再生水灌溉土壤人工合成麝香累积模型模拟

人工合成麝香(HHCB/AHTN)是近几年来受关注较多的药品与个人护理品(PPCPs)类新型污染物之一,再生水灌溉是HHCB/AHTN输入土壤的主要途径.本研究结合再生水灌溉土壤的实地检测结果,采用HYDRUS-1D模型,模拟了长期灌溉再生水条件下土壤中HHCB和AHTN的迁移转化和累积趋势.结果表明,尽管土壤中这两种麝香的含量极低,但是再生水灌溉土壤中的含量是自来水灌溉土壤的5倍;再生水灌溉下HHCB/AHTN累积趋势从lgKoc较低为3.44时的指数型增加,到lgKoc较高为4.12和4.86时的线性增加;半衰期的变化对再生水灌溉途径输入土壤的HHCB/AHTN的表层累积影响并不明显;再生水灌溉下土壤中HHCB/AHTN的垂直迁移能力较小,灌溉40 a以后最大迁移距离只有53 cm,且受Koc变化的影响较大;通过灌溉水途径进入土壤的HHCB和AHTN通过生物降解与植物吸收途径消解的比例较低,最高只占输入总量的7.69%,但是随着lgKoc的减小和灌溉时间增加,通过生物降解和根系吸收的消解率增加.本研究结果能够为准确评估再生水灌溉途径引起的土壤中人工合成麝香HHCB/AHTN的生态风险提供依据.     

吐纳麝香长期暴露下蚯蚓体内金属硫蛋白和谷胱甘肽变化

吐纳麝香(AHTN)作为人工合成麝香中多环麝香的典型代表,具有挥发性、易生物富集等特性,由于其在环境中的浓度日益升高,呈现出一定的生物效应,可能对生态系统的稳态存在着潜在的威胁,为探讨上述课题,试验通过采用自然土壤法以赤子爱胜蚓(Eiseniafetida)作为试验动物,首次研究测定蚯蚓在AHTN的长期暴露条件下,其体内金属硫蛋白和谷胱甘肽含量的变化。试验结果得出低浓度的AHTN能够抑制机体内金属硫蛋白和谷胱甘肽的生成,使得金属硫蛋白和谷胱甘肽的含量显著减少,在一定浓度范围内的AHTN对机体无明显不利影响,而高浓度的AHTN能够诱导机体内金属硫蛋白和谷胱甘肽的生成,使得金属硫蛋白和谷胱甘肽的含量显著增多(P<0.05),从而对土壤环境存在着潜在的生态风险。     

人工合成麝香对小麦种子发芽的生态毒性

采用土培实验,研究了佳乐麝香(HHCB)和吐纳麝香(AHTN)对小麦种子发芽的生态毒性,测定了这2种人工合成麝香对小麦种子发芽率、根伸长抑制率和芽伸长抑制率的影响.结果表明,小麦种子的发芽率与这2种人工合成麝香浓度之间剂量-效应关系不明显,低剂量条件下(佳乐麝香≤150 mg·kg-1,吐纳麝香≤200 mg·kg-1...     

多环麝香对蚯蚓的急性和亚急性毒性效应

为探讨多环麝香对土壤动物的毒性效应,以赤子爱胜蚓(Eisenia fetida)为供试生物,采用滤纸接触法与自然土壤法,考察了吐纳麝香(AHTN)和佳乐麝香(HHCB)对蚯蚓的急性和亚急性毒性效应。结果显示,滤纸法测得的AHTN和HHCB对蚯蚓的急性经皮毒性为中等毒性,对蚯蚓的48h-LC_(50)分别为20.76和11.87μg·cm~(-2),而自然土壤法测得的AHTN和HHCB对蚯蚓的14d-LC_(50)分别为436.3和392.4μg·g~(-1),2种多环麝香皆属低毒物质。HHCB对蚯蚓的急性毒性大于AHTN,但2种毒性测定方法中不同的染毒介质和毒性作用途径使AHTN和HHCB的急性毒性等级的界定有所差异。AHTN和HHCB对蚯蚓繁殖率的抑制作用较对生长速率更为明显,2种多环麝香对蚯蚓繁殖率的无可见效应浓度(NOEC)均为30μg·g~(-1),最低可见效应浓度(LOEC)均为50μg·g~(-1)。研究表明,蚯蚓繁殖率可作为一种潜在的生物标志物,用于监测或表征土壤中多环麝香的污染水平及其亚急性毒性效应。     

多环麝香污染胁迫对蚯蚓特异性蛋白基因表达的影响

为了探讨蚯蚓特异性蛋白基因表达在监测多环麝香低水平长期暴露污染中的应用,选择蚯蚓热休克蛋白(HSP70)、钙网蛋白(CRT)、亲环素A(cyPA)、翻译控制肿瘤蛋白(TCTP)等代表性蛋白基因作为供试基因.采用自然土壤污染模拟实验,基于mRNA表达分子水平,研究吐纳麝香(AHTN)与佳乐麝香(HHCB)长期(28 d)污染胁迫对以上各特异性蛋白基因响应表达的影响.通过序列同源性比较与荧光定量PCR熔解曲线结果分析,表明设计的引物适合供试基因mRNA表达水平的检测.染毒暴露28 d后,当AHTN染毒浓度小于30μg.g-1或HHCB浓度小于50μg.g-1时,蚯蚓HSP70基因表达水平无显著变化,而AHTN浓度等于或大于30μg.g-1和HHCB浓度等于或大于50μg.g-1时,HSP70基因表达水平呈显著下调趋势;而各AHTN或HHCB浓度处理组中蚯蚓CRT基因显著上调表达;cyPA和TCTP基因表达水平与对照组比较均无呈现显著性差异.研究结果表明,HSP70与CRT等基因的响应表达有望成为表征多环麝香土壤污染暴露水平及生态毒理效应的潜在生物标志物.     

