High-Throughput Fluorometric Assay For Quantifying Polysorbate In Biopharmaceutical Products Using Micelle Activated Fluorescence Probe N-Phenyl-1-Naphthylamine.

PURPOSE: Polysorbates are among the most used surfactants in biopharmaceutical products containing proteins. Our work aims to develop a high-throughput fluorometric assay to further diversify the analytical toolbox for quantification of PSs. METHOD: The assay leverages the micelle activated fluorescence signal from N-Phenyl-1-Naphthylamine (NPN). The development and optimization of assay parameters were guided by the pre-defined analytical target profile. Furthermore, NMR was used to probe the interaction between protein, PS80 and NPN in the measurement system and understand protein interference. RESULTS: All assay parameters including excitation and emission wavelengths, standard curve, NPN concentration, and incubation time have been optimized and adapted to a microplate format, making it compatible with automated solutions that will be pursued in the near future to drive consistency and efficiency in our workflows. The specificity, accuracy, and precision of the assay have been demonstrated through a case study. Furthermore, NMR results provided additional insight into the change of the interaction dynamics between PS80 and NPN as the protein concentration increases. The results indicate minimal interaction between the protein and PS80 at lower concentration. However, when the concentration exceeds 75 mg/mL, there is a significant interaction between the protein and PS-80 micelle and monomer. CONCLUSION: A high-throughput fluorometric assay has been developed for quantification of polysorbates in biopharmaceutical samples including in-process samples, drug substance and drug product. The assay reported herein could serve as a powerful analytical tool for polysorbate quantification and control, complementing the widely used liquid chromatography with charged aerosol detection method.

Characterizing Volatile Emissions and Combustion Byproducts from Aqueous Film-Forming Foams Using Online Chemical Ionization Mass Spectrometry.

Aqueous film-forming foams (AFFFs) are used in firefighting applications and often contain per- and polyfluoroalkyl substances (PFAS), which can detrimentally impact environmental and biological health. Incineration is a potential disposal method for AFFFs, which may produce secondary PFAS and other air pollutants. We used online chemical ionization mass spectrometry (CIMS) to measure volatile PFAS emissions from incinerating AFFF concentrate solutions. We quantified perfluorinated carboxylic acids (PFCAs) during the incineration of legacy and contemporary AFFFs. These included trifluoroacetic acid, which reached mg m-3 quantities in the incinerator exhaust. These PFCAs likely arose as products of incomplete combustion of AFFF fluorosurfactants with lower peak furnace temperatures yielding higher PFCA concentrations. We also detected other short-chain PFAS, and other novel chemical products in AFFF combustion emissions. The volatile headspace above AFFF solutions contained larger (C ≥ 8), less oxidized PFAS detected by CIMS. We identified neutral PFAS resembling fluorotelomer surfactants (e.g., fluorotelomer sulfonamide alkylbetaines and fluorotelomer thioether amido sulfonates) and fluorotelomer alcohols in contemporary AFFF headspaces. Directly comparing the distinct chemical spaces of AFFF volatile headspace and combustion byproducts as measured by CIMS provides insight toward the chemistry of PFAS during thermal treatment of AFFFs.

Biodegradation of oil-contaminated aqueous ecosystem using an immobilized fungi biomass and kinetic study.

Remediation of environmental oil pollution with the usage of fungal organisms has proven to be a successful cleanup bioremediation method for organic contaminants. To investigate the breakdown of oil pollutants in water environments, biosurfactant-producing fungi have been isolated from oil-polluted soil samples. 16s rRNA sequencing technique was performed to identify the fungal organism and phylogenetic tree has been constructed. A variety of biosurfactant screening tests have demonstrated the better biosurfactant producing ability of fungi. The emulsion's stability, which is essential for the biodegradation process, was indicated by the emulsification index of 68.48% and emulsification activity of 1.3. In the isolated biosurfactant, important functional groups such as amino groups, lipids, and sugars were found according to thin layer chromatography analysis with a maximum retention value of 0.85. A maximum oil degradation of around 64% was observed with immobilized beads within 12 days. The half-life, and degradation removal rate constant of 20.21 days and 0.03 day-1, respectively, have been determined by the degradation kinetic analysis. GCMS analysis confirmed the highly degraded hydrocarbons such as nonanoic acid and pyrrolidine. The immobilized fungi exhibit better oil biodegradability in aqueous solutions.

