Development and Application of a Multidimensional Database for the Detection of Quaternary Ammonium Compounds and Their Phase I Hepatic Metabolites in Humans.

The COVID-19 pandemic has led to significantly increased human exposure to the widely used disinfectants quaternary ammonium compounds (QACs). Xenobiotic metabolism serves a critical role in the clearance of environmental molecules, yet limited data are available on the routes of QAC metabolism or metabolite levels in humans. To address this gap and to advance QAC biomonitoring capabilities, we analyzed 19 commonly used QACs and their phase I metabolites by liquid chromatography-ion mobility-tandem mass spectrometry (LC-IM-MS/MS). In vitro generation of QAC metabolites by human liver microsomes produced a series of oxidized metabolites, with metabolism generally occurring on the alkyl chain group, as supported by MS/MS fragmentation. Discernible trends were observed in the gas-phase IM behavior of QAC metabolites, which, despite their increased mass, displayed smaller collision cross-section (CCS) values than those of their respective parent compounds. We then constructed a multidimensional reference SQLite database consisting of m/z, CCS, retention time (rt), and MS/MS spectra for 19 parent QACs and 81 QAC metabolites. Using this database, we confidently identified 13 parent QACs and 35 metabolites in de-identified human fecal samples. This is the first study to integrate in vitro metabolite biosynthesis with LC-IM-MS/MS for the simultaneous monitoring of parent QACs and their metabolites in humans.

An exposure assessment of 27 quaternary ammonium compounds in pet dogs and cats from New York State, USA.

Benzylalkyldimethylammonium (BACs), dialkyldimethylammonium (DDACs), and alkyltrimethylammonium compounds (ATMACs) are quaternary ammonium compounds (QACs) used widely as biocides, disinfectants, and sanitizers. Owing to their toxicity, human exposure to this class of chemicals is a concern. Pet animals are sentinels of human exposure to several indoor environmental chemicals. For the first time, we measured 7 BACs, 6 DDACs, 6 ATMACs, and 8 metabolites of BACs in urine and feces of pet dogs and cats from New York State, USA. We found widespread occurrence of QACs in feces, with median concentration of ∑All (sum concentration of all 27 QAC analytes) at 9680 and 1260 ng/g dry weight (dw) in dog and cat feces, respectively. BACs were the most abundant compounds among the four types of QACs, accounting for 64 % and 57 % of ∑All in dog and cat feces, respectively, followed by DDACs (33 % and 34 %, respectively), ATMACs (4 % and 9 %, respectively), and BAC metabolites (0.2 % and 0.3 %, respectively). However, in urine, only ω-carboxylic acid metabolites of BACs were found at median concentrations at 2.08 and 0.28 ng/mL in dogs and cats, respectively. Samples collected from animal shelters contained elevated levels of QACs than those from homes of pet owners. A significant positive correlation was found among the four types of QACs analyzed, which suggested usage of these chemicals in combination as mixtures. Based on the concentrations measured in feces, and through a reverse dosimetry approach, the median cumulative daily intakes (CDIs) of QACs were estimated to be 49.4 and 4.75 µg/kg body weight (BW)/day for dogs and cats, respectively. This study provides first evidence that pet dogs and cats are exposed to QACs at significant levels that warrant further attention.

Method validation and environmental monitoring of triethanolamine ester quaternary ammonium compounds.

In this study water and sediment samples, collected from the River Nene (Northamptonshire) at several sites in the vicinity of the Great Billing sewage treatment plant (STP), were analysed for triethanolamine quaternary compounds (TEAQ, ester quats). A method was developed using liquid chromatography tandem mass spectrometry (LC/MS/MS) with a electrospray ionisation source (ESI). Ten components were determined using a characterised commercial sample of Tallow TEAQ as a standard. To our knowledge this is the first time environmental concentrations of a wide spectrum of individual homologues of TEAQ have been reliably quantified covering a broad range of environmental matrices (STP influent, STP effluent, surface waters and sediments), due to the challenging nature of the analytical method. The method featured novel solutions for the determination of long and multiple chain length alkyl quats, controlling loss processes, background contamination and chromatographic performance. TEAQ compounds were found to be highly removed in the sewage treatment plant resulting in low effluent concentrations. Low concentrations in both river water and sediment samples were found also. In many cases levels were below the Method Detection Limit (MDL). In river water samples, mean values of TEAQ compounds found were 210-398 ng/L for C16:0/C18:0 TEAQ diester and 126-287 ng/L for C18:0/C18:0 TEAQ diester. River sediment was found to contain mean TEAQ levels of 7.07-12.5, 19.7 to 40.3 and 7.04-35.1 µg/kg dry weight for C16:0/C16:0, C16:0/C18:0, and C18:0/C18:0 TEAQ, respectively. At Great Billing STP monoesters and diesters of TEAQ were shown to be efficiently removed (>97 and 99 %, respectively), although limited samples were taken on this occasion.

