大同市空气中多环芳烃与人尿中1-羟基芘的分析

用GC~2/MS和HPLC鉴定出大同市空气中的多环芳烃化合物35种.对大同市不同功能区空气中苯并(a)芘(BaP)和人尿中1-羟基芘同步采样分析.结果表明,不同功能区BaP浓度有显著差别:采暖期浓度急剧增加,城区浓度为对照点的17倍,日均值达330ng/m~3.人尿中1-羟基芘的浓度与空气中BaP的浓度显著相关.采暖期城区尿中1-羟基芘的几何均值为1.86μmol/mol肌酐,非采暖期为1.14μmol/mol肌酐,均较北京市的均值高出五倍多.证明大同市由于直接燃煤,造成空气中多环芳烃的严重污染.     

人尿中1—羟基芘与空气中多环芳烃的定量关系

本文对不同采样点人尿中的1-羟基芘含量和受试人携带的个体空气采样器中以及所在环境中固定采样器中多环芳烃的浓度进行了测定。数理统计结果表明,尿中1-羟基芘与个体采样器中的芘或苯并(a)芘有显著的正相关。个体采样器的测定结果较客观地反映了受试人吸入空气中多环芳烃的浓度,证明尿中1-羟基芘在人体接触多环芳烃的健康风险评价中,是一个有效的生物监测指标。     

苯并[a]芘和1-羟基芘诱导人胚胎干细胞分化心肌细胞ROS、CYP基因表达和DNA损伤

多环芳烃(PAHs)化合物中的苯并[a]芘和PAHs暴露检测标志物1-羟基芘与心脏功能障碍有关,但其生物学机制尚不清楚。为研究苯并[a]芘和1-羟基芘对心脏的毒性作用,基于人胚胎干细胞分化心肌细胞(hESC-CM)研究了苯并[a]芘和1-羟基芘对心肌细胞活性氧(ROS)生成、CYP基因表达和DNA损伤等的影响。结果表明,苯并[a]芘和1-羟基芘对h ESC-CM活性无影响,但能显著增强细胞ROS水平,诱导DNA损伤。此外,苯并[a]芘还能诱导细胞线粒体促凋亡基因的表达。研究表明,苯并[a]芘和1-羟基芘能通过诱导氧化应激和DNA损伤事件导致h ESC-CM损伤,在一定程度上解释了多环芳烃暴露导致心脏疾病的分子机制。     

Determination of three endocrine disrupting chemicals,triclosan, 4-n-nonylphenol,and di-n-butyl phthalate using stir bar sorptive extraction in samples of different matrices

Three endocrine disrupting chemicals (EDCs), triclosan (TCS), 4-n-nonylphenol (4-n-NP), and di-n-butyl phthalate (DBP) were determined using stir bar sorptive extraction (SBSE) along with high-performance liquid chromatography/photodiode array detection (HPLC/DAD). Benzyl butyl phthalate was used as an internal standard. The targeted analytes could be rapidly determined with limits of quantification (LOQ) ranging from 4.1 (DBP), 10 (TCS), to 34 (4-n-NP)?µg?L^?1 in real samples such as bottled waters, personal care products, soaps, lotions, and urine. The results show that the developed analytical scheme is solvent-saving, efficient, and capable of fast screening samples for these common EDCs.     

HCH residues in point-source contaminated samples of the Teltow Canal in Berlin,Germany

Contaminated groundwater and a riverine sediment core heavily affected by the same industrial point source were analysed for hexachlorocyclohexanes (HCH) and its degradation products. A detailed quantification by GC/MS revealed contamination levels up to 730 μg/L and 396 ng/g in sum for the water and sediment samples, respectively. The isomer pattern differed significantly in both compartments. The ground water samples were depleted in γ-HCH, whereas a significant loss of α-HCH was evident in the sediments as compared to the technical composition. The data obtained revealed interesting insights into the transformation behaviour and fate of HCH mixtures in anaerobic environmental compartments. In the affected groundwater system an ongoing microbial degradation was pointed out by the identification of indicative anaerobic metabolites. On the contrary in the sedimentary system a high environmental stability or rather a hindered degradation was observed as indicated by unaltered concentration levels as compared to production rates as well as by the absence of metabolites. Interestingly, the environmental fate of HCH in subaquatic sediments as well as in anaerobic ground water differs highly in contrast to the behaviour in anaerobic soil or surface water systems. Further on, it has to be stated, that the knowledge about the long-term behaviour of HCH residues in sedimentary material under anaerobic conditions is rather limited so far.     