吐纳麝香与镉联合暴露对赤子爱胜蚓体内谷胱甘肽与金属硫蛋白的影响

广泛应用于个人护理产品和香味添加剂中的吐纳麝香(6-乙酰基-1,1,2,4,4,7-六甲基四氢萘,AHTN)是一种新型污染物,重金属镉(Cd2+)是土壤中常见的污染物,两者在土壤生态系统中存在联合暴露的可能。实验以赤子爱胜蚓为受试生物,通过24h暴露滤纸染毒实验测试了AHTN单一,Cd2+单一,以及AHTN与Cd2+联合暴露条件下蚯蚓体内谷胱甘肽(GSH)和金属硫蛋白(MT)的变化趋势。结果显示:Cd2+单一暴露时,GSH与MT随Cd剂量增加有明显上升趋势;AHTN单一暴露时,随着AHTN剂量增加,GSH与MT同步呈现先增多后减少的趋势;联合暴露情况下,AHTN在高剂量下对MT与GSH同样产生了抑制作用,使Cd2+对MT的诱导未达到Cd2+单一染毒时的水平。     

抗氧化酶基因作为多环麝香污染分子标志物研究

为研究土壤中低剂量合成麝香暴露的分子毒理效应,以蚯蚓超氧化物歧化酶(SOD)和过氧化氢酶(CAT)基因为供试基因,建立mRNA表达水平的Sybr GreenⅠ荧光定量PCR检测方法;并且采用自然土壤染毒实验,检测了吐纳麝香(AHTN)或佳乐麝香(HHCB)胁迫诱导SOD、CAT mRNA的表达水平变化.序列同源性比较与熔解曲线分析表明设计的引物适合供试基因mRNA的检测.SOD与CAT基因构建的荧光定量标准曲线的线性关系分别为0.997和0.994,且PCR扩增效率均接近于100%,故可实现两基因mRNA表达的相对定量分析.土壤染毒暴露28 d后,丙二醛(MDA)含量水平显著升高,表明自由基诱导的细胞氧化损伤是AHTN或HHCB毒性效应的主要途径方式.SOD、CAT mRNA总体表现为上调表达趋势,且表达量与MDA含量呈显著正相关,表明抗氧化酶基因的诱导表达与氧化应激水平有关联.而且,SOD、CAT mRNA表达水平与AHTN或HHCB浓度存在正相关剂量-效应关系.综上表明,SOD与CAT基因可成为潜在的分子生物标志物,用于表征合成麝香污染暴露水平及其毒理效应.     

Transformation products and reaction kinetics of fragrances in advanced wastewater treatment with ozone

The reaction of the fragrance compounds 4,6,6,7,8,8-hexamethyl-1,3,4,7-tetrahydrocyclopenta[g]isochromene (HHCB), 1-(3,5,5,6,8,8-hexamethyl-6,7-dihydronaphthalen-2-yl)ethanone (AHTN), 1-tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene (musk xylene/MX), 1-(4-tert-butyl-2,6-dimethyl-3,5-dinitrophenyl)ethanone (musk ketone/MK), and 1-(2,3,8,8-tetramethyl-1,3,4,5,6,7-hexahydronaphthalen-2-yl)ethanone (OTNE) with ozone in tap water as well as waste water treatment plant (WWTP) effluents is described. Several transformation products are characterized by means of gas chromatography coupled to mass spectrometry. One transformation product (HHCB-Lactone) was confirmed by means of a true standard. Musk xylene and musk ketone do not react with ozone under the conditions used in this study. AHTN and HHCB reacted slowly to a multitude of transformation products, while OTNE reacted quickly to several stable transformation products. The reaction constants and half lives are used to predict removal efficiencies for full scale reactors.     

Occurrence and removal of selected polycyclic musks in two sewage treatment plants in Xi’an, China

Polycyclic musks are widely used for cosmetics and other personal care and household cleaning products. The occurrence and removal of two representative polycyclic musks, galaxolide (HHCB) and tonalide (AHTN) were investigated in three different processes of two sewage treatment plants (STPs) in Xi’an, China. The samples were preconcentrated by solid phase extraction procedure and analyzed using a gas chromatography mass spectrometry (GC/MS) by a modified procedure. The HHCB was in the range of 82.8 to 182.5 ng·L^-1 in the influents and 22.6 to 103.9 ng·L^-1 in the effluents. The AHTN ranged from 11.0 to 19.3 ng·L^-1 in the influents and 2.2 to 8.8 ng·L^-1 in the effluents. The removal efficiency of the two musks varied in the ranges of 43.1%–70.4% for HHCB and 54.2%–84.4% for AHTN. Concentrations of the two musks in aqueous phase of three processes slightly increased along the primary process, and significantly removed during the biologic treatment processes, revealing that the selected musks could be remarkably removed in varied activated sludge processes. Advanced processes of activated sludge did not show a significant superiority on selected musk removal compared to the conventional process. The selected musk removal mainly resulted from the adsorption function of activated sludge. There was no significant change of HHCB/AHTN ratios along the treatment flow, indicating that each sewage treatment structure had a similar removal efficiency for the two musks.