Comparative toxicity study of a novel non-ionic surfactant, vanillin ethoxylates, and nonylphenol ethoxylates in Chinese hamster ovary cells in vitro

Surfactants such as alkylphenol polyethoxylates (APEOs) and nonylphenol ethoxylates (NPEOs) are commonly used worldwide, but the majority of these compounds, together with their metabolites, have been reported to induce severe biological toxicity. Here, we evaluated for the first time the cytotoxicity, genotoxicity and mitochondrial damage in Chinese hamster ovary (CHO-K1) cells caused by a novel non-ionic surfactant, vanillin ethoxylates (VAEOs), an alternative to APEOs. In parallel, the same in vitro bioassays were conducted on NPEOs along with their metabolic byproducts 4-nonylphenol (4-NP) and vanillin. The results showed that the cytotoxic potency order was NPEOs?>?4-NP?>?VAEOs > vanillin using CCK-8 assays. Also, 4-NP showed potential direct DNA damage in SOS/umu tests, whereas NPEOs, VAEOs and vanillin showed no positive result with and without S9 addition. In addition, none of the test compounds showed obvious genotoxic effects with low olive tail moment value using comet assays. However, all test compounds were shown to cause mitochondrial impairment by increasing mitochondrial mass and decreasing mitochondrial membrane potential in a concentration-dependent manner. And further analysis of reactive oxygen species (ROS) and mitochondrial superoxide (MNSOD) measurement showed that mitochondrial impairment was induced by oxidative stress with intracellular ROS and MNSOD overproduction. It's worth noting that VAEOs and vanillin cause relative lower cytotoxic, genotoxic and mitochondrial damage effects than NPEOs and 4-NP, indicating that VAEOs have the potential to substitute NPEOs as suitable surfactants. Take together, this study elucidates the toxicity profiles of VAEOs and NPEOs relatively comprehensively, and further toxicity analyses are suggested in the population, community and ecosystem.     

污水处理厂污泥中几种典型酚类内分泌干扰物的调查

采用超声萃取-C18柱富集净化和柱前衍生气相色谱/质谱方法,检测了我国北方某市四个典型污水处理厂不同工艺段污泥中烷基酚和聚氧乙烯醚的几种典型中间降解产物以及双酚A等内分泌干扰物质.2003年,2004年和2006年三年的分析结果表明,所有的污泥样品中都检测到了壬基酚类物质的存在,总浓度范围为1.00-128.45 mg·kg-1之间,在活性污泥中以壬基酚单氧乙烯醚和壬基酚二氧乙烯醚为主,消化污泥和浓缩污泥中则以壬基酚为主.随着时间的推移,这类物质在城市污泥中有逐渐降低的趋势.辛基酚和双酚A都低于检出限.     

Endocrine disrupter nonylphenol and bisphenol A contamination in Okinawa and Ishigaki Islands, Japan--within coral reefs and adjacent river mouths

Certain chemicals possess the potential to modulate endocrine systems, and thereby interfere with reproduction and developmental processes in the wild. We analyzed endocrine disrupters nonylphenol (NP) and bisphenol A (BPA) levels at various sites in Okinawa and Ishigaki Islands, Japan. River-water samples showed undetectable to low concentrations of NP and BPA at most of the sites investigated. However, an appreciable amount of BPA was detected in sediments at one coral reef site. In addition, significant numbers of river sediment samples showed appreciable amounts of NP and BPA. Most of the sampling sites for this study are located within a distance of 1 km from the coral reefs, which are under influence of river-waters to a variable extent. Therefore, influence of endocrine disrupters may have already begun on adjacent coral reefs. Both endocrine disrupters were positively correlated with human population densities, but not with the contents of red soil generated by farm land reformation. Therefore, it is concluded that NP and BPA pollution is a consequence of human waste discharge, both domestic and industrial, and not by agricultural activities.     