Synthetic surfactants in drinking and surface waters in Armenia and apparent non-association with some diseases.

The main goal of this study is to compare the concentrations of anionic synthetic surfactants (ASS) in drinking and surface waters in Armenia and to explore possible relationship with diseases of the skin and digestive system. Surfactants are widely employed in numerous field of the economy, are in contact with the entire population throughout life and can be harmful to human health.The samples of drinking and surface waters (n = 144) were collected in Kotayk province to analyze ASS concentrations, physicochemical parameters and phytotoxic activity. The prevalence of diseases was analyzed for different population groups. ASS concentrations in surface waters were significantly higher in summer compared to spring (p = 0.006). In drinking water, concentrations were also higher in summer, but not significantly. In surface waters, ASS levels were 2.4-3 times higher compared to drinking (p = 0.03) and exceeded the permissible limit by 1.4-2.9 times in summer and fall. No phytotoxic activity and differences in both classes of diseases and age groups were revealed. The determination of ASS in both surface and drinking waters with the same trend showed their interrelation to a certain extent. This study provides important information for future research and action which will contribute to the sustainable development of local communities.

The surfactant Dioctyl Sodium Sulfosuccinate (DOSS) exposure causes adverse effects in embryos and adults of zebrafish (Danio rerio).

Dioctyl Sodium Sulfosuccinate (DOSS, CAS 577-11-7) is a chemical emulsifying surfactant that is widely used in the food and the cosmetic industry, and it is also the major component of the crude oil chemical dispersant Corexit™. Despite of its wide use, the studies related to its negative effect have been evaluated mainly in marine environments showing that DOSS is highly bioactive, extremely low volatile, and potential to persist in the environment longer than other dispersant components. Up to date, there is no available information of DOSS concentration in freshwater environments, little is known about its downstream fate after excretion and its effect on freshwater organisms. The objective of this study was to evaluate the effect of DOSS at different concentrations in embryos and adults of zebrafish Danio rerio in an acute-static bioassays of 96 h. The median lethal concentration in embryos was 33.3 mg/L. Malformations started to be observed at 10 mg/L. In adults, the gene expression analysis in gill tissues showed a deregulation in genes associated with the antioxidant system and the nucleotide excision repair mechanism. Additionally, Micronuclei (DNA damage) in erythrocytes, and fat degeneration in liver, hypertrophy and hyperplasia in gills, and hyaline drops in kidney tissues were also observed. In conclusion, the concentrations of DOSS evaluated here would be of health relevance to fish based on morphological alterations in embryos and changes in the gene expression profile, DNA damage and tissue impairment in adults.

Utilization of surface-active compounds derived from biosolids to remediate polycyclic aromatic hydrocarbons contaminated sediment soil.

In the present study, surface-active compounds (SAC) were extracted from biosolids using an alkaline treatment process. They were tested for their remediation efficiency of crude oil-contaminated sediment soil and was compared with Triton x-100. The SAC exhibited a similar soil washing efficiency to that of the commercial Triton x-100, and under the optimized soil washing parameters, SAC exhibited a maximum of 91% total polycyclic aromatic hydrocarbons removal. Further, on analysing the toxicity of the soil residue after washing, it was observed that SAC from biosolids washed soil exhibited an average of 1.5-fold lesser toxicity compared to that of Triton x-100 on different test models-earthworm, a monocot, and dicot plants. The analysis of the key soil parameters revealed that the commercial surfactant reduced the soil organic matter and porosity by an average of 1.3-fold compared to SAC. Further, the ability of surfactants to induce toxicity was confirmed by the adsorption of the surfactants on the surface of the soil particles which was in the order of Triton x-100 > SAC. Thus, this study suggests that SAC can be applied as an effective bioremediation approach for contaminated soil for a greener and sustainable ecosystem.

Challenges in direct determination of Glyphosate and aminomethylphosphonic acid in water by liquid chromatography-tandem mass spectrometry at modified reverse phase columns: Effect of matrix interferences in fresh and hard water systems.

