我要做纺织品检测，测博士是按美标还是国标还是企标来做呢？_百度知道
我要做纺织品检测，测博士是按美标还是国标还是企标来做呢？
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这个主要是和用途有关 如果是出口美国的话是用美标 平常一般国标就可以了
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测 博 士 可以做袜子抗菌检测吗 要给工商局备案用的
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是属于纺织品抗菌的测试范畴，是纺织抗菌：确定检测类型。在我国，要选择正规抗菌检测公司，抗菌检测是非常严肃的测试项目，只有少数的权威的国家国际认可的实验室和检测机构才能检测，同时出具的抗菌检测报告才有信服力袜子的抗菌性能检测。一般做抗菌检测，您要做这几步、欧标还是美标，不同的测试标准，对应不同的销售范围；确定检测公司；确定抗菌标准，国标、塑料抗菌、还是涂料漆膜抗菌
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TrendsTrends in Analytical Chemistry, Vol. 28, No. 10, 2009Determination of alkylphenol ethoxylates and their degradation products in liquid and solid samples? T. Vega Morales, M.E. Torres Padron, Z. Sosa Ferrera, J.J. Santana Rodr?guez ?Alkylphenol polyethoxylates (APEOs) are a group of non-ionic surfactants used extensively in industrial, agricultural and domestic applications. Their metabolites, generated by the biotransformation of APEOs in wastewater-treatment plants and natural water bodies, are more toxic and more persistent than the parent compounds, can mimic natural hormones and disrupt endocrine functions by interacting with estrogen receptors. Since the discovery of the adverse effects of these pollutants on wildlife and human health, analytical methods have been developed to determine them in environmental matrices. This article is an overview of the current methods employed in trace analysis of APEOs and their degradation products. We compare the analytical techniques used and we discuss potential advantages and disadvantages of the major detection and quanti?cation techniques that have been coupled to liquid chromatography for the analysis of mixtures of APEOs in the past decade. ? 2009 Elsevier Ltd. All rights reserved.Keywords: Alkylphenol ethoxylate (APEO); Degradation product (DP); Ethoxy unit (EO); Liquid chromatography (LC); Mass spectrometry (MS); Nonylphenol (NP); Nonylphenol ethoxylate (NPEO); Octylphenol (OP); Octylphenol ethoxylate (OPEO); Sample preparation1. IntroductionT. Vega Morales, ? M.E. Torres Padron, Z. Sosa Ferrera, ? J.J. Santana Rodr?guez* Department of Chemistry, Faculty of Marine Sciences, University of Las Palmas de Gran Canaria, 35017 Las Palmas de Gran Canaria, Spain*Corresponding author. Tel.: +34 928 452 915; Fax: +34 928 452 922; E-mail: jsantana@dqui.ulpgc.esAlkylphenol polyethoxylates (APEOs) are a class of non-ionic surfactants that are used extensively as detergents, emulsi?ers, wetting agents, and dispersing agents in industrial, agricultural and household applications. These compounds can be used in cleaning products, personal-care products, plastics, paints, textiles, resins, preservative coatings, pulp and paper, petroleum re?ning, pesticides and metal processing [1,2]. The two main kinds of APEOs are nonylphenol ethoxylates (NPEOs) and octylphenol ethoxylates (OPEOs), which represent approximately 80% and 20% of total APEO production, respectively [3]. It is estimated that $60C65% of the total production of these compounds is incorporated into the aquatic environment [4], primarily through industrial and municipal wastewater discharges. The fate of APEOs in different environmental compartments (surface water, groundwater, sediment, soil and air) is controlled predominantly by their physicochemical properties that, in turn, in?u-ence their degradation. It is known that APEOs break down in wastewater-treatment plants (WWTPs), mainly during biological treatment, with a subsequent loss of ethoxy (EO) units [4,5]. This biotransformation leads to the formation of sub-products more toxic, more lipophilic, more estrogenic and more persistent than the parent substances [6,7]. The products formed in aerobic conditions included mono-, di-, and tri-ethoxylated NP and OP (NP1C3EO and OP1C3EO), and more polar short-chain and long-chain AP ethoxycarboxylate (APEC) and carboxylated AP ether carboxylate (CAPEC) derivatives [8,9]. However, the APs used as raw material in the synthesis of ethoxylated compounds, NP and OP, are formed only in anaerobic conditions [10]. Moreover, both APEOs, like their (bio)degradation products (DPs), are susceptible to be transformed into halogenated derivatives during chlorine disinfection in the presence of bromide ions [11]. These breakdown processes are also observed in natural water bodies [12,13]. In the past 20 years, several publications have reported that this class of1186/$ - see front matter ? 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.trac.Trends in Analytical Chemistry, Vol. 28, No. 10, 2009Trendscompounds presents bioaccumulation in aquatic organism [14] and chronic toxicity [15], and can mimic natural hormones and disrupt endocrine functions by interacting with estrogen receptors [10,16,17]. The widespread use of APEOs, coupled with the characteristics listed above, have led to the incorporation of NP and OP in the list of 33 priority hazardous compounds of the European Union (EU) Water Framework Directive (WFD) [18,19]. Furthermore, European Directive 2003/53/EC [20] has also established restrictions on the use, production and marketing of these compounds. The total production of APEOs in the Western Europe has therefore considerably reduced in the past few years [21]. Despite this, ‘‘high’’ concentrations of EO compounds and derivatives are still found in environmental samples, especially in areas affected by wastewater discharges. Great public concern about the effects of APEOs and their metabolites on wildlife and human health, and about their environmental fate, has led to the development of different analytical methods for the determination of these substances in different matrices. Traditional methods of analysis are based on gas chromatography coupled to mass spectrometry (GC-MS), which is limited to NP, OP, and AP1C3EO, unless a derivatization step is included in the analytical procedure, which allows the determination of long-chain APEO compounds [22,23]. Nevertheless, the conversion of surfactants into volatile derivatives presents some disadvantages (e.g., more time for analysis) and, consequently, greater error [22]. To solve the problems presented by GC for the analysis of APEOs and their DPs, high-performance liquid chromatography (HPLC) methods have been employed with different detection systems, mainly spectrometric [24C27]. We review the last analytical methods for the analysis of APEOs and their DPs. We discuss and compare advanced extraction and clean-up techniques, and separation and quanti?cation systems [e.g., LC with ?uorescence detection (LC-FD), LC-MS and especially LC with tandem MS (LC-MS2)] for solid and liquid samples.2. Sample-preparation methods The reliability of results obtained in the analysis of environmental samples is closely linked to sampling