天津市环境空气中苯并[a]芘的变化趋势

分析了天津市环境空气中苯并[a]芘污染的程度及变化趋势,结果表明,天津市大气中苯并[a]芘污染成逐年下降趋势,同一年中苯并[a]芘浓度是非采暖期低于采暖期,月均值变化规律是夏季<春、秋季<冬季,天津市环境空气中苯并[a]芘污染总体来说处于较低的水平。     

大气飘尘中苯并[a]芘的激光诱导荧光法测定

以激光诱导荧光法测定大气飘尘中的苯并[a]芘。方法的检测限为0.01μg·l~(-1),降低了常规荧光法的检测限。综合溶剂提取、柱色层及纸色层分离技术,测定了上海市某些地区大气飘尘样品中苯并[a]芘的含量。     

真菌对土壤中苯并[a]芘的共代谢降解

研究了模拟生物泥浆法修复多环芳烃污染土壤.选择了几种从石油污染土壤中分离出来的真菌,研究它们对土壤内苯并[a]芘的降解,并研究了土壤内共存底物:菲、芘、邻苯二甲酸对苯并[a]芘降解的影响,及其之间的共代谢过程.结果表明,芘可以促进镰刀菌、毛霉对苯并[a]芘的降解,并认为这是共代谢作用的结果;菲也可以促进镰刀菌对苯并[a]芘的降解,但抑制了毛霉和青霉对苯并[a]芘的降解;而邻苯二甲酸对青霉和毛霉降解苯并[a]芘的过程均有抑制作用.      

基于反演模型的焦炉无组织苯并[a]芘排放因子研究

由于焦炉无组织苯并[a]芘排放因子难以测量,导致了焦炉苯并[a]芘大气污染研究存在一定的不确定性.针对上述问题,本研究根据1999年~2003年上海某焦化厂的产量、空气质量监测等数据,建立了基于AERMOD(AMS/EPA REGULATORY MODEL)模型反演苯并[a]芘排放因子的方法.结果显示,企业周边3个监测点年平均浓度结果分别为0.033,0.0024,0.0031μg/m³,均超过了2012年颁布的环境空气质量标准,通过AERMOD模型反演得到该焦化厂苯并[a]芘平均排放因子为14.71mg/t焦煤, 苯并[a]芘预测浓度超标面积125km²,超标区域主要集中在焦化厂周围,超标焦炉苯并[a]芘防护距离为6300m.     

兰州市大气中苯并(a)芘与儿童尿中1-羟基芘的分析及风险评价

对兰州市不同区域空气中苯并(a)芘和儿童尿液中1-羟基芘同步采样,分别采用气相色谱-质谱联用法和高效液相色谱法进行检测.结果表明:不同区域苯并(a)芘浓度有显著差别,研究区日均浓度约为对照区日均浓度的两倍.冬季大气中的浓度明显高于夏季,其中研究区冬季均值约为夏季的26.46倍,对照区冬季均值约为夏季的29.41倍.儿童尿中1-羟基芘的浓度与空气中苯并(a)芘的浓度呈一致的变化,冬季研究区儿童尿中1-羟基芘的均值为0.86μmol·(mol肌酐)-1,对照区为0.63μmol·(mol肌酐)-1.冬季研究区儿童的终生超额危险度最高,达到2.32×10-4,接近不可接受水平.     

南京市环境空气中苯并[a]芘的时空分布

通过在南京市大气国控点采集PM10样品,测量苯并[a]芘浓度。结果表明:南京市大气中苯并[a]芘月均值浓度呈双峰型变化,季节变化是夏季<春季<秋季<冬季,受工业污染的影响,呈现北高南低的局面。南京市苯并[a]芘浓度在国内外部分大城市中处于较低污染水平。     

