Biomedical subjects

Andreas Schäffer

Publications and source records attributed to Andreas Schäffer.

12 recordsLinked to original sources

PubMed2006

Fate of a 14C-labeled nonylphenol isomer in a laboratory-scale membrane bioreactor.

This study aimed at giving a better insight into the possible fate of nonylphenol (NP) during wastewater treatment by using a lab-scale membrane bioreactor (MBR) designed and optimized for fate studies carried out with radiolabeled compounds. After a single pulse of 14C-labeled-NP isomer (4-[1-ethyl-1,3-dimethylpentyl]phenol) as radiotracer, the applied radioactivity was monitored in the MBR system over 34 days. The mass balance of NP residues at the end of the study showed that 42% of the applied radioactivity was recovered in the effluent as degradation products of NP, 21% was removed with the daily excess sludge from the MBR, and 34% was recovered as adsorbed in the component parts of the MBR. A high amount of NP was associated to the sludge during the test period, while degradation compounds were mainly found in the effluent. Partial identification of these metabolites by means of HPLC-tandem mass spectrometry coupled to radio-detection showed they are alkyl-chain oxidation products of NP. The use of this MBR and a radiolabeled test compound was found suitable for demonstrating that under the applied conditions, the elimination of NP through mineralization and volatilization processes (both less than 1%) was negligible. However, the removal of NP via sorption and the continuous release of oxidation products of NP in permeate were of relevance.

Biodegradation, Environmental↗

PubMed2006

Safety evaluation for a biodiesel process using prion-contaminated animal fat as a source.

BACKGROUND: Due to the bovine spongiform encephalopathy (BSE), specified risk material (SRM) as well as animal meat and bone meal (MBM) are banned from the food and feed chain because of a possible infection with pathogenic prions (PrP(Sc)). Nowadays, prions are widely accepted to be responsible for TSE(transmissible spongiform encephalopathies)-caused illnesses like BSE and scrapie, and especially for the occurrence of the new variant of CJD in humans. Presently, SRM and MBM are burnt under high temperatures to avoid any hazards for humans, animals or the environment. The aim of this study was to evaluate a method using animal fat separated from Category I material which includes SRM and the carcasses of TSE-infected animals, or animals suspected of being infected with TSE, as a source for producing biodiesel by transesterification, analogous to the biodiesel process using vegetable oil. METHODS: For this purpose, animal fat was spiked with scrapie-infected hamster brain equivalents--as representative for a TSE-infected animal--and the biodiesel manufacturing process was downscaled and performed under lab-scale conditions. RESULTS AND DISCUSSION: The results analysed by Western blotting showed clearly that almost each single step of the process leads to a significant reduction of the concentration of the pathogenic prion protein (PrP(Sc)) in the main and side-products. CONCLUSION: The data revealed that the biodiesel production, even from material with a high concentration of pathogenic prions, can be considered as safe. RECOMMENDATIONS AND OUTLOOK: The obtained results indicated that biodiesel produced from prion-contaminated fat was safe under the tested process conditions. However, it has to be pointed out that the results cannot be generalized because a different process control using other conditions may lead to different results and then has to be analysed independently. It is clear that the production of biodiesel from high risk material represents a more economic usage than the combustion of such material.

Animals↗

PubMed2005

Occurrence of a nitro metabolite of a defined nonylphenol isomer in soil/sewage sludge mixtures.

Uniformly [14C]-ring-labeled 4-(3,5-dimethyl-3-heptyl)phenol (353-nonylphenol) is a highly relevant isomer of the technical nonylphenol mixture. We studied the sorption, desorption, and degradation of the synthesized isomer in an agricultural sandy loam at various soil/sewage sludge ratios. Sorption of 353-nonylphenol was high and differed with the amount of suspended soil in water. log Koc values, which are used to assess the risk of nonylphenol, ranged from 3.80 to 5.75. Desorption was slow and low and resulted in constant concentrations of about 15 ng/L353-nonylphenol in water after several desorption steps. In degradation studies up to 6% of the applied 353-nonylphenol in soil was volatilized; we consider this an important source of nonylphenol in the environment. With increasing amounts of sewage sludge in the soil/sewage sludge mixtures, 353-nonylphenol was stabilized, probably because of the lack of oxygen in sludge aggregates even under oxic conditions in flow-through systems. Unexpectedly, a less-polar metabolite was detected in amounts up to 40% of the applied nonylphenol after 135 days of incubation. This novel metabolite was identified as 4-(3,5-dimethyl-3-heptyl)-2-nitrophenol. This product formation might indicate the existence of novel metabolic pathways of nonylphenol in the environment.