and storage procedures. In order to prevent the loss of analytes by abiotic reactions (e.g., hydrolysis) and biological degradation [28], several authors have used procedures to improve the stability of the analytes in complex environmental matrices and to ensure the integrity of the sample. Often, formaldehyde [29] and formalin (1% w/w of 37% solution of formaldehyde in water) [28] have been used to prevent biological degradation of APEOs, preserving the sample by freezing or by storage at 4°C. For volatile organic compounds, the US Envi-ronmental Protection Agency (EPA) recommends acidi?cation of the sample to pH &3, which is the most common procedure for conserving APEOs. To a lesser extent, chemical preservatives (e.g., mercury (II) chloride [30], sul?te and bisul?te [28]) have also been used, but have obtained worse results for long periods of storage. Some publications have reported on the stability of these compounds in solid-phase extraction (SPE) cartridges used to solve the problems of transporting, handling, and storing large volumes of sample after the ? extraction step. Petrovic and Barcelo [28] studied the stability of a mixture of NPEOs, with an average of 6 EO units, in C18 SPE cartridges under different storage conditions and in different water matrices. For wastewater analysis, they obtained complete recovery at ?20°C for a period of 60 days. In the same way, Loyo-Rosales and co-workers [31] studied the stability of APs and APEOs with a range of 1C5 EO units in deionized water matrices. In this case, they employed hydroxylated poly(styrene-divinylbenzene) (PSDB) co-polymer SPE cartridges, ?nding recoveries of 63C116% for APEOs with less than 4 EO units after 1 year of storage at ?20°C. The results of both works [28,31] were in good agreement, and clearly demonstrated that the use of SPE cartridges is more effective method for stabilizing AP and APEOs than the simple storage using conventional procedures and under conventional conditions [31]. To preserve the target analytes in solid matrices, it is recommended to remove water from the solid matrix and to store the samples dry [32]. The more common and reliable procedure for dry solid samples is freeze drying [33C36]. However, in some studies, water is removed by air drying, despite the possible loss of more volatile compounds (e.g., APs). Subsequently, samples are homogenized, sieved and then stored at ?4°C to ?20°C or, less frequently, at room temperature while maintaining the sample in a desiccator [33]. When solid samples are collected as particulate matter, centrifugation is a common procedure before the drying step [11,37]. Nevertheless, some authors often choose to ?lter the samples using conventional glass-?ber ?lters (GF/Fs) and then stored them at ?20°C, extracting the compounds directly from the GF/Fs [38]. 2.1. Liquid matrices Since these organic compounds appear in the environment at trace and even ultra-trace levels, besides having systems of detection and quanti?cation suf?ciently sensitive and selective, it is necessary to use multi-step sample-pretreatment techniques with the major objective of eliminating potential matrix interferences to isolate the target compounds and ?nally to enrich the sample extracts. This type of procedure signi?cantly improves the overall sensitivity of the analytical method.http://www.elsevier.com/locate/trac1187TrendsTrends in Analytical Chemistry, Vol. 28, No. 10, 2009Initially, the conventional analytical methods used to extract AP compounds from liquid samples were based on liquid-liquid extraction (LLE), followed by GC or LC and determination with different detection methods. Despite the LLE technique offering ef?cient and precise results, it is relatively time consuming, harmful, due to the use of large volumes of organic solvents that are frequently toxic, and very expensive. Although this technique is still in use in a few cases [39], there is an increasing tendency to replace LLE by SPE for liquid samples. Developed in the 1980s, SPE has emerged as a powerful tool for chemical isolation and puri?cation. This method is an alternative to LLE because it reduces consumption of organic solvents and analysis time, and because it can be automated [40]. SPE has been developed in the off-line and on-line modes, although the on-line approach is preferred due to its advantages (e.g., greater sensitivity and fewer requirements for manipulation of samples). Several kinds of sorbents present in cartridges, columns and syringes have been employed successfully for the extraction or preconcentration of AP compounds. Basically, all the sorbents employed in SPE of APEOs can be conceived as modi?cations of three basic types of sorbents: silicabased, polymer-based (essentially PSDB) and carbonbased. Non-polar reversed-phase (RP) sorbents with a silica base were the ?rst used in SPE of AP compounds from water samples. Among these sorbents (C2, C8 and C18), C18 was the most accepted. Retention of APEOs by C18 cartridges is mainly due to non-polar Van der Waals interactions between the analytes and the sorbent. Despite evidence that C18 sorbents present good recoveries for a wide range of APEO oligomers [41], they also show low breakthrough volumes for high oligomers, described as hydrophilic or ‘‘water-soluble’’ [42], and usually poor recoveries for NP and OP. Jonkers et al. [9] reported recoveries of 69% and 95% for NP and NP10EO respectively, but only by passing a sample volume of 100 ml through the cartridges. In the same way, Koh and coworkers [43] obtained similar recoveries (62C98% for APs, APEOs and APECs) for 250 mL of settled sewage samples. Subsequently, new highly cross-linked PSDB packing materials [e.g., Isolute ENV (International Sorbent Technology Ltd., Hengoed, UK) or LIChrolut EN (Merck, Darmstadt, Germany)] have obtained similar recoveries to those of C18 silica-based materials [31,38]. Nevertheless, these hydrophobic polymeric sorbents are the most suitable, due to their broad range of physicochemical characteristics and their greater chemical stability [44]. The retention mechanism in these cases is based on not only non-polar Van der Waals interactions, but also p-p interactions between the analytes and the aromatic rings that make up the sorbent structure. These hyper-cross-linked polymeric sorbents have a 1188http://www.elsevier.com/locate/tracspeci?c surface area up to 800 m2/g, which allows more p-p interactions than traditional polymeric macroporous PS-DVB sorbents [44]. Overall, this means that the breakthrough volumes will be greater than those obtained when C18 sorbents are used. Loyo-Rosales et al. developed an off-line SPE procedure to extract APs, short-chain APEOs (AP1C5EO) [31] and long-chain APEOs (AP6C16EO) [38] in water using Isolute ENV cartridges. Recoveries