Urinary 8-oxo-7, 8-dihydro-2′-deoxyguanosine concentrations after frying of bacon,a pilot study

Cooking fumes contain compounds that may give rise to oxidative stress and mutations when inhaled. The aim of this study was to evaluate if cooking fumes from frying of bacon induce oxidative stress by measurement of urinary 8-oxo-7,8-dihydro-2 deoxyguanosine, a marker of oxidatively damaged DNA. Three non-smoking women fried bacon for 3 h. Urine samples were taken as early morning void at the same time on four days; the morning before frying, the morning after first frying, the morning after three days of frying and one week after first urine sample. 8-Oxo-7,8-dihydro-2 deoxyguanosine, 1-hydroxypyrene and 2-hydroxyphenanthrene, metabolites of polycyclic aromatic hydrocarbons, were measured by liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS). 8-Oxo-7,8-dihydro-2 deoxyguanosine correlated weakly with concentrations of 1-hydroxypyrene (r = 0.31, p = 0.042), but it did not correlate with 2-hydroxyphenanthrene (r = ?0.074; p = 0.64). Average urinary 8-oxo-7,8-dihydro-2 deoxyguanosine concentrations increased from the day before frying (16.3 ± 4.2 nmol/L) to the third day of frying (26.2 ± 10.2 nmol/L), although not statistically significantly. Our pilot study shows that frying of bacon may result in increased oxidative stress which further emphasises the possible carcinogenic potential of cooking fumes.     

Metabolic fate of aromatic amines in the mussel Mytilus galloprovincialis

The postmitochondrial fraction of the digestive gland from the marine mussel Mytilus galloprovincialis possesses FAD-containing monooxygenase (EC 1.14.38) but lacks cytochrome P-450 dependent benzo(a)pyrene monooxygenase (EC 11.4.14.1). This is also evidenced by the ability of the mussel preparation to activate carcinogenic aromatic amines, but not carcinogenic benzo(a)pyrene, to Salmonella typhimurium TA 98 mutagens. This metabolic activity is NADPH dependent. Mussel digestive gland postmitochondrial fraction also possesses the enzymes needed for the detoxicating part of the aromatic amine metabolism: UDP-glucuronyl transferase (EC 2.4.1.17) and -glucuronidase (EC 3.2.1.31). Under the experimental conditions used here, this aromatic amine metabolic pathway converts up to 8% of 2-acetylamino(9-¹⁴C)fluorene, but not (G-³H)benzo(a)pyrene, to water soluble glucuronides. Glucuronic acid stimulates the formation of these glucuronides. The metabolites liberated from these glucuronides by the -glucuronidase treatment could be converted to TA 98 strain mutagens by the carp liver postmitochondrial fraction, but not by the mussel's digestive gland preparation. The presence of such a selective potential for the bioactivation and detoxication of aromatic amines, and not polycyclic aromatic hydrocarbons, in the marine invertebrate(s) may bring new insight to our understanding of the effects and the fate of carcinogens in the marine environment.     

Impact of exposure to secondhand smoke on the levels of selected polycyclic aromatic hydrocarbons among the US children and adolescents

The impact of secondhand smoke (SHS) on the levels of polycyclic aromatic hydrocarbons metabolites among the US children and adolescents was evaluated. The data from the National Health and Nutrition Examination Survey for 2003–2008 were analyzed by regression models. SHS at home for children was associated with statistically significantly higher unadjusted levels of 2-hydroxynapthalane, 2-, 3-, and 9-hydroxyfluorene, 1-, 2-, and 3-hydroxyphenanthrene, and 1-hydroxypyrene. Also, SHS at home for adolescents was associated with statistically significantly higher unadjusted levels of 2- and 9-hydroxyfluorene, 2- and 3-hydroxyphenanthrene, and 1-hydroxypyrene. Further, SHS exposure at home was associated with (1) higher adjusted levels of 9-hydroxyfluorene for 6–12 years old (p < 0.01) and (2) lower adjusted levels of 1-hydroxynaphthalene for 12–19 years old (p < 0.01).     

