A combination of micro-porous membrane liquid-gas extraction and solid-phase trapping for ultra trace determination of benzene in urine

A method was developed for the determination of benzene in urine. The sample was pumped through the donor channel of a membrane extraction unit with a micro-porous membrane, separating the donor channel from an identical acceptor channel purged with nitrogen. The analyte reached the acceptor channel by diffusion through the membrane and was then swept by the carrier to a solid sorbent tube, where it was trapped. The analyte was subsequently thermally desorbed and analyzed by gas chromatography (GC) with mass selective detection (MS). After optimization, the recovery was close to quantitative, or 95%. Purging the membrane unit with pure water in between the samples eliminated any memory effects. The linearity was good in the concentration range examined (20-4000 ng l(-1)), with a correlation coefficient of 0.9996. The repeatability at 50 ng l(-1) and 400 ng l(-1) was 1.4% and 1.2%, respectively. The limit of detection was 12 ng l(-1) and the limit of quantification 35 ng l(-1). This enables assessment of benzene exposures of occupationally exposed subjects, of smokers and the majority of the general population. The developed method can be easily automated.     

Perfluorinated chemicals in relation to other persistent organic pollutants in human blood

In order to evaluate blood levels of some perfluorinated chemicals (PFCs) and compare them to current levels of classical persistent organic pollutants (POPs) whole blood samples from Sweden were analyzed with respect to 12 PFCs, 37 polychlorinated biphenyls (PCBs), p,p'-dichlorodiphenyl-dichloroethylene (DDE), hexachlorobenzene (HCB), six chlordanes and three polybrominated diphenyl ethers (PBDEs). The median concentration, on whole blood basis, of the sum of PFCs was 20-50 times higher compared to the sum of PCBs and p,p'-DDE, 300-450 times higher than HCB, sum of chlordanes and sum of PBDEs. Estimations of the total body amount of PFCs and lipophilic POPs point at similar body burdens. While levels of for example PCBs and PBDEs are normalized to the lipid content of blood, there is no such general procedure for PFCs in blood. The distributions of a number of perfluorinated compounds between whole blood and plasma were therefore studied. Plasma concentrations were higher than whole blood concentrations for four perfluoroalkylated acids with plasma/whole blood ratios between 1.1 and 1.4, whereas the ratio for perflurooctanesulfonamide (PFOSA) was considerably lower (0.2). This suggests that the comparison of levels of PFCs determined in plasma with levels determined in whole blood should be made with caution. We also conclude that Swedish residents are exposed to a large number of PFCs to the same extent as in USA, Japan, Colombia and the few other countries from which data is available today.     

Monitoring aromatic hydrocarbon biodegradation by functional marker genes

The development of biological treatment technologies for contaminated environments requires tools for obtaining direct information about the biodegradation of specific contaminants. The potential of functional gene array analysis to monitor changes in the amount of functional marker genes as indicators of contaminant biodegradation was investigated. A prototype functional gene array was developed for targeting key functions in the biodegradation of naphthalene, toluene and xylenes. Internal standard probe based normalization was introduced to facilitate comparison across multiple samples. Coupled with one-colour hybridization, the signal normalization improved the consistency among replicate hybridizations resulting in better discrimination for the differences in the amount of target DNA. During the naphthalene biodegradation in a PAH-contaminated soil slurry microcosm, the normalized hybridization signals in naphthalene catabolic gene probes were in good agreement with the amount of naphthalene-degradation genes and the production of 14CO2. Gene arrays provide efficient means for monitoring of contaminant biodegradation in the environment.     

Benzyl-penicillin (Penicillin G) transformation in aqueous solution at low temperature under controlled laboratory conditions

Antibiotics are released into the environment in a variety of ways: via wastewater effluent as a result of incomplete metabolism in the body after use in human therapy, as runoff after use in agriculture, through improper disposal by private households or hospitals or through insufficient removal by water treatment plants. Unlike in most European countries, in Arctic regions effluents are not suitably treated prior to their release into the aquatic environment. Also, many of the scattered human settlements in remote regions of the Arctic do not possess sewage treatment facilities and pharmaceutical residues therefore enter the aqueous environment untreated. Only limited data are available on the biodegradation of antibiotics under Arctic conditions. However, such information is needed to estimate the potential harm of antibiotics for the environment. Pen-G is used in this study since it is a widely prescribed antibiotic compound whose environmental properties have not yet been investigated in detail. Thus, for a very first assessment, the OECD approved biodegradation Zahn-Wellens test (ZWT, OECD 302 B) was used to study biodegradation and non-biotic elimination of the antibiotic Benzyl-penicillin (Pen-G) at different temperatures (5°C, 12.5°C and 20°C). The testing period was extended from the OECD standard of 28-42d. In addition to dissolved organic carbon (DOC), Pen-G levels and major transformation products were recorded continuously by LC-ion-trap-MS/MS. DOC monitoring revealed considerable temperature dependence for the degradation process of Pen-G. DOC loss was slowest at 5°C and considerably faster at 12.5°C and 20°C. In the initial step of degradation it was found that Pen-G was hydrolyzed. This hydrolyzed Pen-G was subsequently further degraded by decarboxylation, the result of which was 2-(5,5-dimethyl-1,3-thiazolidin-2-yl)-2-(2-phenylacetamido)acetic acid. Furthermore, direct elimination of 2-phenyl-acetaldehyde from the hydrolyzed and decarboxylated Pen-G also led to the formation of 2-[amino(carboxy)methyl]-5,5-dimethyl-1,3-thiazolidone-4-carboxylic acid. Since biodegradation slows down considerably at a low temperature, the resulting transformation products had considerably longer residence times at 5°C compared to higher temperature conditions within the 42-d experiment. The results presented here clearly demonstrate that a risk assessment for pharmaceuticals present in low ambient temperature environments (i.e. the Arctic) cannot be based on test results obtained under standard laboratory conditions (i.e. 20°C ambient temperatures).     