for the APs and shortchain APEOs were above 81% for all analytes, with variations in response in the range 1C14% (RSD). Although long-chain APEOs were extracted using the same protocol, the recoveries for this fraction were highly conditioned by the hydrophobic nature of the packing material. Thus, the greater the number of EO units, the smaller the recovery in the range 71C21% for NP6EOC NP16EO. Although recoveries obtained for long-chain APEOs were inef?cient, Loyo-Rosales et al. achieved a rapid extraction of up to 4 L of sample, in contrast to the few hundred mL of sample that octadecyl-silica sorbents allowed to pass through the cartridges. To solve the lack of retention of the most polar compounds, other hydrophilic polymeric sorbents have already been studied in order to obtain better recoveries of the ‘‘water soluble’’ (EO & 5 units) fraction of APEO oligomers and acidic metabolites. Loos et al. [45] employed Oasis HLB cartridges (Waters, Milford, MA, USA) for the clean up and extraction of APs, their ethoxylates and their more polar carboxylates from textile-industry WWTP ef?uent and surface waters. This packing material is a hydrophilic macroporous poly(N-vinylpyrrolidone-divinylbenzene) (PVP-DVB) copolymer and has a speci?c surface area of $800 m2/g. Recoveries obtained in this study were in the range 50C90%. Results close to 50% corresponded to more hydrophobic compounds (NP and OP), while the better recoveries corresponded to high oligomers and carboxylated derivatives. Jahnke et al. [46] also employed Oasis HLB cartridges in the extraction of APs, AP1C2EO and more polar alkylphenoxy acetic-acid derivatives (AP1EC). They reported good recoveries for carboxylated compounds (110% and 99% for NP1EC and OP1EC, respectively), but the results shown for hydrophobic species are clearly lower, especially for NP and their ethoxylates (recoveries were &70%). Both OP and OP1C2EO presented higher recoveries (close to 80%) than their nonyl isomers, indicating the predominant in?uence of hydrophobic chain length in the extraction [7]. The fact that NP was not adequately recovered from Oasis HLB cartridges constituted a important disadvantage of these methods, due to the great relevance of NP for the control of potential endocrine disrupters (EDs), but the high recoveries that this sorbent shows for more polar analytes offer new perspectives [e.g., their use in sequential SPE (SSPE)] [47] to cover a broad range of EO compounds. SSPE has been employed successfully usingTrends in Analytical Chemistry, Vol. 28, No. 10, 2009Trendsdifferent sorbents (two cartridges of different SPE material coupled in series) [48] or selective elution employing solvents of different desorption potential and polarity [49,50]. Graphitized carbon black (GCB) is the third kind of sorbent usually employed in SPE of APEO species. Carbon is a non-porous sorbent, so cartridges ?lled with this material have a high resistance to the water ?ow, so the extraction is usually slower than that obtained using the sorbents described above. Another drawback of this kind of sorbent is that DVB polymers would allow a more selective extraction than GCB [38]. This means that the sample extract would contain more interfering compounds that would therefore affect the posterior quanti?cation (e.g., matrix suppression effects in MS). Nevertheless, several procedures used for sample extraction of NPEOs employing GCB have reported [23,29,40] good recoveries, especially for high ethoxylated compounds and even passing volumes up to 1 L through the cartridges. Although most analytical approaches to the determination of APEOs and their DPs include SPE, conventional LLE and even steam distillation or solvent sublation [24], solid-phase microextraction (SPME) has gained importance in recent years, especially in extraction and enrichment of APs, short-chain APEOs (1C3 EO units) and their acidic metabolites followed by GC determination. It has been reported that SPME procedures without derivatization have been used to determine APs in water samples [51]. However, derivatization of APs (methylation, acetylation or silylation) is preferred due to some advantages (e.g., improving the quality and the sensitivity of GC analysis) [52]. Several kinds of ?ber have therefore been tested for extracting these substances. Among commerciallyavailable SPME ?bers, polyacrylate (PA) and polydimethylsiloxane-divinylbenzene (PDMS-DVB) have usually been recommended for the extraction of polar compounds, while PDMS ?bers were recommended for enrichment of non-polar compounds [53,54]. For the relatively large partition coef?cients of NP and NP1C3EO in the octanol/water system (log Kow values of 4.48 and 3.90, respectively) [55], the maximum extraction yields would be expected to be obtainable using PDMS ?bers. Braun et al. [56] examined these three kinds of ?ber for the determination of technical NP (t-NP), obtaining the best sensitivity with the 100-lm PDMS ?ber. However, APs also exhibit good enrichment behavior on PA and PDMS-DVB ?bers [56]. For the simultaneous determination of NP, NP1C2EO and their brominated derivatives, D?az et al. [57] devel? oped and applied a SPME-GC-MS procedure using DVBCarboxen-PDMS (DVB-CAR-PDMS) ?ber. By comparing the results with those obtained by SPE (C18 cartridge), they reported that both results were in good agreement, but the SPME procedure showed some advantages [e.g.,lower limits of detection (LODs), shorter analysis time and avoiding use of organic solvents]. Several procedures based on SPME-GC-MS for the determination of these ED substances have been published. Nevertheless, there are only a few relating to SPME of non-ionic surfactants by HPLC determination. Mitani et al. [58] developed an in-tube SPME-HPLC-UV method for determination of EDs (including NP and OP) in liquid medicines and intravenous solutions. Recoveries of these compounds spiked to the intravenous injection solutions were over 80%. Boyd-Boland and Pawliszyn reported another SPME-HPLC-UV method for the determination of NPEOs using a Carbowax-template resin [59]. Among all the methods reviewed based on SPME-HPLC, we have not found any work that employs MS detection, despite the clear advantages that this separation technique shows (described below). 