Quaternary Ammonium Compounds (QACs) in Wastewater Influent and Effluent Throughout the COVID-19 Pandemic.

Quaternary ammonium compounds (QACs) are used in consumer and industrial products, including disinfectants. Due to the COVID-19 pandemic, disinfectant use has increased, purportedly increasing loads to wastewater treatment plants and the environment. To understand how the increased usage has affected QAC loadings to treatment plants and to determine how effectively plants remove QACs from liquid effluent that is discharged to surface and groundwaters, influent and effluent wastewater samples were collected from four treatment plants (treatment capacities < 5 MGD to > 100 MGD) for 21 months beginning in May 2020. Influent QAC concentrations were hundreds of µg/L and effluent QAC concentrations were < 1 µg/L, corresponding to an average removal of 98% from all four plants. The most prevalent QACs in influent were those used most commonly in disinfectants, specifically benzylalkyldimethylammonium compounds (BACs) and short-chain dialkyldimethylammonium compounds (DADMACs), and influent levels of these compounds were correlated with QAC sales. Prior to this study, ethylbenzylalkyldimethylammonium compounds (EtBACs) had not been studied, and they comprised 13 ± 6% of QACs in influent. While removal was high at all plants, low µg/L concentrations were still continuously discharged into the environment. For QACs with equivalent alkyl chain lengths, those with aromatic substituents (BACs and EtBACs) appear to be removed more effectively than those with only alkyl chains (DADMACs).

Hypo-osmotic Stress Increases Permeability of Individual Barriers in Escherichia coli Cell Envelope, Enabling Rapid Drug Transport.

Survival of foodborne Gram-negative bacteria during osmotic stress often leads to multidrug resistance development. However, despite the concern, how osmoadaptation alters drug penetration across the Gram-negative bacterial cell envelope has remained inconclusive for years. Here, we have investigated drug permeation and accumulation inside hypo-osmotically shocked Escherichia coli. Three different quaternary ammonium compounds (QACs) are used as cationic amine-containing drug representatives; they also serve as envelope permeability indicators in different assays. Propidium iodide fluorescence reveals cytoplasmic accumulation and overall envelope permeability, while crystal violet sorption and second harmonic generation (SHG) spectroscopy reveal periplasmic accumulation and outer membrane permeability. Malachite green sorption and SHG results reveal transport across both the outer and inner membranes and accumulation in the periplasm as well as cytoplasm. The findings are found to be complementary to one another, collectively revealing enhanced permeabilities of both membranes and the periplasmic space in response to hypo-osmotic stress in E. coli. Enhanced permeability leads to faster QACs transport and higher accumulation in subcellular compartments, whereas transport and accumulation both are negligible under isosmotic conditions. The QACs' transport rates are found to be highly influenced by the osmolytes used, where phosphate ion emerges as a key facilitator of transport across the periplasm into the cytoplasm. E. coli is found viable, with morphology unchanged under extreme hypo-osmotic stress; i.e., it adapts to the situation. The outcome shows that the hypo-osmotic shock to E. coli, specifically using phosphate as an osmolyte, can be beneficial for drug delivery.

Identification and characterization of quaternary ammonium compounds in Flemish indoor dust by ion-mobility high-resolution mass spectrometry.