Removal of 17β-estradiol in laccase catalyzed treatment processes

The removal of 17β-estradiol (E2) in laccase catalyzed oxidative coupling processes was systematically studied in this work. We focused on the influence of pH and natural organic matter (NOM) on the performance of the enzymatic treatment processes. It was found that the optimal pH for E2 removal was between 4 and 6. The removal of E2 was slightly inhibited in the presence of NOM. Enzymatic transformation of E2 was second-order in kinetics with first-order to both the concentrations of the enzyme and contaminant. Mass spectrum (MS) analysis suggested that coupling products were formed through radical-radical coupling mechanism. The results of this study demonstrated that laccase catalyzed oxidative coupling process could potentially serve as a treatment strategy to control steroid estrogens.     

Metalaxyl—its persistence and metabolism in soil

Different biotic and abiotic factors were found to play a vital role in attenuating metalaxyl residues in soil. In addition to metalaxyl many other products were found by HPLC and GC‐MS analysis while studying its soil metabolism in presence of natural sunlight. Three compounds were identified and characterized: 2,6‐dimethylaniline, 2,6‐dimethyl‐N‐ethylacetanilide and N‐(2,6‐dimethyl phenyl) alanine methyl ester.     

Occurrence of and risk posed by highly carcinogenic dibenzo[def,p]chrysene isomers in urban soil

Dibenzopyrene and its isomers are considered the most potent carcinogens of all polycyclic aromatic hydrocarbons tested to date. However, despite public concerns over their deleterious effects, they have not been extensively studied. The occurrence of four highly carcinogenic isomers of dibenzopyrene – dibenzo[def,p]chrysene, dibenzo[a,e]pyrene, dibenzo[a,i]pyrene, and dibenzo[a,h]pyrene in urban soil samples from Shanghai, China, have been determined in this study, as well as that of benzo[a]pyrene and coronene. A total of 14 peaks with ions at m/z 302 were detected by gas chromatography-mass spectrometry. Although the concentrations of benzo[a]pyrene and the sum of the 16 priority polycyclic aromatic hydrocarbons were greater than that of dibenzopyrene and its isomers, the carcinogenic potency of the latter was higher than that of benzo[a]pyrene. The results also indicate that the relative carcinogenic potency of the four dibenzopyrene isomers in the samples is higher than that of the 16 priority polycyclic aromatic hydrocarbons.     

A unified approach for including non-extractable residues (NER) of chemicals and pesticides in the assessment of persistence