2.2. Solid matrices As discussed above, APEO-breakdown processes in WWTPs or in the environment leads to the formation of more persistent, more toxic and more estrogenic metabolites [essentially APs and shorter-chain oligomers (Fig. 1)]. These (bio)DPs have high log Kow values, in the range 3.90C4.48 [7,55], with NP having the highest log Kow. They also show low solubilities in water, due to the small number of polar groups forming the hydrophilic part of the molecules [42]. Organic carbon-sorption constants (Koc) have high values for these metabolites. Ferguson et al. [60] reported Koc for NP of 245 L/kg, while NP1C4EOs have Koc in the range 74C288 L/kg. Koc for OP was 151 L/kg, indicating the in?uence of the hydrophobic chain length (alkyl group) on the constant. These physico-chemical pro?les suggest that these DPs have a strong af?nity to aquatic particles and organic matter, due to their highly lipophilic nature and lower water solubilities. They therefore tend to bind tightly to sediments [42] and bioaccumulate in the aquatic organism [14]. These factors contribute to the persistence of these compounds in the environment, and, most importantly, allow the entry of these xenobiotics into foods of animal origin, which are thought to represent one of the major sources of human exposure to many organic pollutants. Classical approaches to the extraction of AP compounds in solid matrices are mainly based on Soxhlet extraction and steam distillation, which were employed almost exclusively in the 1980s and 1990s. Methanol, acetonitrile, dichloromethane, n-hexane or mixtures of hexane/acetone, dichloromethane/hexane, or hexane/ i-propanol were typical solvents in Soxhlet extraction [32]. Despite this technique offering high percentages of recovery for a broad range of oligomers (depending on appropriate selection of the solvent) [35], Soxhlethttp://www.elsevier.com/locate/trac1189TrendsTrends in Analytical Chemistry, Vol. 28, No. 10, 2009Figure 1. Breakdown processes of long-chain alkylphenol polyethoxylates (APEOs) under aerobic and anaerobic conditions, and the formation of their halogenated derivatives.1190http://www.elsevier.com/locate/tracTrends in Analytical Chemistry, Vol. 28, No. 10, 2009Trendsextraction makes the analysis procedure excessively time consuming (up to 48 h) and, moreover, requires large amounts of hazardous organic solvents (50C300 mL) [32]. However, Soxhlet is still used to a lesser extent fundamentally for the extraction of APs and APEOs adsorbed into particulate matter (separated from the water matrix by simple ?ltration techniques) [38] and for comparing the results obtained by more versatile extraction systems [38,61]. During the past decade, a lot of extraction techniques have been developed to isolate these analytes in solid samples, to reduce the organic solvent consumption and to increase the speed of the process. Ultrasonic extraction has been presented by the scienti?c community as an attractive alternative to the conventional extraction systems. Although sonication is faster than Soxhlet extraction, it also requires relative large volumes of toxic and expensive organic solvents (30C60 mL). The solvents used most for the extraction of APEOs employing ultrasonic irradiation are acetone, hexane, dichloromethane and mixtures of them in different proportions [32]. Aparicio et al. [62] recently employed this approach to extract NP and NP1C2EO oligomers in sludge from WWTP samples. They used hexane as extraction solvent, with a global extraction time of 70 min for each sample. Fountoulakis et al. [63] showed much lower recoveries for the same analytes using a mixture of dichloromethane/methanol (30:70) as solvent. However, they took only 20 min for sonication and no further procedures to enhance the extraction ef?ciencies. Some modi?cations of this extraction technique have been reported. Ferguson et al. [41] employed a novel continuous?ow, high-temperature sonication system to isolate short-chain-APEO metabolites from sediment samples. Similarly, Nunez et al. [64] developed a sonication? assisted extraction in small columns (SAESC) procedure to isolate NP and NPEOs in environmental solid samples. They used a mixture of water/methanol (70:30) in order to obtain better recoveries for more hydrophilic metabolites. They reported excellent recoveries for all compounds, in the range of 91% for long-chain NPEOs to 108% for NP. Pressurized liquid extraction (PLE), also known as pressurized ?uid extraction (PFE) or accelerated solvent extraction (ASE), is, by far, the main extraction technique for these compounds in solid matrices. PLE offers a great reduction in solvent consumption (15C30 mL), and provides faster sample processing and a high level of automation [35,37]. This technique also offers the advantage that only two variables need to be optimized C extraction time and temperature C since the solvents chosen for PLE can be the same as those used in Soxhlet extraction [37] or sonication extraction [32]. High temperature and high pressure help to increase the dif-fusion rates, solubility and mass transfer and to maintain the solvent in the liquid state. Moreover, PLE provides cleaner extracts than Soxhlet and ultrasonic extraction, reducing the background noise in the subsequent determination, which is especially important in LC-MS analysis due to ion-suppression effects. PLE therefore provides rapid, ef?cient extraction for a wide range of APEO oligomers, even in complex matrices {e.g., sludge, soil [34,65,66] and biological tissues [67] (see Table 2)}. The high initial cost is the main drawback of thes however, the large savings in solvent consumption and extraction time could depreciate that cost rapidly. In the past decade, microwave energy has been investigated and widely applied in analytical chemistry to accelerate sample digestion, and to extract analytes from different matrices and in chemical reactions. Microwave-assisted extraction (MAE) is an ef?cient extraction technique for solid samples. MAE is applicable to thermally stable compounds. Since its development, MAE has became a viable alternative to conventional methods due to it having had many substantial improvements over other sample-preparation techniques (e.g., shorter extraction time, smaller amounts of solvent and multiple samples analyzed at the same time) [68]. Temperature, extraction time and power, solvent volume and concentration of different solvent mixtures are the most common parameters to optimize. The number of papers reporting the use of MAE has therefore increased considerably [68]. Croce et al. [69] compared MAE versus PLE for the isolation of NP and NPEOs from river sediments. They concluded that MAE has an important disadvantage compared to PLE extraction C the need for sample centrifugation and ?ltration C which can have critical effects on analytical accuracy. However, this drawback can be overcome by using proper accessories for automatic sample handling. Moreover, MAE also offers the ability to extract several samples simultaneously, while, in PLE, samples are always run one at a time. MAE has therefore become the most suitable extraction system for monitoring programs due to its capability of handling a large number of samples in a short period of time [68]. To a lesser