This study validated two underivatized methods (M1 and M2) according to the Eurachem guidelines to analyze the herbicide Glyphosate and its major metabolite aminomethylphosphonic acid simultaneously by liquid chromatography-tandem mass spectrometry in both fresh and hard waters. Samples were analyzed directly after filtration through 0.22 µm syringe filters in M1, while samples were acidified with acetic acid before filtration in M2. Spike recoveries were greater than 80% for Glyphosate and aminomethylphosphonic acid in both methods. The limit of quantitation was 0.5 µg/L for M1, and 0.1 µg/L for M2 by using matrix-matched calibrations. The linear regression coefficient of both methods was greater than 0.995. The expanded uncertainty was found to be less than 25% for both. Moreover, M1 has an additional mass spectral confirmation ability, and the column and the mobile phase used in M2 can be used to analyze the inert surfactant used in Glyphosate formulations, Polyethoxylated tallow amine. The accuracy of the developed methods was assured by participating in a proficiency testing program against M2 and conducting the t-test for results generated by both M1 and M2. Both methods, therefore, can be used to determine Glyphosate and aminomethylphosphonic acid content concurrently in fresh and hard waters.

Implications of microbial enhanced oil recovery and waterflooding for geochemical interpretation of recovered oils.

Biosurfactants and waterflooding have been widely reported thus far for enhancing oil production. Nevertheless, there is a lack of literature to explore enhanced oil recovered methods effects on its chemical composition. The aim of this work is to investigate the effects of a biosurfactant produced by Bacillus safensis and brine injection on the recovered petroleum composition, and their implications for geochemical interpretation. Original and oils recovered from displacement tests were analyzed by gas chromatography and ultra-high-resolution mass spectrometry, emphasizing saturated and aromatic biomarkers and basic and acidic polar compounds. Geochemical parameters based on some saturated compounds were subtly affected by the recovery methods, showing their reliable applicability in geochemical studies. Contrarily, parameters based on some aromatic compounds were more affected by biosurfactant flooding, mostly the low molecular weight compounds. Thus, these aromatic parameters should be applied with caution after such methods. The distribution of basic and acidic polar compounds can also be modified affecting the geochemical interpretation. In the case of the basic ones, the biosurfactant greatly influenced the N class species with favorable loss of lower aromaticity compounds. In addition to water solubilization, the compositional changes described in this study can be related to fractionation due to adsorption on reservoir rocks.

The Role of pH, Electrodes, Surfactants, and Electrolytes in Electrokinetic Remediation of Contaminated Soil.

Electrokinetic remediation has, in recent years, shown great potential in remediating polluted environments. The technology can efficiently remove heavy metals, chlorophenols, polychlorinated biphenyls, phenols, trichloroethane, benzene, toluene, ethylbenzene, and xylene (BTEX) compounds and entire petroleum hydrocarbons. Electrokinetic remediation makes use of electrolysis, electroosmosis, electrophoresis, diffusion, and electromigration as the five fundamental processes in achieving decontamination of polluted environments. These five processes depend on pH swings, voltage, electrodes, and electrolytes used in the electrochemical system. To apply this technology at the field scale, it is necessary to pursue the design of effective processes with low environmental impact to meet global sustainability standards. It is, therefore, imperative to understand the roles of the fundamental processes and their interactions in achieving effective and sustainable electrokinetic remediation in order to identify cleaner alternative solutions. This paper presents an overview of different processes involved in electrokinetic remediation with a focus on the effect of pH, electrodes, surfactants, and electrolytes that are applied in the remediation of contaminated soil and how these can be combined with cleaner technologies or alternative additives to achieve sustainable electrokinetic remediation. The electrokinetic phenomenon is described, followed by an evaluation of the impact of pH, surfactants, voltage, electrodes, and electrolytes in achieving effective and sustainable remediation.

Benefit of coconut-based hair oil via hair porosity quantification.