Adsorption↗

PubMed2005

Synthesis of [13C]- and [14C]-labeled phenolic humus and lignin monomers.

Natural phenolic monomers are ubiquitous in the environment and are involved in the stabilization of atmospheric carbon and the transformation of xenobiotics. Investigations on the stabilization of phenolic carbons and their environmental fate are hampered by the unavailability of commercial [13C]- and [14C]-labeled phenols. Here we report the complete chemical synthesis of the lignin and humus structural monomers p-coumaric, ferulic, and caffeic acids, p-hydroxybenzaldehyde, protocatechualdehyde, vanillin, catechol, and guaiacol, uniformly [13C]- or [14C]-labeled in the aromatic ring, starting from commercially available [U-ring-13C]- or [U-ring-14C]-labeled phenol. The synthesis of these compounds involved selective ortho-hydroxylation of the aromatic ring, Friedel-Crafts alkylation, and Knoevenagel condensation. [U-ring-13C]- or [U-ring-14C]-p-coumaric acid was synthesized via p-hydroxybenzaldehyde with a 75% yield with respect to phenol. Synthesis of [U-ring-13C]- or [U-ring-14C]-ferulic acid, consisting of six single steps via guaiacol and vanillin, had an overall yield of up to 45%. Uniformly ring-labeled caffeic acid was synthesized either via catechol and protocatechualdehyde in five single steps, yielding [U-ring-14C]-caffeic acid with a 37% yield, or via guaiacol, vanillin, and ferulic acid in seven steps, yielding [U-ring-13C]-caffeic acid with an 18% yield. Ferulic acid, [14C]-labeled at beta-C of the propenoic side chain, was synthesized from [2-14C]-malonic acid under Knoevenagel conditions with a 67% yield with respect to malonic acid. Demethylation of the [beta-14C]-ferulic acid with BBr3 in CH3CN resulted in [beta-14C]-caffeic acid with a 62% yield. All [U-ring-13C]-labeled phenolic products were analyzed by 13C nuclear magnetic resonance (13C-NMR) spectroscopy and gas chromatography-mass spectrometry (GC-MS).

Alkylation↗

PubMed2004

Use of 15N-depleted artificial compost in bound residue studies.

Association of bound residues to soil humic matter may be accomplished by different binding mechanisms such as sequestration in hydrophobic interiors of the organic material or covalent linkage to the organic matter. The structures and chemical environments of compounds can be observed by NMR spectroscopy. We applied 15N-NMR spectroscopy to study the soil-bound residues of 15N-labeled simazine. As the 15N-isotope has a low sensitivity and natural abundance 15N-NMR experiments require long measurement times and often result in low signal-to-noise (S/N) ratios. Therefore, in addition to the use of 15N-labeled simazine, 15N-depleted compost was used to reduce the amount of background signal and enhance the sensitivity. The compost was produced from maize and wheat plants grown on sand with 15N-depleted NH4NO3 as sole nitrogen source. The plants were freeze-dried, ground and mixed with sand for composting. After a composting period of 224 days analysis of the compost revealed a 15N-content of 267 ppm as opposed to a natural abundance of 3650 ppm. Characterization of this artificial compost produced parameter values similar to those of a natural compost. The 13C-NMR-spectra of the humic and fulvic acids during different stages of maturity showed that there was a shift from single-bond functional groups to more complex double-bond and aromatic structures. Experiments with this compost showed an increased signal intensity. The improved sensitivity made it possible to obtain interpretable NMR signals in contrast to experiments with 15N-simazine on native soil where no signals were detectable. The data indicated that the bound residues of simazine are composed of metabolites resulting from N-dealkylation and triazine ring destruction. Silylation of the bound residues showed a very strong binding of the residues to the matrix as only a small fraction could be solubilized.

Chromatography, Gel↗

PubMed2004

Pesticide volatilization from plants: improvement of the PEC model PELMO based on a boundary-layer concept.

Calculation of pesticide volatilization from plants as an integral component of pesticide fate models is of utmost importance, especially as part of PEC (predicted environmental concentrations) models used in the registration procedures for pesticides. A mechanistic approach using a laminar air-boundary layer concept to predict volatilization from plant surfaces was compared to data obtained in a wind-tunnel study after simultaneous application of parathion-methyl, fenpropimorph, and quinoxyfen to winter wheat. Parathion-methyl was shown to have the highest volatilization during the wind-tunnel study of 10 days (29.2%). Volatilization of quinoxyfen was about 15.0%, revealing a higher volatilization tendency than fenpropimorph (6.0%), which is attributed to enhanced penetration of fenpropimorph counteracting volatilization. Predictions of the boundary-layer approach were markedly influenced by the selected values for the equivalent thickness of the boundary layer and rate coefficients, thus indicating that future improvements of the approach will require a deeper understanding of the kinetics of the underlying processes, e.g. phototransformation and penetration. The boundary-layer volatilization module was included in the European registration model PELMO, enabling simultaneous calculation of volatilization from plants and soil. Application of PELMO to experimental findings were the first comprehensive PEC model calculations to imply the relevant processes affecting the postapplication fate of pesticides.

