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合成麝香(synthetic musks,SMs)作为天然麝香的廉价替代品被应用于众多日化产品中,如香水与化妆品、洗漱用品、家用清洁剂和空气清新剂等[1]。其中,硝基麝香是早期使用的合成麝香,但因其显著的毒性效应而被逐渐限用/禁用[1],目前仅在一些低端日化产品中添加使用二甲苯麝香(1-tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene,MX)和酮麝香(4-tert-butyl-2,6-dimethyl-3,5- dinitroacetophenone,MK)[2]。多环麝香逐步替代硝基麝香成为目前香精香料市场中重要的香味物质,其中佳乐麝香(1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)2-benzopyrane,HHCB)和吐纳麝香(7-acetyl-1,1,3,4,4,6-hexamethyltetraline,AHTN)是其中两种最为常用的多环麝香。据统计,上述4种化合物占据了全球合成麝香总生产量95%以上[3]。毒理研究显示,HHCB和AHTN具有不同的毒性效应,如内分泌干扰活性、遗传毒性、氧化损伤等,被认为是“披着羊皮的狼”[3-4]。一般而言,合成麝香主要经由下水道或者城市污水处理系统直接/间接进入自然水体[5-6],通过饮水直接或以食物链传递方式间接进入人体[7],对人体健康造成潜在影响。合成麝香并非持久性化合物,但由于持续排放进入环境而显现出“伪持久性”,同时具有各种潜在的毒性和生物蓄积性[2-4, 7]。合成麝香被认定为“新污染物”吸引了众多研究人员和公众的关注。针对不同环境介质开展了大量研究 [8-11],发现合成麝香在不同环境介质中广泛分布,是地表河流和湖泊中的高频检出污染物,其污染已经扩散至偏远的海域和极地地区。Li等[11]详细评述了水体环境中合成麝香分布、来源和毒性。
沱江起源于四川西北九顶山南麓,流至金堂县后与青白江、湔江及石亭江合流成为沱江干流。沱江干流流经德阳、成都、简阳、资阳、内江、自贡,经泸州汇入长江[12],是长江上游的重要支流。沱江流域是四川省人口密集区域,沿线城市工农业发达,沉积物中氮[13]、磷[14]污染严重,已经成为上覆水层氮磷污染的重要来源,部分水体水质已经低于劣V类[15]。上游河段工矿企业较为集中,重金属染污显著[16]。沱江水系同时又是沿线城市工农业用水以及居民饮用水水源,水质安全对于沿岸居民生产生活至关重要。但是,过去关于沱江水体的研究较少,且多集中于常规水质监测,甚少关于有机污染物的报道 [12,17]。居民日常生活对沱江水体水质是否有影响,影响如何,目前尚少见公开报道。
本研究拟以合成麝香作为目标污染物,研究合成麝香在沱江沉积物的污染水平、分布特征;以HHCB和AHTN作为生活污水排放的标志物,初步评估生活污水排放对沱江流域水体的影响;进而初步评估沉积物中合成麝香分布对生态系统的潜在影响。研究结果可望为沱江流域水质安全和风险管控提供基础数据。
沱江流域沉积物中合成麝香的分布特征及其潜在生态风险评估
Occurrence and distribution of synthetic musks in sediments from Tuojiang and their potential ecological risk
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摘要: 沱江是四川省内重要水系,也是长江上游重要支流。沱江既是流域内纳污河流,也是工农业生产用水和居民饮用水水源。本文在沱江流域采集表层沉积物样品46个,研究了9种合成麝香的污染水平和分布特征。在所有沉积物中均检出佳乐麝香(HHCB)和吐纳麝香(AHTN),浓度范围分别为0.736—25.0 ng·g−1(中值为3.68 ng·g−1)和0.320—24.4 ng·g−1(中值为1.55 ng·g−1),研究结果揭示出生活污水排放对沱江沉积物的影响。Pearson相关性分析表明HHCB与AHTN有显著正相关(r=0.894,P
<0.01),说明它们具有相似来源和环境地球化学行为。沉积物中AHTN和HHCB实测浓度远低于各化合物对应的预测无效应浓度,风险熵值远小于1,表明其生态风险有限。 Abstract: Tuojiang, one of the important tributaries of Yangtze River, drains across Sichuan Province receiving a large amount of wastewater, and acts as important source water for drinking water as well as industrial and agriculture production. In the present study, 46 surface sediment samples were collected, then the concentrations and spatial distributions of 9 synthetic musks were investigated. The results indicated that HHCB and AHTN were found as main components in all samples, with concentrations