Metabolism of alcohol ethoxylates (AEs) in rat, hamster, and human hepatocytes and liver S9: a pilot study for metabolic stability, metabolic pathway, and metabolites identification in vitro and in silico.

Alcohol ethoxylates (AEs) are a well-known class of non-ionic surfactants widely used by the personal care market. The aim of this study was to evaluate and characterize the in vitro metabolism of AEs and identify metabolites. Five selected individual homologue AEs (C8EO4, C10EO5, C12EO4, C16EO8, and C18EO3) were incubated using human, rat, and hamster liver S9 fraction and cryopreserved hepatocytes. LC-MS was used to identify metabolites following the incubation of AEs by liver S9 and hepatocytes of all three species. All AEs were metabolized in these systems with a half-life ranging from 2 to 139 min. In general, incubation of AE with human liver S9 showed a shorter half-life compared to rat liver S9. While rat hepatocytes metabolized AEs faster than human hepatocytes. Both hydrophobic alkyl chain and hydrophilic EO head group groups of AEs were found to be target sites of metabolism. Metabolites were identified that show primary hydroxylation and dehydrogenation, followed by O-dealkylation (shortening of EO head groups) and glucuronidation. Additionally, the detection of whole EO groups indicates the cleavage of the ether bond between the alkyl chain and the EO groups as a minor metabolic pathway in the current testing system. Furthermore, no difference in metabolic patterns of each individual homologue AE investigated was observed, regardless of alkyl chain length or the number of EO groups. Moreover, there is an excellent agreement between the in vitro experimental data and the metabolite profile simulations using in silico approaches (OECD QSAR Toolbox). Altogether, these data indicate fast metabolism of all AEs with a qualitatively similar metabolic pathway with some quantitative differences observed in the metabolite profiles. These metabolic studies using different species can provide important reference values for further safety evaluation.

Cetyl Alcohol Polyethoxylates Disrupt Metabolic Health in Developmentally Exposed Zebrafish.

Alcohol polyethoxylates (AEOs), such as cetyl alcohol ethoxylates (CetAEOs), are high-production-volume surfactants used in laundry detergents, hard-surface cleaners, pesticide formulations, textile production, oils, paints, and other products. AEOs have been suggested as lower toxicity replacements for alkylphenol polyethoxylates (APEOs), such as the nonylphenol and octylphenol polyethoxylates. We previously demonstrated that nonylphenol polyethoxylates induced triglyceride accumulation in several in vitro adipogenesis models and promoted adiposity and increased body weights in developmentally exposed zebrafish. We also demonstrated that diverse APEOs and AEOs were able to increase triglyceride accumulation and/or pre-adipocyte proliferation in a murine pre-adipocyte model. As such, the goals of this study were to assess the potential of CetAEOs to promote adiposity and alter growth and/or development (toxicity, length, weight, behavior, energy expenditure) of developmentally exposed zebrafish (Danio rerio). We also sought to expand our understanding of ethoxylate chain-length dependent effects through interrogation of varying chain-length CetAEOs. We demonstrated consistent adipogenic effects in two separate human bone-marrow-derived mesenchymal stem cell models as well as murine pre-adipocytes. Immediately following chemical exposures in zebrafish, we reported disrupted neurodevelopment and aberrant behavior in light/dark activity testing, with medium chain-length CetAEO-exposed fish exhibiting hyperactivity across both light and dark phases. By day 30, we demonstrated that cetyl alcohol and CetAEOs disrupted adipose deposition in developmentally exposed zebrafish, despite no apparent impacts on standard length or gross body weight. This research suggests metabolic health concerns for these common environmental contaminants, suggesting further need to assess molecular mechanisms and better characterize environmental concentrations for human health risk assessments.

Gut epithelial barrier damage caused by dishwasher detergents and rinse aids.