extent, supercritical-?uid extraction (SFE) has been reported for extraction of AP compounds in solid samples. SFE with solid trapping has proved better than conventional liquid-solvent-extraction methods, with several advantages (e.g., rapid extraction, low solvent requirement, low cost and higher ef?ciencies). Among all the solvents used in SFE, pure CO2 is the most popular, due to its low critical properties, chemical inertness, low toxicity and cost, and its ability to dissolve a wide range of organic compounds, including those having high molecular mass. Nevertheless, pure CO2 leads to low recoveries for polar compounds (e.g., longchain APEOs).http://www.elsevier.com/locate/trac1191TrendsTrends in Analytical Chemistry, Vol. 28, No. 10, 2009The lack of extraction ef?ciency for these polar compounds can be overcome by adding modi?ers or co-solvents to the pure CO2, with water and methanol being the most common solvent modi?ers used. Lee et al. [70] were among the ?rst to set up an SFE method for the extraction of NPEOs and carboxylated derivatives from dried sewage-treatment-plant sludge. By using water as the CO2-solvent modi?er, they obtained recoveries in the range 86C105% for NP1C17EOs oligomers, with NP17EO showing the worst result. With the same objectives, Minamiyama et al. [71] recently studied the effect of adding methanol in the extraction of NP and NPEOs using SFE for sewage-sludge samples. They reported that adding methanol to the pure CO2 increased the quantities of NP and NPnEO extracted by 1.7C5 times. Earlier in this decade, some attempts were made to use environmentally-friendly approaches employing non-ionic surfactants for the extraction of lipophilic AP compounds from sediment and biological matrices [61,69]. The use of surfactant solutions offers several advantages over organic solvent-like extractants (e.g., reduction in the amounts of solvents used, low cost, easy handling and non-toxic procedures). In this way, Patrolecco et al. [61] developed a readily applicable method using aqueous non-ionic surfactant solutions (Tween 80) for the extraction of EDs, including NP, NP1EO and NP2EO as target compounds. They reported recoveries of 89C95% after 3 h of extraction. This extraction time is relatively long compared to those for conventional techniques, and poses the biggest disadvantage of the method. Employing the same extraction protocol, Croce et al. [69] reported recoveries of 84C95% for the same analytes. They also compared this ‘‘new trend’’ with ASE and MAE, concluding that the recovery and the reproducibility of these different extraction methods are comparable and all methods give reliable results for the extraction of short-chain AP compounds. Due to the complexity of many solid matrices, especially biological tissues and sludge samples, puri?cation of the extracts by different clean-up procedures after extraction has become crucial in order to obtain the maximum sensitivity in the subsequent detection of analytes. Among all methods employed for this purpose, the conventional approaches based on use of offline SPE cartridges or solid-liquid adsorption chromatography remain the most important clean-up and fractionation methods to eliminate interfering compounds. In order to reduce the sample-pretreatment time and to improve the isolation of analytes, advanced methods {e.g., coupling in series two HPLC columns or integrating LC-sample preparation and analysis on a dual-column system (column switching) [65]} have been developed for puri?cation of APEOs from solid matrices. 1192http://www.elsevier.com/locate/trac3. Analysis 3.1. Liquid chromatography Chromatographic separation of APEOs and their metabolites in a single run presents several dif?culties that make it complicated to choose an appropriate analytical column and a mode of separation. The great complexity of commercially-available technical products (mixtures of EO homologues and alkyl isomers), besides the broad range of polarities that APEOs exhibit from the more lipophilic APs to the more hydrophilic long-chain oligomers, is the main drawback to obtaining a good chromatographic performance needed to conduct proper quantitative analysis. Reversed-phase liquid chromatography (RPLC) has been used extensively for LC-MS analysis of APEOs and their DPs. RP columns (silica-based C18 and C8, aluminabased C18 or polyethylene-coated alumina) separate according to the nature of the hydrophobic moieties, so mixtures of surfactants containing several hydrophobic moieties (e.g., nonyl, octyl and heptyl) can be determined correctly since the quanti?cation is simpli?ed [47]. However, RPLC separation on C18 columns is not affected by the length of EO units, and only the APs and AP1C2EO can be successfully separated from other EO oligomers, which often co-elute in a single peak. Each peak therefore represents a single alkyl chain length and contains the whole range of EO chain lengths. Despite many authors describing this aspect as an advantage, claiming that co-elution enhances signal-peak response and hence sensitivity, quanti?cation is severely compromised because the response factors of each homologue vary signi?cantly, with poor sensitivity for the monoethoxylate compounds [72]. Moreover, this coelution also leads to competitive ionization during the electrospray processes [40,41] and to isobaric interferences between singly- and doubly-charged adducts [34] when MS systems are employed (as discussed below). Broadly, this approach is not suitable for the determination of the full range of APEOs [39]. In this case, the distinction between the long-chain oligomers is made only by MS detection [see mass spectrum (Fig. 2)], and other detection techniques [e.g., FD or ultraviolet-diode array (UV-DAD)] are not particularly recommended for the determination of every single APEO oligomer. Given the dif?culties from co-elution of alkyl homologues, normal-phase liquid chromatography (NPLC) has been tested for LC analysis of APEOs. NPLC allows the separation of APEO oligomers according to the increasing number of EO units, while the alkyl chain has virtually no effects on the chromatographic separation [64]. Thus, oligomers with the same number of EO units, but different alkyl chains, co-elute in a single peak (e.g., NP4EO and OP4EO).Trends in Analytical Chemistry, Vol. 28, No. 10, 2009TrendsFigure 2. Mass spectra of oligomeric mixture of nonylphenol ethoxylates (NPEOs) with an average of 4 EO units using an electrospray ionization (ESI) interface [47].Figure 3. Chromatographic separations of oligomeric mixture of nonylphenol ethoxylates (NPEOs) and nonylphenol (NP) using different highperformance liquid chromatography (HPLC) columns. 