膜-生物反应器和传统活性污泥法去除两种内分泌干扰物的对比研究

采用不主动排泥的运行模式,在相同污泥负荷条件下,对比研究了膜-生物反应器(MBR)与传统活性污泥反应器(CASR)对两种典型内分泌干扰物--双酚A(BPA)与壬基酚聚氧乙烯醚(NPnEO,n=1～4)的去除效果.结果表明,在BPA-污泥负荷与NPnEO-污泥负荷分别为0.046～10.2 g·kg-1·d-1与0.097-0.701 g·kg-1·d-1的范围内,MBR与CASR均能有效去除这2种内分泌干扰物.随着运行时间的延长,污泥对目标物质的去除能力逐渐加强;相比CASB,MBR对目标物质的去除更强且稳定.在获得相同的出水目标物质浓度条件下,MBR可以耐受更高的容积负荷.2种内分泌干扰物的投加对MBR和CASR的COD和NH4-N的去除均没有明显影响.     

二氧化钛复合纸板对壬基酚聚氧乙烯醚水溶液的光催化降解

制备了一系列无机物含量大于80%的植物纤维/吸附剂/二氧化钛复合纸板,考察了复合纸板对壬基酚聚氧乙稀醚(NP-10)水溶液的光催化降解性能.结果表明,二氧化钛复合纸板对NP-10具有优良光催化降解性能,紫外光照34h后浓度为50mg·mL-1的NP-10的降解率达80%以上,光照前后NP-10水溶液的化学需氧量(COD)的变化表明,光催化降解可导致NP-10矿化.活性炭对二氧化钛光催化降解有协同作用,其在无机粉体中的质量分数为15%时,复合纸板的光催化降解性能最好.过氧化氢可大幅提高复合纸板的光催化降解性能,其最佳浓度为20mg·mL-1.二氧化钛复合纸板在NP-10水溶液中的稳定性好,重复使用10次后其质量损失小于2%,光催化降解性能不变.     

壬基酚聚氧乙烯醚在印染废水处理工艺中的去除研究

为减少印染助剂壬基酚聚氧乙烯醚(nonylphenol ethoxylates,NPEO)及其降解产物壬基酚(nonylphenol,NP)随印染废水进入水体造成的不利环境影响,对2种常规印染废水处理净水工艺处理含NPEO的模拟印染废水效率开展了研究。研究发现,结合厌氧水解和曝气氧化的生物处理工艺能迅速地将废水中NPEO去除,去除率达到90%以上,但排水中残余一定含量的NP、短链NPEO和短链壬基酚聚氧乙烯醚酸酯(nonylphenol polyethoxycarboxylate,NPEC),在减少排水中NP、短链NPEO和短链NPEC浓度方面,接触氧化法比活性污泥法效果更好。排水中的NP和短链NPEO来自厌氧水解阶段长链NPEO的降解;减少排水中NP、短链NPEO需要减少厌氧水解阶段产生的短链NPEO。     