OBJECTIVE: The present study is intended to characterize the surfactant damage suffered by the hair cortex in routine washing and the mechanistic effect of Coconut Based Hair Oils (CBHO) to mitigate the damage. METHODS: Surfactants which diffuse into the hair structure solubilize protein moieties, leading to an increase in porosity and internal surface area as well as the pore volume. The changes in hair pores occurring in the hair cortex are measured by nitrogen sorption method in line with the Brunauer-Emmett-Teller (BET) theory. Single fiber tensile parameters were measured using Diastron MTT 175. Color protection was measured quantitatively using spectrophotometer as well as visual rating by trained panelists. RESULTS: The pore surface area data clearly show the benefit of introducing coconut-based hair oils (CBHO) into the hair by preventing increase in hair porosity. A statistically significant decrease in break stress and toughness were observed and the same were reversed by the application of CBHO. A pronounced color protection effect was also recorded with the application of CBHO. CONCLUSION: The porosity reduction effect seen with the use of CBHO is attributed to the CBHO molecules blocking the diffusion pathways in the endocuticle and the matrix part of the cortical cells, limiting protein surfactant interaction resulting in reduced solubilization and loss. Since, the color molecules are likely to be much smaller than the protein moieties, a pronounced color protection effect suggests that the penetrated CBHO molecules form a dense diffusion barrier in the matrix, cell membrane complex (CMC) and the endocuticle regions of hair - which are the main diffusion pathways out of hair. The study confirms the damage repair potential of CBHO and that it works by increasing the hydrophobicity of hair - both on the hair surface and in the cortex.

OBJECTIF: La présente étude a pour but de caractériser les dommages causés par les surfactants au cortex pilaire lors des lavages de routine et l'effet mécanique des huiles capillaires à base de noix de coco (CBHO) pour atténuer ces dommages. MÉTHODES: Les tensioactifs qui diffusent dans la structure du cheveu solubilisent les fractions de protéines, ce qui entraîne une augmentation de la porosité et de la surface interne ainsi que du volume des pores. Les modifications des pores du cheveu survenant dans le cortex pilaire sont mesurées par la méthode de sorption de l'azote, conformément à la théorie de Brunauer-Emmett-Teller (BET). Les paramètres de traction de la fibre unique ont été mesurés à l'aide du Diastron MTT 175. La protection de la couleur a été mesurée quantitativement en utilisant un spectrophotomètre ainsi qu'une évaluation visuelle par des panélistes formés. LES RÉSULTATS: Les données sur la surface des pores montrent clairement l'avantage d'introduire des huiles capillaires à base de noix de coco (CBHO) dans les cheveux en empêchant l'augmentation de la porosité des cheveux. Une diminution statistiquement significative de la contrainte de rupture et de la résistance a été observée, qui a été inversée par l'application de CBHO. Un effet prononcé de protection de la couleur a également été enregistré avec l'application de CBHO. LA CONCLUSION: L'effet de réduction de la porosité observé avec l'utilisation de CBHO est attribué aux molécules de CBHO bloquant les voies de diffusion dans l'endocuticule et la partie matricielle des cellules corticales, limitant l'interaction protéine surfactant résultant en une solubilisation et une perte réduite. Étant donné que les molécules de couleur sont probablement beaucoup plus petites que les parties protéiques, un effet prononcé de protection de la couleur suggère que les molécules CBHO pénétrées forment une barrière de diffusion dense dans la matrice, le complexe de la membrane cellulaire (CMC) et les régions endocuticulaires des cheveux - qui sont les principales voies de diffusion hors des cheveux. L'étude confirme le potentiel de réparation des dommages du CBHO et le fait qu'il agit en augmentant l'hydrophobie des cheveux - à la fois sur la surface du cheveu et dans le cortex.

Physico-chemical and thermal characteristics of sandy loam soils contaminated by single and mixed pollutants (mineral and vegetable oils).

Samples of contaminated top soil (0-30 cm) and uncontaminated soil (control) from two locations in Precambrian basement complex area were analyzed to assess the effects of single and mixed oil contaminants on the physico-chemical and thermal properties of soils. Pearson's correlation and analysis of variance (ANOVA) were used to study the interrelationships of the studied parameters as well as variation of studied soil characteristics under the different oil contaminants, respectively. Results showed insignificant impact of pollutant(s) on the textural class of contaminated soils. The highest and lowest mean soil resistivity (SR) values were found in petrol-contaminated and mixed surfactants (shampoo + conditioner) -contaminated soils, respectively. The least values of mean specific heat capacity (SHC), heat capacity (HC), and soil water diffusivity (SWD) were found in soils contaminated by mixed surfactants-contaminants. However, mixed mineral oils (petrol + diesel + engine oil) and mixed vegetable oils (palm oil + groundnut oil) had mean SHC values lower than those of control soils at the two sampling locations. The mixed surfactants-polluted soil is characterized by lowest mean bulk density (BD) and highest mean gravimetric water content (GWC) while lowest mean GWC and highest mean SWD characterized engine oil-contaminated soils. The analysis of variance (ANOVA) result revealed significant variation in % sand at 5% level (p < 0.05) for petroleum-derived contaminants but no significant differences in mean values of all analyzed soil properties under vegetable oil contaminants.