BACKGROUND: The increased prevalence of many chronic inflammatory diseases linked to gut epithelial barrier leakiness has prompted us to investigate the role of extensive use of dishwasher detergents, among other factors. OBJECTIVE: We sought to investigate the effects of professional and household dishwashers, and rinse agents, on cytotoxicity, barrier function, transcriptome, and protein expression in gastrointestinal epithelial cells. METHODS: Enterocytic liquid-liquid interfaces were established on permeable supports, and direct cellular cytotoxicity, transepithelial electrical resistance, paracellular flux, immunofluorescence staining, RNA-sequencing transcriptome, and targeted proteomics were performed. RESULTS: The observed detergent toxicity was attributed to exposure to rinse aid in a dose-dependent manner up to 1:20,000 v/v dilution. A disrupted epithelial barrier, particularly by rinse aid, was observed in liquid-liquid interface cultures, organoids, and gut-on-a-chip, demonstrating decreased transepithelial electrical resistance, increased paracellular flux, and irregular and heterogeneous tight junction immunostaining. When individual components of the rinse aid were investigated separately, alcohol ethoxylates elicited a strong toxic and barrier-damaging effect. RNA-sequencing transcriptome and proteomics data revealed upregulation in cell death, signaling and communication, development, metabolism, proliferation, and immune and inflammatory responses of epithelial cells. Interestingly, detergent residue from professional dishwashers demonstrated the remnant of a significant amount of cytotoxic and epithelial barrier-damaging rinse aid remaining on washed and ready-to-use dishware. CONCLUSIONS: The expression of genes involved in cell survival, epithelial barrier, cytokine signaling, and metabolism was altered by rinse aid in concentrations used in professional dishwashers. The alcohol ethoxylates present in the rinse aid were identified as the culprit component causing the epithelial inflammation and barrier damage.

Phenylethyl Isothiocyanate Extracted from Watercress By-Products with Aqueous Micellar Systems: Development and Optimisation.

Phenylethyl isothiocyanate (PEITC) was reported as a useful antioxidant, anti-inflammatory, and chemopreventive agent. Due to technological and stability issues, it is necessary to be able to extract PEITC from its natural matrix (watercress) through sustainable and scalable methodologies. In this article, we explored, for the first time, the extractive capacity of aqueous micellar systems (AMSs) of two non-ionic surfactants. For this, we compared the AMSs with conventional organic solvents. Furthermore, we developed and optimised a new integral PEITC production and extraction process by a multifactorial experimental design. Finally, we analysed the antioxidant capacity by the oxygen radical absorbance capacity (ORAC) and ABTS methods. As results, the AMSs were able to extract PEITC at the same level as the tested conventional solvents. In addition, we optimised by response surface methodology the integrated process (2.0% m/m, 25.0 °C, pH 9.0), which was equally effective (ca. 2900 µg PEITC/g watercress), regardless of the surfactant used. The optimal extracts showed greater antioxidant capacity than pure PEITC, due to other antioxidant compounds extracted in the process. In conclusion, by the present work, we developed an innovative cost-effective and low environmental impact process for obtaining PEITC extracts from watercress by-products.

Characterization and analysis of non-ionic surfactants by supercritical fluid chromatography combined with ion mobility spectrometry-mass spectrometry.

Comprehensive separation and analysis of non-ionic surfactants have been conducted by coupling supercritical fluid chromatography (SFC) with ion mobility spectrometry-mass spectrometry (IMS-MS). Representative non-ionic surfactants were investigated, including alkylphenol ethoxylates (APEOs), e.g., octylphenol ethoxylates (OPEOs) and fatty alcohol ethoxylates (FAEs), e.g., lauryl alcohol ethoxylates (LAEs). A sub-2-µm high-density diol column was used for chromatographic separation by the first-dimensional SFC due to the differences in ethoxy chain prior to electrospray ionization (ESI). Maintaining the fidelity of pre-ionization separation in the first dimension, the introduction of IMS provided additional post-ionization resolution by broadly fractionating the oligometric ethoxymers based on their size and electric charge within 13.78 ms. Distinguishable series of singly and multiply charged non-ionic species could be clearly observed. The millisecond timescale ion mobility separation perfectly fits the elution time of a chromatographic peak, while effectively feeding components into the fast-scanning time-of-flight (TOF) mass analyzer for characterization and analysis. The orthogonality of the developed separation and analysis system was evaluated, revealing a correlation coefficient and peak spreading angle of 0.2729 and 74.16° for the studied OPEOs and 0.1962 and 78.69° for LAEs. Significant enhancement in peak capacity was achieved for the developed SFC-IMS-MS system with the actual peak capacity measured to be approximately 41 and 160 times higher than that of the dimensions of SFC and IMS, respectively, when used alone. Graphical abstract.

Alcohol ethoxylate degradation of activated sludge is enhanced by bioaugmentation with Pseudomonas sp. LZ-B.

