Diffusive sampling of methyl isocyanate using 4-nitro-7-piperazinobenzo-2-oxa-1,3-diazole (NBDPZ) as derivatizing agent

A diffusive sampling method for the determination of methyl isocyanate (MIC) in air is introduced. MIC is collected using a glass fiber filter impregnated with 4-nitro-7-piperazinobenzo-2-oxa-1,3-diazole (NBDPZ). The urea derivative formed is desorbed from the filter with acetonitrile and analyzed by means of high-performance liquid chromatography (HPLC) using fluorescence detection (FLD) with lambdaex = 471 nm and lambdaex = 540 nm. Additionally, a method was developed using tandem mass spectrometric (MS-MS) detection, which was performed as selected reaction monitoring (SRM) on the transition [MIC-NBDPZ + H]+ (m/z 307) to [NBDPZ + H]+ (m/z 250). The diffusive sampler was tested with MIC concentrations between 1 and 35 microg m(-3). The sampling periods varied from 15 min to 8 h, and the relative humidity (RH) was set from 20% up to 80%. The sampling rate for all 15 min experiments was determined to be 15.0 mL min(-1) (using HPLC-FLD) with a relative standard deviation of 9.9% for 56 experiments. At 80% RH, only 15 min sampling gave acceptable results. Further experiments revealed that humidity did not affect the MIC derivative but the reagent on the filter prior to and during sampling. The sampling rate for all experiments (including long term sampling) performed at 20% RH was found to be 15.0 mL min(-1) with a relative standard deviation of 6.3% (N = 42). The limit of quantification was 3 microg m(-3) (LC-MS-MS: 1.3 microg m(-3)) for 15 min sampling periods and 0.2 microg m(-3) (LC-MS-MS: 0.15 microg m(-3)) for 8 h sampling runs applying fluorescence detection.     

Development of a diffusive sampling method for determination of methyl isocyanate in air

A diffusive sampling method for determination of methyl isocyanate in air has been developed. A glass fibre filter impregnated with 1-(2-methoxyphenyl)piperazine in a commercially available diffusive sampling device was used to collect methyl isocyanate and the derivative formed was analysed with LC-MS/MS. The sampling rate was determined to be 15.6 ml min(-1), with a relative standard deviation of 7.3%. The sampler was validated for sampling periods from 15 min to 8 h, for relative humidities from 20% to 80% and for concentrations from I to 46 microg m(-3). A field validation was also made and the diffusive sampling results showed no difference compared to a pumped reference method. The impregnated filters have to be stored apart from the diffusive sampler housing and loaded into the sampler prior to each sampling.     

Evaluation of two adsorbents for diffusive sampling and thermal desorption-gas chromatographic analysis of monoterpenes in air

Tube type samplers with two different adsorbents, Chromosorb 106 and Tenax TA, were evaluated by laboratory experiments and field tests for simultaneous diffusive sampling of alpha-pinene, beta-pinene and delta 3-carene and subsequent thermal desorption-gas chromatographic analysis. No statistically significant effects of exposure time, concentrations of monoterpenes or relative humidity were found for samplers with Chromosorb 106 when running a factorial design, with the exception of the adsorption of delta 3-carene, for which some weak effects were noted. Samplers with Tenax TA were affected by the sampling time as well as the concentration for all terpenes, with a strong interaction effect between these two factors. The terpenes showed good storage stability on both adsorbents. No effect of back-diffusion was noted when using Chromosorb 106, while Tenax TA showed some back-diffusion effects. The uptake rates, in ml min-1, for the terpenes on Chromosorb 106 were 0.36 for alpha-pinene, 0.36 for beta-pinene and 0.40 for delta 3-carene. The corresponding average values on Tenax TA were 0.30 for alpha-pinene, 0.32 for beta-pinene and 0.38 for delta 3-carene. The field validation proved that diffusive sampling on Chromosorb 106 agreed well with pumped sampling on charcoal for stationary samples, while the personal samples indicated a discrepancy of 25% between Chromosorb 106 and charcoal samples. Tenax TA generally gave lower results than Chromosorb 106 in all field samples. Samplers packed with Chromosorb 106 could be used to monitor terpene levels in workplaces such as sawmills. The major advantages with this method are the sampling procedure, which is simple to perform compared to other techniques, the easily automated analysis procedure and the possibility to reuse the samplers.     