All chemicals form non-extractable residues (NER) to various extents in environmental media like soil, sediment, plants and animals. NER can be quantified in environmental fate studies using isotope-labeled (such as ¹⁴C or ¹³C) tracer compounds. Previous NER definitions have led to a mismatch of legislation and state of knowledge in research: the residues are assumed to be either irreversibly bound degradation products or at least parts of these residues can be released. In the latter assumption, soils and sediments are a long-term source of slowly released residues. We here present a conceptual experimental and modeling approach to characterize non-extractable residues and provide guidance how they should be considered in the persistence assessment of chemicals and pesticides. Three types of NER can be experimentally discriminated: sequestered and entrapped residues (type I), containing either the parent substance or xenobiotic transformation products or both and having the potential to be released, which has indeed been observed. Type II NER are residues that are covalently bound to organic matter in soils or sediments or to biological tissue in organisms and that are considered being strongly bound with very low remobilization rates like that of humic matter degradation rates. Type III NER comprises biogenic NER (bioNER) after degradation of the xenobiotic chemical and anabolic formation of natural biomolecules like amino acids and phospholipids, and other biomass compounds. We developed the microbial turnover to biomass (MTB) model to predict the formation of bioNER based on the structural properties of chemicals. Further, we proposed an extraction sequence to obtain a matrix containing only NER. Finally, we summarized experimental methods to distinguish the three NER types. Type I NER and type II NER should be considered as potentially remobilizable residues in persistence assessment but the probability of type II release is much lower than that of type I NER, i.e., type II NER in soil are “operationally spoken” irreversibly bound and can be released only in minute amounts and at very slow rates, if at all. The potential of remobilization can be evaluated by chemical, physical and biological methods. BioNER are of no environmental concern and, therefore, can be assessed as such in persistence assessment. The general concept presented is to consider the total amount of NER minus potential bioNER as the amount of xenoNER, type I?+?II. If a clear differentiation of type I and type II is possible, for the calculation of half-life type I NER are considered as not degraded parent substance or transformation product(s). On the contrary, type II NER may generally be considered as (at least temporarily) removed. Providing proof for type II NER is the most critical issue in NER assessment and requires additional research. If no characterization and additional information on NER are available, it is recommended to assess the total amount as potentially remobilizable. We propose our unified approach of NER characterization and evaluation to be implemented into the persistence and environmental hazard assessment strategies for REACH chemicals and biocides, human and veterinary pharmaceuticals, and pesticides, irrespective of the different regulatory frameworks.     

Determination of canthaxanthin in the red coral (<Emphasis Type="Italic">Corallium rubrum</Emphasis>) from Marseille by HPLC combined with UV and MS detection

Corallium rubrum is the most famous and precious coral due to the intense characteristic red colour of its skeleton. We have determined the presence of carotenoids in natural samples of C. rubrum from Marseille, Riou, and investigated their chemical composition. Analysis was performed both on soft tissues and hard tissues including spicules and skeleton. Since hard tissues are made of a mineral fraction and an organic fraction obtained after demineralization, extraction was performed both with and without demineralization by EDTA. The extracts were analyzed by complementary methods of TLC, HPLC/DAD and HPLC/MS. The components were separated by RP-18 chromatography column using acetonitrile/methanol for HPLC/DAD and acetonitrile/water gradient for HPLC/MS analysis. Our results give the first evidence of the presence of canthaxanthin, 4,4′-diketo-β-carotene, as the major carotenoid in all samples. Spicules exhibited higher content in carotenoids than skeleton. Demineralization treatment improved the efficiency of carotenoid extraction by an average factor of 5 and showed that organic matrix contains canthaxanthin.     

Removal of 17β-estradiol in laccase catalyzed treatment processes

The removal of 17β-estradiol （E2） in laccase catalyzed oxidative coupling processes was systematically studied in this work. We focused on the influence of pH and natural organic matter （NOM） on the performance of the enzymatic treatment processes. It was found that the optimal pH for E2 removal was between 4 and 6. The removal of E2 was slightly inhibited in the presence of NOM. Enzymatic transformation of E2 was second-order in kinetics with first-order to both the concentrations of the enzyme and contaminant. Mass spectrum （MS） analysis suggested that coupling products were formed through radical-radical coupling mechanism. The results of this study demonstrated that laccase catalyzed oxidative coupling process could potentially serve as a treatment strategy to control steroid estrogens.     

Metabolic fate of mancozeb in tomato (Lycopersicon esculentum)

The metabolic fate of mancozeb in tomato (Lycopersicon esculentum Mill.) fruits was evaluated. Results indicate rapid dissipation of mancozeb and its metabolic conversion to ethylenethiourea (ETU), the carcinogenic metabolite. Treatment with mancozeb at flowering stage resulted translocation of ETU in newly emerged fruits indicating the systemic nature of ETU. ETU was detected within one hour of final spraying of mancozeb at the doses of 1.5 and 3?kg a.i./ha. The residue level of ETU increased up to 3-day for both the treatments, which then rapidly dissipated to safer metabolite ethyleneurea (EU) and reached the below detectable limit within 25 days. Cooking of fresh tomatoes caused decontamination of mancozeb residues, which was associated with simultaneous increase in ETU residues. The degradation pattern of ETU after application of mancozeb was slower as compared to the spraying of ETU as such on the crop. A pre-harvest interval of 25 days is recommended.     