An effective bioaugmentation strategy was developed for the removal of alcohol ethoxylates (AEs) from municipal wastewater. An AE-degrading strain, Pseudomonas sp. LZ-B, was isolated from an activated sludge. Strain LZ-B was able to degrade 96.8% of 200 mg/L C12E4 (Brij 30) within 24 h and showed significant biomass increase and removal of total oxygen concentration (TOC). The optimal degradation temperature and pH value were 37 °C and 6.0, respectively. The strain demonstrated greater potential to degrade five different molecular weight AEs within 5 days. HPLC-MS/MS analysis demonstrated that the major metabolites obtained were polyethylene glycol (PEG) and carboxylated AE chains. Activated sludge has a low ability to remove AEs. After inoculation of strain LZ-B into the activated sludge reactor, Strain LZ-B successfully colonized the activated sludge, and AE removal efficiency increased to more than 95% when the hydraulic retention time (HRT) was 10 h. After strain LZ-B cleaved the AE chains, the sludge microbial communities easily removed PEG fragments to facilitate complete biodegradation of AEs. This is the first report describing bioaugmentation to increase AE degradation in an activated sludge system.

Characterization of polydisperse macrogols and macrogol-based excipients via HPLC and charged aerosol detection.

Macrogol-based emulsifiers and their respective precursor substances, i.e. macrogols (PEG), fatty acids (FA), and fatty alcohols (FAA), are widely used excipients which are usually characterized by a series of tests described within the European Pharmacopoeia (Ph. Eur.). Examples are bulk parameters such as the hydroxyl value, the peroxide value, and the determination of fatty acids composition by gas chromatography. The choice of tests depends on the emulsifier considered and its possible precursors. Though all methods are well established, most of them are time consuming and, in some cases, prone to errors and exhibit a low reproducibility. Here, an alternative and supplemental method was developed, using a HPLC-system coupled to a charged aerosol detector (CAD). Seven PEG samples, five saturated as well as two nonsaturated FA samples, and two FAA samples were analyzed. Together with these precursors, 13 macrogol-based emulsifiers of 3 different groups, i.e. macrogol ethers with FAA, macrogol esters with FA, and polysorbates, were successfully analyzed for oligomeric distribution and free precursor molecules in one run.

Alcohol ethoxylates significantly synergize pesticides than alkylphenol ethoxylates considering bioactivity against three pests and joint toxicity to Daphnia magna.

Seeking alternatives for alkylphenol ethoxylates (APEOs) have been a heavily researched topic in the surfactant industry and agricultural systems. In this study, the combined effects of different ethoxylates and pesticides on the bioactivity against three pests and toxicological risks to Daphnia magna were investigated. Results showed that alcohol ethoxylates (AEOs) had higher synergistic effects on the bioactivity of pesticides against Spodoptera exigua, Agrotis ipsilon and Aphis citricola than did APEOs. In terms of the joint toxicity of the ethoxylates and pesticides to D. magna, additive index method, toxicity unit method, V value method and isobologram method were used in the tests. All of these methods indicated that the joint effects of APEOs + acetamiprid and APEOs + indoxacarb upon D. magna turned from synergism to antagonism with the increasing EO (ethylene oxide) numbers. Those of AEOs exhibited similar trends. Overall, AEOs may be potential alternatives for APEOs in agriculture as they synergize pesticides against three pests significantly more than do APEOs. However, further research should investigate the compounds' environmental risks to aquatic organisms because the AEOs were highly toxic to D. magna.

Determination of Dodecanol and Short-Chained Ethoxylated Dodecanols by LC-MS/MS (with Electrospray Ionization) After Their Derivatization (with Phenyl Isocyanate).

ABSTRACT: This report describes the application of LC-MS/MS for the separation of dodecanol (C12OH) and homogenous fatty alcohols ethoxylated (AE) containing a dodecyl moiety and 1-9 ethoxy groups. These ethoxylates and free alcohol were derivatized for LC-MS/MS analysis with phenyl isocyanate (PIC). The derivatives of analytes with PIC were separated using a C18 column. Gradient elution with a mixture of ethyl acetate and acetonitrile (5 mM) was employed. The described determination method is characterized by low detection limits (range from 0.005 µg L-1 for: C12OH, C12EO2-7 to 1 µg L-1 for C12EO1) and quantification limits (range from 0.01 µg L-1 for: C12EO5-7 to 2 µg L-1 for C12EO1). The developed and validated method was used in combination with liquid-liquid extraction (using ethyl acetate) in order to identify and quantitatively determine the C12OH and C12EO1-9 present in environmental samples collected from Warta river water in Poznan.

