Ion Chromatography Tandem Mass Spectrometry Research Articles

Production and biological activity of β-1,3-xylo-oligosaccharides using xylanase from Caulerpa lentillifera

In this study, β-1,3-xylanase (Xyl3088) was designed and prepared by constructing the expression vector plasmid and expressing and purifying the fusion protein. β-1,3-xylo-oligosaccharides were obtained through the specific enzymatic degradation of β-1, 3-xylan from Caulerpa lentillifera. The enzymolysis conditions were established and optimized as follows: Tris-HCl solution 0.05 mol/L, temperature of 37 °C, enzyme amount of 250 μL, and enzymolysis time of 24 h. The oligosaccharides' compositions and structural characterization were identified by thin-layer chromatography (TLC), ion chromatography (IC) and liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS). The IC50 values for scavenging 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2-azino-bis-3-ethyl-benzothiazoline-p-sulfonic acid (ABTS+), and superoxide anion radical (•O2−) were 13.108, 1.258, and 65.926 mg/mL for β-1,3-xylo-oligosaccharides, respectively, and 27.588, 373.048, and 269.12 mg/mL for β-1,4-xylo-oligosaccharides, respectively. Compared with β-1,4-xylo-oligosaccharides, β-1,3-xylo-oligosaccharides had substantial antioxidant activity and their antioxidant effects were concentration dependent. β-1,3-xylo-oligosaccharides also possessed a stronger anti-inflammatory effect on RAW 264.7 cells stimulated by lipopolysaccharide (LPS) than β-1,4-xylo-oligosaccharides. At a working concentration of 100 μg/mL, β-1,3-xylo-oligosaccharides inhibited the release of NO and affected the expression of IL-1β, TNF-α, and other proteins secreted by cells, effectively promoting the release of pro-inflammatory mediators by immune cells in response to external stimuli and achieving anti-inflammatory effects. Therefore, β-1,3-xylo-oligosaccharides are valuable products in food and pharmaceutical industries.

Changes and Significance of Central Carbon Metabolism before and after Metformin Treatment of Type 2 Diabetes Based on Mass Spectrometry.

An imbalance in energy metabolism serves as a causal factor for type 2 diabetes (T2D). Although metformin has been known to ameliorate the overall energy metabolism imbalance, but the direct correlation between metformin and central carbon metabolism (CCM) has not been thoroughly investigated. In this study, we employed a high-performance ion chromatography-tandem mass spectrometry (HPIC-MS/MS) technique to examine the alterations and significance of CCM both before and after metformin treatment for T2D. We recruited 29 participants, comprising 10 individuals recently diagnosed with T2D (T2D group). Among these, 10 patients underwent a 4-6-week treatment with metformin (MET group). Additionally, we included 9 healthy subjects (CON group). Employing HPIC-MS/MS, we quantitatively analyzed 56 metabolites across 18 biologically relevant metabolic pathways associated with CCM. Univariate and multivariate statistical analyses were utilized to identify differential metabolites. Subsequently, correlation analyses and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analysis were conducted on the identified differential metabolites. We identified seven distinct metabolites in individuals with T2D (p < 0.05). Notably, cyclic 3',5'-Adenosine MonoPhosphate (AMP), Glucose 6-phosphate, L-lactic acid, Maleic acid, and Malic acid exhibited a reversal to normal levels following metformin treatment. Furthermore, Malic acid demonstrated a positive correlation with L-lactic acid (r = 0.94, p < 0.05), as did succinic acid with malic acid (r = 0.81, p < 0.05), L-lactic acid with succinic acid (r = 0.78, p < 0.05), and L-lactic acid with glucose-6-phosphate (r = 0.72, p < 0.05). These metabolites were notably enriched in pyruvate metabolism (p = 0.005), tricarboxylic acid cycle (TCA) (p = 0.007), propanoate metabolism (p = 0.007), and glycolysis or gluconeogenesis (p = 0.009), respectively. We employed HPIC-MS/MS to uncover alterations in CCM among individuals recently diagnosed with T2D before and after metformin treatment. The findings suggest that metformin may ameliorate the energy metabolism imbalance in T2D by reducing intermediates within the CCM pathway.

