Alkylphenols analysis

The complete analysis of alcohol sulfates is described in the Standard Methods of the International Organization of Standards (ISO) [200] and of the American Society for Testing and Materials (ASTM) [201]. These methods describe the analysis of inorganic sulfate content, chloride content, unsulfated matter, and water as well as other analytical values. Other ISO standards describe the analysis of sodium secondary alkyl sulfates [202], determination of pH [203], determination of water content [204,205], chlorides [206], total active matter in sul fated ethoxylated alcohols and alkylphenols [207], mean relative molecular mass in sulfated ethoxylated alcohols and alkylphenols [208], sulfate content... 

FD-MS is also an effective analytical method for direct analysis of many rubber and plastic additives. Lattimer and Welch [113,114] showed that FD-MS gives excellent molecular ion spectra for a variety of polymer additives, including rubber accelerators (dithiocar-bamates, guanidines, benzothiazyl, and thiuram derivatives), antioxidants (hindered phenols, aromatic amines), p-phcnylenediamine-based antiozonants, processing oils and phthalate plasticisers. Alkylphenol ethoxylate surfactants have been characterised by FD-MS [115]. Jack-son et al. [116] analysed some plastic additives (hindered phenol AOs and benzotriazole UVA) by FD-MS. Reaction products of a p-phenylenediaminc antiozonant and d.v-9-lricoscnc (a model olefin) were assessed by FD-MS [117],... 

It is important that any method for surfactant analysis maintains the same oligomer distribution in the extracted samples. LLE and SPE are generally combined with chromatographic methods for separation and resolution of non-ionic surfactants into their ethoxamers. An alternative is the use of SPME-HPLC, recently reported by Chen and Pawliszyn [141]. Alkylphenol ethoxylate surfactants such as Triton X-100 and various Rexol grades in water were determined by means of SPME-NPLC-UV (at 220 nm) [142]. Detection limits for individual alkylphenol ethoxamers were at low ppb level. 

Analysis of potential endocrine disrupters, such as alkylphenols (degradation products of non-ionic surfactants), diphenolalkanes (cumylphenol, bisphenol-A, bisphenol-F) and benzophenones (from the paper industry) with RPLC-SSI-QITMS in the negative ion mode has been described [631]. 

Similar results were shown for the analysis of alkylphenol ethoxylates, which could only be separated on Spherisorb silica using acetonitrile and water (Rissler 1994). Since water-acetonitrile gradients give better resolution over water-methanol gradients for the analysis of PEG S, it was proposed that methanol shields residual... 

An integrated analysis of four different environmental compartments - SW, GW, SE, and soil - is performed applying MCR-ALS. The concentration of four different families of compounds - OCs, PAHs, pesticides, and alkylphenols (APs) -were analyzed during six different sampling campaigns (from year 2004 to 2006) at various locations distributed within the entire Ebro River basin. SW and GW were sampled twice a year, in spring and fall, whereas SE and soil were only sampled in fall. 

Fig. 6 General structures of the most important surfactants and metabolites alkylphenol polyethoxylate (APE) alkylphenol (AP) alkyl ether (AE) alkylphenol ethoxy carboxylate (APEC) linear alkylbenzenesulfonates (LAS) alkyltrimethylammonium compounds (ATMAC) dialkyldimethylammonium compounds (DADMAC) alkyldimethylbenzylammonium compounds (ADMBAC) esterquat (EQ) diesterquats (DEQ). X is usually a chlorine or bromine atom. DDAC (didecyldimethylammonium chloride) and BDD12AC (benzyldimethyldode-cylammonium) are the two target analytes with a reported immunochemical technique developed for their analysis [153,154]...

Gas chromatography (GC) has developed into the most powerful and versatile analytical separation method for organic compounds nowadays. A large number of applications for the analysis of surfactants have emerged since the early 1960s when the first GC papers on separation of non-ionics were published. The only major drawback for application of GC to surfactants is their lack of volatility. This can be easily overcome by chemical modification (derivatisation), examples of which will be discussed extensively in the following paragraphs. This chapter focuses on surfactant types, and in addition discusses some structural aspects of alkylphenol ethoxylates (APEOs) that are important for, as well as illustrative of, aspects of separation and identification that are linked to the complexity of the mixtures of surfactants that are involved. 