苯并[a]芘对刺参SOD和CAT酶活性影响研究

研究了实验室条件下刺参(Stichopus japonicus)暴露于不同浓度苯并[a]芘后,刺参体内超氧化物歧化酶(SOD)、过氧化氢酶(CAT)的变化规律。实验设置了4个处理组(1、5、10、20μg/L)、空白对照组和丙酮溶剂对照组,在染毒2 h、6 h、12 h、24 h、2 d、4 d、7 d、14 d和21 d取样分析,其中第14天放入清洁海水中恢复7 d,分析了苯并[a]芘与刺参SOD、CAT之间的剂量、时间-效应关系。结果表明,在苯并[a]芘作用下,刺参的SOD酶活性在第6小时、12小时和21天时与苯并[a]芘浓度呈显著负相关,R_(6h)=0.959 2(P0.05)、R_(12h)=0.945 8(P0.05)、R_(21d)=0.959 6(P0.05)。刺参CAT的诱导随水体苯并[a]芘浓度的升高而增强,在第2天、第4天有显著的线性关系,其相关系数分别为R_(2d)=0.790 6(0.01P0.05)、R_(4d)=0.953 3(0.01P0.05)。由此表明,在苯并[a]芘染毒作用下,刺参组织解毒代谢指标SOD和CAT都出现了明显的时间-剂量效应,经相关性分析提出刺参组织SOD和CAT酶活力可以作为评价苯并[a]芘污染的生物标志物。     

苯并[a]芘降解菌SL-1的筛选、鉴定及其降解特性

从土壤中筛选出一株以苯并[a]芘为唯一碳源的高效降解菌SL-1,经形态观察、生理生化分析以及16SrDNA基因序列分析,该菌株鉴定为假单胞菌（Pseudomonassp．）。28℃震荡培养10d后,菌株SL-1对5mg·L^-1苯并[a]芘的降解率为35．7％;同时测定该降解菌的生长曲线、降解率变化曲线、最佳培养条件;土壤修复试验表明,42d时,降解菌SL-1对苯并芘的降解率达到76．3％。     

蚯蚓细胞色素P450酶系对土壤中芘或苯并[a]芘的响应

以赤子爱胜蚓(Eisenia fetida)为受试生物,通过人工污染草甸棕壤微宇宙试验方法,研究了暴露于不同环境浓度芘或苯并[a]芘(添加量分别为0.12、0.24、0.48、0.96 mg·kg~(-1))污染的土壤中14 d后,蚯蚓体内细胞色素P450(CYPs)酶系,如CYPs总量、CYP1A1及CYP2C9活性的变化.结果显示,芘或苯并[a]芘暴露导致蚯蚓CYPs总量、CYP1A1及CYP2C9活性的变化不同.其中,CYPs总量与CYP1A1活性对芘的响应趋势相似:试验3 d后,0.96 mg·kg~(-1)芘导致二者都显著高于对照水平;14 d后,都显著低于对照水平;CYP1A1活性对芘的响应更为敏感.CYPs总量与CYP2C9活性对苯并[a]芘的响应趋势相似:暴露初期,苯并[a]芘最高暴露剂量(0.96 mg·kg~(-1))导致二者都显著低于对照水平;试验结束后,苯并[a]芘最低暴露剂量(0.12 mg·kg~(-1))导致二者都显著高于对照水平,最高剂量暴露导致二者都显著低于对照水平,CYP2C9活性对苯并[a]芘的响应更为敏感.因此,推断CYPs亚酶对污染物的响应具有选择性且亚酶的响应敏感度高于CYPs总量.将CYPs总量与CYP1A1活性结合,或与CYP2C9活性结合分别诊断土壤芘污染或并[a]芘污染,较为准确有效.     

超声萃取-高效液相色谱法测定土壤中苯并[a]芘研究

采用超声萃取-高效液相色谱荧光检测法对土壤中苯并[a]芘含量进行定性、定量分析.土壤样品用正己烷/二氯甲烷(1+1)超声萃取,萃取液经硅胶柱或佛罗里硅土柱净化浓缩定容,乙腈-水为流动相,线性梯度洗脱,流速为1.0 mL/min,荧光检测器激发波长为280 nm,发射波长为420 nm,外标法峰面积定量.结果显示:该方法检出限低,苯并[a]芘的检出限为0.15μg/kg.这种方法具有很好的精密度,相对标准偏差为3.9%~8.4%.实际水样加标回收率范围在72.5%~85.8%.能够满足土壤的监测要求.     

Metabolism of benzo[a]pyrene in peroxynitrite/Fe（Ⅲ） porphyrin system

The peroxynitrite/porphyrin biomimetic system was established to investigate the effects of peroxynitrite on benzo[a]pyrene （B[a]P） metabolism. Three model systems consisting of different iron porphyrins were compared, and the results showed that the peroxynitdte/T（p-Cl）PPFeCl system was the highest catalytic efficiency in the metabolism of B [a]P. We analyzed the B [a]P metabolites produced from this system by RP-HPLC method and firstly identified the formation of nitrobenzo[a]pyrenes which are the special metabolites of B [a]P induced by peroxynitrite.     