Boron quantification using ion chromatography tandem triple quadrupole mass spectrometry. Application to retention analysis in boron-treated wood

Boron compounds play a crucial role in various industries, and accurate quantification of boron is essential for quality control and environmental monitoring. This study presents a simple, rapid, and reliable method for determining boron in aqueous solutions using suppressed ion chromatography coupled to electrospray ionisation-triple quadrupole mass spectrometry (IC-ESI-QqQ-MS). Boric acid (B(OH)3) was retained as the tetrahydroxyborate ion (B(OH)4−) on a CarboPac PA300-4 μm anion-exchange column using isocratic elution with 40 mM KOH. During the neutralization process at the suppressor, B(OH)4− was converted to B(OH)3, which subsequently generated the metaborate ion [BO2]− (m/z 43) within the electrospray ionisation source. By employing a pseudo-selected reaction monitoring (SRM) transition from m/z 43 to m/z 43, the method achieved a limit of detection (LOD) of 2.45 μg/L of boron, the lowest reported in the literature to-date for an IC-based method. The analytical performance of the method demonstrated no carry-over issues, no matrix interferences, and excellent intra- and inter-run repeatability of 2.03% and 3.41%, respectively. The method was applied to the evaluation of boron uptake and retention by Tasmanian Oak timber blocks, treated by dip-diffusion in a boric acid solution of 2.5% Boric Acid Equivalent (BAE, m/m) under controlled laboratory conditions. Quantitative determination of the retained and unretained boron allowed a mass balance evaluation and confirmed the accuracy and reliability of the method, with recoveries ranging from 99.3% to 100.2%.

Targeted metabolomics reveals the aberrant energy status in diabetic peripheral neuropathy and the neuroprotective mechanism of traditional Chinese medicine JinMaiTong

Diabetic peripheral neuropathy (DPN) is a common and devastating complication of diabetes, for which effective therapies are currently lacking. Disturbed energy status plays a crucial role in DPN pathogenesis. However, the integrated profile of energy metabolism, especially the central carbohydrate metabolism, remains unclear in DPN. Here, we developed a metabolomics approach by targeting 56 metabolites using high-performance ion chromatography-tandem mass spectrometry (HPIC-MS/MS) to illustrate the integrative characteristics of central carbohydrate metabolism in patients with DPN and streptozotocin-induced DPN rats. Furthermore, JinMaiTong (JMT), a traditional Chinese medicine (TCM) formula, was found to be effective for DPN, improving the peripheral neurological function and alleviating the neuropathology of DPN rats even after demyelination and axonal degeneration. JMT ameliorated DPN by regulating the aberrant energy balance and mitochondrial functions, including excessive glycolysis restoration, tricarboxylic acid cycle improvement, and increased adenosine triphosphate (ATP) generation. Bioenergetic profile was aberrant in cultured rat Schwann cells under high-glucose conditions, which was remarkably corrected by JMT treatment. In-vivo and in-vitro studies revealed that these effects of JMT were mainly attributed to the activation of adenosine monophosphate (AMP)-activated protein kinase (AMPK) and downstream peroxisome proliferator-activated receptor gamma coactivator 1-alpha (PGC-1α). Our results expand the therapeutic framework for DPN and suggest the integrative modulation of energy metabolism using TCMs, such as JMT, as an effective strategy for its treatment.

Simultaneous analysis of degradation products of Novichok agents and conventional nerve agents in human urine by ion chromatography-tandem mass spectrometry using ammonium regeneration solution

An ion chromatography (IC)-tandem mass spectrometry (MS/MS) method to analyze nerve agent degradation products in human urine was developed. Six degradation products of conventional nerve agents and six Novichok agent degradation products were analyzed simultaneously despite their differences in hydrophilicity and acidity. Using ammonium regeneration solution improved the peak shapes greatly compared with the results obtained with the ordinary IC-MS/MS configuration. For urine samples, a simple pretreatment method of dilution with water and ultrafiltration was used. The detection limits of the nerve agent degradation products were sufficiently low (10–250 ng/mL) and the calibration curves showed acceptable linearity. Due to the absence of a derivatization step, throughput was higher than for our previous derivatization-liquid chromatography-MS/MS method.