Quaternary ammonium compounds (QACs) are a class of surfactants commonly used in disinfecting and cleaning products. Their use has substantially increased during the COVID-19 pandemic leading to increasing human exposure. QACs have been associated with hypersensitivity reactions and an increased risk of asthma. This study introduces the first identification, characterization and semi-quantification of QACs in European indoor dust using ion-mobility high-resolution mass spectrometry (IM-HRMS), including the acquisition of collision cross section values (DTCCSN2) for targeted and suspect QACs. A total of 46 indoor dust samples collected in Belgium were analyzed using target and suspect screening. Targeted QACs (n = 21) were detected with detection frequencies ranging between 4.2 and 100 %, while 15 QACs showed detection frequencies > 90 %. Semi-quantified concentrations of individual QACs showed a maximum of 32.23 µg/g with a median ∑QAC concentration of 13.05 µg/g and allowed the calculation of Estimated Daily Intakes for adults and toddlers. Most abundant QACs matched the patterns reported in indoor dust collected in the United States. Suspect screening allowed the identification of 17 additional QACs. A dialkyl dimethyl ammonium compound with mixed chain lengths (C16:C18) was characterized as a major QAC homologue with a maximum semi-quantified concentration of 24.90 µg/g. The high detection frequencies and structural variabilities observed call for more European studies on potential human exposure to these compounds. For all targeted QACs, drift tube IM-HRMS derived collision cross section values (DTCCSN2) are reported. Reference DTCCSN2 values allowed the characterization of CCS-m/z trendlines for each of the targeted QAC classes. Experimental CCS-m/z ratios of suspect QACs were compared with the CCS-m/z trendlines. The alignment between the two datasets served as an additional confirmation of the assigned suspect QACs. The use of the 4bit multiplexing acquisition mode with consecutive high-resolution demultiplexing confirmed the presence of isomers for two of the suspect QACs.

Determination of 25 quaternary ammonium compounds in sludge by liquid chromatography-mass spectrometry.

With the pandemic of COVID-19, the application of quaternary ammonium compounds (QACs), which can be used in SARS-CoV-2 disinfection products, has increased substantially. QACs cumulated in sewer system are ultimately deposited and enriched in sludge. QACs in the environment can adversely affect human health and the environment. In this study, a liquid chromatography-mass spectrometry method was established for the simultaneous determination of 25 QACs in sludge samples. Ultrasonic extraction and filtration of the samples was performed using a 50 mM hydrochloric acid-methanol solution. The samples were separated by liquid chromatography and detected in multiple reaction monitoring mode. The matrix effects of the sludge on the 25 QACs ranged from - 25.5% to 7.2%. All substances showed good linearity in the range of 0.5-100 ng/mL, with all determination coefficients (R2) greater than 0.999. The method detection limits (MDLs) were 9.0 ng/g for alkyltrimethylammonium chloride (ATMAC), 3.0 ng/g for benzylalkyldimethylammonium chloride (BAC), and 3.0 ng/g for dialkyldimethylammonium chloride (DADMAC). The spiked recovery rates were in the range of 74-107%, while the relative standard deviations were in the range of 0.8-20.6%. Considering its sensitivity, accuracy, and easy operation, the proposed method in this study was used to determine 22 sludge samples collected from a comprehensive wastewater treatment plant. The results showed that the concentrations of ΣATMACs, ΣBACs, and ΣDADMACs were 19.684, 3.199, and 8.344 µg/g, respectively. The main components included ATMAC-C16, ATMAC-C18, ATMAC-C20, ATMAC-C22, BAC-C12, and DADMAC-C18:C18, with concentrations exceeding 1.0 µg/g. The concentration relationships of different components in the congeners showed that some components were of similar origin.

Use of QuEChERS as a manual and automated high-throughput protocol for investigating environmental matrices.

