Castillo M, Martínez E, Ginebreda A, Tirapu L, Barceló D
Department of Environmental Chemistry, IIQAB-CSIC, Barcelona, Spain.
Analyst. 2000 Oct;125(10):1733-9. doi: 10.1039/b004071l.
Non-ionic polyethoxylated surfactants (nonylphenol polyethoxylates, alcohol polyethoxylates), their breakdown products (polyethylene glycol, polyethoxylated nonylphenol carboxylates and polyethoxylated alcohol carboxylates) and other compounds were identified and measured in various waste-water treatment samples (influent, effluent and sludge). A generic protocol involving the use of sequential solid-phase extraction (SSPE) with octadecylsilica and styrene-divinylbenzene cartridges in series and differential elution was used. Fractionated extracts were analyzed by liquid chromatography-mass spectrometry (LC-MS) using atmospheric pressure chemical ionization (APCI) in the positive and negative ionization modes. For sewage treatment plant (STP) sludge, the extraction protocol involved lyophilization of the sludge followed by sonication with MeOH-CH2Cl2 (7 + 3) and final clean-up using the SSPE protocol. Limits of detection for target analytes ranging from 1.1 to 4.1 micrograms L-1 for water samples and from 0.11 to 0.28 mg kg-1 for sludge were achieved. The results obtained demonstrated the inefficient removal of the target analytes in physico-chemical STPs whereas their elimination factors in STPs with biological treatment reached average values of 77, 92 and 98% for alcohol polyethoxylates, nonylphenol polyethoxylates (NPEOs) and polyethylene glycols (PEGs), respectively. Quantitative elimination of coconut fatty acid diethanolamide (CDEA) surfactants in the activated sludge process occurred. In contrast, total removal of NPEOs led to the formation of persistent and toxic metabolites such as nonylphenol which was present in treated effluent as well as in sludge samples with average concentrations ranging from 15.0 to 251.2 micrograms L-1 and from 13.5 to 74.2 mg kg-1, respectively. Polyethoxylated carboxylates and short chain NPEOs were also detected at similar levels in the effluents and sludges. In addition, a linear correlation between the total phenolic concentration (Total Ph) measured by the 4-aminoantipyrine method and the total concentration of nonylphenolic compounds (Total NP) measured by SSPE-LC-APCI-MS was observed.
在各种废水处理样品（进水、出水和污泥）中鉴定并测量了非离子聚乙氧基化表面活性剂（壬基酚聚乙氧基化物、醇聚乙氧基化物）、它们的分解产物（聚乙二醇、聚乙氧基化壬基酚羧酸盐和聚乙氧基化醇羧酸盐）以及其他化合物。使用了一种通用方案，该方案包括串联使用十八烷基硅胶和苯乙烯 - 二乙烯基苯柱进行连续固相萃取（SSPE）以及差异洗脱。分馏提取物通过液相色谱 - 质谱联用仪（LC - MS），采用大气压化学电离（APCI）在正离子和负离子模式下进行分析。对于污水处理厂（STP）污泥，提取方案包括污泥冻干，然后用甲醇 - 二氯甲烷（7 + 3）超声处理，最后使用SSPE方案进行净化。水样中目标分析物的检测限为1.1至4.1微克/升，污泥中为0.11至0.28毫克/千克。所得结果表明，在物理化学污水处理厂中目标分析物的去除效率低下，而在有生物处理的污水处理厂中，醇聚乙氧基化物、壬基酚聚乙氧基化物（NPEOs）和聚乙二醇（PEGs）的去除率分别达到77%、92%和98%的平均值。在活性污泥法中，椰子脂肪酸二乙醇酰胺（CDEA）表面活性剂被定量去除。相比之下，NPEOs的完全去除导致形成了持久性和有毒的代谢产物，如壬基酚，其在处理后的出水以及污泥样品中均有存在，平均浓度分别为15.0至251.2微克/升和13.5至74.2毫克/千克。聚乙氧基化羧酸盐和短链NPEOs在出水和污泥中的含量也处于相似水平。此外，观察到通过4 - 氨基安替比林法测量的总酚浓度（Total Ph）与通过SSPE - LC - APCI - MS测量的壬基酚类化合物总浓度（Total NP）之间存在线性相关性。