Carbon Radioisotopes↗

PubMed2004

Characterization of the bound residues of the fungicide cyprodinil formed in plant cell suspension cultures of wheat.

The non-extractable residues of the fungicide cyprodinil formed in heterotrophic cell suspension cultures of wheat were studied by application of [2-pyrimidyl-14C] or [2-pyrimidyl-13C]cyprodinil. The main objective was to examine whether solid-state and liquid 13C NMR spectroscopy can be used to examine plant bound residues of pesticides. For 14C experiments, wheat suspensions grown on glucose as carbon source were treated with 10 mg litre(-1) of 14C-cyprodinil. After incubation for 12 days, 20% of applied 14C was detected as non-extractable residues. The cell debris were treated with 0.1 M HCl (reflux), 1.0 M HCl (reflux), buffer, or 2 M NaOH (50 degrees C); Björkman lignin and acidolysis lignin fractions were also prepared from the debris. Radioactivity liberated and solubilized by these procedures was examined by thin-layer chromatography and high-performance liquid chromatography. The results showed that cyprodinil and primary metabolites contributed to the fungicide's bound residues. Most of the residues (12% of applied 14C) remained associated with polar or polymeric/oligomeric endogenous cell materials in a stable manner. For the study with 13C-cyprodinil, wheat suspensions were cultivated on 13C-depleted glucose for four growth cycles, resulting in maximum 13C depletion of the natural cell components to about 0.10%. During the fourth cycle, 13C-labelled cyprodinil was applied, and cells were incubated (12 days). Cell debris was prepared and examined by solid-state 13C NMR spectroscopy. Debris was then treated as described above in the 14C experiment. Solubilized fractions were analyzed by liquid 13C NMR spectroscopy. However, none of the 13C NMR spectra recorded gave utilizable or unambiguous results, and all exhibited large inconsistencies, especially concerning the data from the conventional 14C experiment.

Binding Sites↗

PubMed2004

Investigation on the chemical structure of nonextractable residues of the fungicide cyprodinil in spring wheat using 13C-C1-phenyl-cyprodinil on 13C-depleted plants-an alternative approach to investigate nonextractable residues.

13C-labelled cyprodinil was applied on 13C-depleted wheat plants with 27-fold field application rate. A control experiment applying same amounts of 14C-cyprodinil showed that main portions of the residues were detected in the cellulose (15% NER), hemicellulose (28.3% NER), and lignin fraction (23.3% NER). 16.7% were detected in water soluble polymers, 6% in both, pectin and protein fraction, and 4% in the starch containing fraction. Free cyprodinil was detectable by TLC in all fractions except lignin. A direct characterization of the residues in vivo by CP-MAS was not successful. Cell wall fractions were further analysed by liquid state NMR to determine the structure of the mobilized highly polymer/polar residues: Within lignin, where most of the residues were located at field application rate, neither intact cyprodinil nor its metabolites could not be detected. The 13C-label introduced was probably incorporated in the polymer as natural lignin monomers and thus are not considered as bound residues according to IUPAC definition.

Carbon Isotopes↗

PubMed2003

Sorption and dialysis experiments to assess the binding of phenolic xenobiotics to dissolved organic matter in soil.

The binding of two phenolic compounds, nonylphenol (NP) and bisphenol A (BPA), and the herbicide metabolite hydroxydesethyl terbuthylazine (HDT) to dissolved organic matter (DOM) as well as its impact on the environmental fate of the compounds in soil have been investigated. In sorption studies with an acidic silty loam soil and a neutral loam soil, no impact of added DOM on adsorption and desorption coefficients was observed. Adsorption coefficients normalized to soil organic carbon (Koc) of the compounds on the loamy silt soil spanned three orders of magnitude: 90, 890, and 9,140 L/kg for HDT, BPA, and NP, respectively. Significantly lower Koc values for HDT on the neutral loam soil as compared to the acidic loamy silt soil indicated additional polar interactions between the latter and the basic herbicide metabolite. In dialysis experiments with fulvic acid from silty loam soil (FA) and peat humic acid (HA), a formation of analyte-DOM associates was observed only for HA. The degree of association was characterized by distribution coefficients normalized to the dissolved organic carbon concentration (KDOC). Values for NP (8,970 L/kg) and BPA (860 L/kg) corresponded with the respective soil sorption coefficients, suggesting similar binding mechanisms in both cases.