Environmental pollution has strong links to adverse human health outcomes with risks of pollution through production, use, ineffective wastewater (WW) remediation, and/or leachate from landfill. 'Fit-for-purpose' monitoring approaches are critical for better pollution control and mitigation of harm, with current sample preparation methods for complex environmental matrices typically time-consuming and labour intensive, unsuitable for high-throughput screening. This study has shown that a modified 'Quick Easy Cheap Effective Rugged and Safe' (QuEChERS) sample preparation is a viable alternative for selected environmental matrices required for pollution monitoring (e.g. WW effluent, treated sludge cake and homogenised biota tissue). As a manual approach, reduced extraction times (hours to ∼20 min/sample) with largely reproducible (albeit lower) recoveries of a range of pharmaceuticals and biocidal surfactants have been reported. Its application has shown clear differentiation of matrices via chemometrics, and the measurement of pollutants of interest to the UK WW industry at concentrations significantly above suggested instrument detection limits (IDL) for sludge, indicating insufficient removal and/or bioaccumulation during WW treatment. Furthermore, new pollutant candidates of emerging concern were identified - these included detergents, polymers and pharmaceuticals, with quaternary ammonium compound (QAC) biocides observed at 2.3-70.4 mg/kg, and above levels associated with priority substances for environmental quality regulation (EQSD). Finally, the QuEChERS protocol was adapted to function as a fully automated workflow, further reducing the resource to complete both the preparation and analysis to <40 min. This operated with improved recovery for soil and biota (>62%), and when applied to a largely un-investigated clay matrix, acceptable recovery (88.0-131.1%) and precision (≤10.3% RSD) for the tested pharmaceuticals and biocides was maintained. Therefore, this preliminary study has shown the successful application of a high-throughput QuEChERS protocol across a range of environmental solids for potential deployment in a regulated laboratory.

A review of the existing and emerging technologies for wastewaters containing tetramethyl ammonium hydroxide (TMAH) and waste management systems in micro-chip microelectronic industries.

The present work aims to describe and review the available technologies and the recent advancements in treating industrial wastewater containing tetramethylammonium hydroxide (TMAH). It is a quaternary ammonium salt and widely used in the microelectronics industry; this kind of company produces large quantities of wastewater containing TMAH. The exhausted solutions must be treated appropriately since TMAH is corrosive, toxic to human health, and ecotoxic. Regarding the concentration at discharge, currently there are no European regulations. Still, it has been indicated that the substance has a negative influence on the oxygen balance and cause eutrophication, and fall into the relevant categories. In the first part of the work, the available technologies and the recent advancements for the treatment of TMAH contained in industrial wastewater are reviewed. Separation methods as such adsorption, ion exchange, membrane processes, and destruction technologies classified as advanced oxidation processes and biological processes have been considered. In the second part of the manuscript, industrial patented wastewater treatments have been described. Biological processes are those more used, being more economically feasible, require very long times not always sustainable.

Multi-route exposure sampling of quaternary ammonium compounds and ethanol surface disinfectants in a K-8 school.

The frequency of surface disinfectant use has increased over the last several years in public settings such as schools, especially during the COVID-19 pandemic. Although these products are important for infection control and prevention, their increased use may intensify the exposure to both persons applying the disinfection product as well as bystanders. Safety assessments have demonstrated that these products, when used as intended, are considered safe for use and effective; however, point-of-contact effects (such as respiratory or dermal irritation) may still occur. Additionally, relative exposures may vary significantly due to the wide variation in disinfectant formulation and application methods. Quantitative estimations of exposures to two commonly used active ingredients, quaternary ammonium compounds (QACs) and ethanol, are not well characterized during product use and application scenarios. To assess the potential for health risks attributable to increased use in classroom settings, as well as to quantitatively evaluate the potential exposure to both ethanol and QACs, student and adult bystander surface and air measurements were collected in a K-8 school setting in Ohio, United States, over a three-day period. Direct-reading instruments were utilized to collect real-time air samples that characterized mass fraction concentrations following the use of the QAC- and ethanol-based disinfectants. Furthermore, surface and air sampling of microbial species were conducted to establish the overall bioburden and effectiveness of each disinfectant to inform the comparative risk and health effect impacts from the tested products use scenario. Both tested products were approximately equally effective at reducing bioburdens on desk surfaces. In some classrooms, concentrations of QAC congeners were significantly increased on desk surfaces following the application of the disinfectant spray; however, the magnitude of the change in concentration was small. Ethanol was not measured on surfaces due to its volatility. Airborne concentrations increased immediately following spray of each disinfectant product but rapidly returned to baseline. Each of the QAC congeners listed in the product safety data sheets were detected and measurable on desk surfaces; however, air concentrations were generally below the limit of detection. The 15-min time-weighted averages (TWAs) of both QACs and ethanol in the air were below respective health effects benchmarks, and therefore, the negative impact on health outcomes is considered to be minimal from short-term, repeated use of ethanol- or QAC-based spray products in a school setting when the products are used as directed.

The first detection of quaternary ammonium compounds in breast milk: Implications for early-life exposure.