Separation and determination of alkyl sulfate surfactants in wastewater by capillary electrophoresis coupled with contactless conductivity detection after preconcentration by simultaneous adsorption using alumina beads.

The aim of the present study is to determine four anionic alkyl sulfate (AS) surfactants with different alkyl chains, namely, C8, C10, C12, and C14, in wastewater by CE with capacitively coupled contactless conductivity detection (CE-C4 D). The conditions effective for the separation of the four AS surfactants were systematically optimized and found to be in a Tris-His (50 mM/20 mM) BGE solution at a pH of 8.95, using a separation voltage of +15 kV, hydrodynamic injection by siphoning using a 20 cm injection height and an injection time of 20 s. The LODs for C8, C10, C12, and C14 were 2.58, 2.30, 2.08, and 3.16 mg/L, respectively. The conditions used to achieve the simultaneous adsorption and preconcentration of the AS surfactants using Al2 O3 beads were pH of 3 and 0.1 mM NaCl. The adsorption efficiencies were found to be 45.6, 50.8, 81.7, and 99.9%, while the desorption efficiencies reached 66.1, 70.4, 83.9, and 100.0% for C8, C10, C12, and C14, respectively. The concentrations of the AS surfactants in wastewater samples were quantified by CE-C4 D after preconcentration by simultaneous adsorption using Al2 O3 beads. The results obtained from the proposed method were consistent with those obtained by HPLC-MS/MS, with a deviation of less than 15%. Our results indicate that the CE-C4 D performed after preconcentration by an adsorption technique using Al2 O3 beads is a new, inexpensive, and suitable method for quantifying AS surfactants in wastewater samples.

Seeking faster, alternative methods for glycolipid biosurfactant characterization and purification.

Biosurfactants have been investigated as potential alternatives for synthetic surfactants in several areas, for example, in environmental and pharmaceutical fields. In that regard, extensive research has been carried out with sophorolipids and rhamnolipids that also present various biological properties with therapeutic significance. These biosurfactants are obtained as complex mixtures of slightly different molecules, and thus when studying these microbial glycolipids, the ability to identify and purify the produced compounds is of extreme importance. This study aimed to develop improved methodologies for the identification, separation, and purification of sophorolipids and rhamnolipids. Therefore, an ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was modified to ensure faster characterization of both sophorolipids and rhamnolipids, enabling the identification and fragmentation pattern description of 10 and 13 congeners, respectively. The separation and purification of these biosurfactants was achieved with novel reversed-phase solid-phase extraction methods guaranteeing the isolation of different glycolipids, including those considered for their significant biological activity (e.g. antimicrobial, anticancer). It was possible to isolate sophorolipids and rhamnolipids with purity of 94% and 99%, respectively. The methods presented herein can be easily implemented and are expected to make purification of these biosurfactants easier, facilitating the study of their individual properties in further works.

Isomer separation and analysis of amphiphilic polysialogangliosides using reversed-phase liquid chromatography-mass spectrometry.

Gangliosides are amphiphilic, acidic glycosphingolipids possessing one or more sialic acid residues and several isobaric structural isomers with different abundances and bioactivities. Therefore, the distinction between these isomers is crucial for their proper profiling. Although liquid chromatography-mass spectrometry has been successfully employed for this purpose, the distinction process can still be improved, particularly regarding liquid chromatography. Recently, a reversed-phase liquid chromatography method that could separate disialoganglioside isomers was reported; however, the distinction of trisialoganglioside isomers using reversed-phase liquid chromatography has not been demonstrated. Here, we investigated the practicality of a reversed-phase liquid chromatography with an octadecylsilane column for separating polysialoganglioside isomers and successfully achieved the isomer separation of disialogangliosides and trisialogangliosides for the first time. We also confirmed several crucial factors in the mobile-phase composition, which affect the differential retention and mass spectral response of the isomers. First, an organic modifier, acetonitrile, exhibited superior selectivity against polysialogangliosides over methanol. Second, ammonium bicarbonate was the best ammonium salt additive among those tested, in terms of the separation efficiency and mass spectral response. Third, as the ammonium salt concentration increased, the negative electrospray ionization response was extensively suppressed, and the retention of gangliosides increased.