Determination of Biogenic Amines in Wine from Chinese Markets Using Ion Chromatography-Tandem Mass Spectrometry.

A method for the determination of nine biogenic amines (BAs) in wine was established using ion chromatography-tandem mass spectrometry (IC-MS/MS) without derivatization. BAs were separated by a cation exchange column (IonPac CG17, 50 mm × 4 mm, 7 µm) with a gradient aqueous formic acid elution. Good linearity was obtained for nine BAs with coefficients of determination (R2) > 0.9972 within the range of 0.01-50 mg/L. The limits of detection and quantification were within the ranges of 0.6-40 µg/L and 2.0-135 µg/L, respectively, with the exception of spermine (SPM). The recoveries were demonstrated within the range of 82.6-103.0%, with relative standard deviations (RSDs) of less than 4.2%. This simple method featuring excellent sensitivity and selectivity was suitable for the quantification of BAs in wines. The occurrence of BAs in 236 wine samples that are commercially available in China was determined. The BA levels in wines of different geographical origins varied significantly. The acute dietary exposure assessment of BAs was carried out by calculating the estimated short-term intake (ESTI) and comparing the acute reference dose (ARfD) specified by the European Food Safety Authority (EFSA). Results showed that the exposure to histamine (HIS) and tyramine (TYR) via the consumption of wines was much lower than the recommended ARfD level for healthy individuals. However, exposure could lead to symptoms in susceptible individuals. These results provided basic data regarding the occurrence and risk of BAs in wines for wine production, health guidance and consumer safety.

Simple, fast and inexpensive quantification of glycolate in the urine of patients with primary hyperoxaluria type 1

In primary hyperoxaluria type 1 excessive endogenous production of oxalate and glycolate leads to increased urinary excretion of these metabolites. Although genetic testing is the most definitive and preferred diagnostic method, quantification of these metabolites is important for the diagnosis and evaluation of potential therapeutic interventions. Current metabolite quantification methods use laborious, technically highly complex and expensive liquid, gas or ion chromatography tandem mass spectrometry, which are available only in selected laboratories worldwide. Incubation of ortho-aminobenzaldehyde (oABA) with glyoxylate generated from glycolate using recombinant mouse glycolate oxidase (GO) and glycine leads to the formation of a stable dihydroquinazoline double aromatic ring chromophore with specific peak absorption at 440 nm. The urinary limit of detection and estimated limit of quantification derived from eight standard curves were 14.3 and 28.7 µmol glycolate per mmol creatinine, respectively. High concentrations of oxalate, lactate and L-glycerate do not interfere in this assay format. The correlation coefficient between the absorption and an ion chromatography tandem mass spectrometry method is 93% with a p value < 0.00001. The Bland–Altmann plot indicates acceptable agreement between the two methods. The glycolate quantification method using conversion of glycolate via recombinant mouse GO and fusion of oABA and glycine with glyoxylate is fast, simple, robust and inexpensive. Furthermore this method might be readily implemented into routine clinical diagnostic laboratories for glycolate measurements in primary hyperoxaluria type 1.

A fast and simple extraction method for analysing levoglucosan and its isomers in sediments by ion chromatography tandem mass spectrometry.

The ability to trace current and past biomass burning events is important for understanding the links between human activity, fire frequency, and climate. One method of tracing biomass burning is to measure the concentrations of certain monosaccharides anhydrides (MAs), specifically levoglucosan (LEV) and its isomers, mannosan (MAN) and galactosan (GAL), which are products of cellulose and hemicellulose pyrolysis. This work presents a simple extraction method allowing for the rapid, sensitive, and selective determination of MAs in sediments. MAs detection was performed using suppressed ion chromatography with electrospray - triple-stage quadrupole tandem mass spectrometry (IC-TSQ-MS). The extraction method involves ultrasound probe sonication using water as the solvent. Extraction time, amplitude, and sonication mode were optimised. Recoveries higher than 86% for all MAs tested were achieved by applying 70% amplitude in continuous mode for 60 s. Analytical performance of the method included instrumental LODs of 0.10, 0.12 and 0.50 μg L-1 for LEV, MAN and GAL, respectively. No carryover issues, no matrix effect and no co-elution of targeted MAs with other sugars likely present in sediments samples were observed. The developed extraction method was further validated by the analysis of LEV and MAN in NIST® 1649b urban dust reference material and the resulting concentrations were in excellent agreement with previously reported values. MAs quantification in 70 lake sediment samples were carried out with concentrations found to range from 0.009 to 0.390 μg g-1 for LEV and from 0.009 to 0.194 μg g-1 for MAN. Plotting MAs concentrations versus approximate sediment age allowed the reconstruction of recent fire events impacting two locations in the Central Highlands of Tasmania, Australia.