Efficient methanogenic degradation of alcohol ethoxylates and microbial community acclimation in treatment of municipal wastewater using a submerged anaerobic membrane bioreactor.

The effect of alcohol ethoxylates on the treatment of municipal wastewater by a submerged anaerobic membrane bioreactor was investigated by a 400days operation including the treatment efficiency, methanogenic activity of sludge and microbial community structure. The results indicated that alcohol ethoxylates (5.0-200mg/L) was efficiently degraded and converted into methane due to the similar COD removal 95.5-98.8% and rising biogas production rate (2.30-4.25L/d) compared with control (96.8% and 2.55L/d). The microbes in sludge could copy with the presence of alcohol ethoxylates in wastewater by releasing more SMP and EPS, which caused a higher membrane fouling rate. Moreover, via long term acclimation, the specific methanogenic activity of sludge was greatly enhanced due to the changes of microbial community structure. Hence, the sludge self-acclimation to alcohol ethoxylates was responsible to the efficient methane recovery in treatment of municipal wastewater.

Comparison of Oleo- vs Petro-Sourcing of Fatty Alcohols via Cradle-to-Gate Life Cycle Assessment.

Alcohol ethoxylates surfactants are produced via ethoxylation of fatty alcohol (FA) with ethylene oxide. The source of FA could be either palm kernel oil (PKO) or petrochemicals. The study aimed to compare the potential environmental impacts for PKO-derived FA (PKO-FA) and petrochemicals-derived FA (petro-FA). Cradle-to-gate life cycle assessment has been performed for this purpose because it enables understanding of the impacts across the life cycle and impact categories. The results show that petro-FA has overall lower average greenhouse gas (GHG) emissions (~2.97 kg CO2e) compared to PKO-FA (~5.27 kg CO2e). (1) The practices in land use change for palm plantations, (2) end-of-life treatment for palm oil mill wastewater effluent and (3) end-of-life treatment for empty fruit bunches are the three determining factors for the environmental impacts of PKO-FA. For petro-FA, n-olefin production, ethylene production and thermal energy production are the main factors. We found the judicious decisions on land use change, effluent treatment and solid waste treatment are key to making PKO-FA environmentally sustainable. The sensitivity results show the broad distribution for PKO-FA due to varying practices in palm cultivation. PKO-FA has higher impacts on average for 12 out of 18 impact categories evaluated. For the base case, when accounted for uncertainty and sensitivity analyses results, the study finds that marine eutrophication, agricultural land occupation, natural land occupation, fossil depletion, particulate matter formation, and water depletion are affected by the sourcing decision. The sourcing of FA involves trade-offs and depends on the specific practices through the PKO life cycle from an environmental impact perspective.

Determination of the four major surfactant classes in cleaning products by reversed-phase liquid chromatography using serially connected UV and evaporative light-scattering detection.

A method for the simultaneous determination of the most frequently used surfactant families -linear alkyl benzenesulphonates (LAS), alkyl ether sulphates (AES), fatty alcohol ethoxylates (FAE) and oleins (soaps, fatty acid salts) - in cleaning products, has been developed. The common reversed phase octyl (C8), pentafluorophenyl and biphenyl columns were not capable of separating the anionic LAS and AES classes; however, since only LAS absorbs in the UV, these two classes were independently quantified using a C8 column and serially connected UV and ELSD detection. The best compromise to resolve the four surfactant classes and the oligomers within the classes was achieved with a C8 column and an ACN/water gradient. To enhance retention of the anionic surfactants, ammonium acetate, as an ion-pairing agent compatible with ELSD detection, was used. Also, to shift the olein peaks with respect to that of the FAE oligomers, acetic acid was used. In the optimized method, modulation of the mobile phase, using ammonium acetate during elution of LAS and AES, and acetic acid after elution of LAS and AES, was provided. Quantitation of the overlapped LAS and AES classes was achieved by using the UV detector to quantitate LAS and the ELSD to determine AES by difference. Accuracy in the determination of AES was achieved by using a quadratic model, and by correcting the predicted AES concentration according to the LAS concentration previously established using the UV chromatogram. Another approach also leading to accurate predictions of the AES concentration was to increase the AES concentrations in the samples by adding a standard solution. In the samples reinforced with AES, correction of the predicted AES concentration was not required. FAE and olein were quantified using also quadratic calibration.

Water Sorption Isotherms of Surfactants: A Tool To Evaluate Humectancy.