Another approach consists of an in-situ acetylation and extraction of NPEOs and further analysis of the acetyl derivatives. The method has been applied to analyse effluent water and sewage sludges [102,103], sediments [104] and river waters [105]. Silylated derivatives [106] using BSA or BSTFA have also been used to determine NPEO (n < 6) in seawater [107] and wastewater [107,108], sediments [109] and sludges from wool scour effluents [110]. Halogenated derivatives of alkylphenols (AP) can also be formed as a result of chlorination practices in water treatment or wastewater if bromide is present. Brominated OPs and NPs (BrAPEOs) have been identified by GC-MS in sewage [111] and tap water [89], respectively. 

The trend of discovering the analytical field of environmental analysis of surfactants by LC-MS is described in detail in Chapters 2.6-2.13 and also reflected by the method collection in Chapter 3.1 (Table 3.1.1), which gives an overview on analytical determinations of surfactants in aqueous matrices. Most methods have focused on high volume surfactants and their metabolites, such as the alkylphenol ethoxylates (APEO, Chapter 2.6), linear alkylbenzene sulfonates (LAS, Chapter 2.10) and alcohol ethoxylates (AE, Chapter 2.9). Surfactants with lower consumption rates such as the cationics (Chapter 2.12) and esterquats (Chapter 2.13) or the fluorinated surfactants perfluoro alkane sulfonates (PFAS) and perfluoro alkane carboxylates (PFAC) used in fire fighting foams (Chapter 2.11) are also covered in this book, but have received less attention. 

Fig. 2.6.18. LC-MS-MS analysis of halogenated alkylphenolic compounds in chlorinated river water (the Llobregat river, Spain). MRM mode (a) 253 —> 167 for detection of 35C1 nonylphenolic compounds (b) 297 — 79 for 79BrNP (c) 355 —> 297 for 79BrNPE C (d) 399 — 297 for 79BrNPE2C. Reprinted with permission from Ref. [39] 2002 American...

Shang et al. [5] used ASE for the extraction of NP and NPEO from estuarine sediments. A sample of 15-25 g was extracted three times using hexane/acetone at 100°C and 103 atm. This was followed by a clean-up step using CN-SPE. A blank sample was extracted between all samples to avoid contamination. Hexane/acetone was also used in the ASE method for alkylphenols and NPEO by Heemken et al. [12]. Extraction conditions for samples of 0.5-1 g were 100°C, 150 atm, with a static extraction step of 15 min, and a rinse step with 20 mL solvent. After a clean-up by HPLC, the analytes were derivatised with heptafluorobutyric acid anhydride for GC analysis. 

The quantitative environmental analysis of surfactants, such as alcohol ethoxylates, alkylphenol ethoxylates (APEOs) and linear alkylbenzene sulfonates (LASs), is complicated by the presence of a multitude of isomers and oligomers in the source mixtures (see Chapter 2). This issue bears many similarities to the quantitation problems that have occurred with halogenated aromatic compound mixtures, e.g. polychlorinated biphenyls (PCBs) [1]. 

Analysis of alkylphenol ethoxylates and degradation products in drinking water... 

There is disagreement in the literature on the influence of reactant structure on activation energy. Some authors (e.g. refs. 212, 213 and 227) have found different activation energies for different reactants but their treatment of the rate data was rather simplified and the rate coefficients obtained were not separated from adsorption coefficients. However, in the studies where the kinetic analysis was more detailed and a true rate coefficient was calculated, the same activation energy was determined for all members of a series of alkylbenzenes [210] and a series of alkylphenols [204],... 

Benjamin Tan, L.L., Mustafa, A.M., 2003. Analysis of selected pesticides and alkylphenols in human cord blood by gas chromatograph-mass spectrometer. Talanta 61, 385-391. 

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