A chemical mechanism for dry deposition—the role of biogenic hydrocarbon (Terpene) emissions in the dry deposition of O3, SO2 and NOx in forest areas

Terpenes react quite rapidly with ambient ozone and lead via ozonides to highly oxidizing radicals and consecutive products forming aerosols. In the presence of SO₂ sulphur containing compounds, mainly as sulphate, are formed. By means of gas chromatography/mass spectrometry and by comparison with known spectra the main products of the reaction of ß‐pinene (as a model compound) with ozone and sulphur dioxide could be identified.

Reaction of terpenes with NO₃‐radicals, which build up in the atmosphere at night‐time, leads to the formation of organic nitrates that form aerosols. The kinetics as well as the products of the reaction between NO₃‐radicals and ß‐pinene have been studied by FTIR and MS.     

分散固相萃取-超高效液相色谱-串联质谱联用快速检测大豆及土壤中氟磺胺草醚残留

采用分散固相萃取(QuEChERS)样品前处理方法,建立了超高效液相色谱-串联质谱(UPLC-MS/MS)快速检测大豆和土壤中氟磺胺草醚的残留分析方法.大豆和土壤样品采用乙腈(含0.5%甲酸)提取,N-丙基乙二胺(PSA)或石墨化碳黑(GCB)净化,UPLC-MS/MS外标法检测定量.在0.005—0.5 mg.kg-1添加范围内,氟磺胺草醚在土壤、大豆和大豆植株中的平均回收率在79.4%—109.0%之间,变异系数在3.6%—10.1%之间.在山东、河南、吉林进行了氟磺胺草醚在大豆植株和土壤中的降解动态研究,结果表明,试验点中氟磺胺草醚在土壤中的降解半衰期为8.5—23.7 d;在大豆植株中的降解半衰期为2.7—9.8 d.     

Sorption of pyrene from water by oil shale ash and mineral particles

The aim of this work was to estimate the sorption of pyrene from water solutions on mineral substrates, e.g., alumina, silica, and oil shale ash, from the Estonian thermal plant. Results obtained from this study indicate that the sorption of pyrene on mineral oxides and oil shale ash particles from water can be described with a linear equation. The sorptive capacity per weight of oil shale ash in aqueous systems was significantly lower compared with mineral adsorbents. The distribution coefficient (K_d) for pyrene in the system with particles of oil shale ash was 10–12 times lower as than for mineral adsorbents.     

双齿围沙蚕对芘的生物可利用性研究

为近海岸沉积质中PAHs的生态风险评价及其污染生境的修复提供理论依据,以双齿围沙蚕为研究对象,以芘为暴露污染物,开展双齿围沙蚕对芘的生物可利用性研究,分别考察了芘对双齿围沙蚕抗氧化酶活性的影响以及芘在双齿围沙蚕体内的生物富集特征。结果表明,双齿围沙蚕SOD、CAT和GSH-PX活性均随诱导时间的增加而升高,且SOD活性随芘浓度的增加出现显著性抑制,CAT和GSH-PX活性则随芘浓度的增加出现显著性升高。芘在双齿围沙蚕体内的生物富集特征如下:双齿围沙蚕体内芘的蓄积量随暴露浓度的增加而增加,各处理组双齿围沙蚕体内芘的蓄积量随时间的变化均呈类凸形的二次曲线关系,在第10天达到蓄积的最大值,最大蓄积量依次为(6.18±0.62)mg·kg~(-1)、(12.37±1.23)mg·kg~(-1)和(24.76±1.51)mg·kg~(-1)。生物富集系数BCF随芘浓度的增加而减小,分别为0.0692、0.0684和0.0674。上述研究结果表明,在一定浓度范围内,双齿围沙蚕抗氧化酶活性对芘的暴露具有很好的指示作用;此外,在短期内,双齿围沙蚕对芘具有明显的富集效应。