Human plasma levels of POPs,and diet among native people from Uelen,Chukotka

Some of the people living in the Chukotka Peninsula of Russia depend heavily on marine mammals, but little is known of the exact dietary patterns and plasma levels of POPs among these populations. In this study, POPs levels in plasma from 50 participants from the isolated community of Uelen (Bering Strait) were determined and related to dietary information obtained through a food frequency questionnaire. The intake of marine mammals was high and the combined intake of blubber from walrus, seal and whale was a significant predictor (p < 0.01) of plasma concentrations of sum PCBs and borderline for sum CDs (p = 0.02) and sum DDTs (p = 0.04). There was a significant gender difference in the levels of POPs, and among women there was a significant increase with age. Extensive breastfeeding and lower blubber intake among women could be possible explanations for this gender difference. Despite the high intake of blubber the plasma levels of PCBs and DDTs were lower than some of those reported for the East Coast of Greenland. The geometric mean values for sum PCBs (17 congeners) and sum DDTs were 1316 ng g(-1) lipids and 563 ng g(-1) lipids, respectively. PCB 163, which partly co-eluted with PCB 138, was found in high concentrations (40% of PCB 138). This raises questions regarding the validity of using PCB 138 and PCB 153 to calculate the level of Arochlor 1260. The geometric mean of sum CDs was 518 ng g(-1) lipids. Concentrations of beta-HCH (geometric mean; 410 ng g(-1) lipids) were higher than observed for other native populations depending on marine mammals. Transportation of beta-HCH by ocean currents through the Bering Strait into the Arctic Ocean or regional point sources might explain these elevated levels.     

The effect of octopamine on behavioral responses of free-foraging bumblebees to a change in food source profitability

The invertebrate neuromodulator octopamine is known to be involved in bees' associative learning, enhancing the responsiveness of a bee to a conditioned stimulus. In this study, we tested the effect of octopamine on the choice behavior of free-flying bumblebees using a two-phase experiment in an array of artificial flowers. During the first phase of the experiment, the bee was allowed to collect octopamine-laden sugar water from two types of equally rewarding flowers (yellow versus blue). In the second phase, one type of flower was set to be unrewarding. The behavior of the bee (proportion of visits to the unrewarding flowers) over the two phases was fitted to a sigmoid regression model. Our results show that octopamine had no significant effect on the bees' equilibrium choice or on the overall rate of the behavioral change in response to the change in reward. Rather, octopamine significantly affected the time interval between the change in reward status and the initiation of behavioral change in the bee.     

Use of Artificial Roost Structures by Bats at the Indianapolis International Airport

From 1992–1996, 3204 artificial roosts of 9 types were placed in woodlots near Indianapolis International Airport in an effort to provide habitat for the federally-endangered Indiana myotis (Myotis sodalis) and to determine the feasibility of using these structures to manage bats in a rapidly developing suburban area. We surveyed these structures at least annually during 1992–1999 and found only northern myotis (Myotis septentrionalis) regularly using the structures. Four other species were occasionally found using structures including big brown bats (Eptesicus fuscus, n = 14 individuals), little brown myotis (Myotis lucifugus, n = 2), Indiana myotis (Myotis sodalis, n = 2), and one silver-haired bat (Lasionycteris noctivagans). Single, triple, and Missouri-style batboxes were almost always used, rather than the six other types of experimental roosts that had been in place. However, after 10 years in place, it appears that Indiana bats are acclimated to boxes, as 6 of them were being used rather regularly by Indiana myotis. Bat boxes can provide roosting habitat for some species under conditions where few suitable roosts exist, but assuring an abundance of natural habitats is usually more desirable for conservation of tree-roosting bats.     

