBDE products. The OctaBDE congener BDE-202 was detected in sediments, representing a transformation product that is not reported in any of the technical PBDE products. Comparison of OctaBDE congener patterns in sediments with OctaBDE congener patterns from known sources reveals that (i) they were distinctively different from the congener patterns in technical PBDE products and (ii) that they were similar to the OctaBDE patterns in house dust and photodegradation products of DecaBDE, suggesting contributions from these sources.     

Azole fungicides: occurrence and fate in wastewater and surface waters

The mode of action of azole compounds implies a potential to affect endocrine systems of different organisms and is reason for environmental concern. The occurrence and fate of nine agricultural azole fungicides, some of them also used as biocides, and four azole pharmaceuticals were studied in wastewater treatment plants (WWTPs) and lakes in Switzerland. Two pharmaceuticals (fluconazole, clotrimazole, 10-110 ng L(-1)) and two biocides (propiconazole, tebuconazole, 1-30 ng L(-1)) were consistently observed in WWTP influents. Loads determined in untreated and treated wastewater indicated thatfluconazole, propiconazole, and tebuconazole were largely unaffected by wastewater treatment, but clotrimazole was effectively eliminated (> 80%). Incubation studies with activated sludge showed no degradation for fluconazole and clotrimazole within 24 h, but strong sorption of clotrimazole to activated sludge. Slow degradation and some sorption were observed for tebuconazole and propiconazole (degradation half-lives, 2-3 d). In lakes, fluconazole, propiconazole, and tebuconazole were detected at low nanogram-per-liter levels. Concentrations of the pharmaceutical fluconazole correlated with the expected contamination by domestic wastewater, but not those of the biocides. Per capita loads of propiconazole and tebuconazole in lakes suggested additional inputs; for example, from agricultural use or urban runoff rainwater.     

Detection of wheat adulteration of spelt flour and products by PCR

 To date, no general method to detect wheat [Triticum aestivum vulgare (Vill.) Mackey] adulteration of spelt [T. aestivum spelta (L.) Thell.] exists. Exploiting a published allelic difference in γ-gliadin gene GAG56D, we developed and evaluated three PCR-based methods to determine the proportion of wheat in spelt flour and products. A sensitive wheat-specific PCR system was designed. Moreover, a heterologous internal standard was constructed for quantitative competitive (QC-)PCR. The standard was arbitrarily calibrated to 5% wheat DNA in spelt DNA. A PCR-RFLP system consisting of a GAG56D-specific PCR system with subsequent restriction was used to estimate the relative proportions of wheat and spelt in DNA mixtures. The three methods were successfully applied to seven commercial spelt samples and one self-produced bread. Five and three of the seven samples were found to contain more than 5% and 10% wheat, respectively. One sample appeared to contain no spelt at all. Analyzing the bread crumb with PCR-RFLP, we were able to estimate the wheat content of the flour which was used to produce the bread and thus demonstrated the applicability of PCR-RFLP to quantify processed products. Received: 24 March 2000     

Combined sewer overflows to surface waters detected by the anthropogenic marker caffeine

Continuous progress in wastewater treatment technology and the growing number of households connected to wastewater treatment plants (WWTPs) have generally resulted in decreased environmental loading of many pollutants. Nonetheless, further reduction of pollutant inputs is required to improve the quality of surface waters in densely populated areas. In this context, the relative contribution of combined sewer overflows as sources of wastewater-derived contaminants has attracted more and more attention, but the quantitative importance of these overflows has barely been investigated. In this study, caffeine was successfully used as a chemical marker to estimate the fraction of sewer overflows in the catchment area of lake Greifensee, Switzerland. Caffeine is a ubiquitous compound in raw, domestic wastewater with typical per capita loads of approximately 16 mg person(-1) d(-1). In WWTPs of the Greifensee region, caffeine is largely eliminated (>99%), resulting in much smaller loads of < or = 0.15 mg person(-1) d(-1) in treated wastewater. However, in receiving streams as in the inflows to Greifensee, caffeine loads (0.1-1.6 mg person(-1) d(-1)) were higher than those in WWTP effluents, indicating additional sources. As the loads in the streams correlated with precipitation during sampling, it was concluded that combined sewer overflows were the most likely source of caffeine. Using a mass balance approach, it was possible to determine the fraction of wastewater (in dry weather equivalents) discharged untreated to the receiving streams (up to 10%, annual mean, approximately 2-3%). The concept of caffeine as a marker for combined sewer overflows was then applied to estimate phosphorus inputs to Greifensee with untreated and treated wastewater (approximately 1.5 and 2.0 t P y(-1), respectively), which corresponded well with P inputs determined in a separate study based on hydraulic considerations. For compounds with high elimination in WWTPs such as phosphorus (96-98% in the Greifensee area), inputs from combined sewer overflows are thus of similar magnitude as inputs from treated wastewater. The study demonstrated that caffeine is a suitable marker for untreated wastewater (from combined sewer overflows, direct discharges, etc.), but its sensitivity depends on regional conditions and decreases with decreasing elimination efficiency in WWTPs.     