Metabolism of benzo[a]pyrene in peroxynitrite/Fe(III) porphyrin system

The peroxynitrite/porphyrin biomimetic system was established to investigate the effects of peroxynitrite on benzo[a]pyrene (B[a]P) metabolism. Three model systems consisting of different iron porphyrins were compared, and the results showed that the peroxynitrite/T(p-Cl)PPFeCl system was the highest catalytic efficiency in the metabolism of B[a]P. We analyzed the B[a]P metabolites produced from this system by RP-HPLC method and firstly identified the formation of nitrobenzo[a]pyrenes which are the special metabolites of B[a]P induced by peroxynitrite.     

土壤中多环芳烃的SPMD辅助解吸行为研究

为了开发一种表征土壤中憎水性有机污染物解吸及生物有效性的新方法,建立了半透膜被动采样装置（SPMD）研究土壤中有机污染物解吸行为的方法,利用SPMD分析了多环芳烃菲、芘和苯并［a］芘在3种不同性质土壤中的辅助解吸行为.结果表明,SPMD是一种很好地表征土壤中憎水性有机污染物解吸及生物有效性的手段. SPMD辅助解吸多环芳烃的效率与土壤有机质及多环芳烃性质有关.随着土壤有机质含量的降低,土壤中菲和芘的SPMD解吸率逐渐升高,对于10 mg/kg染毒水平,当土壤有机质含量由18.68%降低到0.3%时,2种化合物的解吸率分别由56.45%和48.28%上升到接近100%;但是对于苯并［a］芘,粘土表现出明显的滞留能力,在有机质含量（0.3%）很低、粘土含量（39.05%）较高的3号土壤中,苯并［a］芘的解吸率仅有66.97%.不同多环芳烃SPMD辅助解吸率差别很大,随着土壤有机质含量的降低,以及污染物浓度的提高,菲和芘的解吸差异逐渐缩小,而苯并［a］芘与上述2种多环芳烃的差异很大,主要是由于苯并［a］芘具有高度亲脂性,并且分子较大,造成其容易滞留在粘土的微孔及有机质的致密结构中.     

二甲基苯蒽和苯并(a)芘对小鼠肝脏金属硫蛋白及氧化损伤的诱导作用

观察两种致癌性多环芳烃化合物二甲基苯蒽（DMBA）和苯并（a)芘（BaP）对小鼠肝脏脂质过氧化产物和金属硫蛋白含量的影响。选用雄性C57BL／OLA129小鼠，观察DMBA和BaP各50mg/kg一次腹腔注射染毒后24、48、72和144h后的动物肝脏重量、金属硫蛋白（MT）含量和脂质过氧化程度的变化。MT测定采用镉－血红蛋白亲和分析法；脂质过氧化指标为硫代巴比妥酸测定丙二醛法。结果表明，DMBA和BaP均能引起小鼠肝脏重量增加、MT含量增加和MDA含量增加。随着DMBA和BaP染毒后的时间延长小鼠肝脏的重量不断增加，呈现时间效应关系。小鼠肝脏MT的含量在染毒后24和48h后明显增加1倍。肝脏MDA的含量增加在染毒后24h后达到高峰。本研究观察到DMBA和Bap可以MT增加。MT的增加与MDA的增加呈现一定平行的关。提示MT诱导可能与多环芳烃化合物所致的氧化损伤有关。     

Health risk assessment of dietary exposure to polycyclic aromatic hydrocarbons in Taiyuan, China

Sixteen polycyclic aromatic hydrocarbons （PAHs） were determined in 24 duplicate-diet samples from people in Taiyuan during summer and winter in 2009. Dietary intake of PAHs for 2862 participants was subsequently estimated by a survey in Taiyuan. Results from these 24 samples were compared with a raw food study in Taiyuan in 2008. Three main sources of dietary PAHs are vegetables, wheat flour and fruits, the sum of which contributes 75.95% of PAHs in dietary food. Compared to the estimated value in raw food, much more B[a]Peq （benzo[a]pyrene equivalents） were detected in food samples collected in the duplicate-diet study in Taiyuan （60.75 ng/day）. The cooking process may introduce more B[a]Peq into food, and the relative contribution of 16 PAHs in the diet would be changed during the cooking procedure.     

