Immersed solid phase microextraction to measure chemical activity of lipophilic organic contaminants in fatty tissue samples

It is known that solid phase microextraction (SPME) fibers can be equilibrated directly within environmental matrices such as water, sediment and soil slurries. Here it is shown that this method can also be applied to biological tissue. SPME extraction of biological matrices reportedly causes lipophilic fouling of the fiber. However, we found no significant measurement bias when combining equilibrium sampling with fiber surface cleaning. The uptake of lipophilic organic pollutants from the tissue and into the SPME fiber coating was characterized by fast equilibrium partitioning without sample depletion and without impacting the sorptive properties of the fiber. The precision of the method when applied to hexachlorobenzene and several PCB congeners in harbor porpoise blubber was 15%, which includes the variation between SPME samplings, manual injections and the instrumental analysis. A good correlation (r(2)=0.95) was obtained between SPME measurements of PCB 153 in blubber and concentrations obtained via a traditional analytical approach. These results indicate that SPME is a promising technique for measuring chemical activity in biological tissue, which would make it a useful tool for studying chemical distribution in organisms as well as biodilution and biomagnification phenomena.     

Sample preparation and biomass determination of SRF model mixture using cryogenic milling and the adapted balance method

The biogenic fraction of a simple solid recovered fuel (SRF) mixture (80 wt% printer paper/20 wt% high density polyethylene) is analyzed with the in-house developed adapted balance method (aBM). This fairly new approach is a combination of combustion elemental analysis (CHNS) and a data reconciliation algorithm based on successive linearisation for evaluation of the analysis results. This method shows a great potential as an alternative way to determine the biomass content in SRF. However, the employed analytical technique (CHNS elemental analysis) restricts the probed sample mass to low amounts in the range of a few hundred milligrams. This requires sample comminution to small grain sizes (<200 μm) to generate representative SRF specimen. This is not easily accomplished for certain material mixtures (e.g. SRF with rubber content) by conventional means of sample size reduction.This paper presents a proof of principle investigation of the sample preparation and analysis of an SRF model mixture with the use of cryogenic impact milling (final sample comminution) and the adapted balance method (determination of biomass content). The so derived sample preparation methodology (cutting mills and cryogenic impact milling) shows a better performance in accuracy and precision for the determination of the biomass content than one solely based on cutting mills. The results for the determination of the biogenic fraction are within 1–5% of the data obtained by the reference methods, selective dissolution method (SDM) and ¹⁴C-method (¹⁴C-M).     

Anaerobic Degradation of Phenolic Compounds

Mononuclear aromatic compounds are degraded anaerobically through three main pathways, the benzoyl-CoA pathway, the resorcinol pathway, and the phloroglucinol pathway. Various modification reactions channel a broad variety of mononuclear aromatics including aromatic hydrocarbons into either one of these three pathways. Recently, a further pathway was discovered with hydroxyhydroquinone as central intermediate through which especially nitrate-reducing bacteria degrade phenolic compounds and some hydroxylated benzoates. Comparison of the various strategies taken for the degradation of aromatics in the absence of oxygen demonstrates that the biochemistry of breakdown of these compounds is determined largely by the overall reaction energetics and, more precisely, by the redox potentials of the electron acceptor systems used. Nitrate reducers differ in their strategies significantly from those used by sulfate-reducing or fermenting bacteria.     

Aufnahmepfade von POPs in Biota

Zusammenfassung  POPs (persistente organische Schadstoffe), die an aquatischen Sedimenten binden, k?nnen zurück in Nahrungsnetze gelangen und so zu einem Risiko für aquatische Organismen werden. Dabei kann die Bioakkumulation solcher Substanzen in endobenthischen, sedimentfressenden Invertebraten (z.B. aquatische Oligochaeten) eine gro?e Rolle spielen. Diese Würmer dienen vielen benthivoren Fischen als Nahrung. Letztere nehmen über diesen Weg sedimentgebundene Chemikalien auf und k?nnen hierbei deutlich h?here K?rperkonzentrationen (body residues) erreichen als durch die Anreicherung aus der Wasserphase. Die angereicherten Rückst?nde k?nnen im weiteren Verlauf der Nahrungskette an Glieder h?herer trophischer Ebenen weitergegeben werden. Zur standardisierten Bestimmung der Bioakkumulation und — magnifikation wurde eine einfache, zwei trophische Stufen umfassende Labornahrungskette etabliert. Diese bestand aus dem endobenthischen Oligochaeten Tubifex tubifex und dem Dreistachligen Stichling (Gasterosteus aculeatus) als Pr?dator. Die Experimente wurden mit ¹⁴C-markiertem Hexachlorbenzol in dotiertem künstlichem Sediment und rekonstituiertem Wasser durchgeführt. Um den Einfluss benthischer Beuteorganismen zu quantifizieren, wurden die Fische gegenüber dotiertem Wasser bzw. Sediment (Biokonzentration), vorexponierten Würmern (Biomagnifikation) und Kombinationen dieser Aufnahmepfade exponiert. HCB wurde entlang der Labornahrungskette deutlich angereichert. Es konnte gezeigt werden, dass die Exposition gegenüber der Kombination s?mtlicher Aufnahmepfade zu deutlich h?herer Anreicherung in den Fischen führte als im Falle einzelner Expositionspfade. Der Vergleich der Einzelergebnisse lie? den Schluss zu, dass neben dem freien Wasserk?rper die kontaminierte Nahrung der Hauptaufnahmeweg für den Fisch war. Bei der Bewertung von POPs wie HCB hinsichtlich Biomagnifikation und ‘secondary poisoning’ sollten daher Nahrung und Sediment als Expositionspfade unter Verwendung von Nahrungsketten-modellen und/oder Labortests st?rker berücksichtigt werden. Reter Spr?rlein war bis Januar 2000 als Ingenieur für Umweltverfahrenstechnik bei der ECT Oekotoxikologie GmbH besch?ftigt und für die HPLC-analytische Aufarbeitung der experimentellen Proben verantwortlich.     