Polybrominated diphenyl ethers (PBDEs) in leachates from selected landfill sites in South Africa

The last few decades have seen dramatic growth in the scale of production and the use of polybrominated diphenyl ethers (PBDEs) as flame retardants. Consequently, PBDEs such as BDE -28, -47, -66, -71, -75, -77, -85, -99, -100, -119, -138, -153, -154, and -183 have been detected in various environmental matrices. Generally, in South Africa, once the products containing these chemicals have outlived their usefulness, they are discarded into landfill sites. Consequently, the levels of PBDEs in leachates from landfill sites may give an indication of the general exposure and use of these compounds. The present study was aimed at determining the occurrence and concentrations of most common PBDEs in leachates from selected landfill sites. The extraction capacities of the solvents were also tested. Spiked landfill leachate samples were used for the recovery tests. Separation and determination of the PBDE congeners were carried out with a gas chromatograph equipped with Ni63 electron capture detector. The mean percentage recoveries ranged from 63% to 108% (n=3) for landfill leachate samples with petroleum ether giving the highest percentage extraction. The mean concentrations of PBDEs obtained ranged from ND to 2670pgl(-1), ND to 6638pgl(-1), ND to 7230pgl(-1), 41 to 4009pgl(-1), 90 to 9793pgl(-1) for the Garankuwa, Hatherly, Kwaggarsrand, Soshanguve and Temba landfill sites, respectively. Also BDE -28, -47, -71 and BDE-77 were detected in the leachate samples from all the landfill sites; and all the congeners were detected in two of the oldest landfill sites. The peak concentrations were recorded for BDE-47 at three sites and BDE-71 and BDE-75 at two sites. The highest concentration, 9793+/-1.5pgl(-1), was obtained for the Temba landfill site with the highest BOD value. This may suggest some influence of organics on the level of PBDEs. Considering the leaching characteristics of brominated flame retardants, there is a high possibility that with time these compounds may infiltrate into the groundwater around the sites since most of the sites are not adequately lined.     

Estrogenic activity associated with organochlorine compounds in fish extracts from European mountain lakes

Fish muscle extracts from ten European mountain lakes were analyzed for organochlorine compounds (OCs) and estrogenic activity, the latter by a recombinant yeast assay based on the human estrogen receptor. Seventy percent of the samples showed estrogenic activity above detection limits and a subset of five samples showed estrogenic activities, equivalent to more than 10,000 pg/g of estradiol. These highly estrogenic samples occurred in two lakes, Velké Hin?ovo in the Tatra Mountains and Redon in the Pyrenees. Principal component analysis correlated estrogenic activity of muscle extracts to fish age and concentrations of the more chlorinated polychlorobiphenyls (PCBs). This is consistent with previously observed correlations of these PCBs with fish age. In addition, most fish with high estrogenic activity were found in lakes containing high OC levels in the sediments, which gives further ground to atmospheric deposition of anthropogenic pollutants as main process leading to the observed endocrine disruption effects.     

Bioavailability of copper,cadmium, zinc,and lead in tropical savanna soils assessed by diffusive gradient in thin films (DGT) and ion exchange resin membranes

The technique of diffusion gradient in thin films (DGT) for assessing bioavailable metals has not been tested under field conditions. We assessed the relationships of DGT- and cation exchange resin-membrane-measured concentrations of Cd, Cu, Pb, and Zn with plant uptake of the metals under greenhouse and field conditions. In the greenhouse, the effective concentrations of Cu, Pb, and Zn by DGT correlated significantly with uptake by sorghum (Sorghum bicolor), but cation exchange resin-membrane-measured concentrations of Cd, Pb, and Zn did not correlate with sorghum uptake. In the field, the DGT-measured concentrations of Cd, Pb, and Zn were not linearly related to uptake Cd, Pb, and Zn by lettuce (Lactuca sativa) except for Cu uptake (r = 0.87, p < 0.05). Similarly, it was only the resin-membrane-extractable Pb that correlated with Pb uptake by lettuce (r = 0.77; p < 0.05). However, fitting non-linear regression models improved the plant metal uptake predictions by DGT-measured bioavailable Cd, Cu, Pb, and Zn under field conditions. In conclusion, the DGT technique was fairly predictive of bioavailability in the greenhouse, but not in the field.     

Assessment of exposure to DDT and metabolites after indoor residual spraying through the analysis of thatch material from rural African dwellings

Introduction  

We report on the analysis of 4,4′-dichlorodiphenyltrichloroethane (4,4′-DDT) and its metabolites in thatch and branch samples constituting the wall materials of dwellings from South African subtropical areas. This approach was used to assess the exposure to DDT in the residents of the dwellings after indoor residual spraying (IRS) following recommended sanitation practices against malaria vectors.