多种聚氧乙烯牛脂胺混合物MON 0818的水生环境危害评估：脉冲暴露后沉积物、温度和恢复能力的影响

我们对一种商业表面活性剂混合物(多种聚氧乙烯牛脂胺)MON 0818进行了一系列毒性测试：1. 测定底栖无脊椎动物和鱼类在沉积物存在的情况下受到的毒性;2.测定大型蚤(Daphnia magna)和4种初级生产者经过24 h的脉冲暴露之后的恢复能力;3.鉴定水体温度上升对于2种冷水鱼类所受到MON 0818毒性的潜在影响。在沉积物存在的情况下,5种生物中有3种在最高10 mg/L的浓度下短期(24 h)死亡率为零。其余2种物种的中位有效浓度则显著高于仅对水体进行测试的结果。15 ℃下北极红点鲑(Salvelinus alpinus)的半数有效浓度统计上低于10 ℃下。绿藻(Rhabdocelis subcapitata)和普通小球藻(Chlorella vulgaris)在经过24 h 1 mg/L的暴露后的恢复期中显示出生长延迟的状况,表明该暴露可能存在潜在影响。尽管如此,2个物种的最大绝对生长速率并未改变,表明其均可恢复。1.5 mg/L下的蝾螈共生藻(Oophila sp.)和100 mg/L下的浮萍(Lemna minor)经过24 h的暴露并未显示显著反应。24 h 5 mg/L暴露之后的恢复期中,大型蚤显示出潜在的死亡率。然而存活个体的生殖终端指标并未受到影响。结果表明在沉积物的存在下MON 0818的快速损耗可以减轻对于被暴露生物的效果,在不小于环境中可能出现的MON 0818浓度情况下,24 h暴露以后的生物的完全恢复是可能的。
精选自Jose L. Rodriguez-Gil, Ryan Prosser, Gregory Hanta, David Poirier, Linda Lissemore, Mark Hanson, Keith R. Solomon. Aquatic hazard assessment of MON 0818, a commercial mixture of alkylamine ethoxylates commonly used in glyphosate-containing herbicide formulations. Part 2: Roles of sediment, temperature, and capacity for recovery following a pulsed exposure. Environmental Toxicology and Chemistry: Volume 36, Issue 2, pages 512–521, July 2017. DOI: 10.1002/etc.3558
详情请见http://onlinelibrary.wiley.com/wol1/doi/10.1002/etc.3558/full
     

Anaerobic nonylphenol ethoxylate degradation coupled to nitrate reduction in a modified biodegradability batch test

The aim of this work was to elucidate the role of nitrate as a terminal electron acceptor on the biodegradation of NPEO. We have characterized the products of NPEO degradation by mixed microbial communities in anaerobic batch tests by means of HPLC, ¹H NMR and GC–MS. Anaerobic degradation of NPEO was strictly dependent on the presence of nitrate. Within seven days of anoxic incubation, NP2EO appeared as the major degradation product. After 21 days, NP was the main species detected, and was not degraded further even after 35 days. Nitrate concentration decreased in parallel with NPEO de-ethoxylation. A transient accumulation of nitrite was observed within the time period in which NP formation reached its maximum production. The observed generation of nonylphenol coupled to nitrate reduction suggests that the microbial consortium possessed an alternate pathway for the degradation of NPEO, which was not accessible under aerobic conditions.     

烷基酚聚氧乙烯醚类物质的环境雌激素效应

随着环境污染的加剧,环境污染物的雌激素效应成为当前科学研究的一个热点,烷基酚聚氧乙烯醚（APEs）类物质即为具有雌激素效应的环境污染物之一、APEs为一类非离子表面活性剂在工业生产和家庭洗涤中应用广泛,APEs类物质进入环境后可以降解为一些中间代谢物,这些中间代谢物具有环境持久性,很难在环境中进一步降解．研究人员通过3种活体外生物评估法研究发现APEs的中间代谢物具有雌激素活性,可以诱导水体中雄性鱼类等生物的雌性化,同时对哺乳动物和人类健康也具有潜在危害,因此进行更加深入研究,确定APEs类物质对人体的危害,限制APEs的使用已成为当务之急     

壬基酚聚氧乙烯醚降解前后的激素效应和诱变活性

采用重组基因酵母和SOS/Umu试验研究了壬基酚聚氧乙烯醚(NP₁₀EO)经生物降解前后的雌激素活性和致突变活性.结果表明,在降解反应开始后的4d内降解产物的雌激素活性较低且不具有致突变性.随着降解时间的不断增加,降解产物的雌激素活性和致突变性不断增强.降解20d后,降解产物的雌激素活性相当于1nmol 17-β雌二醇的61.6%,诱变比值大于2,表明壬基酚聚氧乙烯醚的生物降解产物同时具有雌激素活性和致突变活性,且两者在产生时间和活性数值方面均是同步的和成正相关的.因此致突变活性很可能是此类降解产物对生物机体具有雌激素活性的基础.