Photodegradation of the herbicide goal

Photodegradation products of the herbicide Goal active ingredient were obtained with a xenon lamp and analyzed using direct inlet mass spectrometry, MS/MS and GC/MS. A number of products were identified and their generation pathways were established to be mainly Ar—O bond cleavage, dechlorination and photocyclisation. The latter process gives chlorinated and unchlorinated dibenzofurans some of which may be toxic.     

Mass spectral studies of 6‐n‐propyl‐2‐thiouracil,its oxygen,selenium and fluorinated congeners∗

The electron ionization mass spectra of the clinically used antithyroid agent 6‐n‐propyl‐2‐thiouracil (la), its minor metabolite, 6‐n‐propyluracil (lb) and their synthetic selenium and fluorinated analogs (1c and d) have been examined. The fragmentation pattern of these thiouracil and selenouracil studied bear strong similarities with those previously derived from a study of uracil analogs. Thus, the first step in the fragmentation is a retro Diel‐Alder decomposition with the loss of HCNX (X=O, S or Se) and the production of an ion radical which undergoes further fragmentation pathways which are discussed. 6‐n‐Propyl‐2‐selenouracil (1c) did show more complicated spectra due to the six natural isotopic abundance exhibited by the selenium atom. While the fluorinated analogs (1d) did substantiate the fact that the fragmentation pattern of these derivatives proceed through fragmentation between C₂ and N₃ bond since this produces the more resonance stabilized ion.     

Cadmium and chromium in human lung tissue in relation to smoking and lung cancer

The pulmonary Cd and Cr content was determined from 53 lung cancer patients operated for cancer and from 39 patients who died of non‐malignant diseases. The results were correlated with smoking habits, pulmonary emphysema and occupational history. Both the pulmonary Cd and Cr increased with the amount of smoking. In ex‐smokers the Cr content in lung tissue did not diminish with the time since stopping smoking, but the Cd did follow the half‐life of about 9 years. The pulmonary Cd, compared with smoking habits, behaved similarly in both the lung cancer and control patients, whereas Cr in the lung cancer patients could not be explained solely by smoking, but some of the cancer patients may have been occupationally exposed to Cr. Speciation was not studied.     

Seasonal behaviour of lead concentration in poplar leaves∗

Seasonal variation of lead concentration in urban area in poplar leaves, is discussed as part of the more general problem of the interactions of gaseous and nongaseous air pollutants with terrestrial vegetation.     

Organochlorine insecticide residues in Egyptian mothers’ milk

Two hundred ninety‐two mother's milk samples were collected during 1994 from ten Egyptian governorates representing rural, metropolitan, and newly reclaimed desert areas. The samples were analyzed for 14 organochlorine insecticides and metabolites using electron capture gas chromatography and confirmed by gas chromatography/mass spectrometry (GC/MS). The overall samples average showed that the most abundant organochlorine insecticide residues were p,p'‐DDE, α‐endosulfan, β‐HCH and, p,p’‐DDT. Residues in the range of not detectable to less than 14μg/l whole milk were recorded for α‐HCH, heptachlor, heptachlor epoxide, aldrin, dieldrin, endrin endrin aldehyde and p,p'‐DDD. The percentage of samples exceeding the acceptable daily intake for children (ADIs) set by the FAO/WHO ranged from 19% to 44% in all governorates included in the study except the governorate of Minia in which only 2.6% of the samples exceeded the ADI values. The insecticides exceeding ADI values are mostly heptachlor and heptaclor epoxide (ADI = 3.12 μg/1 whole milk).     

Dissipation of fluvalinate and characterisation of its degradation products on chickpea crop by mass spectroscopy

Fluvalinate was applied on chickpea crop at (i) 0.056, (ii) 0.112 and (iii) 0.56 kg a.i. ha^‐1 to evaluate its rate of dissipation. Two major degradation products of fluvalinate formed on the crop were identified and characterised as phenoxybenzoic acid and 2‐[2‐chloro‐4‐(trifluoromethyl)anilino]‐3‐methylbutanoic acid. They were estimated in day‐5 and day‐10 samples of chickpea crop as their methyl esters by gas liquid chromatography.     

考虑岩体各向异性强度的隧洞围岩稳定性分析

岩体中普遍存在着大量的节理裂隙等不连续面,这些不连续面对岩体的强度有着重要的影响。以具有较密集成组节理的岩体为研究对象,以Drucker-Prager准则和裂隙应力张开准则为基础,分别考虑岩块和节理面各自的物理力学性质,研究岩体在各向异性强度准则下的理论方法,并建立了岩体各向异性本构模型,用以描述节理岩体在强度方面的各向异性及其破坏特征。将该模型用于隧洞围岩稳定性分析工程中,研究表明,该模型可以较好地解释节理岩体围岩的破坏特征,与工程实践相符。研究成果对我国地下石油、核废料储存以及深埋地下工程的设计与施工具有重要的指导意义。     

加速溶剂萃取-固相萃取净化-超高效液相色谱串联质谱法测定土壤中11种全氟化合物

采用超高效液相色谱-串联质谱联用法（UPLC-ESI-MS/MS）,建立了分析土壤中11种全氟化合物（PFCs）的方法.以甲醇作为萃取剂,样品经加速溶剂萃取仪（ASE）萃取,固相萃取净化后,使用UPLC-ESI-MS/MS联用仪分析样品中11种PFCs.在6 min内就可快速稳定地将所选取的11种全氟化合物分离,且最低检测浓度为0.518—3.520 pg.g-1之间,这些化合物在土壤中的平均添加回收率在71.2%—119.2%之间.应用此方法测得宜兴市水稻土样品中所选取的PFCs含量为0.006—0.780 ng.g-1之间.     

固相萃取/气相色谱质谱法测定灰尘中的氯代多环芳烃

建立了固相萃取(SPE)/气相色谱质谱(GC/MS)联用检测灰尘中氯代多环芳烃(ClPAHs)的方法.以正己烷和二氯甲烷混合液为提取溶剂,索氏提取灰尘样品中的20种ClPAHs,活性硅胶层析柱与活性炭混合硅胶SPE柱协同净化.净化后的提取液采用GC/MS测定,SIM模式扫描,并用质谱特征离子定量分析.结果表明,填充量为0.2 g(W(活性炭)∶W(硅胶)=1∶40)的活性炭混合硅胶SPE小柱能有效地将ClPAHs分离出来,载样后采用反向溶剂洗脱,既提高了回收率又减少了洗脱剂甲苯的用量,净化效果好.处理灰尘样品后检测分析,20种ClPAHs的平均回收率稳定在60.4%—120.1%,相关系数>0.99,检出限为0.04—0.17 ng.g-1,相对标准偏差为1.6%—10.2%.本方法前处理简单,定性、定量准确可靠,可广泛应用于环境介质中氯代多环芳烃的检测.