BACKGROUND: Quaternary ammonium compounds (QACs), commonly used in cleaning, disinfecting, and personal care products, have recently gained worldwide attention due to the massive use of disinfectants during the COVID-19 pandemic. However, despite extensive use of these chemicals, no studies have focused on the analysis of QACs in human milk, a major route of exposure for infants. OBJECTIVE: Our objectives were to identify and measure QACs in breast milk and evaluate early-life exposure to this group of compounds for nursing infants. METHODS: Eighteen QACs, including 6 benzylalkyldimethyl ammonium compounds (BACs, with alkyl chain lengths of C8-C18), 6 dialkyldimethyl ammonium compounds (DDACs, C8-C18), and 6 alkyltrimethyl ammonium compounds (ATMACs, C8-C18), were measured in breast milk samples collected from U.S. mothers. Daily lactational intake was estimated based on the determined concentrations for 0-12 month old nursing infants. RESULTS: Thirteen of the 18 QACs were detected in breast milk and 7 of them were found in more than half of the samples. The total QAC concentrations (ΣQAC) ranged from 0.33 to 7.4 ng/mL (median 1.5 ng/mL). The most abundant QAC was C14-BAC with a median concentration of 0.45 ng/mL. The highest median ΣQAC estimated daily intake (EDI) was determined for <1-month old infants based on the average (using the median concentration) and high (using the 95th percentile concentration) exposure scenarios (230 and 750 ng/kg body weight/day, respectively). SIGNIFICANCE: Our findings provide the first evidence of the detection of several QACs in breast milk and identify breastfeeding as an exposure pathway to QACs for nursing infants. IMPACT STATEMENT: Our findings provide the first evidence of QAC occurrence in breast milk and identify breastfeeding as one of the exposure pathways to QACs for nursing infants.

Development and applicability of a multi-residue method for dyes, including new residue markers, to detect drug misuse in aquaculture.

A qualitative and quantitative liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for the sensitive and exhaustive analysis of residues from triarylmethane dyes, triarylmethane-derivative dyes, phenothiazines, phenoxazines and xanthenes in aquaculture samples. For a wider and more robust detection of dye misuse on farms, other residue markers were also included the leuco forms of brilliant green, crystal violet and malachite green; one direct metabolite of Victoria pure blue BO and methylene blue and three bile acids, which are endogenous markers of the effects of dye contamination in fish. We optimised the extraction method by comparing several extraction solvents and sample solvents reported in the literature to have the best extraction efficiency. The residues were determined using a positive electrospray ionisation source. We assessed the parameters of this LC-MS/MS method by evaluating the matrix effects, identification and quantitative parameters according to the criteria stipulated in the European Commission Decision No. 2002/657/EC. A study on the applicability of the method was conducted on various aquaculture species and on a positive catfish.

Microbial properties of the granular sludge in a psychrophilic UASB reactor fed with electronics industry wastewater containing organic chemicals.

In this study, a lab-scale upflow anaerobic sludge blanket (UASB) reactor was applied to the treatment of artificial electronics industry wastewater containing tetramethylammonium-hydroxide (TMAH), monoethanolamine (MEA), and isopropyl-alcohol (IPA) in order to evaluate process performance and degradation properties. During 800 days of operation, 96% efficiency of chemical oxygen demand (COD) removal was stably achieved at an organic loading rate of 8.5 kgCOD/m3/day at 18-19 °C. MEA degradation, carried out by acid-forming eubacteria, was confirmed within a week. The physical properties of the retained granular sludge were degraded by feeding with TMAH wastewater, but maintained by feeding with MEA wastewater due to an accumulation of species from the genus Methanosaeta and family Geobacteraceae. Analysis of the microbial community structure via SEM and 16S rRNA genes showed a proliferation of Methanomethylovorans-like cells and Methanosaeta-like cells at the surface and in the core of the granular sludge with TMAH, MEA and IPA acclimation. Furthermore, a batch degradation experiment confirmed that process inhibition due to increasing chemical concentration was relatively stronger for TMAH than for MEA or IPA. Thus, controlling the TMAH concentration of the influent to below 1 gCOD/L will be important for the stable treatment of electronics industry wastewater by UASB technology.

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.

Increasing Intracellular Levels of Iron with Ferric Ammonium Citrate Leads to Reduced P-glycoprotein Expression in Human Immortalised Brain Microvascular Endothelial Cells.