Determination of 10 organic acids in alcoholic products by ion chromatography-tandem mass spectrometry

A method was developed for the determination of 10 organic acids in liquor, yellow rice wine, and dry red wine by ion chromatography-triple quadrupole mass spectrometry (IC-MS/MS). First, the liquor samples were diluted with deionized water, degassed with nitrogen, and analyzed by IC-MS/MS. Then, the yellow rice wine and dry red wine samples were purified with different solid-phase extraction cartridges. Finally, the GCB solid-phase extraction cartridge was selected for purification, diluted with deionized water, and analyzed by IC-MS/MS. The samples were separated using a Dionex IonPac AS11-HC anion analysis column with high capacity and strong hydrophilicity, with an KOH aqueous solution as the eluent, which was produced by an automatic generator for gradient elution. After being suppressed using a suppressor, the eluent was injected directly into the electrospray ionization tandem mass spectrometry (ESI-MS/MS), ionized in negative ion mode, detected in multiple reaction monitoring (MRM) mode, and quantified using an external standard method. Oxalic acid, fumaric acid, maleic acid, malic acid, tartaric acid, citric acid, quinic acid, and aconitic acid showed good linear relationships in the range of 0.05-2 mg/L. Succinic acid and lactic acid showed good linearities in the range of 0.05-5 mg/L and 0.05-10 mg/L, respectively. The correlation coefficients (r2) were >0.99. The limits of detection (LODs) and limits of quantification (LOQs) were 1.0-8.0 μg/L and 3.5-26.5 μg/L, respectively. The average recoveries ranged from 83.0% to 112.1%, and the relative standard deviations (RSDs) were <9.1% in spiked samples at three levels. The proposed method allowed easy pretreatment without using organic solvents or derivatization processing. Overall, the proposed method is accurate, rapid, sensitive, and it is suitable for the qualitative and quantitative analyses of the 10 organic acids in three wine samples. Moreover, it can be used for the determination of flavor and quality of alcoholic products.

Analysis of degradation products of nerve agents in biological fluids by ion chromatography-tandem mass spectrometry.

The detection of hydrolysis products of nerve agents (alkyl methylphosphonic acids; RMPAs) in biological samples from victims is important to confirm exposure to nerve agents. However, analysis of RMPAs is difficult due to their high hydrophilicity. The aim of this study was to develop ion chromatography-tandem mass spectrometry (IC-MS/MS) methods using commercially available equipment and columns to analyze RMPAs in human urine and serum with high sensitivity and without using complicate techniques. A Dionex IonPac AS11-HC anion-exchange column was used to analyze six RMPAs (MPA, EMPA, IMPA, iBuMPA, CHMPA, and PMPA). For pretreatments of biological fluids, we developed two pretreatment methods (Method 1: dilution and ultrafiltration; Method 2: removal of chloride ions with Ag cartridges). Six RMPAs including highly hydrophilic methylphosphonic acid and ethyl methylphosphonic acid could be analyzed with sufficient retention times and peak shape. The detection limits of RMPAs were improved using Dionex OnGuard II Ba/Ag/H cartridges and MetaSEP IC-Ag cartridges (urine: 0.5-5ng/mL; serum: 1-5ng/mL). These methods were also applied to the test samples for the Organisation for the Prohibition of Chemical Weapons Biomedical Proficiency Tests. RMPAs could be sufficiently analyzed by IC-MS/MS. In addition, the limits of detection were superior to those obtained in our previous study involving LC-MS/MS or derivatization-LC-MS/MS method. For analysis of biological samples, an appropriate pretreatment method can be chosen according to the amount of sample available for analysis and expected RMPA concentrations.

