Monobromo and higher brominated congeners of the marine halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1)

The marine halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1) is widely distributed in the environment. In this study, we screened samples which have previously been found to contain remarkably high residues of Q1 (blubber of marine mammals from Australia, samples from Antarctica, human milk from the Faroe Island) for the additional presence of mixed chlorinated and brominated congeners. Using GC/ECNI-MS, all samples tested were positive and many contained four out of five possible bromohexachloro congeners (BrCl6-MBPs), five out of 14 possible dibromopentachloro congeners (Br2Cl5-MBPs), five of 21 possible tribromotetrachloro-congeners (Br3Cl4-MBPs), as well as several higher brominated congeners. About 20 heptahalo congeners of Q1 are described for the first time in the scientific literature. Isomers eluted within about one minute, respectively. Hence it is possible, that the peak clusters identified may be composed of more, co-eluting congeners. Similarities in the GC/ECNI-MS mass spectra with polychlorinated biphenyls (PCBs) were addressed. We also suggest an acronym system similar to that in use for polychlorinated biphenyls that may simplify the use of this substance class in scientific papers. In the samples from Australia, BrCl6-MBPs and Br2Cl5-MBPs amounted for 7-27.5% and 0.4-4.2% of Q1, respectively whereas Br3Cl4-MBPs and higher brominated MBPs were found in the range of <1% of Q1 or less.     

Chemical composition of the slippery epicuticular wax blooms on Macaranga (Euphorbiaceae) ant-plants

Summary. The stems of many Macaranga ant-plants (Euphorbiaceae) are covered by epicuticular wax crystals rendering the surface very slippery for most insects. These wax blooms act as selective barriers protecting the symbiotic ant partners, which are specialized “wax-runners”, against the competition of other ants. Glaucous stems occur almost exclusively among the ant-plants of the genus Macaranga (). We analyzed the cuticular lipids of 16 Macaranga species by GC-MS and investigated the wax crystal morphology using SEM. Presence of crystalline wax blooms was strongly correlated with high concentrations (52%–88%) of triterpenoids. In contrast epicuticular waxes of glossy Macaranga surfaces contained only 0% to 36% of these dominant components. Therefore we conclude that triterpenoids are responsible for the formation of the thread-like Macaranga wax crystals. In all Macaranga ant-plants investigated, the principal components were epitaraxerol and taraxerone accompanied by smaller portions of taraxerol, β-amyrin and friedelin. Only in the case of the non-myrmecophytic M. tanarius did β-amyrin predominate. Moreover, we found that only in M. tanarius, the dense wax crystal lacework is torn into large mosaic-like pieces in the course of secondary stem diameter growth. Both chemical and macroscopic differences may contribute to a reduced slipperiness of M. tanarius stems and appear to be functionally important. The distribution of wax crystals and their composition amongst different sections of the genus suggests that glaucousness is a polyphyletic character within Macaranga. Received 7 October 1999; accepted 3 December 1999     

Erprobung und Erfolgskontrolle eines Phytoremediationsverfahrens zur Sanierung Sprengstoff-kontaminierter Böden

On the area of a former ordnance plant (‘Werk Tanne’, Clausthal-Zellerfeld, Germany), a field experiment for phytoremediation of TNT-contaminated soils has been carried out since May 1999. The concept is based on a stepwise degradation of TNT by white-rot fungi and mycorrhiza within the rhizosphere of site-specific seedlings. An appropiate site with contaminants in the surface-soil was prepared with a large-scale soil grader and subsequently divided into different experimental plots, including an uncontaminated control as well as a contaminated plot without treatment. Planting of the selected trees and shrubs (infected with mycorrhiza during nursery) and inoculation with wood chips (inoculated with white-rot fungi) is followed by a detailed monitoring of the experimental plots (chemical analyses, biotest-battery, ecological field indicators). For the evaluation of the results, multivariate methods are applied.     