Adsorption↗

PubMed2003

Structural and functional approach to studying pesticide side-effects on specific soil functions.

The microbial communities in the soil are responsible for material cycling and thus also for maintaining the fertility of agricultural soils. In order to assess pesticide side effects on the soil processes, detailed knowledge is required about the structure and function of the soil microflora. Therefore, the degradation and humification of 14C-labeled maize straw was studied in process-oriented microcosms. Apart from a native orthic luvisol, a heat-treated soil was used that has been freed from organic carbon by incineration at 600 degrees C. Microbial communities involved in the turnover of the crop residues were investigated using denaturing gradient gel electrophoresis (DGGE) of 16S rDNA sequences. Both 13C-nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography were used to analyze humic acids produced in the microcosms. To evaluate the sensitivity of the microcosms, the influence of the fungicide dithianon was used in a case study at a concentration of 50 mg/kg. Microbial activity was reduced because of the application of the pesticide, especially in the native soils, while mineralization of 14C-labeled maize straw was only slightly affected. The buildup of fungal biomass was inhibited for at least three weeks. Despite these effects on the microbial communities, no significant differences in the humification products after 26 weeks of incubation were observed.

Anthraquinones↗

PubMed2003

A new tool for laboratory studies on volatilization: extension of applicability of the photovolatility chamber.

Volatilization from soil and plant surfaces after application is an important source of pesticide residues to the atmosphere. The laboratory photovolatility chamber allows the simultaneous measurement of volatilization and photodegradation of 14C-labeled pesticides under controlled climatic conditions. Both continuous air sampling, which quantifies volatile organic compounds and 14CO2 separately, and the detection of surface-located residues allow for a mass balance of radioactivity. The setup of the photovolatility chamber was optimized, and additional sensors were installed to characterize the influence of soil moisture, soil temperature, and evaporation on volatilization. The modified flow profile in the glass dome of the chamber arising from the use of a high-performance metal bellows pump was measured. Diminished air velocity near the soil surface and a wind velocity of 0.2 m/s in 3 cm height allowed the requirements of the German guideline on assessing pesticide volatilization for registration purposes to be fulfilled. Determination of soil moisture profiles of the upper soil layer illustrated that defined water content in the soil up to a depth of 4 cm could be achieved by water saturation of air. Cumulative volatilization of [phenyl-UL-14C]parathion-methyl ranged from 2.4% under dry conditions to 32.9% under moist conditions and revealed the clear dependence of volatilization on the water content in the top layer.

Air↗

PubMedDate not supplied

Pesticide volatilization from soil: lysimeter measurements versus predictions of European registration models.

A comparison was drawn between model predictions and experimentally determined volatilization rates to evaluate the volatilization approaches of European registration models. Volatilization rates of pesticides (14C-labeled parathion-methyl, fenpropimorph, and terbuthylazine and nonlabeled chlorpyrifos) were determined in a wind-tunnel experiment after simultaneous soil surface application on Gleyic Cambisol. Both continuous air sampling, which quantifies volatile losses of 14C-organic compounds and 14CO2 separately, and the detection of soil residues allow for a mass balance of radioactivity of the 14C-labeled pesticides. Recoveries were found to be > 94% of the applied radioactivity. The following descending order of cumulative volatilization was observed: chlorpyrifos > parathion-methyl > terbuthylazine > fenpropimorph. Due to its high air-water partitioning coefficient, nonlabeled chlorpyrifos was found to have the highest cumulative volatilization (44.4%) over the course of the experiment. Volatilization flux rates were measured up to 993 microg m(-2) h(-1) during the first hours after application. Parameterization of the Pesticide Emission Assessment at Regional and Local Scales (PEARL) model and the Pesticide Leaching Model (PELMO) was performed to mirror the experimental boundary conditions. In general, model predictions deviated markedly from measured volatilization rates and showed limitations of current volatilization models, such as the uppermost compartment thickness, making an enormous influence on predicted volatilization losses. Experimental findings revealed soil moisture to be an important factor influencing volatilization from soil, yet its influence was not reflected by the model calculations. Future versions of PEARL and PELMO ought to include improved descriptions of aerodynamic resistances and soil moisture dependent soil-air partitioning coefficients.

Environmental Monitoring↗