Higher Levels of Urinary Thiocyanate, a Biomarker of Cruciferous Vegetable Intake, Were Associated With Lower Risks of Cardiovascular Disease and All-Cause Mortality Among Non-smoking Subjects.

BackgroundEpidemiologic studies on cruciferous vegetable (CV) intake and cardiovascular disease (CVD) were inconclusive.ObjectiveTo investigate the associations of urinary thiocyanate, a biomarker of CV intake, with CVD and all-cause mortality among non-smoking adults.MethodsThis prospective cohort study comprised 10,489 non-smoking adults (weighted mean age, 46.8 years; 43.4% male) from the National Health and Nutrition Examination Survey 2001–2014. Non-smokers were defined as subjects with serum cotinine < 3 ng/mL. Urinary thiocyanate was measured with ion chromatography tandem mass spectrometry at baseline, and CVD and all-cause mortality were identified through linkage to National Death Index until December 31, 2015. Cox proportional hazards model was applied to estimate the hazard ratios (HRs) with 95% confidence intervals (CIs) for CVD and all-cause mortality.ResultsA total of 800 deaths, of which 136 died of CVD, were ascertained within a median 7.8 years of follow-up. Urinary thiocyanate was positively correlated with total CV intake among non-smoking adults (rs = 0.088, P < 0.001). Comparing extreme quartiles, the multivariate-adjusted HRs for CVD and all-cause mortality were 0.50 (95% CI: 0.29–0.85) and 0.75 (95% CI: 0.60–0.92), respectively. Each 1 μg/g creatinine increment of log-transformed urinary thiocyanate was associated with a 25% (HR: 0.75; 95% CI: 0.62–0.91) reduced CVD mortality risk and 12% (HR: 0.88; 95% CI: 0.81–0.96) reduced all-cause mortality risk. The documented inverse associations persisted in sensitivity analyses.ConclusionIncreased levels of urinary thiocyanate, a candidate biomarker of CV intake, were associated with low risks of CVD and total mortality among non-smoking adults. This prospective biomarker-based study provided further evidence to support the cardiovascular benefits of CVs.

An ion chromatography tandem mass spectrometry (IC-MS/MS) method for glyphosate and amino methyl phosphoric acid in serum of occupational workers

A non-suppressed ion chromatography tandem mass spectrometry (IC-MS/MS) has been established to measure glyphosate (GLY) and amino methyl phosphoric acid (AMPA) in serum of the occupational workers. After the inhibition of metal-chelating with EDTA aqueous solution and protein precipitation with acetonitrile, the samples were purified with a modified liquid–liquid extraction method and separated on an ion chromatographic column (250 mm × 2.1 mm) by using a gradient program of 0.4 mol/L methylamine aqueous solution and acetonitrile as mobile phase. Multiple reactions monitoring (MRM) model was used to obtain the sensitivity of the method, and the isotopically labelled internal standards were applied in the calibration process. Good linearities and recoveries were obtained in the validation process. The recovery experiment provided satisfied results with a range of 91%~101% for GLY and 92%~99% for AMPA in human serum and RSD values for both two analytes were <4%. The limits of detection for GLY and AMPA were 0.6 ng/mL and 1.2 ng/mL, respectively. The association between the posts in workplace and the concentration of two contaminants in serum samples was investigated throughout the analysis of the 307 worker serum samples. The data analysis results indicated the distribution of compounds in human serum was significantly related to the exposure probability and duration during the manufacture process of GLY.

