Expanding Per- and Polyfluoroalkyl Substances Coverage in Nontargeted Analysis Using Data-Independent Analysis and IonDecon.

Per- and polyfluoroalkyl substances (PFAS) are widespread, persistent environmental contaminants that have been linked to various health issues. Comprehensive PFAS analysis often relies on ultra-high-performance liquid chromatography coupled with high-resolution mass spectrometry (UHPLC HRMS) and molecular fragmentation (MS/MS). However, the selection and fragmentation of ions for MS/MS analysis using data-dependent analysis results in only the topmost abundant ions being selected. To overcome these limitations, All Ions fragmentation (AIF) can be used alongside data-dependent analysis. In AIF, ions across the entire m/z range are simultaneously fragmented; hence, precursor-fragment relationships are lost, leading to a high false positive rate. We introduce IonDecon, which filters All Ions data to only those fragments correlating with precursor ions. This software can be used to deconvolute any All Ions files and generates an open source DDA formatted file, which can be used in any downstream nontargeted analysis workflow. In a neat solution, annotation of PFAS standards using IonDecon and All Ions had the exact same false positive rate as when using DDA; this suggests accurate annotation using All Ions and IonDecon. Furthermore, deconvoluted All Ions spectra retained the most abundant peaks also observed in DDA, while filtering out much of the artifact peaks. In complex samples, incorporating AIF and IonDecon into workflows can enhance the MS/MS coverage of PFAS (more than tripling the number of annotations in domestic sewage). Deconvolution in complex samples of All Ions data using IonDecon did retain some false fragments (fragments not observed when using ion selection, which were not isotopes or multimers), and therefore DDA and intelligent acquisition methods should still be acquired when possible alongside All Ions to decrease the false positive rate. Increased coverage of PFAS can inform on the development of regulations to address the entire PFAS problem, including both legacy and newly discovered PFAS.

Detection of naphthenic acid uptake into root and shoot tissues indicates a direct role for plants in the remediation of oil sands process-affected water.

Bitumen extraction from surface-mined oil sands deposits results in the accumulation of large volumes of oil sands process-affected water (OSPW). Naphthenic acids (NAs) are primary contributors to OSPW toxicity and have been a focal point for the development of OSPW remediation strategies. Phytoremediation is an approach that utilizes plants and their associated microbes to remediate contaminants from soil and groundwater. While previous evidence has indicated a role for phytoremediation in OSPW treatment through the transformation and degradation of NAs, there are no reports that demonstrate the direct uptake of NAs into plant tissue. Using NAs labelled with 14C radioisotopes (14C-NAs) paired with whole-plant autoradiography, we show that NAs representing aliphatic (linear), single-ring, and diamondoid compounds were effectively removed from hydroponic solution and OSPW-treated soil by sandbar willow (Salix interior) and slender wheatgrass (Elymus trachycaulus) and their associated microbiomes. The NA-derived 14C label accumulated in root and shoot tissues of both plant species and was concentrated in vascular tissue and rapidly growing sink tissues, indicating that 14C-NAs or their metabolic derivatives were incorporated into physiological processes within the plants. Slender wheatgrass seedlings grown under axenic (sterile) hydroponic and soil conditions also effectively removed all 14C-NAs, including a highly stable diamondoid NA, demonstrating that plants can directly take up simple and complex NAs without the assistance of microbes. Furthermore, root and shoot tissue fractionation into major biomolecule groups suggests that NA-derived carbon is allocated toward biomolecule synthesis rapidly after NA treatment. These findings provide evidence of plant-mediated uptake of NAs and support a direct role for plants and their associated microbes in the development of future large-scale OSPW phytoremediation strategies.

The strength in numbers: comprehensive characterization of house dust using complementary mass spectrometric techniques.

Untargeted analysis of a composite house dust sample has been performed as part of a collaborative effort to evaluate the progress in the field of suspect and nontarget screening and build an extensive database of organic indoor environment contaminants. Twenty-one participants reported results that were curated by the organizers of the collaborative trial. In total, nearly 2350 compounds were identified (18%) or tentatively identified (25% at confidence level 2 and 58% at confidence level 3), making the collaborative trial a success. However, a relatively small share (37%) of all compounds were reported by more than one participant, which shows that there is plenty of room for improvement in the field of suspect and nontarget screening. An even a smaller share (5%) of the total number of compounds were detected using both liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS). Thus, the two MS techniques are highly complementary. Most of the compounds were detected using LC with electrospray ionization (ESI) MS and comprehensive 2D GC (GC×GC) with atmospheric pressure chemical ionization (APCI) and electron ionization (EI), respectively. Collectively, the three techniques accounted for more than 75% of the reported compounds. Glycols, pharmaceuticals, pesticides, and various biogenic compounds dominated among the compounds reported by LC-MS participants, while hydrocarbons, hydrocarbon derivatives, and chlorinated paraffins and chlorinated biphenyls were primarily reported by GC-MS participants. Plastics additives, flavor and fragrances, and personal care products were reported by both LC-MS and GC-MS participants. It was concluded that the use of multiple analytical techniques was required for a comprehensive characterization of house dust contaminants. Further, several recommendations are given for improved suspect and nontarget screening of house dust and other indoor environment samples, including the use of open-source data processing tools. One of the tools allowed provisional identification of almost 500 compounds that had not been reported by participants.

