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.     

Stable carbon isotope ratios of POPs--a tracer that can lead to the origins of pollution

An elemental analyzer in combination with stable isotope ratio mass spectrometry (EA-IRMS) was used to demonstrate that two samples of the chloropesticide Melipax discovered in two countries varied only by 0.1 per thousand in their delta 13C values. Gas chromatography interfaced to a stable isotope mass spectrometer (GC-IRMS) was used to study the delta 13C values of individual congeners in two technical polybrominated diphenyl ether products, i. e. DE-71 and DE-79, at three different concentration levels. Injections of 4 microg and 5.2 microg of DE-71 and DE-79 were most suited for the determinations. In both products, the delta 13C values were usually the more negative the higher the degree of bromination was. The delta 13C values of three hexabromo isomers BDE 138, BDE 153, and BDE 154 could be determined in both products. In all cases the delta 13C values of the three hexaBDEs were more depleted in delta 13C in the higher brominated technical octabromo diphenyl ether DE-79.     

Control of blueberry thrips,frankliniella vaccinii morgan,with permethrin and effect on yield and residue in fruit

Abstract

Permethrin at 0.4 kg a.i./ha controlled blueberry thrips Frankliniella vaccinii Morgan. There was no plant damage and crop yield was notably increased. Permethrin was extracted from berries with acetone, partitioned in hexane, cleaned‐up on Florisil column and analysed by the electron capture gas chromatography using a 3% OV‐210 column. No permethrin residues were found in the berries. The relative retention times of cis‐, and trans‐permethrins to aldrin were 10.3 and 12.1, respectively. The absence of permethrin from berries was further confirmed by TLC.     

Musterbildung bei Drosophila

Drosophila proved an excellent system to study molecular processes in establishing the body pattern of an embryo. Genes which are active during oogenesis provide localized cues which regulate a cascade of zygotic genes that determines the developmental fate of the blastoderm cells along the longitudinal axis of the embryo.     

基于Verhulst模型的新建隧道顶板下沉预测研究

隧道顶板下沉量预测对隧道安全施工十分重要.通过分析隧道下沉过程,指出其具有"S"型曲线特征,探讨了采用Verhulst模型进行隧道顶板下沉预测的适用性和可行性,并运用MATLAB软件开发相关程序,模拟遵赤高速公路中枢隧道YK39+134.6断面沉降过程,获得相应的预测方程.通过对比其预测结果、回归分析预测结果和实测值,发现该模型的顶板沉降预测值与实测值最接近,证实运用灰色Verhulst模型预测隧道顶板沉降量是合理、可行的.     

Photolytic dehalogenation of the marine halogenated natural product Q1

The marine halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1) has been detected in high-trophic level biota throughout the world. In this study we UV-irradiated Q1 in order to produce hexahalogenated 1'-methylbipyrroles (Cl(6)-MBPs). Q1 was transformed with half-lives of <5 min. Already after 5 min, all of the five existing Cl(6)-MBPs (H1-H5) were detected in the irradiated sample. Only one Cl(6)-MBP (2,3,3',4',5,5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-77, H2) has been previously described in the literature. H5 was identified as 2,3,3',4,4',5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-75) by a specific fragment ion detected by GC/ECNI-MS. Fractionations of the irradiation mixture by reversed-phase HPLC followed by (1)H NMR analysis led to the structure of H4, i.e. 2,3,3',4,4',5-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-74). H1 and H3 showed virtually identical (1)H NMR data. Therefore, it could not determined which of either isomers is 2,3,3',4,5,5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-76) and which is 2,3,4,4',5,5'-hexachloro-1'-methyl-1,2'-bipyrrole (MBP-78). In addition, two pentachloro-MBPs (P1 and P3) could be traced back to MBP-62 and MBP-69. Cl(6)-MBPs were analyzed in whale blubber from Australia and skua adipose tissue from Antarctica. The marine mammals contained all Cl(6)-MBPs except for the most abundant in the irradiation experiment. The concentrations of the Cl(6)-MBPs amounted to 0.04-1.76% of the concentration of Q1. The highest concentrations of Cl(6)-MBP isomers in the biota samples were found for MBP-76, MBP-77, and MBP-78. These congeners appeared to be the most lipophilic ones owing to the highest retention time in RP-HPLC. Nevertheless, it remained unclear whether the Cl(6)-MBPs were actual halogenated natural products or environmental metabolites of Q1.     

Movement and residual toxicity of carbofuran in acid mineral soil

In greenhouse miniplots with soil moisture moving upward from the subsoil, toxicants of carbofuran moved upward and became detectable at the soil surface in ca. 3, 7, and 28 days after 10% granules of the insecticide were banded 1, 3, and 10 cm, respectively, below the surface. The test soil had a pH of 5.2 and contained 2.9% organic matter. Toxic residues reaching the soil surface from a depth of 5–10 cm increased over a period of 8–12 months and gradually decreased thereafter. Fifteen to 20 ppm in the surface soil was highly toxic to flies contacting the soil surface. Amounts in excess of 40 ppm in the surface layer caused knockdown in 10–15 and estimated death in less than 30 s. The LD₅₀ for cabbage maggot eggs on the surface of treated soil was 8.2 ppm and for larvae 0.86 ppm. Chemical analysis records correlated well with those of bio-assay tests. In field microplots, the addition of water during rainstorms (giving a total of 50 mm) demonstrated that toxic residues of carbofuran could be leached downward to at least 45 cm. However, under the normal weather conditions of 1980 and under abnormally dry conditions most of the detectable residues remained near or above the point of application.