Wildfires: Identification of a new suite of aromatic polycarboxylic acids in ash and surface water.

Ash and surface water samples collected after wildfires in four different geographical locations (California, Colorado, Kansas and Alberta) were analyzed. The ash samples were leached with deionized water, and leachates were concentrated by solid phase extraction and analyzed by liquid chromatography/time-of-flight mass spectrometry. In addition, three surface water samples and a lysimeter water sample were collected from watersheds recently affected by fire in California and Colorado, and analyzed in similar fashion. A suite of benzene polycarboxylic acids (BPCAs), with two and three carboxyl groups and their corresponding isomers were identified for the first time in both ash leachates and water samples. Also found was a pyridine carboxylic acid (PCA), 3,5-pyridine dicarboxylic acid. Furthermore, putative identifications were made for other carboxylated aromatic acids: quinolinic, naphthalenic, and benzofuranoic acid carboxylates. The wildfire ashes, a controlled wood ash, and post-fire surface water samples suggest that burned woody material, along with surface plant-material and heated o-horizon soil organic matter, contribute to both BPCAs and PCAs in runoff. This study is the first of its kind to identify this suite of aromatic acids in wildfire ash and surface water samples. These data make an important contribution to the nature of dissolved organic matter from wildfire and are useful to better understand the impact of wildfire on water quality and drinking water sources.

Nontargeted Screening of Water Samples Using Data-Dependent Acquisition with Similar Partition Searching.

A rapid screening method for the detection of nontargeted compounds in surface water samples was developed using MS-MS high-resolution mass spectrometry and data-dependent acquisition. The key parameters for the acquisition method were optimized using five model compounds with diverse chemical characteristics. The parameter selection required optimization between the total number of precursor ions that could be selected in an LC-MS run, the quality of each MS (full range) spectrum, and the quality of each MS-MS fragmentation spectrum. After the acquisition method was optimized, 18 surface water samples from rivers, reservoirs, and effluents from wastewater treatment plants were analyzed, generating 41625 MS-MS spectra in about 14 h. The raw data were then converted into two generic formats using the open-access program MSConvert. A combinatorial approach, similar partition searching (SPS), was then used to putatively identify analytes from the accurate mass of each analyte (adjusted for the adduct mass) and the corresponding MS-MS spectra were obtained. In this approach, the structures of about 250000 common compounds, stored in a large database as mathematical partitions of their exact mass, were compared directly to each MS-MS spectrum. Compounds with a similar mass and retention time were grouped together and labeled as "Analytes", using an Excel Add-In. The isotope ratio data from the MS spectrum, the corresponding MS-MS spectra, and the putative identifications were then imported into an Access relational database to facilitate sorting, searching, filtering, and querying the results. This allowed final inspection to assess confidence of the identifications made through the nontargeted screening.

The Influence of pH and Sodium Hydroxide Exposure Time on Glucosamine and Acrylamide Levels in California-Style Black Ripe Olives.

Acrylic acid, N-acetyl-glucosamine and glucosamine were investigated for their role in the formation of acrylamide in California-style black ripe olives [CBROs]. Levels of acrylic acid and glucosamine are reported for the first time in fresh (333.50 ± 21.88 and 243.59 ± 10.06 nmol/g, respectively) and in brine-stored olives (184.50 ± 6.02 and 165.88 ± 11.51 nmol/g, respectively). Acrylamide levels significantly increased when acrylic acid (35.2%), N-acetyl-glucosamine (29.9%), and glucosamine (124.0%) were added to olives prior to sterilization. However, isotope studies indicate these compounds do not contribute carbon and/or nitrogen atoms to acrylamide. The base-catalyzed degradation of glucosamine is demonstrated in olive pulp and a strong correlation (r2 = 0.9513) between glucosamine in olives before sterilization and acrylamide formed in processed CBROs is observed. Treatment with sodium hydroxide (pH > 12) significantly reduces acrylamide levels over 1 to 5 d without impacting olive fruit texture.

U.S. domestic cats as sentinels for perfluoroalkyl substances: Possible linkages with housing, obesity, and disease.

