II. Aufbau fl?chenrepr?sentativer Probenahmen von Umweltproben zur Schadstoffanalytik am Beispiel der Regenwürmer in landwirtschaftlich genutzten R?umen

Ein sinnvoller Einsatz von Akkumulationsindikatoren erfordert zur Qualit?tssicherung neben den vorhandenen Laborstandards ein anspruchsvolles Probenahmeverfahren, um repr?sentative und reproduzierbate Aussagen über einen Untersuchungsraum treffen zu k?nnen. Am Beispiel der Regenwürmer wird exemplarisch ein Probenahmeverfahren für landwirtschaftliche R?ume entwickelt und vorgeführt. Erste Ergebnisse der in den Wurm- und Kotproben gemessenen polyzyklischen aromatischen Kohlenwasserstoffe, der chlorierten Kohlenwasserstoffe und der Elemente werden dargestellt. Die Schadstoffgehalte der vergleichbaren Wurmproben belegen, da? es die repr?sentative Probenahmestelle in einem Untersuchungsgebiet nicht gibt. Die Heterogenit?t des Untersuchungsraumes kann nur durch eine geschichtete Zufallsstichprobe mit einer ausreichenden Anzahl von Einzelproben erfa?t werden.     

Precipitation and aerosol studies in India

In India, rain water and atmospheric aerosols are observed to bealkaline in nature due to the influence of soil-derivedparticles which are rich in components like Ca and Mg. Thesecomponents increase the neutralization potential of rain waterand have a greater influence at rural site compared to urbansite. However, if there are continuous rains, the concentrationof crustal components becomes lower resulting in lower pH ofrain water. Unlike the characteristics of rain water oncontinent, the pH of rain water has been observed to be acidicin all the events over the Indian Ocean during Pre-campaigns ofIndian Ocean Experiment (INDOEX). The possible reason for acidicrains over Indian Ocean could be the anthropogenic contributionfrom continent transported by NE winds coming towards the oceanduring this period.     

Gloves against mineral oils and mechanical hazards: composites of carboxylated acrylonitrile–butadiene rubber latex

Resistance to permeation of noxious chemical substances should be accompanied by resistance to mechanical factors because the glove material may be torn, cut or punctured in the workplace. This study reports on glove materials, protecting against mineral oils and mechanical hazards, made of carboxylated acrylonitrile–butadiene rubber (XNBR) latex. The obtained materials were characterized by a very high resistance of the produced materials to oil permeation (breakthrough time?>?480?min). The mechanical properties, and especially tear resistance, of the studied materials were improved after the addition of modified bentonite (nanofiller) to the XNBR latex mixture. The nanocomposite meets the requirements in terms of parameters characterizing tear, abrasion, cut and puncture resistance. Therefore, the developed material may be used for the production of multifunctional protective gloves.     

Impact of environmental factors on the sampling rate of β-blockers and sulfonamides from water by a carbon nanotube-passive sampler

Passive techniques are a constantly evolving approach to the long-term monitoring of micropollutants, including pharmaceuticals, in the aquatic environment. This paper presents, for the first time, the calibration results of a new CNTs-PSDs (carbon nanotubes used as a sorbent in passive sampling devices) with an examination of the effect of donor phase salinity, water pH and the concentration of dissolved humic acids (DHAs), using both ultrapure and environmental waters. Sampling rates (R_s) were determined for the developed kinetic samplers. It has been observed that the impact of the examined environmental factors on the R_s values strictly depends on the type of the analytes. In the case of β-blockers, the only environmental parameter affecting their uptake rate was the salinity of water. A certain relationship was noted, namely the higher the salt concentration in water, the lower the R_s values of β-blockers. In the case of sulfonamides, water salinity, water pH 7–9 and DHAs concentration decreased the uptake rate of these compounds by CNTs-PSDs. The determined R_s values differed in particular when the values obtained from the experiments carried out using ultrapure water and environmental waters were compared. The general conclusion is that the calibration of novel CNTs-PSDs should be carried out under physicochemical conditions of the aquatic phase that are similar to the environmental matrix.     

