Study of Distribution, Accumulation and Elimination of 5 Benzene Series in Mussels Using Gas Chromatography Tandem Mass Spectrometry
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摘要: 采用气相色谱三重四极杆质谱(GC-MS/MS)技术,研究了5种苯系物暴露后在贻贝各组织中的分布、蓄积和消除规律. 结果表明,贻贝不同组织中对5种苯系物的生物蓄积具有一定的差异,且分布呈组织特异性. 暴露试验结束后,贻贝各组织中5种苯系物分布及其含量变化趋势基本相同,消化腺和性腺中的苯系物含量增加比其他组织快,且消化腺和性腺中的峰值比其他4种组织中的峰值较高. 消化腺和性腺中的苯系物含量相对较高,有明显的吸收和富集作用. 足、鳃、闭壳肌和外套膜中5种苯系物的含量相对较低,约为消化腺中的20%左右. 消除阶段贻贝各组织中5种苯系物的含量符合一阶非线性衰减模型, 相关系数范围为0.9948~0.999 9. 暴露组净化1 d 后,贻贝对苯、甲苯、间二甲苯、对二甲苯和邻二甲苯的净化率范围分别为98.4%~99.2%、97.3%~98.8%、86.1%~95.8%、90.8%~97.0%和92.1%~96.6%. 净化5 d后,暴露组贻贝各组织中苯系物的含量虽趋于空白组水平,但仍有一定的残留.Abstract: The distribution, accumulation and elimination of 5 benzene series in mussel tissues were studied using the gas chromatography tandem mass spectrometry (GC-MS/MS). The results showed that there were some differences in the bioaccumulation of 5 benzene series in different tissues of mussel, and the distribution was tissue specific. At the end of the exposure experiment, the distribution and the trend of variation in content the five benzene series in the six tissues of mussels were basically the same. The content of benzene series in digestive glands and gonads increased faster than in other tissues, and the peaks values in the digestive gland and gonad were higher than those in the other four tissues. The contents of benzene series in the digestive gland and gonad were relatively higher, which had obvious absorption and enrichment effect. The contents of 5 benzene series in foot, gill, adductor and mantle were relatively lower, about 20% of that in the digestive gland. The contents of 5 benzene series in mussel tissues during elimination stage were consistent with the first-order nonlinear attenuation model, with correlation coefficients ranging from 0.994 8 to 0.999 9. The purification rates of benzene, toluene, m-xylene, p-xylene and o-xylene of mussels were 98.4%~99.2%, 97.3%~98.8%, 86.1%~95.8%, 90.8%~97.0% and 92.1%~96.6% respectively after 1 day of purification in the exposed group. After 5 days of purification, although the content of benzene series in the tissues of the exposed group tended to be at the level of blank group, but there were still some residues.
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Key words:
- GC-MS/MS /
- benzene series /
- mussel /
- distribution /
- accumulation /
- elimination
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表 1 5种苯系物的保留时间和MRM质谱参数
Table 1. Retention times and MRM mass parameters of 5 benzene series
化合物 保留时间/
min离子对/(m/z) 碰撞能
量/eV扫描
时间/ms苯 6.35 78.00>52.00* 15 30 77.00>51.00 12 30 甲苯 8.67 91.00>65.00* 12 30 92.00>65.00 27 30 对二甲苯 11.26 106.00>76.00 24 20 106.00>91.00* 12 20 间二甲苯 11.45 106.00>77.00* 30 20 106.00>91.00 18 20 邻二甲苯 12.73 106.00>63.00* 45 20 106.00>91.00 12 20 *:定量离子对 表 2 5种苯系物在贻贝各组织中拟合所得的消除速率常数(Kd)和半衰期(t1/2)
Table 2. Elimination rate constant (Kd) and half-life (t1/2) obtained by fitting 5 benzene series in mussel tissues
化合物 组织 t1/2 Kd 苯 足 0.14 4.92 闭壳肌 0.14 4.98 外套膜 0.15 4.52 腮 0.16 5.44 性腺 0.15 4.51 消化腺 0.16 4.45 甲苯 足 0.14 4.91 闭壳肌 0.15 4.74 外套膜 0.15 4.49 腮 0.13 5.34 性腺 0.17 3.98 消化腺 0.17 4.09 间二甲苯 足 0.18 3.82 闭壳肌 0.31 2.27 外套膜 0.31 2.27 腮 0.19 4.70 性腺 0.25 2.72 消化腺 0.21 3.27 对二甲苯 足 0.13 4.23 闭壳肌 0.26 2.71 外套膜 0.27 2.59 腮 0.22 4.19 性腺 0.26 2.66 消化腺 0.19 3.66 邻二甲苯 足 0.15 4.64 闭壳肌 0.17 4.18 外套膜 0.26 2.69 腮 0.18 4.83 性腺 0.22 3.22 消化腺 0.18 3.91 -