PURPOSE: P-glycoprotein (P-gp) at the blood-brain barrier (BBB) precludes the brain penetration of many xenobiotics and mediates brain-to-blood clearance of ß-amyloid, which accumulates in the Alzheimer's disease (AD) brain. Zinc and copper are reported to modulate BBB expression and function of P-gp; however, the impact of exogenous iron, which accumulates in AD, on P-gp dynamics remains unknown. METHODS: P-gp protein and MDR1 transcript levels were assessed in immortalised human cerebral microvascular endothelial (hCMEC/D3) cells treated with ferric ammonium citrate (FAC; 250 µM, 72 h), by Western blotting and RT-qPCR, respectively. P-gp function was assessed using rhodamine-123 and [3H]-digoxin accumulation. Intracellular reactive oxygen species (ROS) levels were determined using 2',7'-dichlorofluorescin diacetate and intracellular iron levels quantified using a ferrozine assay. RESULTS: FAC treatment significantly reduced P-gp protein (36%) and MDR1 mRNA (16%) levels, with no significant change in rhodamine-123 or [3H]-digoxin accumulation. While P-gp/MDR1 downregulation was associated with elevated ROS and intracellular iron, MDR1 downregulation was not attenuated with the antioxidant N-acetylcysteine nor the iron chelators desferrioxamine and deferiprone, suggesting the involvement of a ROS-independent mechanism or incomplete iron chelation. CONCLUSIONS: These studies demonstrate that iron negatively regulates P-gp expression at the BBB, potentially impacting CNS drug delivery and brain ß-amyloid clearance.

Colorimetric detection of residual quaternary ammonium compounds on dry surfaces and prediction of antimicrobial activity using bromophenol blue.

Controlling and monitoring the residual activity of quaternary ammonium compounds (QACs) are critical for maintaining safe yet effective levels of these agents in the environment. This study investigates the utility of bromophenol blue (BPB) as a safe, rapid and user-friendly indicator to detect in situ residual QACs dried on hard, non-porous surfaces, as well a means to assess their antimicrobial efficacy. At pH 7, BPB has a purple colour which turns blue upon its complexation with QACs such as didecyldimethylammonium chloride (DDAC). BPB itself has no antimicrobial properties up to 400 ppm. Within the range of 0-400 ppm, BPB colour change was tied to specific DDAC antimicrobial performances with a detection threshold of 100 ppm. BPB concentration and application volume could be adjusted such that a colour shift from purple to blue correlated with a set percent reduction (>99·9%) in test bacteria (Staphylococcus aureus and Klebsiella aerogenes). The BPB solutions developed in this study yielded similar colour shifts on polycarbonate and stainless steel surfaces and did not cross-react with chemical ingredients commonly found in sanitizers and disinfectant products. Overall, this study suggests that BPB provides a simple solution to safely monitor the post-application level and biocidal activity of residual dried QACs on surfaces.

Cyanuric chloride-imidazole dendrimer functionalized nanoparticles as an adsorbent for magnetic solid phase extraction of quaternary ammonium compounds from fruit and vegetable puree based infant foods.

A novel magnetic solid-phase extraction (MSPE) material (Fe3O4@SiO2-NH2-G2) had been prepared and employed for adsorption and analysis of seven quaternary ammonium compounds (QACs) in infant fruit and vegetable products coupled with high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). In this paper, Fe3O4@SiO2-NH2-G2 was synthesized based on Fe3O4@SiO2-NH2 and dendrimer (G2) consisting of cyanuric chloride and imidazole. The morphology, configuration and magnetic behavior of the magnetic material were characterized by transmission electron microscopy (TEM), Fourier transform infrared spectrometry (FT-IR), X-ray diffraction (XRD), and vibrating sample magnetometer (VSM). Critical parameters affecting extraction efficiency, such as the adsorbent amount, sample pH, extraction time, the type of eluent, and desorption time, were optimized. The proposed method provided good linearity with the correlation coefficients (R2) of 0.9992-0.9999, low limits of detection (LODs) (0.05-0.50 µg kg-1) and limits of quantitation (LOQs) (0.20-2.00 µg kg-1). The satisfactory method recoveries in three spiked infant fruit and vegetable products samples were between 80.12% and 101.35% with the relative standard deviations (RSDs) less than 12.04%. In summary, the established method was an effective sample preparation method and showed good prospect for the analysis of QACs in complex matrices.

