Membrane Sampling Separates Naphthenic Acids from Biogenic Dissolved Organic Matter for Direct Analysis by Mass Spectrometry

Environmental Science & Technology

Published On 2022/2/17

Oil sands process waters can release toxic naphthenic acids (NAs) into aquatic environments. Analytical techniques for NAs are challenged by sample complexity and interference from naturally occurring dissolved organic matter (DOM). Herein, we report the use of a poly(dimethylsiloxane) (PDMS) polymer membrane for the on-line separation of NAs from DOM and use direct infusion electrospray ionization mass spectrometry to yield meaningful qualitative and quantitative information with minimal sample cleanup. We compare the composition of membrane-permeable species from natural waters fortified with a commercial NA mixture to those derived from weak anion exchange solid-phase extraction (SPE) using high-resolution mass spectrometry. The results show that SPE retains a wide range of carboxylic acids, including biogenic DOM, while permeation through PDMS was selective for petrogenic classically …

Journal

Environmental Science & Technology

Published On

2022/2/17

Volume

56

Issue

5

Page

3096-3105

Authors

Jonas Bergquist

Jonas Bergquist

Uppsala Universitet

Position

Professor in Analytical Chemistry and Neurochemistry Sweden

H-Index(all)

78

H-Index(since 2020)

39

I-10 Index(all)

0

I-10 Index(since 2020)

0

Citation(all)

0

Citation(since 2020)

0

Cited By

0

Research Interests

NeurochemistryAnalyticalChemistry

University Profile Page

Jeffrey Hawkes

Jeffrey Hawkes

Uppsala Universitet

Position

H-Index(all)

27

H-Index(since 2020)

23

I-10 Index(all)

0

I-10 Index(since 2020)

0

Citation(all)

0

Citation(since 2020)

0

Cited By

0

Research Interests

Dissolved Organic Matter

Mass Spectrometry

University Profile Page

CG Gill

CG Gill

Vancouver Island University

Position

Professor of Chemistry

H-Index(all)

25

H-Index(since 2020)

18

I-10 Index(all)

0

I-10 Index(since 2020)

0

Citation(all)

0

Citation(since 2020)

0

Cited By

0

Research Interests

mass spectrometry

analytical chemistry

membrane introduction mass spectrometry

environmental chemistry

analytical instrument

University Profile Page

Kyle Duncan

Kyle Duncan

Vancouver Island University

Position

Department of Chemistry Nanaimo BC Canada

H-Index(all)

13

H-Index(since 2020)

12

I-10 Index(all)

0

I-10 Index(since 2020)

0

Citation(all)

0

Citation(since 2020)

0

Cited By

0

Research Interests

mass spectrometry

bioanalytical chemistry

electrospray ionization

mass spectrometry imaging

University Profile Page

Other Articles from authors

CG Gill

CG Gill

Vancouver Island University

Harm Reduction Journal

Beyond a spec: assessing heterogeneity in the unregulated opioid supply

BackgroundDrug checking services aim to provide compositional information for the illicit drug supply and are being employed in public health responses to extreme rates of overdose associated with fentanyl within street opioids. The technologies used within these services range from basic qualitative tests, such as immunoassay test strips, to comprehensive quantitative analyses, such as mass spectrometry. In general, there is concern that heterogeneity of a drug mixture adds significant uncertainty when using drug checking results based on a small subsamples. The presence of hot spots of active drug components in this context is often termed the ‘chocolate chip cookie effect’. Establishing the limitations of the service are essential for interpretation of the results.MethodsThis study assesses the consequence of drug heterogeneity and sampling of consumer level opioid purchased in Victoria, British Columbia …

CG Gill

CG Gill

Vancouver Island University

Drug testing and analysis

Toward automated infrared spectral analysis in community drug checking

The body of knowledge surrounding infrared spectral analysis of drug mixtures continues to grow alongside the physical expansion of drug checking services. Technicians trained in the analysis of spectroscopic data are essential for reasons that go beyond the accuracy of the analytical results. Significant barriers faced by people who use drugs in engaging with drug checking services include the speed and accuracy of the results, and the availability and accessibility of the service. These barriers can be overcome by the automation of interpretations. A random forest model for the detection of two compounds, MDA and fluorofentanyl, was trained and optimized with drug samples acquired at a community drug checking site. This resulted in a 79% true positive and 100% true negative rate for MDA, and 61% true positive and 97% true negative rate for fluorofentanyl. The trained models were applied to selected drug …

Jonas Bergquist

Jonas Bergquist

Uppsala Universitet

Analytical Methods

Analysis of tryptophan metabolites and related compounds in human and murine tissue: development and validation of a quantitative and semi-quantitative method using high …

This study explores the metabolic differences between human and murine plasma in addition to differences between murine subcutaneous and visceral white adipose tissue. A quantitative and semi-quantitative targeted method was developed and validated for this purpose. The quantitative method includes tryptophan and its metabolites in addition to tyrosine, phenylalanine, taurine, B vitamins, neopterin, cystathionine and hypoxanthine. While the semi-quantitative method includes; 3-indoleacetic acid, 5-hydroxyindoleacetic acid, acetylcholine, asymmetric dimethylarginine, citrulline and methionine. Sample preparation was based on protein precipitation, while quantification was conducted using ultrahigh-performance liquid chromatography coupled to a quadrupole Orbitrap tandem mass spectrometer with electrospray ionization in the parallel reaction monitoring (PRM) mode. The low limit of quantification for all …