PCDD/F levels in food and canteen meals from southern Germany

Analysis of food samples collected in 1997 and 1998 in Bavaria, Germany showed that PCDD/F levels in food of animal origin, with the exception of fish, have decreased to low levels way below 1 pg I-TEQ/g fat. Lowest PCDD/F contents were found in pork (mean: 0.27 pg I-TEQ/g fat) followed by poultry and cow's milk (mean: approx. 0.5 pg I-TEQ/g fat). Average contamination levels determined in beef and eggs lay in the range from 0.7 to 0.8 pg I-TEQ/g fat. PCDD/F levels in fish were clearly higher than levels in meat, milk and egg samples (mean: 5.6 pg I-TEQ/g fat). Comparison of topical levels with former results from Bavaria show that the recently detected decline of contamination of food has continued during the past few years. In addition to investigations of unprepared food, we analysed prepared canteen meals over a period of 1 year. The average PCDD/F level found in canteen food (0.37 pg I-TEQ/g fat) was in good conformity with determined PCDD/F levels in unprepared food regarding the estimated fat composition of prepared meals. The average consumption of fat per meal via canteen food was 21.1 g and the average PCDD/F intake per meal was 7.6 pg I-TEQ. On the supposition that determined PCDD/F levels in canteen food on fat basis are representative of total fat consumed by humans (102 g fat/day), the daily PCDD/F intake would amount to a mean value of 36.7 pg I-TEQ corresponding to 0.52 pg I-TEQ/kg body weight.     

Status of Piping Plovers in the Great Plains of North America: A Demographic Simulation Model

A stochastic population growth model using empirical demographic data confirmed that the Piping Plover population of the Great Plains of North America is declining by more than 7% annually. Unchecked, this decline would result in extirpation in approximately 80 years. When recent adult (0.66) and immature (0.60) survival rates were held constant, a 31% increase—from 0.86 to 1.13 chicks fledged per pair—was needed to stabilize the population. Annual population increases of 1% and 2% required 1.16 and 1.19 chicks per pair, respectively. Such growth would result in the Great Plains population reaching the level—(2550 pairs)—needed for delisting from the U.S. Endangered Species Act protection in 53 and 30 years, respectively. One- and five-year delays in the initiation of 1% population growth caused 13 and 67 year delays respectively in reaching recovery.     

Current EU-27 technical potential of organic waste streams for biogas and energy production

Anaerobic digestion of organic waste generated by households, businesses, agriculture, and industry is an important approach as method of waste treatment – especially with regard to its potential as an alternative energy source and its cost-effectiveness. Separate collection of biowaste from households or vegetal waste from public green spaces is already established in some EU-27 countries. The material recovery in composting plants is common for biowaste and vegetal waste. Brewery waste fractions generated by beer production are often used for animal feeding after a suitable preparation. Waste streams from paper industry generated by pulp and paper production such as black liquor or paper sludge are often highly contaminated with toxic substances. Recovery of chemicals and the use in thermal processes like incineration, pyrolysis, and gasification are typical utilization paths. The current utilization of organic waste from households and institutions (without agricultural waste) was investigated for EU-27 countries with Germany as an in-depth example. Besides of biowaste little is known about the suitability of waste streams from brewery and paper industry for anaerobic digestion. Therefore, an evaluation of the most important biogas process parameters for different substrates was carried out, in order to calculate the biogas utilization potential of these waste quantities. Furthermore, a calculation of biogas energy potentials was carried out for defined waste fractions which are most suitable for anaerobic digestion. Up to 1% of the primary energy demand can be covered by the calculated total biogas energy potential. By using a “best-practice-scenario” for separately collected biowaste, the coverage of primary energy demand may be increased above 2% for several countries. By using sector-specific waste streams, for example the German paper industry could cover up to 4.7% and the German brewery industry up to 71.2% of its total energy demand.