A microfluidic column of water index-matched packed microspheres for label-free observation of water pollutants.

A microfluidic, label-free optical sensor for water pollutants, which is based on a packed micro-column of microspheres with refractive index similar to that of water, is presented. The perfluoropolyether microspheres are synthetized by membrane emulsification followed by UV irradiation. The microfluidic channel hosting the packed column is transparent when filled with pure water as a consequence of refractive index matching, whereas it scatters light in presence of compounds with lipophilic moieties that spontaneously adsorb on the fluorinated microspheres. The device is characterized by investigating the response to cationic and anionic surfactants. Both the signal growth rate and the recovery rate measured during washing with water depend on the type and concentration of the compounds. The cationic surfactants tested display a larger signal increase, linearly scaling with concentration. A limit of detection of 1 µM is obtained in the current configuration. The water index-matched microspheres enable to access an additional analytical parameter, that is the propagation velocity of the scattering signal along the column. This parameter is also found to scale linearly with concentration, hence providing a complementary analytical tool sensitive to the adhesion kinetics.

Potentiometric Surfactant Sensor Based on 1,3-Dihexadecyl-1H-benzo[d]imidazol-3-ium for Anionic Surfactants in Detergents and Household Care Products.

A 1,3-dihexadecyl-1H-benzo[d]imidazol-3-ium-tetraphenylborate (DHBI-TPB) ion-pair implemented in DHBI-TPB surfactant sensor was used for the potentiometric quantification of anionic surfactants in detergents and commercial household care products. The DHBI-TPB ion-pair was characterized by FTIR spectroscopy and computational analysis which revealed a crucial contribution of the C-H∙∙∙π contacts for the optimal complex formation. The DHBI-TPB sensor potentiometric response showed excellent analytical properties and Nernstian slope for SDS (60.1 mV/decade) with LOD 3.2 × 10-7 M; and DBS (58.4 mV/decade) with LOD 6.1 × 10-7 M was obtained. The sensor possesses exceptional resistance to different organic and inorganic interferences in broad pH (2-10) range. DMIC used as a titrant demonstrated superior analytical performances for potentiometric titrations of SDS, compared to other tested cationic surfactants (DMIC > CTAB > CPC > Hyamine 1622). The combination of DHBI-TPB sensor and DMIC was successfully employed to perform titrations of the highly soluble alkane sulfonate homologues. Nonionic surfactants (increased concentration and number of EO groups) had a negative impact on anionic surfactant titration curves and a signal change. The DHBI-TPB sensor was effectively employed for the determination of technical grade anionic surfactants presenting the recoveries from 99.5 to 101.3%. The sensor was applied on twelve powered samples as well as liquid-gel and handwashing home care detergents containing anionic surfactants. The obtained results showed good agreement compared to the outcomes measured by ISE surfactant sensor and a two-phase titration method. The developed DHBI-TPB surfactant sensor could be used for quality control in industry and has great potential in environmental monitoring.

Application of genetic algorithm and multivariate methods for the detection and measurement of milk-surfactant adulteration by attenuated total reflection and near-infrared spectroscopy.

BACKGROUND: The adulteration of milk by hazardous chemicals like surfactants has recently increased. It conceals the quality of the product to gain profit. As milk and milk-based products are consumed by many people, novel analytical procedures are needed to detect these adulterants. This study focused on Fourier-transform infrared (FTIR) spectroscopy equipped with an attenuated total reflection (ATR) accessory, and near-infrared (NIR) spectroscopy for the determination of milk-surfactant adulteration using a genetic algorithm (GA) coupled with multivariate methods. The model surfactant was sodium dodecyl sulfate (SDS), and its concentration varied from 1.94-19.4 gkg-1 in adulterated samples. RESULTS: Prominent peaks in the spectral range of 5500-6400 cm-1 , 1160-1260 cm-1 and 1049-1080 cm-1 may correspond to the sulfonate group in SDS. A genetic algorithm could significantly reduce the number of variables to almost one third by selecting the specific wavenumber region. Principal component analysis (PCA) for ATR and NIR data indicated separate clusters of samples in terms of the concentration level of SDS (P ≤ 0.05). Partial least squares regression (PLSR) was used to determine the maximum R2 value for ATR and NIR data for calibration, cross-validation and prediction, which were 0.980, 0.972, 0.980, and 0.970, 0.937, and 0.956 respectively. The results showed apparent differences between unadulterated and adulterated samples using partial least squares-discriminant analysis (PLS-DA), which was validated by the permutation test. CONCLUSION: The results clearly show the successful application of the proposed methods with multivariate analysis in the selection of variables, classification, clustering, and identification of the adulterant in amounts as low as 1.94 gkg-1 in milk. © 2020 Society of Chemical Industry.