[1] ACGIH. 2014 TLVs and BElsthreshold limit&biologic exposure indices[S]. Printed in the United States. [2] 王聪, 董雪瑞, 谢磊, 等. 固相微萃取-气相色谱-质谱法测定地表水中10种痕量苯系物[J]. 理化检验-化学分册,2022,58(9):1017-1021WANG Cong, DONG Xuerui, XIE Lei, et al. Determination of 10 trace benzene series in surface water by gas chromatography-mass spectrometry with solid phase micro-extraction[J]. Physical Testing and Chemical Analysis (Part B:Chemical Analysis),2022,58 (9):1017-1021. [3] 陈国胜, 王少涵, 陈月媚, 等. 固相微萃取联用气相色谱-质谱法快速分析水中痕量苯系物[J]. 大学化学,2022,37(5):76-83CHEN Guosheng, WANG Shaohan, CHEN Yuemei, et al. Rapid analysis of trace BTEX in water by solid phase microextraction coupled with gas chromatography-mass spectrometry[J]. University Chemistry,2022,37 (5):76-83. [4] Cavalcante R M, de Andrade M V F, Marins R V, et al. Development of a headspace-gas chromatography (HS-GC-PID-FID) method for the determination of VOCs in environmental aqueous matrices: Optimization, verification and elimination of matrix effect and VOC distribution on the Fortaleza Coast, Brazil[J]. Microchemical Journal,2010,96 (2):337-343. doi: 10.1016/j.microc.2010.05.014 [5] 周秀锦, 杨会成, 邵宏宏, 等. HS-GC-MS/MS法检测海产品中的7种苯系物[J]. 分析试验室,2019,38(2):141-146 doi: 10.13595/j.cnki.issn1000-0720.2018.042401ZHOU Xiujin, YANG Huicheng, SHAO Honghong, et al. Determination of 7 benzene series in seafood by headspace GC-MS/MS[J]. Chinese Journal of Analysis Laboratory,2019,38 (2):141-146. doi: 10.13595/j.cnki.issn1000-0720.2018.042401 [6] 余颖. 吹扫捕集-气相色谱-三重四极杆串联质谱法测定水产品中苯系物残留[J]. 食品安全质量检测学报,2022,13(1):40-47 doi: 10.3969/j.issn.2095-0381.2022.1.spaqzljcjs202201006YU Ying. Determination of benzeneseries residues in aquatic products by purge-and-trap and gas chromatography-triple quadrupole mass spectrometry[J]. Journal of Food Safety & Quality,2022,13 (1):40-47. doi: 10.3969/j.issn.2095-0381.2022.1.spaqzljcjs202201006 [7] 林勇, 葛璇, 杜明月. 顶空-气相色谱质谱法测定土壤和沉积物中7种苯系物[C]//2020中国环境科学学会科学技术年会论文集(第三卷). 南京, 2020: 355-361. [8] Rocha A C S, Reis-Henriques M A, Galhano V, et al. Toxicity of seven priority hazardous and noxious substances (HNSs) to marine organisms: current status, knowledge gaps and recommendations for future research[J]. Science of the Total Environment,2016,542 :728-749. doi: 10.1016/j.scitotenv.2015.10.049 [9] Palma E, Espinoza Tofalos A, Daghio M, et al. Bioelectrochemical treatment of groundwater containing BTEX in a continuous-flow system: Substrate interactions, microbial community analysis, and impact of sulfate as a co-contaminant[J]. New Biotechnology,2019,53 :41-48. doi: 10.1016/j.nbt.2019.06.004 [10] 王摆, 贺凌, 高杉, 等. 6种苯系物对虾夷扇贝的生殖毒性作用[J]. 生态毒理学报,2014,9(6):1083-1090WANG Bai, HE Ling, GAO Shan, et al. The reproductive toxicities of six BTEXs to Japanese scallop(mizuhopectenyessoensis)[J]. Asian Journal of Ecotoxicology,2014,9 (6):1083-1090. [11] Neuparth T, Capela R, Pereira S P P, et al. Toxicity effects of hazardous and noxious substances (HNS) to marine organisms: acute and chronic toxicity of p-xylene to the amphipod gammaruslocusta[J]. Journal of Toxicology and Environmental Health, Part A,2014,77 (20):1210-1221. doi: 10.1080/15287394.2014.921867 [12] Duan W Y, Meng F P, Wang FF, et al. Environmental behavior and eco-toxicity of xylene in aquatic environments: a review[J]. Ecotoxicology and Environmental Safety,2017,145 :324-332. doi: 10.1016/j.ecoenv.2017.07.050 [13] 董颖, 王摆, 崔程, 等. 苯系物对仿刺参肠、呼吸树谷胱甘肽过氧化物酶基因表达的影响[J]. 水产科学,2015,34(5):311-315DONG Ying, WANG Bai, CUI Cheng, et al. Effects of BTEXs on expression of glutathione peroxidase gene in intestine and respiratory tree of sea cucumber apostichopusjaponicus[J]. Fisheries Science,2015,34 (5):311-315. [14] 潘泳嘉, 周遵春, 王摆, 等. 