1) reversed-phase LC (RPLC) with C18 column: a) co-elution of several EO oligomers (NPEOx) in a single peak. 2) normal-phase LC (NPLC) with silica column: b) co-elution of short-chain NPEOs (NP1C2EO) and NP; c) separation of alkylphenol-polyethoxylate (APEO) oligomers according to the increasing number of ethylene oxide units. 3) RPLC with C8 column: d) complete separation of NPEO oligomeric mixture with the typical dome-shaped base line [64].http://www.elsevier.com/locate/trac1193TrendsTrends in Analytical Chemistry, Vol. 28, No. 10, 2009The major drawback of NPLC approaches is that the separation of short-chain APEOs, especially mono-ethoxylated and di-ethoxylated compounds, becomes very dif?cult under certain conditions, and the co-elution of AP1EO, AP2EO, and even APs, is almost unavoidable (Fig. 3). Nevertheless, working correctly on the gradientelution pro?les, especially in the ?rst minutes of the chromatograms, this drawback can be partly solved [64]. Other disadvantages of NPLC are that it requires longer equilibration times than RPLC [29,35] and a polar modi?er may have to be added post-column to support ionization of target analytes in MS detection [35]. However, complete separations of APs and a wide range of their EO homologues have been reported using NP columns [29,35]. Another approach to the separation of these compounds is also possible. RPLC using C8 columns provides intermediate separation between RPLC and NPLC. In this case, separation is also done according to the character of the hydrophobic moieties. However, the number of EO units exerts a greater in?uence on the separation than those observed on C18 columns, allowing a good performance of the highly ethoxylated compounds and, most importantly, clear separation between the shortchain compounds. Nevertheless, the hydrophobic behavior of this kind of material compromised the baseline resolution of long-chain APEOs, which are usually dome-shaped, hampering their proper quanti?cation (Fig. 3). In this way, some authors have successfullyemployed C8 columns for the complete separation of mixtures of AP compounds of up to 17 EO units in a single chromatographic run [9,23,36,41,46]. Important advances in APEO separation have been reported using so-called mixed-mode chromatography [72]. This mode of HPLC combines two mechanisms of separation: size exclusion and RP, so compounds are separated according to their molecular weight, allowing the separation of compounds based on their number of EO units, and according to the character of the hydrophobic moieties, allowing the separation of the different alkyl groups (Fig. 4). Ferguson and co-workers [39] were pioneers in using these columns for the chromatographic separation of this family of compounds. Subsequently, Loyo-Rosales et al. employed them to perform strongly in separating short-chain compounds [31] as well as highmolecular-weight oligomers [38] for octyl and nonyl polyethoxylated compounds into the same chromatogram. Liu and Pohl [73] tested a new mixed-mode silicabased stationary phase for the separation of non-ionic EO surfactants. They prepared a new stationary phase that combined both hydrophilic interaction chromatography (HILIC) and RP characteristics, providing two modes of operation that allowed a great performance in separation based on the nature of both alkyl chains and EO units. Surveying the current literature on LC analysis of target AP compounds, we can observe that applications based on mixed-mode separation technology are represented toFigure 4. Separation of nonylphenol (NP) and nonylphenol-ethoxylate (NPEO) oligomeric mixture using a mixed-mode high-performance liquid chromatography (HPLC) column: a) complete separation of alkylphenol-polyethoxylate (APEO) oligomers according to the increasing number of
b) separation between the target compound and its corresponding internal standard (A and B) [39].1194http://www.elsevier.com/locate/tracTrends in Analytical Chemistry, Vol. 28, No. 10, 2009Trendsa much lesser extent than those using conventional separation columns (NPLC and RPLC). This is mainly due to the lack of commercially-available mixed-mode columns and the high cost of acquiring them compared with classical columns. 3.2. Detection systems Although the ?rst analytical approaches were mainly based on GC-MS [24], the low volatility of highly ethoxylated APs and carboxylated derivatives prevented the use of GC-MS methods unless a derivatization step was included in the analytical protocol [22,23]. The impossibility of carrying out a direct analysis, combined with the loss of sample due to additional manipulation, led many researchers to use HPLC procedures to analyze a broad range of EO compounds. Since the early 1990s, HPLC, combined with various detection systems, has been used in this ?eld routinely. 3.2.1. HPLC with FD and UV detection. LC-FD has been applied for the analysis of APEOs in all types of environmental samples [2,24,33,64,74,75]. Other spectrometric detection systems {e.g., UV absorbance [58,63] or evaporative line scattering (ELSD) [24]} have also been employed for the same purpose, but they provide less selectivity and lower sensitivity than FD systems, which show results that can be compared with those obtained with simple MS detectors. It is also important to note that the relatively low cost of FDs, coupled with the steady improvement in clean-up and isolation procedures, convert them into an inexpensive alternative that offers competitive results according to the level of complexity of the samples, and to the quality of the pretreatment procedures employed (including chromatographic separation). Nevertheless, these optical detectors are becoming out of date when faced with MS detection, due mainly to the lack of speci?city in analysis. Table 3 summarizes some methods for the determination of AP compounds using FD and UV detectors. 