Perfluoroalkyl substances (PFAS), such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), are persistent, globally distributed, anthropogenic compounds. The primary source(s) for human exposure are not well understood although within home exposure is likely important since many consumer products have been treated with different PFAS, and people spend much of their lives indoors. Herein, domestic cats were used as sentinels to investigate potential exposure and health linkages. PFAS in serum samples of 72 pet and feral cats, including 11 healthy and 61 with one or more primary disease diagnoses, were quantitated using high-resolution time-of-flight mass spectroscopy. All but one sample had detectable PFAS, with PFOS and perfluorohexane sulfonate (PFHxS) ranging from

Nontargeted Screening of Food Matrices: Development of a Chemometric Software Strategy To Identify Unknowns in Liquid Chromatography-Mass Spectrometry Data.

The ability to identify contaminants or adulterants in diverse, complex sample matrixes is necessary in food safety. Thus, nontargeted screening approaches must be implemented to detect and identify unexpected, unknown hazardous compounds that may be present. Molecular formulas can be generated for detected compounds from high-resolution mass spectrometry data, but analysis can be lengthy when thousands of compounds are detected in a single sample. Efficient data mining methods to analyze these complex data sets are necessary given the inherent chemical diversity and variability of food matrixes. The aim of this work is to determine necessary requirements to successfully apply data analysis strategies to distinguish suspect and control samples. Infant formula and orange juice samples were analyzed with one lot of each matrix containing varying concentrations of a four compound mixture to represent a suspect sample set. Small molecular differences were parsed from the data, where analytes as low as 10 ppb were revealed. This was accomplished, in part, by analyzing a quality control standard, matrix spiked with an analytical standard mixture, technical replicates, a representative number of sample lots, and blanks within the sample sequence; this enabled the development of a data analysis workflow and ensured that the employed method is sufficient for mining relevant molecular features from the data.

Ultrahigh-pressure liquid chromatography triple-quadrupole tandem mass spectrometry quantitation of polyphenols and secoiridoids in california-style black ripe olives and dry salt-cured olives.

The chemical composition of finished table olive products is influenced by the olive variety and the processing method used to debitter or cure table olives. Herein, a rapid ultrahigh-pressure liquid chromatography triple-quadrupole tandem mass spectrometry method, using dynamic multiple reaction monitoring, was developed for the quantitation of 12 predominant phenolic and secoiridoid compounds in olive fruit, including hydroxytyrosol, oleuropein, hydroxytyrosol-4-O-glucoside, luteolin-7-O-glucoside, rutin, verbascoside, oleoside-11-methyl ester, 2,6-dimethoxy-p-benzoquinone, phenolic acids (chlorogenic and o-coumaric acids), oleuropein aglycone, and ligstroside aglycone. Levels of these compounds were measured in fresh and California-style black ripe processed Manzanilla olives and two dry salt-cured olive varieties (Mission from California and Throuba Thassos from Greece). Results indicate that the variety and debittering processing method have strong impact on the profile of phenolic and secoiridoid compounds in table olives. The dry salt-cured olives contained higher amounts of most compounds studied, especially oleuropein (1459.5 ± 100.1 µg/g), whereas California-style black ripe olives had a significant reduction or loss of these bioactive compounds (e.g., oleuropein level at 36.7 ± 3.1 µg/g).

An integrated approach utilising chemometrics and GC/MS for classification of chamomile flowers, essential oils and commercial products.

As part of an ongoing research program on authentication, safety and biological evaluation of phytochemicals and dietary supplements, an in-depth chemical investigation of different types of chamomile was performed. A collection of chamomile samples including authenticated plants, commercial products and essential oils was analysed by GC/MS. Twenty-seven authenticated plant samples representing three types of chamomile, viz. German chamomile, Roman chamomile and Juhua were analysed. This set of data was employed to construct a sample class prediction (SCP) model based on stepwise reduction of data dimensionality followed by principle component analysis (PCA) and partial least squares discriminant analysis (PLS-DA). The model was cross-validated with samples including authenticated plants and commercial products. The model demonstrated 100.0% accuracy for both recognition and prediction abilities. In addition, 35 commercial products and 11 essential oils purported to contain chamomile were subsequently predicted by the validated PLS-DA model. Furthermore, tentative identification of the marker compounds correlated with different types of chamomile was explored.