in the range of 0.736—25.0 ng·g−1 (median value of 3.68 ng·g−1) and 0.320—24.4 ng·g−1 (median value of 1.55 ng·g−1), respectively. The Pearson correlation analysis showed that there was a significant positive correlation between HHCB and AHTN (r = 0.894, P<0.01), indicating their similar emission sources and environmental geochemical behavior. The calculated RQs values, based on the measured concentrations of AHTN and HHCB, were far lower than 1, and suggested their limited ecological risk to aquatic organisms in the Tuojiang. -
Key words:
- Tuojiang /
- sediments /
- synthetic musk /
- ecological risk
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表 1 沱江流域沉积物合成麝香含量及分布
Table 1. Concentrations and distribution of synthetic musks in sediment from Tuojiang
采样地
Location数量
n合成麝香(SMs)/(ng·g−1) HHCB AHTN ∑SMs 绵远河段
Mianyuan2 中值
范围5.83
0.736—10.92.20
0.320—4.098.04
1.05—15.0金堂段
Jintang4 中值 2.24 1.59 3.81 范围 1.16—5.89 0.876—2.37 2.98—7.36 简阳段
Jianyang5 中值 3.16 1.05 4.21 范围 1.42—13.6 0.427—3.91 1.85—17.5 资阳段
Ziyang7 中值 5.33 1.45 6.78 范围 2.18—17.9 0.743—13.4 2.97—31.3 内江段
Neijiang14 中值 4.24 1.53 5.48 范围 1.44—11.8 0.681—9.66 2.12—21.5 富顺段
Fushun7 中值 3.48 1.69 4.74 范围 1.23—25.0 0.524—24.4 1.76—49.4 自贡段
Zigong7 中值 5.36 2.31 7.67 范围 2.22—6.75 1.28—6.09 3.51—12.8 表 2 国内外河流沉积物样品中合成麝香含量与分布(ng·g−1)
Table 2. Concentrations and distribution of synthetic musks in river sediment worldwide (ng·g−1)
数量
n参考文献
referencesDPMI ADBI AHMI MA ATII HHCB MX AHTN MK 太湖入湖口
river mouths of Taihu Lake7 ND <LOD <LOD ND ND 0.0792—1.17 ND 0.123—1.29 ND [18] 黄埔江
Huangpu River74 — — — — — ND—61.7 ND—7.48 ND—2.78 ND—23.4 [22] 松花江
Songhua River9 — 0—2.77 0—2.92 — — 0—17.46 ND 0—5.73 0—3.26 [21] 浑河
Hun River40 — ND—0.643 ND—LOD — — 0.117—245 — 0.098—213 — [25] 北运河
North Canal River42 — — — — — 4.1—818 — 1.21-731 — [26] 巢湖及其支流
Chaohu60 <1.27—13.9 < 1.36 < 0.96 — — < 1.66—65.8 — 1.27—56.4 < 0.94—7.88 [23] 珠江水源地
source water in the
Pearl Delta15 ND ND—6.41 ND—1.34 ND—23.1 ND LOD—547 LOD—1.01 4.31—439 LOD—0.808 [19] 黄河三角洲
Yellow River Delta Wetland24 — ND ND — ND 1.42—8.60 LOD—ND LOD—3.63 LOD—ND [20] 本研究
This research46 ND <LOD ND ND ND 0.736—25.0 ND 0.320—24.4 ND 新西兰
new Zealand8 — — — — — <0.001—0.018 — — — [27] 突尼斯
Bizerte Lagoon, Tunisia13 — <LOD <LOD — <LOD 1.09—2.8 <LOD 0.30—1.7 <LOD [28] 西班牙
Spain7 — — — — — ND—7.22 — ND—0.92 — [29] -
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