Polycyclic aromatic hydrocarbons in pine and spruce shoots-temporal trends and spatial distribution

In the framework of the German environmental specimen bank one-year old spruce shoots (Picea abies) and pine shoots (Pinus sylvestris) serve as bioindicators for the atmospheric pollution. Sampling is performed in two urbanized areas in western and eastern Germany (Warndt and Duebener Heide, respectively), and in seven different rural locations. Prior to archiving conifer shoots are continuously analyzed for a set of 17 individual polycyclic aromatic hydrocarbons (PAHs). The results from the two urbanized areas show that the atmospheric contamination with PAH has declined by about 75% between 1985 and 2004 at Warndt and by about 85% between 1991 and 2004 at Duebener Heide. However, summation operatorPAH concentrations stayed virtually constant at both locations since the end of the 1990s at levels of about 100 ng g(-1) wet weight (ww). In spruce shoots from rural areas current concentrations of PAHs are significantly lower and vary between 8 and 61 ng g(-1) ww. In all shoot samples the four low molecular aromatics phenanthrene, fluoranthene, pyrene, and chrysene dominate the pattern by contributing 60 to 90% to summation operatorPAH. The group of high molecular weight aromatics is dominated by benzo[b,j,k]fluoranthene, especially in spruce shoots originating from greater altitudes remarkable amounts of six and seven ringed PAHs could be detected. Despite the strong decrease of PAH concentrations in urban areas patterns of aromatics remained nearly unchanged in the observation period 1985 to 2004.     

Fungal inoculum properties: extracellular enzyme expression and pentachlorophenol removal in highly contaminated field soils

This study was conducted to improve the pentachlorophenol (PCP) bioremediation ability of white-rot fungi in highly contaminated field soils by manipulating bioaugmentation variables. These were the dry weight percentage of fungal inoculum addition (31-175 g kg(-1)), PCP concentration (100-2137 mg kg(-1) PCP), fungal inoculum formulation, and time (1-7 wk). Five fungal isolates were used: the New Zealand isolates Trametes versicolor (L.: Fr.) HR131 and Trametes sp. HR577; the North American isolates Phanerochaete chrysosporium Burds. (two isolates) and Phanerochaete sordida (Karst.) Erikss. & Ryv. Pentachlorophenol removal, manganese peroxidase, and laccase activity, and the formation of chloroanisoles in the contaminated field soils were measured. The majority of PCP removed by the Trametes isolates was in the first week after bioaugmentation. The maximum PCP removal by the fungi varied from 50 to 65% from a 1065 mg kg(-1) PCP contaminated field soil. Pentachlorophenol was preferentially converted to pentachloroanisole (PCA) by the Phanerochaete isolates (>60%), while 2 to 9% of the PCP removed by two Trametes isolates was converted to PCA. A pH increase was measured following bioaugmentation that was dependent on PCP concentration, fungal inoculum addition, and formulation. This, together with rapid initial PCP removal, possibly changed the bioavailability of the remaining PCP to the fungi and significantly decreased the sequestering of PCP in the contaminated field soils. The research supports the conclusion that New Zealand Trametes spp. can rapidly remove PCP in contaminated field soils. Bioavailability and extractability of PCP in the contaminated field soil may significantly increase after bioaugmentation.     

Degradation of macrolide antibiotics by ozone: a mechanistic case study with clarithromycin

Macrolide antibiotics are widely used (in the order of 1g per person per year). They pass the body largely unchanged and are also not degraded in wastewater treatment plants. With not too much effort, they may be eliminated from their effluents by ozonation. The macrolide antibiotics have all a dimethylamino group at one of the carbohydrate residues in common. This functional group is the target of the ozone reaction, and clarithromycin has been selected here for a more detailed study. Since only the free amine reacts with ozone, the rate of reaction is pH dependent (at pH 7: k = 4 x 10(4) M(-1) s(-1)). In analogy to the ozonolysis of trimethylamine, the main reaction is a transfer of an O-atom yielding the N-oxide (identified by HPLC/MS-MS). A minor product (10%, based on formaldehyde yields) is demethylated clarithromycin (identified by HPLC/MS-MS). The dimethylamino group is thought to be essential for the binding of the macrolide antibiotics to their target. As a consequence, chemical changes of this functional group, notably the formation of the N-oxide that is no longer a proton acceptor, inactivates these drugs as assayed by the suppression of the growth of Pseudomonas putida. This is most important for wastewater treatment, as mineralization of clarithromycin by ozone would require 100 times as much ozone.