苯系物联合暴露仿刺参管足转录组差异表达基因分析[J]. 生态毒理学报,2016,11(6):82-92PAN Yongjia, ZHOU Zunchun, WANG Bai, et al. Analysis of differentially expressed genes in the tube feet of sea cucumber (apostichopusjaponicus) co-exposed to BTEXs by transcriptome sequencing[J]. Asian Journal of Ecotoxicology,2016,11 (6):82-92. [15] 陈昳, 邵卓, 桂峰, 等. 海水养殖业循环经济能值评价指标的构建应用[J]. 农村经济与科技,2019,30(21):69-71, 80 doi: 10.3969/j.issn.1007-7103.2019.21.029CHENYi, SHAO Zhuo, GUI Feng, et al. Construction and application of emergy evaluation index of circular economy in marine aquaculture[J]. Rural Economy and Science-Technology,2019,30 (21):69-71, 80. doi: 10.3969/j.issn.1007-7103.2019.21.029 [16] Beyer J, Green N W, Brooks S, et al. Blue mussels (Mytilusedulis spp ) as sentinel organisms in coastal pollution monitoring: a review[J]. Marine Environmental Research,2017,130 :338-365. doi: 10.1016/j.marenvres.2017.07.024 [17] Farrington J W, Tripp B W, Tanabe S, et al. Edward D Goldberg’s proposal of “the mussel watch”: reflections after 40years[J]. Marine Pollution Bulletin,2016,110 (1):501-510. doi: 10.1016/j.marpolbul.2016.05.074 [18] 吴金浩, 杜静, 张玉凤, 等. 不同环境条件下海水中苯系物的挥发过程研究[J]. 海洋环境科学,2018,37(5):699-704 doi: 10.12111/j.cnki.mes20180511WU Jinhao, DU Jing, ZHANG Yufeng, et al. Study on the volatilization process of benzene series in seawater under different environmental conditions[J]. Marine Environmental Science,2018,37 (5):699-704. doi: 10.12111/j.cnki.mes20180511 [19] 吴金浩, 杜静, 张玉凤, 等. 海水中苯系物的衰减及其微生物降解的贡献[J]. 海洋与湖沼,2018,49(6):1243-1250 doi: 10.11693/hyhz20180100015WU Jinhao, DU Jing, ZHANG Yufeng, et al. Attenuation of benzene series in seawater and the contribution of microbial degradation[J]. OceanologiaetLimnologiaSinica,2018,49 (6):1243-1250. doi: 10.11693/hyhz20180100015 [20] Han D Q, Ma W Y, Chen D Y. Determination of biodegradation products from benzene, toluene, ethylbenzene and xylenes in seawater by purge and trap gas chromatography[J]. Chinese Journal of Analytical Chemistry,2006,34 (10):1361-1365. doi: 10.1016/S1872-2040(07)60006-1 [21] Jing W X, Lang L, Lin Z G, et al. Cadmium bioaccumulation and elimination in tissues of the freshwater mussel Anodontawoodiana[J]. Chemosphere,2019,219 :321-327. doi: 10.1016/j.chemosphere.2018.12.033 [22] MarasingheWadige C P M, Taylor A M, Krikowa F, et al. Exposure of the freshwater bivalve Hyridellaaustralis to metal contaminated sediments in the field and laboratory microcosms: metal uptake and effects[J]. Ecotoxicology,2017,26 (3):415-434. doi: 10.1007/s10646-017-1774-7 [23] 崔文杰, 刘晓玉, 孙晓杰, 等. 全氟辛酸在紫贻贝体内的富集、分布与消除[J]. 中国环境科学,2020,40(9):4091-4098 doi: 10.3969/j.issn.1000-6923.2020.09.041CUI Wenjie, LIU Xiaoyu, SUN Xiaojie, et al. Accumulation, distribution and elimination of perfluorooctanoicacid (PFOA) in mussels (Mytilusgalloprpvincialis)[J]. China Environmental Science,2020,40 (9):4091-4098. doi: 10.3969/j.issn.1000-6923.2020.09.041 [24] Agency for Toxic Substances and Disease Registry. Toxicological profile for xylene[R]. U. S. Department of Health and Human Services Public Health Service Agency for Toxic Substances and Disease Registry, 2007. [25] Agency for Toxic Substances and Disease Registry. Toxicological profile for benzene[R]. U. S. Department of Health and Human Services Public Health Service Agency for Toxic Substances and Disease Registry, 2007. [26] Agency for Toxic Substances and Disease Registry. Toxicological profile for toluene[R]. U. S. Department of Health and Human Services Public Health Service Agency for Toxic Substances and Disease Registry, 2017. -