Analytical methodologies for the detection of sucralose in water.

A detailed evaluation of two liquid chromatography-mass spectrometry techniques, quadrupole time-of-flight mass spectrometry (LC/Q-TOF-MS) and triple quadrupole mass spectrometry (LC/MS-MS), was carried out in terms of sensitivity, selectivity, and ionization mode for the detection of sucralose in environmental water samples, which is an important environmental topic in water analysis. Interesting findings were made in regards to fragmentation and sensitivity when both techniques and both ionization modes of operation were compared. In positive ion mode, sucralose was detected by its sodium adduct [M + Na](+) at m/z 419.0038. Fragmentation by MS-MS of the sodiated molecule was possible using either LC/MS-MS or LC/Q-TOF-MS under positive ionization. Accurate mass measurements provided exact structural confirmation of the sodiated fragments obtained (m/z 221.0187 and m/z 238.9848). In negative ion mode, the deprotonated molecule was observed ([M - H](-) at m/z 395.0073), and fragmentation by MS-MS yielded two characteristic fragment ions (m/z 359.0306 and m/z 34.9694). Because sucralose contains three chlorine atoms, time-of-flight analyses provided a valuable amount of isotopic accurate mass information for its detection. With LC/MS-MS, the sensitivity was 10 times higher in positive ion mode than in negative ion mode, with limits of detection of 15 ng/L. Similarly, when time-of-flight mass spectrometry was used, the sensitivity was slightly better in positive ion mode, with limits of detection of 400 ng/L. Matrix effects were observed for surface and wastewater samples; thus the use of a deuterated standard (sucralose-d6) was crucial for precise quantitation. The most sensitive analytical methodology for the analysis of sucralose in water samples was LC/MS-MS using triple quadrupole under positive ion mode.

Identification of imidacloprid metabolites in onion (Allium cepa L.) using high-resolution mass spectrometry and accurate mass tools.

RATIONALE: Imidacloprid is a potent and widely used insecticide on vegetable crops, such as onion (Allium cepa L.). Because of possible toxicity to beneficial insects, imidacloprid and several metabolites have raised safety concerns for pollenating insects, such as honey bees. Thus, imidacloprid metabolites continue to be an important subject for new methods that better understand its dissipation and fate in plants, such as onions. METHODS: One month after a single addition of imidacloprid to soil containing onion plants, imidacloprid and its metabolites were extracted from pulverized onion with a methanol/water-buffer mixture and analyzed by liquid chromatography/quadrupole time-of-flight mass spectrometry (LC/QTOF-MS) using a labeled imidacloprid internal standard and tandem mass spectrometric (MS/MS) analysis. RESULTS: Accurate mass tools were developed and applied to detect seven new metabolites of imidacloprid with the goal to better understand its fate in onion. The accurate mass tools include: database searching, diagnostic ions, chlorine mass filters, Mass Profiler software, and manual use of metabolic analogy. The new metabolites discovered included an amine reduction product (m/z 226.0854), and its methylated analogue (m/z 240.1010), and five other metabolites, all of unknown toxicity to insects. CONCLUSIONS: The accurate mass tools were combined with LC/QTOF-MS and were able to detect both known and new metabolites of imidacloprid using fragmentation studies of both parent and labeled standards. New metabolites and their structures were inferred from these MS/MS studies with accurate mass, which makes it possible to better understand imidacloprid metabolism in onion as well as new metabolite targets for toxicity studies.

Analysis of isobaric pesticides in pepper with high-resolution liquid chromatography and mass spectrometry: complementary or redundant?