A novel ion chromatography tandem mass spectrometry (IC-MS/MS) method for the determination of chlorate and prechlorate in freshly brewed coffee

Coffee is one of the most popular beverages in the world. A sensitive and fast method has been established and validated to measure chlorate and perchlorate in freshly brewed coffee beverages based on ion chromatography tandem mass spectrometry (IC-MS/MS) in this study. After the extraction with water and protein precipitation with acetonitrile, the samples were purified with MCX columns and then separated on an ion chromatographic column (250 mm × 2.1 mm) by using a gradient program of 0.4 mol/L methylamine aqueous solution and acetonitrile as mobile phase. Multiple reactions monitoring (MRM) model was used to obtain the sufficient sensitivity for the method, and the isotope internal standards, potassium 18O3-chlorate and sodium 18O4-perchlorate, were applied for the calibration. The validation results provided good linearity in the range of 25.0–1000 μg/L for chlorate and 6.25–250 μg/L for perchlorate. The recovery rates were 84.6%–99.8% for chlorate and 99.7%–112% for perchlorate in six different kinds fancy coffee samples at three known concentration levels and the relative coefficients were lower than 8%. The limit of quantification of method was 15.0 μg/L, 1.50 μg/L for chlorate and perchlorate, respectively. Finally, the method was applied in the measurement of two chlorine oxides in the retail freshly brewed coffee products from local coffee shops in Nanjing. The concentration of chlorate and perchlorate in coffee indicated the widespread of chlorate and perchlorate in these beverages. The established method was sensitive and suitable for the detection of chlorate and perchlorate in coffee products.

Quantification of glyphosate and other organophosphorus compounds in human urine via ion chromatography isotope dilution tandem mass spectrometry

Organophosphorus pesticides are the most used pesticides in the United States. Most organophosphorus pesticides are composed of a phosphate (or phosphorothioate or phosphorodithioate) moiety and a variable organic group. Organophosphorus pesticides are scrutinized by regulatory bodies and agencies because of their toxicity or suspected carcinogenicity. Upon exposure, organophosphorus pesticides and their metabolites eliminate in urine; these urinary biomarkers are useful to evaluate human exposure. We developed a method using stable isotope dilution, ion chromatography tandem mass spectrometry for quantification in urine of 6 O,O-dialkylphosphates, metabolites of organophosphorus insecticides, and glyphosate, the most used herbicide in the United States. With simple and minimal sample preparation, the analytical method is selective and sensitive (limits of detection are 0.2-0.8 μg/L), accurate (>85%) and precise (relative standard deviation <20%), depending on the analyte. To assess the suitability of the method in real exposure scenarios, we analyzed samples collected anonymously from subjects with suspected exposure to pesticides (n = 40) or who had been on an organic diet (n = 50). We detected glyphosate in 80% of subjects reporting an organic diet and in 78% of those with suspected glyphosate exposure; concentrations ranged from <0.2 to 28.6 μg/L. Median concentrations were 0.39 μg/L for the organic diet group and 0.40 μg/L for individuals with suspected exposure. Interestingly, interquartile ranges were considerably higher among those reporting pesticide exposure (0.63 μg/L) than those consuming organic diets (0.42 μg/L). These data suggest that the method meets typical validation benchmark values and is sensitive to investigate background exposures in the general population.

Analysis of glyphosate, AMPA, Glufosinate and MPPA with ION chromatography tandem mass spectrometry using A membrane suppressor in the ammonium form application to surface water of low to moderate salinity