3.2.2. HPLC with MS detection. In the past decade, LCMS technologies have surged to become an important tool for the identi?cation and the quanti?cation of APEOs. Today, electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) interfaces are the most widely employed for the LC-MS analysis of this kind of surfactant. It has been reported that ESI is 30C50 times more sensitive than APCI in negative-ionization (NI) mode [47]; however, APCI provides additional structure information (number of EO units in the molecules), which no one can get using an ESI interface. However, the sensitivity of APCI is almost as good as ESI in positive-ion (PI) mode [76] and is generally less sensitive to matrix interferences in environmental samples.For all the AP compounds that can be detected using this technology, the NI mode is employed almost exclusively for the determination of DPs: fully de-ethoxylated APs, short-chain and long-chain carboxylated derivatives, and short-chain halogenated derivatives. In this last case, it has been reported that the LODs obtained using an ESI source are 2C3 times lower than those obtained by an APCI source [76]. Other APEOs containing at least one EO unit, are usually detected under PI conditions. The strong af?nity of APEOs for alkali-metal ions and other cations going into the ESI source leads to the formation of different adducts [M ? ?K? ; Na? ; H? ?; M? NH? ], although evenly-spaced sodium adducts [M+Na]+ 4 (Fig. 2), with mass differences of 44 Da (one EO unit), are the most representative ions in the mass spectra. Despite these cations prevailing over the other adducts formed, including the protonated molecules [M+H]+, several authors recommend fortifying the sample extracts with sodium ions [for selected ion monitoring (SIM)] or ammonium salts [for multiple-reaction monitoring (MRM)] in order to enhance the ionization processes and, therefore, reproducibility and sensitivity. Earlier this decade, this analytical approach was applied several times using a single quadrupole analyzer in SIM mode [9,27,29,51], the ?rst commercially-available analyzer for coupling with LC. To improve identi?cation of APEOs and related compounds in complex matrices, several LC-MS2 methods were developed in recent years [23,31,38,45,46]. The use of triple-quadrupole (QqQ) analyzers in MRM mode obtained more selective, more sensitive detection, resulting in LODs far lower than those reported by single-quadrupole systems (Tables 1 and 2). In this way, using MRM, AP compounds in environmental samples can be identi?ed unequivocally. To avoid false positives, identi?cation criteria were established in Commission Decision 657/2002/CE [77]. Essentially, these criteria are mainly based on the use of identi?cation points (IPs) (parent and fragment ions), a system whereby the relative intensities of the diagnostic fragment ions must match those of the standard analyte within a maximum permitted tolerance, and the analytes must elute at the retention time of the standard (±2.5%). Novel hybrid-MS systems [e.g., quadrupole-time-of?ight (QqTOF) QqQ-linear ion-trap MS (QTRAP)] have begun to be used for environmental analysis of APEOs and derivatives. These analyzers can provide a more versatile recognition of DPs and metabolites due to their high accurate-mass measurements, low LODs, speed and sophisticated MS-scan techniques [76]. However, their sensitivities still remain, generally, below to those of QqQ analyzers (even several orders of magnitude). As a result, these techniques would not be entirely suitable for the analysis of almost any environmental contaminant.http://www.elsevier.com/locate/trac11951196http://www.elsevier.com/locate/tracTrendsTable 1. Methods for the determination of alkylphenolic compounds in liquid samples Compounds XAPEOs, APECs, APEOs Matrix Surface water, drinking water, wastewater Estuarine water River water Surface water Surface water Wastewater Surface, wastewater Sewage water Wastewater Sample pretreatment Filtration 0.45 lm Extraction technique SPE Characteristics (cartridge type, ?ber type, solvent) LIChrolut C18, MeOH Recoveries (%) 73C98 LOD (ng/L) 20C100 Instrumental analysis LC-MS Ref. [11]AP1-3EOs, XNP NPEOs NPEOs, NPECs AP1-5EOs NP6-16EOs, APECs APs, APEOs, APECs APs, AP1-2EOs, AP1-2ECs NP, NP1-2EO, XNP1-2EO Abbreviations: See Appendix.Filtration 0.7 lm, sulfuric acid (pH 2) Filtration 0.45 lm, Formaldehyde (1%) 37% formaldehyde Filtration 0.7 lm Filtration 0.7 lm Decantation Filtration 1.2 lm Sodium thiosulfateSPE SPE SPE SPE SPE, LLE SPE SPE SPMEBondesil 0.40 lm, Acetone ENVI-Carb (GCB), MeOH, DCM. ENVI-Carb (GCB), DCM. Isolute ENV, DCM, MeOH, acetone. LiChrolut ENV, DCM, MeOH, acetone. Oasis HLB, MeOH, acetone, ethyl acetate Oasis HLB, MeOH, DCM. DVBCCARC PDMS78C91 93C117 78C107 36C110 21C71 50C90 25C110 C0.04C0.92 0.5C 0.004C0.3 2C29 1C100 0.04C12 30C150LC-MS LC-MS LC-MS-MS LC-MS-MS LC-MS-MS LC-MS-MS LC-MS-MS GC-MS[41] [29] [23] [31] [38] [45] [46] [51]Table 2. Methods for the determination of alkylphenolic compounds in solid samples Compounds NP, NP1C19EOs NP, NPEOs NP, NP1C2EOs AP1C3EOs, XNP APs APs APs, AP1C15EOs APs, APEOs, APECs, XAPEOs NP, NPEOs NP, NP1C2EOs OP NP1C17EOs NP, NP1C2EOs Abbreviations: See Appendix. Matrix Marine sediments Sewage sludge WWTP sludges Surface water Fish liver Meat Amended soil River sediments Sewage sludge Estuarine sediments Fish tissue Sewage sludges River sediments, suspended matter, benthonic organisms Sample pretreatment Freezing 1% formaldehyde Lyophilization, sieving Freezing Lyophilization Homogenization Air-drying, sieving Lyophilization, sieving 1% formaldehyde Lyophilization, sieving Freezing Air-drying, sieving Freezing Extraction technique Soxhlet Soxhlet Ultrasonic Ultrasonic PLE PLE PLE PLE MAE MAE MAE SFE Tween-80 Characteristics (solvent) Hexane:IPA (30:70) MeOH Hexane MeOH Acetone-n-hexane (50:50) DCM-hexane (50:50) Acetone-hexane (50:50) Acetone-MeOH (50:50) DCM-MeOH (30:70) Acetone DCM-hexane (2:1 v/v) CO2 Non-ionic surfactant Recoveries (%) 52C104 66C88 93C117 80C94 54 50C90 36C110 C 61C91 C 60C78 86C105 81C94 LOD (ng/g) 2C10 C 189C751 4C 1C100 0.3C30 0.5C2 0 10C50 500 30C60 Instrumental analysis LC-MS LC-FD GC-MS LC-MS LC-MS LC-MS-MS LC- MS LC-MS LC-FD GC-MS LC-MS LC-FD LC-FD Ref. [43] [63] [29] [39] [38] [45] [66] [65] [63] [68] [79] [70] [61]Trends in Analytical Chemistry, Vol. 28, No. 10, 2009Trends in Analytical Chemistry, Vol. 28, No. 10, 2009TrendsTable 3. Methods for the determination of alkylphenolic compounds by fluorescence and UV detectorsLiquid medicines, intravenous solutions River water, wastewater River sediments Fish, shell?sh tissues Sediment compost, sewage sludge Fish tissueCantero et al. used an RPLC/(APCI-IT)-MS technique for separation and quanti?cation of APEOs in sewagesludge, wastewater and river-water samples [36,78]. They reported relatively low LODs (0.09C0.38 mg/kg for sewage sludge, 14C111 ng/L for wastewater in?uent, 10C40 ng/L for wastewater ef?uent and 4C35 ng/L for river water) working on full-scan mode for quanti?cation. They also concluded that Q-IT systems performed better than conventional quadrupole mass-?lter instruments, since similar sensitivity was obtained in both SIM and full-scan mode. Moreover, the ability of Q-IT systems to perform MSn experiments, make them more suitable for identi?cation purposes and MS2 quantitative analysis. Other advanced MS techniques (e.g., TOF-MS and QqTOF-MS) have already been applied to the environmental analysis of surfactants. Both techniques are especially suitable for the analysis of EO nevertheless, the high cost of acquisition compared to QqQ or IT instruments has meant that these other advanced MS techniques have not yet been employed routinely [25,32]. However, there are several advantages in using TOF