Five isobaric pesticides are analyzed in red pepper (Capsicum annuum) by high-resolution chromatography (100,000 theoretical plates/meter) and high-resolution mass spectrometry (resolving power > 25000) to test whether these methods are redundant or complementary when using MS/MS analysis. The five compounds are hexaconazole, isazophos, isoxathion, kresoxim-methyl, and triazophos, with an isobaric mass of m/z 314 and 336. Red pepper was chosen as a complex vegetable matrix with more than 4000 adducted ions (MH(+) and MNa(+)). High-resolution chromatography was found to be a valuable tool to separate the isobaric pesticides from one another, whereas the high resolution of the mass spectrometer separated the matrix ions of red pepper easily from the pesticides due to differences in their mass defect. The combination of techniques is especially valuable in MS/MS analysis because of interfering precursor and fragment ions of the isobaric pesticides rather than the complex pepper matrix--a nonintuitive result.

UHPLC-(ESI)QTOF MS/MS profiling of quercetin metabolites in human plasma postconsumption of applesauce enriched with apple peel and onion.

An ultrahigh pressure liquid chromatography accurate mass quadrupole time-of-flight mass spectrometry with electrospray ionization (UHPLC-(ESI)QTOF MS/MS) method was developed for measuring individual quercetin metabolites in human plasma with high sensitivity and high selectivity. Quercetin (3,3',4',5,7-pentahydroxyflavone) occurs as glycosides in foods. The composition of glycosides is species and cultivar specific. In humans, quercetin undergoes extensive biotransformation, resulting in a range of metabolites. The bioactivity of quercetin metabolites will depend on the type and position of the conjugates. Herein, individual quercetin metabolites (i.e., sulfate, glucuronide or methyl conjugates) were identified by accurate mass MS in human plasma (females = 8 and males = 8) over 24 h after consumption of applesauce enriched with either micronized apple peel (AP) or onion powder (OP). The AP and OP contained ~180 µmol of quercetin glycosides. The relative amounts of quercetin metabolites were quantified in plasma. The complement of identified quercetin metabolites was similar after consumption of AP and OP. Primary metabolites included the following: quercetin sulfate, quercetin glucuronide, and quercetin diglucuronide. A quercetin glutathione adduct was identified in negative ion mode but not apparent in positive ion mode. The pharmacokinetic parameters for AUC0-24 h and Cmax were significantly different for AP and OP. For example, consumption of the AP resulted in Cmax of quercetin sulfate, 4.6 ng/mL; quercetin glucuronide, 15.5 ng/mL; quercetin diglucuronide, 9.3 ng/mL; quercetin glucuronide sulfate, 1.3 ng/mL; methyl quercetin glucuronide, 7.5 ng/mL; and methyl quercetin diglucuronide, 3.6 ng/mL, whereas the OP resulted in Cmax of quercetin sulfate, 37.3 ng/mL; quercetin glucuronide, 212.8 ng/mL; quercetin diglucuronide, 168.8 ng/mL; quercetin glucuronide sulfate, 43.0 ng/mL; methyl quercetin glucuronide, 90.1 ng/mL; methyl quercetin diglucuronide, 65.4 ng/mL. Gender-related differences in the AUC0-24 h for quercetin sulfate and quercetin sulfate glucuronide metabolites were also observed.

Analysis of 70 Environmental Protection Agency priority pharmaceuticals in water by EPA Method 1694.

The U.S. Environmental Protection Agency (EPA) Method 1694 for the determination of pharmaceuticals in water recently brought a new challenge for treatment utilities, where pharmaceuticals have been reported in the drinking water of 41-million Americans. This proposed methodology, designed to address this important issue, consists of solid-phase extraction (SPE) followed by liquid chromatography-mass spectrometry (LC/MS-MS) using triple quadrupole. Under the guidelines of Method 1694, a multi-residue method was developed, validated, and applied to wastewater, surface water and drinking water samples for the analysis of 70 pharmaceuticals. Four distinct chromatographic gradients and LC conditions were used according to the polarity and extraction of the different pharmaceuticals. Positive and negative ion electrospray were used with two MRM transitions (a quantifier and a qualifier ion for each compound), which adds extra confirmation not included in the original Method 1694. Finally, we verify, for the first time, EPA Method 1694 on water samples collected in several locations in Colorado, where positive identifications for several pharmaceuticals were found. This study is a valuable indicator of the potential of LC/MS-MS for routine quantitative multi-residue analysis of pharmaceuticals in drinking water and wastewater samples and will make monitoring studies much easier to develop for water utilities across the US, who are currently seeking guidance on analytical methods for pharmaceuticals in their water supplies.