Combined speciation analysis by X-ray absorption near-edge structure spectroscopy, ion chromatography, and solid-phase microextraction gas chromatography-mass spectrometry to evaluate biotreatment of concentrated selenium wastewaters

In this study we evaluate the potential of anaerobic granular sludge as an inoculum for the bioremediation of selenium-contaminated waters using species-specific analytical methods. Solid species formed by microbial reduction were investigated using X-ray absorption near-edge structure (XANES) spectroscopy at the selenium K-edge. Furthermore, dissolved selenium species were specifically determined by ion chromatography (IC) and solid-phase microextraction gas chromatography-mass spectrometry (SPME-GC-MS). Least-squares linear combination of the XANES spectra for samples incubated with the highest selenate/selenite concentrations (10(-3) M) show the predominance of elemental selenium and a Se(-I) selenide, such as ferroselite, the thermodynamically most stable iron selenide. In contrast, elemental selenium and Se(-II) selenides are the main species detected at the lower selenate/selenite concentrations. In each repeated fed batch incubation, most aqueous selenite anions were converted into solid selenium species, regardless of the type of electron donor used (acetate or H(2)/CO(2)) and the selenium concentration applied. On the other hand, at higher concentrations of selenate (10(-4) and 10(-3) M), significant amounts of the oxyanion remained unconverted after consecutive incubations. SPME-GC-MS demonstrated selenium alkylation with both electron donors investigated, as dimethyl selenide (DMSe) and dimethyl diselenide (DMDSe). Selenite was even more alkylated in the presence of H(2)/CO(2) (maximum 2156 μg of Se/L of DMSe + DMDSe) as compared to acetate (maximum 50 μg of Se/L). In contrast, selenate was less alkylated using both electron donors (maximum 166 and 3 μg of Se/L, respectively). The high alkylation potential for selenite limits its bioremediation in selenium laden waters involving H(2)/CO(2) as the electron donor despite the fact that nontoxic elemental selenium and thermodynamically stable metal selenide species are formed.     

Influence of light on food relevant fungi with emphasis on ochratoxin producing species

The influence of light of varying wavelength on growth and ochratoxin A biosynthesis of Aspergillus carbonarius, A. niger, A. steynii and on Penicillium nordicum and P. verrucosum was analysed. For comparison the influence of light on various other food relevant fungi, including citrinin producers, was also tested. Generally the Aspergilli seem to be more resistant to light treatment than the Penicillia. Interestingly wavelengths from both sides of the spectrum, e. g. red (long wavelength, 627 nm) and blue (short wavelength 470-455 nm) had the strongest inhibitory effects on growth and ochratoxin A biosynthesis. Blue light generally had a stronger effect. Light of moderate wavelength, 590 to 530 nm, (yellow to green) had more a positive than a negative influence on growth or ochratoxin A biosynthesis compared to the control (dark incubation). The light effect on growth and ochratoxin A biosynthesis was dependent on the growth medium. In contrast to malt extract medium (MEA), YES medium, as an especially nutrient rich medium, had an attenuating effect on the reactivity against light. However the tendency of the response in both media was the same. Moreover, the light intensity strongly influences how the fungus reacts. Depending on the intensity and the resistance of the species a complete cessation of growth and/or inhibition of ochratoxin A biosynthesis could be achieved. Light irradiation has the opposite effect on ochratoxin A than citrinin, two mycotoxins which can be produced simultaneously in P. verrucosum. Citrinin was produced essentially under light conditions which inhibited ochratoxin A biosynthesis. The same was true for a derivative of ochratoxin, in particular a derivative of ochratoxin β in A. carbonarius. A. carbonarius produced high amounts of the ochratoxin β derivative under blue light when the production of ochratoxin A was ceased at the most inhibiting conditions used (MEA, royal blue light, 455 nm, 1700 lx). Light has a growth stalling but not inactivating effect on aerial mycelia. If a non-growing colony under light is shifted to the dark it immediately grows normally. However on spores blue light has a deactivating effect. After incubation of spores of P. verrucosum for 24 h under blue light up to 97% of the spores were no longer able to germinate. Again the spores of the Aspergilli were much more resistant.     

Behavior of the polycyclic musks HHCB and AHTN in lakes, two potential anthropogenic markers for domestic wastewater in surface waters

The synthetic polycyclic musks HHCB and AHTN are potential chemical markers for domestic wastewater contamination of surface waters. Understanding their environmental behavior is important to evaluate their suitability as markers. This study focuses on the quantification of the processes that lead to an elimination in lakes. Rate constants for all relevant processes were estimated based on laboratory studies and models previously described. In lake Zurich, during winter time, both compounds are eliminated primarily by outflowing water and due to losses to the atmosphere. In summer, direct photolysis represents the predominant elimination process for AHTN in the epilimnion of lake Zurich (quantum yield, 0.12), whereas for HHCB, photochemical degradation is still negligible. HHCB and AHTN were then measured in effluents of Swiss wastewater treatment plants (WWTPs), in remote and anthropogenically influenced Swiss surface waters, and in Mediterranean seawater using an analytical procedure based on SPE and GC-MS-SIM with D6-HHCB as internal standard (LODs for natural waters, 2 and 1 ng/L, respectively). In winter, concentrations of HHCB and AHTN in lakes (<2-47 and <1-18 ng/L, respectively) correlated with the anthropogenic burden by domestic wastewater (ratio population per water throughflow), demonstrating the suitability of these compounds as quantitative, source-specific markers. In summer, however, no such correlations were observed. Vertical concentration profiles in lake Zurich indicated significant losses in the epilimnion during summer, mainly for AHTN, and could be rationalized with a lake modeling program (MASASlight), considering measured, average loads from WWTP effluents (0.80 +/- 0.22 and 0.32 +/- 0.11 mg person(-1) d(-1) for HHCB and AHTN, respectively) and the estimated rate constants for elimination processes.