Ökotoxikologische und humantoxikologische Risikobewertung PAK-belasteter Böden vor und nach biologischer Behandlung

The goal of the present work is to assess the adverse effects of soil bound polycyclic aromatic hydrocarbons (PAH) which remain in soils after biological remediation. We focus on risk assessment for mammalian species with respect to the oral uptake of contaminated soil particles and compare the results of a biomarker test with those of an ecotoxicological assay, the bioluminescence inhibition test withVibrio fischeri. As a biomarker effect in mammals, we determined the liver microsomal cytochrome P450 enzyme CYP1A1 which is induced by PAH in exposed rats. After biological soil treatment, different amounts of PAH remain in the soil depending on the soil properties and initial pollutant composition. Particularly, higher condensated PAH resists biological treatment due to its hydrophobicity. In addition, high amounts of organic carbon in the soils affect remediation efficiency. In the bioluminescence inhibition test, eluates of all biologically treated soils studied do not reveal any or only low inhibitory effects. In contrast, the oral uptake of biologically treated contaminated soils leads to induction levels for CYP1A1 similar to those in the untreated samples. A good correlation is obtained between CYP1A1 levels and the amount of 5 and 6-ring PAH in the soil samples. The main result is that the remediation efficiency determined by the luminescence test is not reflected by the biomarker test, a finding which indicates the high bioavailability of residual PAH in soils. Consequently, new criteria for human risk assessment can be delineated.     

Laboratory and field evaluation of real-time and near real-time PM2.5 smoke monitors

ABSTRACT

Increases in large wildfire frequency and intensity and a longer fire season in the western United States are resulting in a significant increase in air pollution, including concentrations of PM_2.5 (particulate matter <2.5 µm in aerodynamic diameter) that pose significant health risks to nearby communities. During wildfires, government agencies monitor PM_2.5 mass concentrations providing information and actions needed to protect affected communities; this requires continuously measuring instruments. This study assessed the performance of seven candidate instruments: (1) Met One Environmental beta attenuation monitor (EBAM), (2) Met One ES model 642 (ES642), (3) Grimm Environmental Dust Monitor 164 (EDM), (4) Thermo ADR 1500 (ADR), (5) TSI DRX model 8543 (DRX), (6) Dylos 1700 (Dylos), and (7) Purple Air II (PA-II) in comparison with a BAM 1020 (BAM) reference instrument. With the exception of the EBAM, all candidates use light scattering to determine PM_2.5 mass concentrations. Our comparison study included environmental chamber and field components, with two of each candidate instrument operating next to the reference instrument. The chamber component involved 6 days of comparisons for biomass combustion emissions. The field component involved operating all instruments in an air monitoring station for 39.5 days with hourly average relative humidity (RH) ranging from 19% to 98%. Goals were to assess instrument precision and accuracy and effects of RH, elemental carbon (EC), and organic carbon (OC) concentrations. All replicate candidate instruments showed high hourly correlations (R² ≥ 0.80) and higher daily average correlations (R² ≥ 0.90), where all instruments correlated well (R² ≥ 0.80) with the reference. The DRX and Purple Air overestimated PM_2.5 mass concentrations by a factor of ~two. Differences between candidates and reference were more pronounced at higher PM_2.5 concentrations. All optical instruments were affected by high RH and by the EC/OC ratio. Equations to convert candidate instruments data to FEM BAM type data are provided to enhance the usability of data from candidate instruments.

Implications: This study tested the performance of seven candidate PM_2.5 mass concentration measuring instruments in two settings - environmental chamber and field. The instruments were tested to determine their suitability for use during biomass combustion events and the effects of RH, PM mass concentrations, and concentrations of EC and OC on their performance. The accuracy and precision of each monitor and effect of RH, PM concentration, EC and OC concentrations are varied. The data show that most of these candidate instruments are suitable for measuring PM_2.5 concentration during biomass combustions with a proper correction factor for each instrument type.     

Arousal by sexual stimuli accelerates the re-entrainment of hamsters to phase advanced light-dark cycles

Summary The arousal caused by the 3 h presentation of female socio-sexual cues to male hamsters given an 8 h advance of the light-dark cycle caused an acceleration in the rate of re-entrainment to this new light-dark cycle. This accelerating effect was seen most clearly in animals allowed to run in their wheels in response to a nearby female hamster in estrous condition. However, wheel-running was not a necessary condition for enhancement. In one experiment, males with their wheels prevented from rotating also showed an accelerated rate of re-entrainment; in another experiment, the effect was almost significant (P=0.058). Mating itself seemed to counteract this accelerating effect. Males aroused by nearby but inaccessible estrous females re-entrained quicker than males allowed to mate with an estrous female. Lastly, male hamsters placed in a novel wheel but not allowed to run showed a variable rate of re-entrainment to an 8 h light-dark cycle advance; individuals judged to be sleeping during most of the 3 h in the novel wheel took longer to re-entrain than those judged to be awake during most of the 3 h. These results suggest that there is a general arousal mechanism through which non-specific, non-photic events can enhance the phase advancing actions of a lightentrainable clock.