This paper describes a simple and reliable method for the sensitive and selective determination of the pesticides Glyphosate and Glufosinate and their main metabolites aminomethylphosphonic acid (AMPA) and 3-[hydroxy(methyl)phosphinoyl]propionic acid (MPPA) in surface water. The developed method is based on ion chromatography hyphenated to electrospray tandem mass spectrometry and does not require derivatization. A membrane suppressor, regenerated at pH 9, has been used in this work to strongly improve the peak shape of AMPA, which suffered from huge tailing due to the interaction of this compound with acidic membrane suppressors. With this modified suppressor the sensitivity for AMPA improved about 100 times. Moreover, addition of 40% methanol to the hydroxy eluent improved MS sensitivity for all compounds by 1.3–2.8 times. The separation is performed on a strong anion exchange column. Glyphosate and AMPA are detected in the negative ion ESI mode, whereas Glufosinate and MPPA show much better sensitivity in the positive ion ESI mode. Surface water samples were spiked with the labelled parent compounds. Sample preparation comprised a filtering step over coupled solid phase extraction Ba, Ag and Na cartridges to remove chloride and sulphate ions. The performance characteristics of the method were determined with real surface water samples. Samples containing 12.6 g L−1 chloride were also used in the validation process and showed no problem.Nitrate is not removed from the samples and may give ion-suppression for Glyphosate.Linearity of the method was established over at least three orders of magnitude in the measuring range 10–2000 ng L−1 for surface water. The reliability of the results was ensured by the application of the criteria from the Dutch Technical Agreement (NTA 8379) concerning “identification”, “indication”, and “absence” of substances. The limit of quantitation with regard to identification was 10 ng L−1 for all compounds and the limits of detection with regard to indication were 6.5–9.6 ng L−1. The recovery (94–104%) and reproducibility variance (5.5–6.2%) were excellent. The suitability of the developed method was demonstrated by the analysis of 172 surface water samples of low to moderate salinity from different parts of The Netherlands. AMPA was identified in 99% of the samples and always exceeded the maximum allowable concentration of 100 ng L−1. The maximal concentration found in surface water was 9900 ng L−1. Glyphosate was identified in 82% of the samples and in only 6% Glyphosate exceeded the maximum allowable concentration of 100 ng L−1. MPPA was identified in about 75% of the samples whereas Glufosinate was rarely detected and never exceeded the limit of quantitation.

Analysis of levoglucosan and its isomers in atmospheric samples by ion chromatography with electrospray lithium cationisation - Triple quadrupole tandem mass spectrometry

Biomass burning (BB) emissions are a significant source of particles to the atmosphere, especially in the Southern Hemisphere, where the occurrence of anthropogenic and natural wild fires is common. These emissions can threaten human health through increased exposure, whilst simultaneously representing a significant source of trace metals and nutrients to the ocean. One well known method to track BB emissions is through monitoring the atmospheric concentration of specific monosaccharide anhydrides (MAs), specifically levoglucosan and its isomers, mannosan and galactosan. Herein, a new method for the determination of levoglucosan and its isomers in marine and terrestrial aerosol samples is presented, which delivers both high selectivity and sensitivity, through the coupling of ion chromatography and triple quadrupole tandem mass spectrometry. Optimal chromatographic conditions, providing baseline separation for target anhydrosugars in under 8 min, were obtained using a Dionex CarboPacⓇ PA-1 column with an electrolytically generated KOH gradient. To improve the ionisation efficiency for MS detection, an organic make-up solvent was fed into the IC column effluent before the ESI source, and to further increase both sensitivity and selectivity, cationisation of levoglucosan was investigated by adding salts into the make-up solvent, namely, sodium, ammonium and lithium salts. Using positive lithium cationisation with 0.5 mM lithium chloride in methanol as the make-up solvent, delivered at a flow rate of 0.02 mL min–1, the levoglucosan response was improved by factors of 100 and 10, comparing to negative ionisation and positive sodium cationisation, respectively. Detection was carried out in SRM mode for quantitation and identification, achieving an instrumental LOD of 0.10, 0.12 and 0.5 µg L−1 for levoglucosan, mannosan and galactosan, respectively. Finally, the method was applied to the analysis of 41 marine and terrestrial aerosol samples from Australia, its surrounding coastal waters and areas within the remote Southern Ocean, covering a large range of BB marker concentrations.

The utilisation of ion chromatography and tandem mass spectrometry (IC-MS/MS) for the multi-residue simultaneous determination of highly polar anionic pesticides in fruit and vegetables

A robust and sensitive method utilising a hybrid ion chromatography tandem mass spectrometry system (IC-MS/MS) for the simultaneous determination of nine (9) highly polar anionic pesticides (chlorate, ethephon, fosetyl aluminium, glufosinate, glyphosate, N-acetyl AMPA, N-acetyl glyphosate, perchlorate and phosphonic acid) in fruit and vegetables is described. Mean recoveries (n = 6) at two fortification levels ranged from 83 to 112% with %CVs in the range 3–14%. The linearity range was 0.005–0.4 mg kg−1 and R2 values were >0.99 and the sensitivity of the method allowed (20× or 30×) dilution of samples. Provision of qualitative determination of aminomethylphosphonic acid (AMPA) was also facilitated via minor modification of the chromatographic conditions. Compliance with method validation criteria, survey results from the statutory UK/EU Pesticide Residues in Food 2018 programmes i.e. pea, pineapple, melon and successful z-scores for a UK proficiency testing scheme sample (ethephon in pineapple) demonstrate successful application of this IC-MS/MS method.