Blood serum concentrations of perfluorinated compounds in men from Greenlandic Inuit and European populations

Perfluorinated compounds (PFCs), such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), are used in large quantities. They are persistent and found in measurable levels in human serum around the world. They have been associated with developmental, hepatic, and carcinogenic effects in animal studies. The aim of the present study was to describe levels of PFCs in serum among Inuits from Greenland and inhabitants from Warsaw, Poland and Kharkiv, Ukraine. Furthermore, the aim was to define social- and lifestyle related determinants of exposure for these compounds. Serum levels of seven PFCs were analyzed by liquid chromatography/tandem mass spectrometry (LC/MS/MS). The concentrations of PFOS and PFOA were the highest of all PFCs in all three populations with a total amount of almost 90% of the PFCs. The mean levels of PFOS and PFOA were in the Greenlandic Inuits 52 and 4.8 ng mL(-1), in Poland 19 and 5.2 ng mL(-1), and in Ukraine 8.1 and 1.9 ng mL(-1), respectively. Thus, levels of PFCs in the serum of Inuits on Greenland were among the highest described in a general population whereas the levels in Poland were similar to other industrialized countries. The exposure in Ukraine was rather low. In the Greenlandic Inuit population, intake of seafood, tea, age and area of living were significant determinants of PFOS concentrations and explained about 22% of the variation. For the other populations no strong determinants were found.     

Investigation of appropriate initial composition and aeration method for co-composting of yard waste and market wastes

The purpose of this research was to shorten the composting period by speeding up the composting process and to obtain good quality compost that can be used in agriculture. In order to accomplish the acceleration of the process, different mixtures of feedstock were loaded to the composting containers to observe the effect of initial composition on the quality of the compost and the rate of composting. The first feedstock prepared was composed of grass, leaves and market waste whereas the second feedstock composed only of leaves and market wastes. Composting process was accomplished by applying different composting methods such as composting without manual stirring, with manual stirring, with aeration by air, with aeration by oxygen, with manual stirring and aeration by air and finally by with manual stirring and aeration by oxygen to achieve the purpose of the research. Aeration was found as a primary requirement for the acceleration of composting because it was observed that when the aeration was not applied the conversion of nutrients was very low. The high conversion efficiency of the nutrients in the feedstock with market and yard wastes-without grass-resulted in higher quality end product. The organic content of the composted yard and market wastes were monitored and the best operational parameters and methods were identified. Parameters such as temperature, moisture, pH and end-product metal contents were also monitored in the study. and the experiments were run in duplicates. Corrected C/N, (C/N)t/(C/N)initial, were used in the calculations which provided objectivity in comparison of the compost quality with respect to nutritional components. The C/N change was found to be higher in the container that was manually stirred and aerated with oxygen but with regard to the economic feasibility of the system aeration with air was preferred. Compost quality that was achieved in the study was compared to the standards of different countries with respect to the amount of metal contents in the end-product. The applicability of the end-product in agriculture depends on the level of contaminants in the compost, especially metals that have to be present only in trace amounts.     

Using process-based models to filter out natural variability in observed concentrations of nitrogen and phosphorus in river water

Advances in process-based modelling of loads of nitrogen and phosphorus carried by rivers have created new possibilities to interpret time series of water quality data. We examined how model runs with constant anthropogenic forcing can be used to estimate and filter out weather-driven variation in observational data and, thereby, draw attention to other features of such data. An assessment of measured and modelled nutrient concentrations at the outlets of 45 Swedish rivers provided promising results for total nitrogen. In particular, joint analyses of observational data and outputs from the catchment model S-HYPE strengthened the evidence that downward trends in nitrogen were due to mitigation measures in agriculture. Evaluation of modelled and observed total phosphorus concentrations revealed considerable bias in the collection or chemical analysis of water samples and also identified weaknesses in the model outputs. Together, our results highlight the need for more efficient two-way communication between environmental modelling and monitoring.     

Prenatal diagnosis and psychological distress: Amniocentesis or chorionic villus biopsy?

The psychological reactions of 211 women undergoing prenatal diagnosis (PND) with amniocentesis (group A, n = 122) or chorionic villus biopsy (group V, n = 90) were exmained by questionnaires and interviews. The distress experienced while waiting for the test, during the test procedure, and while waiting for the result was reported by the women, both in questionnaires and in interviews. In the questionnaires, no difference between the two diagnostic methods was observed. In the interviews, however, the women undergoing amniocentesis appeared significantly more distressed by the procedure. In group A 97 per cent and in group V 100 per cent wished a method which, like chorionic villus biopsy, could be used in the first weeks of pregnancy. The risk of miscarriage was, as described in other studies, regarded as a serious threat by the pregnant women.