Structure and conductivity of AOT solutions in n-hexadecane-chloroform mixtures.

The structure and conductivity of AOT (sodium bis(2-ethylhexyl) sulfosuccinate) solutions (2.5 × 10-4 -2.5 × 10-1 M) in n-hexadecane-chloroform mixture at the chloroform concentration from 50 to 100 vol% were studied. The diffusion ordered spectroscopy NMR study revealed that in the indicated range, the observed hydrodynamic diameter of micelles depends only on the AOT concentration and does not depend on the chloroform content. Molar fractions of free AOT molecules and those aggregated into micelles were calculated using the Lindman's law: at concentrations above 2.5 × 10-1 М, the solutions contain mostly the micelles, whereas at concentrations below 2.5 × 10-4 M, the solutions contain AOT molecules. The transition region contains both the AOT molecules and the micelles. Conductivity measurements were used to determine free charge carriers in the bulk of solutions and their contributions to conductivity.

Enhanced marine monitoring and toxicity study of oil spill dispersants including Corexit EC9500A in the presence of diluted bitumen.

Observations made for the analysis of the oil spill dispersant tracer dioctyl sulfosuccinate (DOSS) during LC50 toxicity testing, highlighted a stability issue for this tracer compound in seawater. A liquid chromatography high-resolution quadrupole time-of-flight mass spectrometry (LC/QToF) was used to confirm monooctyl sulfosuccinate (MOSS) as the only significant DOSS breakdown product, and not the related isomer, 4-(2-ethylhexyl) 2-sulfobutanedioate. Combined analysis of DOSS and MOSS was shown to be applicable to monitoring of spill dispersants Corexit® EC9500A, Finasol OSR52, Slickgone NS, and Slickgone EW. The unassisted conversion of DOSS to MOSS occurred in all four oil spill dispersants solubilized in seawater, although differences were noted in the rate of MOSS formation. A marine microcosm study of Corexit EC9500A, the formulation most rapid to form MOSS, provided further evidence of the stoichiometric conversion of DOSS to MOSS under conditions relevant to real world dilbit spill. Results supported combined DOSS and MOSS analysis for the monitoring of spill dispersant in a marine environment, with a significant extension of sample collection time by 10 days or longer in cooler conditions. Implications of the unassisted formation of MOSS and combined DOSS:MOSS analysis are discussed in relation to improving dispersant LC50 toxicity studies.

Bubble-Nucleation-Based Method for the Selective and Sensitive Electrochemical Detection of Surfactants.

We present the first bubble-nucleation-based electrochemical method for the selective and sensitive detection of surfactants. Our method takes advantage of the high surface activity of surfactant analyte to affect the electrochemical bubble nucleation and then transduces the change in nucleation condition to electrochemical signal for determining the surfactant concentration. Using this method, we demonstrate the quantitation of perfluorinated surfactants in water, a group of emerging environmental contaminants, with a remarkable limit of detection (LOD) down to 30 µg/L and a linear dynamic range of over 3 orders of magnitude. With the addition of a preconcentration step, we have achieved the LOD: 70 ng/L, the health advisory for perfluorooctanesulfonate (PFOS) and perfluorooctanoic acid (PFOA) in drinking water established by the U.S. Environmental Protection Agency. The experimental results are in quantitative agreement with our theoretical model derived from classical nucleation theory. Our method also exhibits an exceptional specificity for the surfactant analytes even in the presence of 1000-fold excess of nonsurfactant interference. This method has the potential to be further developed into a universal electrochemical detector for surfactant analysis because of its simplicity and the surface-activity-based detection mechanism.