Fundamental experimental data for moisture absorption of non-ionic polydisperse surfactants with differing ethylene oxide (EO) content and variable aliphatic portions were measured at relative humidities between 0 and 95% at 25 °C. Remarkable differences in moisture absorption were observed between surfactant classes but also within one series of surfactants differing in either EO content or the long-chain aliphatic fraction. Both the EO units as well as the entire molecular structure, including also the lipophilic domain, were discussed to account for the humectant activity of surfactants. Water sorption isotherms showed an exponential shape, which was argued to be associated with the formation of a "free" water domain. These humectant properties might be relevant to the behavior of a foliar-applied spray droplet of agrochemical formulation products because the uptake of active ingredients will be enhanced as a result of deferred crystal precipitation.

Single-pump heart-cutting two-dimensional liquid chromatography applied to the determination of fatty alcohol ethoxylates.

A setup for heart-cutting bi-dimensional liquid chromatography (LC-LC), constructed with a chromatograph provided with a single pump, an auxiliary 6-port 2-position valve (V6/2) and a column selector valve (VCS), is described. The possible ways of connecting the two valves for LC-LC, namely with V6/2 first followed by VCS and vice versa, are compared. The possibility of using the setups for preconcentration followed by the backwards transfer of the preconcentrated solutes to the detector or to a second column is also shown. The V6/2-first configuration for LC-LC was applied to the characterization of industrial fatty alcohol ethoxylates (FAEs) using UV-vis detection. For this purpose, the phthalates of the FAE oligomers were first obtained. The hydrocarbon series were separated along the 1st dimension by MeOH/water gradient elution on a C8 column at 60°C. Selected segments of the eluate were transferred to the 2nd dimension, where the EO oligomers of the isolated series were resolved by gradient elution with a complementary ACN/water mobile phase on a C8 column at 25°C. In addition, an average response factor of the hydrocarbon series of FAEs was proposed. To apply the factors, the average EO number of the series is first established by chromatographing one of the series along the 2nd dimension. Then, the factors are used to correct the peak areas of the isolated series which are obtained along the 1st dimension chromatogram, thus allowing the fast and accurate determination of the series in industrial FAEs. The method is particularly useful to characterize FAEs having large average EO numbers or constituted by mixtures of even and odd series.

Separation and determination of homogenous fatty alcohol ethoxylates by liquid chromatography with mulitstage mass spectrometry.

Alcohol ethoxylates (AEs) are a significant component of a stream of surfactants directed to the aquatic environment. The aim of this work was the investigation of the dependence of the analytical signals of homogeneous AE homologues on liquid chromatography with tandem mass spectrometry conditions, as well as the separation of AEs from the water matrix and, on this basis, the development of an analytical procedure suitable for the determination of AEs in environmental samples. Homogeneous homologues containing dodecyl moiety and 2-9 oxyethylene subunits were investigated. The analytical signals of the investigated homologues were optimized in terms of concentration of ammonium acetate in the mobile phase (optimum 5 mM) and a column temperature (optimum 35°C) of the liquid chromatography with tandem mass spectrometry system. A separation of AEs from the water matrix by liquid-liquid extraction (ethyl acetate, chloroform) or solid-phase extraction (C18 , styrene divinylbenzene, H-RX) was investigated. In a model investigation, the best recoveries (>90%) were obtained with a styrene divinylbenzene cartridge eluted with a 1:1 mixture of chloroform and methanol. However, much worse recoveries were obtained from the river water sample. Better results were obtained for liquid-liquid extraction with ethyl acetate. Recoveries of 62-80% were obtained for homologues having 4-9 oxyethylene subunits, at the lowest spike.

Determination of non-ionic and anionic surfactants in industrial products by separation on a weak ion-exchanger, derivatization and liquid chromatography.

A method for the determination of priority surfactants, including fatty alcohol ethoxylates (FAE), alkylether sulfates (AES) and linear alkylbenzene sulfonates (LAS) is described. The samples were diluted with 50% methanol at pH 4 prior to solid-phase extraction on a weak anionic exchanger (WAX). The AES and LAS surfactant classes were retained, whereas the non-ionic components, including most FAE oligomers were eluted. After washing the WAX cartridge to remove cations, the remaining hydrophobic FAE oligomers were eluted using hot 80% methanol at pH 4 (at ca. 50°C). These two eluates were combined to constitute the non-ionic fraction. Then, AES and LAS were eluted using 80% MeOH with 3M NH3 followed by 95% methanol with 0.75M NH3. The two eluates obtained in basic media were combined to constitute the anionic fraction. The solvents were evaporated, the residues were dissolved in 1,4-dioxane, and esterification of the alcohols and transesterification of AES with phthalic anhydride was performed. Separation of the derivatized oligomers was achieved by gradient elution on a C8 column with acetonitrile/water in the presence of 0.1% acetic acid and 0.1M NaClO4. The chromatogram of the non-ionic fraction showed the peaks of the resolved FAE oligomers. The chromatogram of the anionic fraction showed the peaks of the LAS homologues well resolved from those of the AES oligomers. The method was applied to laundry and industrial cleaners, shampoos and a shower gel.