Analysis of perchlorate in baby food on Canadian (Ottawa) markets in 2009 and estimated dietary exposure

ABSTRACTIn order to determine the baseline levels of perchlorate in major brands of baby food, 200 baby food products were collected from retail stores in Ottawa, Canada and analysed for perchlorate in 2010. The seven food groups tested were fruit, juices, vegetables, meat, yogurt, mixed (vegetable mixed with meat) and other (e.g. vegetable mixed with meat and cereal, cheese, egg,). Samples were extracted with a mixture of methanol and 1% acetic acid (4:1, v/v). Determination was conducted by stable isotope dilution ion chromatography tandem mass spectrometry (ID-IC-MS/MS). The complexity of different food matrices required additional method validation. The perchlorate levels in 46 samples were found to be lower than the quantification limit (0.2 ng g−1). The perchlorate levels in the other 154 baby food samples were also low; about 96.7% of the baby foods had perchlorate levels less than 10 ng g−1 (ranged from 0.2 to 22.4 ng g−1, median1.35 ng g−1); only 5 samples had perchlorate levels higher than 10 ng g−1. Dietary exposure to perchlorate from analysed baby food was conservatively estimated to range from 0.007 to 0.121 µg/kg bw/d based on the mean intake for children (1–5 years old).

Improved phosphometabolome profiling applying isotope dilution strategy and capillary ion chromatography-tandem mass spectrometry

The phosphometabolome is comprised of all phosphorylated metabolites including the major metabolite classes sugar phosphates and nucleoside phosphates. Phosphometabolites are invaluable in any cell as a part of primary- and energy- metabolism, and as building blocks in the biosynthesis of macromolecules. Here, we report quantitative profiling of the phosphometabolome by applying capillary ion chromatography-tandem mass spectrometry (capIC-MS/MS), ensuring improved chromatographic separation, robustness and quantitative precision. Baseline separation was achieved for six out of eight tested hexose phosphates. Quantitative precision and reproducibility was improved by introducing a fully uniformly (U) 13C–labeled biological extract and applying an isotope dilution (ID) correction strategy. A 13C–labeled biological extract does in principle contain internal standards (IS) for all metabolites, but low abundant metabolites pose a challenge, and solutions to this are discussed. The extreme reproducibility and reliability of this capIC-MS/MS method was demonstrated by running the instrumentation continuously for ten days.

Ion chromatography tandem mass spectrometry (IC-MS/MS) multimethod for the determination of highly polar pesticides in plant-derived commodities

A new sensitive, fast, and robust analytical method based on a QuPPe (Quick Polar Pesticides) extraction procedure coupled to ion chromatography-tandem mass spectrometry (IC-MS/MS) was developed. The study aimed at the determination of the highly polar pesticides chlorate, perchlorate, ethephon, and 2-hydroxyethylphosphonic acid (HEPA) in different plant food commodities. For achieving an acceptable dynamic range for chlorate and perchlorate and to compensate for matrix effects, the isotopically-labelled internal standards 18O3-chlorate and 18O4-perchlorate and ethephon D4 were applied for calibration. The optimized method was fully validated at levels of 0.010 and 0.100 mg kg−1 for all compounds in the matrices tomato, apple, lemon, sultana, avocado, and wheat according to the actual EU guidance document SANTE/11945/2015. For HEPA and the commodity sultana levels for validation were chosen at 0.050 mg kg−1 and 0.100 mg kg−1. The precision and accuracy of the validation results were determined at hand of five replicates with recovery rates between 93 and 119% and RSDs between 1 and 14%. The use of internal standards for chlorate, perchlorate and ethephon allows the determination in a wide working range between 0.01 and 1 mg kg−1 without interference by matrix effects. The developed analytical methodology is able to meet the strict requirements for the analysis of baby food.