Trace analysis of total naphthenic acids in aqueous environmental matrices by liquid chromatography/mass spectrometry-quadrupole time of flight mass spectrometry direct injection.

A rapid and sensitive liquid chromatography quadrupole time of flight method has been established for the determination of total naphthenic acid concentrations in aqueous samples. This is the first methodology that has been adopted for routine, high resolution, high throughput analysis of total naphthenic acids at trace levels in unprocessed samples. A calibration range from 0.02 to 1.0µgmL(-1) total Merichem naphthenic acids was validated and demonstrated excellent accuracy (97-111% recovery) and precision (1.9% RSD at 0.02µgmL(-1)). Quantitative validation was also demonstrated in a non-commercial oil sands process water (OSPW) acid extractable organics (AEOs) fraction containing a higher percentage of polycarboxylic acid isomers than the Merichem technical mix. The chromatographic method showed good calibration linearity of ≥0.999 RSQ to 0.005µgmL(-1) total naphthenic acids with a precision <3.1% RSD and a calculated detection limit of 0.0004µgmL(-1) employing Merichem technical mix reference material. The method is well suited to monitoring naturally occurring and industrially derived naphthenic acids (and other AEOs) present in surface and ground waters in the vicinity of mining developments. The advantage of the current method is its direct application to unprocessed environmental samples and to examine natural naphthenic acid isomer profiles. It is noted that where the isomer profile of samples differs from that of the reference material, results should be considered semi-quantitative due to the lack of matching isomer content. The fingerprint profile of naphthenic acids is known to be transitory during aging and the present method has the ability to adapt to monitoring of these changes in naphthenic acid content. The method's total ion scan approach allows for data previously collected to be examined retrospectively for specific analyte mass ions of interest. A list of potential naphthenic acid isomers that decrease in response with aging is proposed and a quantitative assay of an adamantane carboxylic acid is reported.

Quantitative analysis of naphthenic acids in water by liquid chromatography-accurate mass time-of-flight mass spectrometry.

This study details the development of a routine method for quantitative analysis of oil sands naphthenic acids, which are a complex class of compounds found naturally and as contaminants in oil sands process waters from Alberta's Athabasca region. Expanding beyond classical naphthenic acids (CnH2n-zO2), those compounds conforming to the formula CnH2n-zOx (where 2≥x≤4) were examined in commercial naphthenic acid and environmental water samples. HPLC facilitated a five-fold reduction in ion suppression when compared to the more commonly used flow injection analysis. A comparison of 39 model naphthenic acids revealed significant variability in response factors, demonstrating the necessity of using naphthenic acid mixtures for quantitation, rather than model compounds. It was also demonstrated that naphthenic acidic heterogeneity (commercial and environmental) necessitates establishing a single NA mix as the standard against which all quantitation is performed. The authors present the first ISO17025 accredited method for the analysis of naphthenic acids in water using HPLC high resolution accurate mass time-of-flight mass spectrometry. The method detection limit was 1mg/L total oxy-naphthenic acids (Sigma technical mix).

Fast, extraction-free analysis of chlorinated phenols in well water by high-performance liquid chromatography-tandem mass spectrometry.

A fast and sensitive analytical method was developed for the chlorinated phenols included in the Canadian Drinking Water Guidelines without the need for costly, time-consuming sample extraction and concentration. Sensitivity and specificity were achieved by derivatization with dansyl chloride and detection via liquid chromatography-tandem mass spectrometry. The dansyl-modified analytes displayed method detection limits in the range of 0.01-1.0 µg/L, enabling the direct determination of chlorophenols from well water without sample enrichment. Recoveries (n=4 days) ranged from 91 to 101% and accuracies were between 79 and 116% (n=4). This method significantly increases sample throughput compared to the current EPA method for phenols in finished drinking water.