Deep eutectic solvent-based liquid-phase microextraction coupled with reversed-phase high-performance liquid chromatography for determination of α-, ß-, γ-, and δ-tocopherol in edible oils.

For simultaneous analysis of four fat-soluble tocopherols (α-, ß-, γ-, and δ-) in edible oils, an efficient and green method using deep eutectic solvent-based liquid-phase microextraction (DES-LPME) coupled with reversed-phase high-performance liquid chromatography (RP-HPLC) was developed. The DESs formed by different quaternary ammonium salts and ethanol were used as the extractants. Tetrabutylammonium chloride (TBAC)-ethanol DES at a molar ratio of 1:2 achieved the best extraction efficiency. Under the optimized conditions, the detection limits were in the range of 2.1-3.0 ng mL-1. The intra-day and inter-day repeatability were in the ranges of 3.9-5.3% and 4.8-7.1%, respectively, and the recoveries for the real samples varied from 80.7% to 105.4%. The developed method was successfully employed for the determination of all four tocopherol homologues with an RP-HPLC system containing a COSMOSIL π-NAP column in five edible oils collected locally. Graphical abstract.

A fast and robust method for the extraction and analysis of quaternary alkyl ammonium compounds from soil and sewage sludge.

Alkyltrimethylammonium compounds (ATMACs), dialkyldimethylammonium compounds (DADMACs) and benzylalkyldimethylethylammonium compounds (BACs) are quaternary alkylammonium compounds (QAAC), which are released into the environment in large quantities after their use in cleaning agents and disinfectants. Despite their potential role as selective agents promoting resistance against QAACs as well as antibiotics, there is a lack of data for QAACs in soil due to the lack of sensitive analytical methods. Therefore, we present a robust and fast method for the extraction and quantification of concentrations of these compounds in soil and sewage sludge. The method is based on ultrasonic extraction (USE) with a mixture of acetonitrile and HCl followed by a solid phase extraction (SPE) cleaning step and a subsequent quantification of concentrations with high performance liquid chromatography with mass spectrometry (HPLC-MS/MS) in multi mass reaction mode (MRM). The proposed method is suitable for the quantification of ATMACs (chain length C-8 to C-16), BACs (C-8 to C-18) and DADMACs (C-8 to C-16). The achieved limits of quantification (LOQ) range from 0.1 µg kg-1 to 2.1 µg kg-1. The recovery rates of spiked soil samples for non-deuterated homologues were between 47% and 57%. The analysis of sewage sludge samples and soil samples revealed that BAC-C12 was the most abundant QAAC with concentrations up to 38600 µg kg-1 in sewage sludge and up to 81 µg kg-1 in a Mexican soil that was irrigated with wastewater. Overall, the presented methods open perspectives for effectively studying fate and effects of QAACs in soils.

Effects of adsorbent carriers in modified ready biodegradability tests of quaternary ammonium salts.

Standard ready biodegradability tests are conducted at unrealistically high test concentration and therefore cannot properly evaluate toxic substances to microorganisms. The present study evaluated the effects of four adsorbent carriers in modified ready biodegradability tests of four quaternary ammonium salts (QASs) demonstrating microbial toxicity according to the Organization for Economic Co-operation and Development Test Guideline 301F and cautions for using carriers were found. In the tests with silica gel, the concentration of all QASs in the test solutions decreased due to adsorption. The percentages of biodegradation of octadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, and benzyldimethyloctadecylammonium chloride, which have a linear alkyl chain, were 89.9%, 80.6%, and 70.1% on day 28, respectively; benzethonium chloride, with a branched alkyl chain, did not undergo biodegradation. In the tests with activated carbon, although the concentrations of QASs greatly decreased, no QASs underwent biodegradation. In the tests with sea sand or quartz sand, QASs were not adsorbed on the carriers and were not biodegraded. Using an adsorbent carrier for toxic substances will increase biodegradation, but it has no effect on highly persistent substances with specific chemical structures, e.g., branched carbons, which is very important because ready biodegradability is not overestimated. Carriers having moderate adsorbability should be selected.