spectrometers (e.g., very good massaccuracy measurements, high mass-resolving power, high ef?ciency and speed in analysis, and, especially, great power in identi?cation). In conclusion, this approach is shown as a powerful tool for the precise identi?cation of parent ions and their fragmentation products based on highly-accurate measurements of mass. ?lez Gonza et al. [79] recently developed a novel method coupling ultra-performance LC (UPLC) to hybrid QqTOFMS for characterization and quantitative analysis of surfactants, including APEOs, and a wide range of their metabolites. They reported instrumental detection limits (IDLs) in the range 20C200 pg injected. They also showed the great power of identi?cation of this kind of analyzer with mass-accuracy measurements (the ratio of the m/z measurement error divided by the true m/z and usually stated in ppm) below 5 ppm for 80% of the target compounds. However, they also reported that this MS analyzer provided a linear dynamic range at least one order the magnitude lower than those observed for QqQ or even IT systems.[73] [33] [74] [64] LC-UV LC-FD LC-FD LC-FD 800CC2 50C520 PA, ACN, water Hexane:IPA (30:70) ACN, hexane, ethyl ether MeOH:water (70:30) SPME PLE Solvent extraction Ultrasonic Filtration 0.45 lm Freezing, homogenization Homogenization C 83C87 77C96 87C104Instrumental analysisLC-DAD-UV[59]LOD (ng/L, ng/g)100C4000Recoveries (%)Characteristics81C86Extraction techniqueSPMEAcetonitrile, waterMatrix-Freezing, homogenizationSample pretreatmentPLEMethylene chloride74C1255C44LC-FD[75]Ref.Abbreviations: See Appendix.4. Conclusions and future trends Sample preparation is one of the most critical steps in the determination of AP compounds in different environmental matrices. Developments in sample-pretreatment techniques enhance the reliability of the analytical performance and are often designed to facilitate the application of advanced extraction techniques (e.g., SPE and SPME in liquid samples, or PLE, SFE and MAE in solid samples). In recent years, there has been a notablehttp://www.elsevier.com/locate/tracAPs NP, NPEOs APs, NP1C2EOs NP, NPEOsAPsNP, NP1C5EOsCompounds1197TrendsTrends in Analytical Chemistry, Vol. 28, No. 10, 2009increase in the volume of literature on novel sampletreatment techniques applied to these compounds. Future trends in this ?eld will be orientated to the development of new extraction protocols for the preconcentration and clean up of these compounds. Since signal suppression is one of the major problems in APEO quanti?cation employing MS detectors, improved extraction and clean-up procedures, materials and formats that reduce signal suppression offer direct ways to obtaining maximum sensitivity and reproducibility [47]. Reductions in signal intensity (sometimes up to 50%) have been discussed by several workers (e.g., [39]), claiming that chromatographic separation alone might be insuf?cient to remove ion-suppression effects [47]. For the same reason, the development of new materials and formats that improve the chromatographic separation of APEOs is a growing research topic. Getting a good chromatographic separation has become a key factor in improving the sensitivity of the ?nal method via reduction of the matrix effects observed at the interface coupling LC to MS. As a result, new so-called mixed-mode stationary phases have already been tested to overcome the drawbacks that classical stationary phases typically have inLC. In this way, really satisfactory results on the chromatographic performance of complex AP mixtures have been reported, showing complete separation based on alkyl-chain length and EO units. However, the lack of commercially-available mixed-mode columns and their high cost of acquisition compared to classical columns have prevented their general use. In recent years, the need to obtain accurate-mass measurements and low LODs has considerably increased the use of advanced MS techniques (e.g., QqTOF-MS or QTRAP) to identify completely unknown DPs that are very dif?cult to determine using low-resolution quadrupole mass ?lters. The great environmental importance of these DPs and the lack of appropriate commerciallyavailable standards make these analyzers the most versatile tools for the unequivocal identi?cation of DPs, due to their MSn capabilities, despite their extremely high cost and relatively high LODs compared with QqQ detectors.Acknowledgements This work was supported by funds provided by the Spanish Ministry of Education of Science (Research Project CTM).Appendix: Abbreviations AP, Alkylphenol IP, Identi?cation Point PVP-DVN, Poly (n-vinylpyrrolidonedivinylbenzene) Q-IT, Quadrupole ion trap QTRAP, Triple quadrupole/linear ion trap mass spectrometer RPLC, Reversed-phase liquid chromatography RSD, Relative standard deviation SAESCs, Sonication-assisted extraction on small columns SBSE, Stir-bar sorptive extraction SIM, Selected ion monitoring SFE, Supercritical ?uid extraction SPE, Solid-phase extraction SPME, Solid-phase microextraction SSPE, Sequential solid-phase extraction TOF-MS, Time-of-?ight mass spectrometry TSP, Thermospray interfaceACN, Acetonitrile IPA, Isopropanol APCI, Atmospheric pressure LC, Liquid chromatography chemical ionization interface APEOs, Alkylphenol polyethoxylates LLE, Liquid-liquid extraction APECs, Alkylphenol carboxylated derivatives ASE, Accelerated solvent extraction CAPEC, Carboxylated alkylphenol ether carboxylate CAR, Carboxen DAD, Diode-array detector DCM, Dichloromethane DPs, Degradation products EDs, Endocrine disrupters ELSD, Evaporative line scattering detector EO, Ethoxy unit LOD, Limit of detection MAE, Microwave-assisted extraction MALDI, Matrix-assisted laser desorption/ionization MeOH, Methanol MRM, Multiple reaction monitoring MS, Mass spectrometry NI, Negative ionization mode NP, Nonylphenol NPEOs, Nonylphenol ethoxylates NPLC, Normal-phase liquid chromatography1198http://www.elsevier.com/locate/tracTrends in Analytical Chemistry, Vol. 28, No. 10, 2009TrendsEPA, Environmental Protection Agency ESI, Electrospray interface EU, European Union FD, Fluorescence detector GC, Gas chromatography GCB, Graphitized carbon black GF/F, Glass ?ber/?lters HILIC, Hydrophilic interaction chromatography IDL, Instrumental detection limitOP, Octylphenol OPEOs, Octylphenol ethoxylates PA, Polyacrylate PB, Particle beam PDMS, Polydimethylsiloxane PFE, Pressurized ?uid extraction PI, Positive ionization mode PLE, Pressurized liquid extraction PS-DVB, Polymeric styrene-divinylbenzeneUAE, Ultrasound-assisted extraction UPLC, Ultra-performance liquid chromatography UV, Ultraviolet WFD, Water Framework Directive (European) WWTPs, Wastewater-treatment plants XAPEO, Alkylphenol halogenated ethoxylatesReferences[1] S.S. 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