Screening and confirmation of 100 pesticides in food samples by liquid chromatography/tandem mass spectrometry.

An analytical method for screening, quantitation and confirmation of a group of 100 pesticides in vegetable and fruit samples was developed using liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS). The pesticides studied belonged to different chemical families of herbicides, insecticides and fungicides; some degradation products were included as well. A thorough optimization was performed for each analyte to achieve individual optimum fragmentor and collision energy voltages. Two transitions per parent compound were monitored in a single chromatographic run containing two time segments. A small particle size C(18) column (1.8 microm) was used for the chromatographic separation of the mixture, providing very narrow peaks and allowing an excellent separation of all the analytes in a 30-min period for maximum peak capacity. The method was validated with blank matrices of green pepper, tomato and orange spiked from 0.1 to 100 microg/kg with the pesticide mix. Quantitation was carried out using matrix-matched standard calibration and linearity of response over 3 orders of magnitude was demonstrated (r > 0.99). Limits of detection based on two transitions and ion-ratio requirements ranged between 0.3 and 50 microg/kg. In general, the sensitivity obtained meets the maximum residue levels (MRLs) established by the European Union regulation for food monitoring programs. The analytical performance of the method was evaluated for different types of vegetables and fruits, showing little or no matrix effects, and examples of screening and confirmation of pesticides in these samples are shown here.

Exact-mass library for pesticides using a molecular-feature database.

An automated molecular-feature database (MFD) consisting of the exact monoisotopic mass of 100 compounds, at least one exact mass product ion for each compound, and chromatographic retention time were used to identify pesticides in food and water samples. The MFD software compiles a list of accurate mass ions, excludes noise, and compares them with the monoisotopic exact masses in the database. The screening criteria consisted of +/-5 ppm accurate mass window, +/-0.2 min retention time window, and a minimum 1000 counts (signal-to-noise (S/N) ratio of approximately 10:1). The limit of detection for 100 tested compounds varied from <0.01 mg/kg for 72% of the compounds to <0.1 mg/kg for 95% of the compounds. The MFD search was useful for rapid screening and identification of pesticides in food and water, as shown in actual samples. The combined use of accurate mass and chromatographic retention time eliminated false positives in the automated analysis. The major weakness of the MFD is matrix interferences and loss of mass accuracy. Strengths of the MFD include rapid screening of 100 compounds at sensitive levels compared with a manual approach and the ease of use of the library for any accurate mass spectrometer instrumentation capable of routine sub-5-ppm mass accuracy.

Discovering metabolites of post-harvest fungicides in citrus with liquid chromatography/time-of-flight mass spectrometry and ion trap tandem mass spectrometry.

In this study, we benefit from the combination of liquid chromatography (LC)/time-of-flight (TOF) MS accurate mass measurements to generate elemental compositions of ions and LC/ion trap multiple MS (MSn) providing complementary structural information, which is useful for the elucidation of unknown organic compounds at trace levels in complex food extracts. We have applied this approach to investigate different citrus fruits extracts, and we have identified two post-harvest fungicides (imazalil and prochloraz), the main degradation product of imazalil ([M + H]+, m/z 257) and a non-previously reported prochloraz degradation product ([M + H]+, m/z 282). The database-mediated identification of the parent compounds was based on the generated elemental composition obtained from accurate mass measurements and additional qualitative information from the high resolution chlorine isotopic clusters of both the protonated molecules (imazalil, [M + H]+ 297.0556, <0.1 ppm error, 2-Cl; prochloraz, [M + H]+ 376.0381, 1.9 ppm error, 3-Cl) and their characteristic fragments ions (imazalil: m/z 255 and 159; prochloraz: m/z 308 and 266). The correlation between the structural information provided by ion trap MS/MS fragmentation pathways of the parent species and the TOF accurate mass elemental composition data of the degradation products were the key to elucidate the structures of the degradation products of both post-harvest fungicides. Finally, where standards were not available (prochloraz), further confirmation was obtained by synthesizing the proposed degradation product by acid hydrolysis of the parent standard and confirmation by LC/TOF-MS.