Metabolism of benzo[a]pyrene in peroxynitrite/Fe(Ⅲ) porphyrin system

The peroxynitrite/porphyrin biomimetic system was established to investigate the effects of peroxynitrite on benzo[a]pyrene (B[a]P) metabolism. Through the comparison of three model systems consisting of different iron porphyrins, we found that the peroxynitrite/T(p-Cl)PPFeCl system showed the highest catalytic efficiency in the metabolism of B[a]P. We analyzed the B[a]P metabolites produced from this system by RP-HPLC method and firstly identified the formation of nitrobenzo[a]pyrenes which are the special metabolites of B[a]P induced by peroxynitrite.     

Isolation of marine benzo[a]pyrene-degrading Ochrobactrum sp. BAP5 and proteins characterization

A bacterial strain BAP5 with a relatively high degradation ability of benzo[a]pyrene (BaP) was isolated from marine sediments of Xiamen Western Sea, China and identified as Ochrobactrum sp. according to 16S rRNA gene sequence as well as Biolog microbial identification system. Strain BAP5 could grow in mineral salt medium with 50 mg/L of BaP and degrade about 20% BaP after 30 d of incubation. Ochrobactrum sp. BAP5 was able to utilize other polycyclic aromatic hydrocarbons (PAHs) (such as phenanthrene, pyrene and fluoranthene) as the sole carbon source and energy source, suggesting its potential application in PAHs bioremediation. The profile of total soluble protein from Ochrobactrum sp. BAP5 was also investigated. Some over- and special-expressed proteins of strain BAP5 when incubated with the presence of BaP were detected by two-dimensional polyacrylamide gel electrophoresis, and found to be related with PAHs metabolism, DNA translation, and energy production based on peptide fingerprint analysis through matrix-assisted laser desorption/ionization-time of flight mass spectrometry.     

Enhanced oxidation of benzo[a]pyrene by crude enzyme extracts produced during interspecific fungal interaction of Trametes versicolor and Phanerochaete chrysosporium

The effects of interspecific fungal interactions between Trametes versicolor and Phanerochaete chrysosporium on laccase activity and enzymatic oxidation of polycyclic aromatic hydrocarbons (PAHs) were investigated. A deadlock between the two mycelia rather than replacement of one fungus by another was observed on an agar medium. The laccase activity in crude enzyme extracts from interaction zones reached a maximum after a 5-day incubation, which was significantly higher than that from regions of T. versicolor or P. chrysosporium alone. The enhanced induction of laccase activity lasted longer in half nutrition than in normal nutrition. A higher potential to oxidize benzo[a]pyrene by a crude enzyme preparation extracted from the interaction zones was demonstrated. After a 48 hr incubation period, the oxidation of benzo[a]pyrene by crude enzyme extracts from interaction zones reached 26.2%, while only 9.5% of benzo[a]pyrene was oxidized by crude extracts from T. versicolor. The oxidation was promoted by the co-oxidant 2,2'-azinobis-3-ethylbenzthiazoline-6-sulphonate diammonium salt (ABTS). These findings indicate that the application of co-culturing of white-rot fungi in bioremediation is a potential ameliorating technique for the restoration of PAH-contaminated soil.     

苯并[a]芘对鲫鱼生物标志物的影响研究

研究了苯并[a]芘暴露对鲫鱼(Carassius auratus)的几种生物标志物的影响.在鲫鱼接受3个不同质量分数苯并[a]芘(BaP)的腹腔注射14 d后,分析了其肝脏7-乙氧基-3-异吩噁唑酮-脱乙基酶(EROD)活性,以及超氧化物歧化酶(SOD)、过氧化氢酶(CAT)、谷胱甘肽过氧化物酶(GPx)等抗氧化酶活性和红细胞核异常(NA)率变化.结果显示:w(BaP)为1 mg/kg处理组的EROD活性显著升高(P＜0.001).w(BaP)为0.1和1 mg/kg处理组SOD活性显著低于对照组(P＜0.001),在暴露结束时,w(BaP)为1 mg/h处理组CAT活性显著低于对照组(P＜0.01),而w(BaP)为0.1和1 mg/kg处理组GPx活性被显著抑制(P＜0.001).表明BaP对EROD活性有诱导作用,而对SOD,CAT和GPx等抗氧化酶活性的抑制作用明显.所有处理组NA率与对照组均无显著差异.因此,鲫鱼EROD,SOD,CAT和GPx等酶活性的改变适于作为生物标志物,可以用来显示暴露于多环芳烃有机污染物鱼类的生活状态.