Occurrence and risk screening of alcohol ethoxylate surfactants in three U.S. river sediments associated with wastewater treatment plants.

Alcohol ethoxylates (AE) are high production volume (HPV) chemicals globally used in detergent and personal care products and are truly a work-horse for the household and personal care industries. Commercial AE generally consist of a mixture of several homologues of varying carbon chain length and degree of ethoxylation. Homologues that are not ethoxylated are also known as aliphatic alcohols or simply fatty alcohols (FA). This group of homologues represents a special interest in the context of environmental risk, as these are also abundant and ubiquitous naturally occurring compounds (e.g. animal fats and in human feces). Hence, in a risk assessment one needs to distinguish between the natural (background) concentrations and the added contribution from anthropogenic activities. We conducted a weight-of-evidence risk assessment in three streams, documenting the exposure and predicted risk, and compared these to the habitat and in situ biota. We found that the parameters (e.g., habitat quality and total perturbations hereunder total suspended solids (TSS) and other abiotic and biotic stressors) contributed to the abundance of biota rather than the predicted risk from AE and FA. Moreover, the documented natural de novo synthesis and rapid degradation of FA highlight the need to carefully consider the procedures for environmental risk assessment of naturally occurring compounds such as FA, e.g. in line with the added risk concept known from metal risk assessment.

Rapid liquid chromatography-tandem mass spectrometry-based method for the analysis of alcohol ethoxylates and alkylphenol ethoxylates in environmental samples.

A sensitive and selective method for the determination of alcohol ethoxylates (AEOs) and alkylphenol ethoxylates (APEOs) using solid-phase extraction (SPE) and LC-MS/MS was developed and applied to the analysis of water samples. All AEO and APEO homologues, a total of 152 analytes, were analyzed within a run time of 11min, and the MS allowed for the detection of ethoxymers containing 2-20 ethoxy units (nEO=2-20). The limits of detection (LOD) were as low as 0.1pg injected, which generally increased as nEO increased (e.g., as high as 300pg for nEO=20). Additionally, the responses of the various ethoxymers varied by orders of magnitude, with ethoxymers with nEO=3-5 being the most sensitive and those with nEO>15 producing the least response in the MS. Absolute extraction recoveries of the analytes ranged from 37% to 69% in ultrapure water (RSD≤20%), with the recovery depending on the length of the alkyl chain. Abiotic stability studies were performed, and C14-18 ethoxylates showed significant degrees of degradation. Water samples from the Colorado River were then analyzed for AEOs and APEOs, with absolute extraction recoveries ranging from 33% to 45% (RSD≤12%). The predominant species observed in most samples were the octylphenol (OP) and nonylphenol (NP) ethoxylates, which contained total concentrations that were greater than 100ng/L APEOs in a couple samples. Other AEO homologues were identified in the river water samples, including C13, C15, C16, and C18 ethoxylates, but these compounds were generally present at much lower levels (i.e., <50ng/L total concentration).

Liposome-water and octanol-water partitioning of alcohol ethoxylates.

Liposome-water partitioning coefficients, (Klipw s), were determined for eight pure alcohol ethoxylates using equilibrium dialysis and ultracentrifugation. Both methods yielded statistically indistinguishable results. The experimentally determined log Klipw s were compared with log Kow values estimated with the fragment method using different literature sources for the fragment constants. Fragments of log Klipw were calculated for the ethoxy group (EO) and the -CH2 - units from the experimentally determined data. An additional -CH2 - unit causes an average increase of log Klipw by 0.45, and an additional EO causes an average decrease of log Klipw by -0.12. With these fragments, the quality of log Klipw estimations can be improved significantly as compared to simple linear regression of log Klipw versus log Kow . The Klipw values calculated according to the new fragment method for pure compounds and for commercial mixtures are shown to be adequate descriptors for quantitative structure-activity relationships of bioaccumulation, toxicity, and sorption to natural organic material.