Jonas Bergquist

Jonas Bergquist

Uppsala Universitet

Acta Physiologica

Ruxolitinib: A new hope for ventilator‐induced diaphragm dysfunction

Aim Mechanical ventilation (MV) results in diminished diaphragm size and strength, termed ventilator‐induced diaphragm dysfunction (VIDD). VID increases dependence, prolongs weaning, and increases discharge mortality rates. The Janus kinase (JAK)/Signal Transducer and Activator of Transcription (STAT) pathway is implicated in VIDD, upregulated following MV. JAK/STAT inhibition alleviates chronic muscle wasting conditions. This study aimed to explore the therapeutic potential of Ruxolitinib, an FDA approved JAK1/2 inhibitor (JI) for the treatment of VIDD. Methods Rats were subjected to 5 days controlled MV (CMV) with and without daily Ruxolitinib gavage. Muscle fiber size and function were assessed. RNAseq, mitochondrial morphology, respirometry, and mass spectrometry were determined. Results CMV significantly reduced diaphragm size and specific force by 45% (p < 0.01), associated with a …

CG Gill

CG Gill

Vancouver Island University

Journal of Mass Spectrometry and Advances in the Clinical Lab

Therapeutic drug monitoring of clozapine in human serum by high-throughput paper spray mass spectrometry

IntroductionMonitoring the atypical antipsychotic drug clozapine is crucial to ensure patient safety. This article showcases a high-throughput analytical method for measuring clozapine and its primary metabolite norclozapine (N-desmethylclozapine) in serum using paper spray mass spectrometry (PS-MS).ObjectivesThis study aimed to assess the viability of a PS-MS method for the rapid measurement of clozapine and norclozapine in human serum samples as an alternative to liquid chromatography mass spectrometry (LC-MS).MethodsSerum samples were processed by protein precipitation followed by deposition of the supernatant containing labelled internal standards onto paper spray substrates mounted in cartridges. Analytes were then analyzed using a triple quadrupole mass spectrometer equipped with a commercial paper spray ionization source. The results obtained from the patient samples were …

Jonas Bergquist

Jonas Bergquist

Uppsala Universitet

Hearing loss and the relation to the proteome of perilymph, cerebrospinal fluid, and tumor tissue in patients with vestibular schwannoma.

Mass spectrometry analysis of the inner ear fluid, perilymph, cerebrospinal fluid, and vestibular schwannoma proteome and its relation to hearing loss in patients with vestibular schwannomas. Patients with severe to profound hearing loss, compared to those with normal hearing or mild hearing loss, exhibited an upregulation of Complement Factor H-related protein 2 (CFHR2) in the perilymph. This is indicative of increased inflammation in the inner ear, suggesting a potential cause of hearing loss in patients with vestibular schwannomas affecting the ear.

Jonas Bergquist

Jonas Bergquist

Uppsala Universitet

Viruses

Proteomic and Lipidomic Profiling of Calves Experimentally Co-Infected with Influenza D Virus and Mycoplasma bovis: Insights into the Host–Pathogen Interactions

The role of Influenza D virus (IDV) in bovine respiratory disease remains unclear. An in vivo experiment resulted in increased clinical signs, lesions, and pathogen replication in calves co-infected with IDV and Mycoplasma bovis (M. bovis), compared to single-infected calves. The present study aimed to elucidate the host–pathogen interactions and profile the kinetics of lipid mediators in the airways of these calves. Bronchoalveolar lavage (BAL) samples collected at 2 days post-infection (dpi) were used for proteomic analyses by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Additionally, lipidomic analyses were performed by LC-MS/MS on BAL samples collected at 2, 7 and 14 dpi. Whereas M. bovis induced the expression of proteins involved in fibrin formation, IDV co-infection counteracted this coagulation mechanism and downregulated other acute-phase response proteins, such as complement component 4 (C4) and plasminogen (PLG). The reduced inflammatory response against M. bovis likely resulted in increased M. bovis replication and delayed M. bovis clearance, which led to a significantly increased abundance of oxylipids in co-infected calves. The identified induced oxylipids mainly derived from arachidonic acid; were likely oxidized by COX-1, COX-2, and LOX-5; and peaked at 7 dpi. This paper presents the first characterization of BAL proteome and lipid mediator kinetics in response to IDV and M. bovis infection in cattle and raises hypotheses regarding how IDV acts as a co-pathogen in bovine respiratory disease.

CG Gill

CG Gill

Vancouver Island University

A state-of-the-science review of alcoholic beverages and polycyclic aromatic hydrocarbons

Background The association between alcohol and certain cancers is well established, yet beyond ethanol and its metabolite acetaldehyde, little is known about the presence of other carcinogenic compounds in alcoholic beverages, including polycyclic aromatic hydrocarbons (PAHs), such as benzo[a]pyrene (a Group I carcinogen). Objectives We summarized the published literature on PAH levels in alcoholic beverages to identify potential gaps in knowledge to inform future research. Methods Medline and Scopus were searched for primary research published from January 1966 to November 2023 that quantified PAH levels among various types of alcoholic beverages, including whisky, rum, brandy, gin, vodka, wine, and beer. Studies that were not primary literature were excluded; only studies that quantified PAH content in the specified alcoholic beverages were included. Results Ten studies published from 1966 …

Kyle Duncan

Kyle Duncan

Vancouver Island University

Mass spectrometry imaging methods for visualizing tumor heterogeneity

HighlightsCurrent strategies to map lipids, metabolites, and proteins in tumor tissues.Recent biological insights obtained from MSI of tumor samples.Challenges in applying MSI to study tumor biology.Profiling spatial distributions of lipids, metabolites, and proteins in tumors can reveal unique cellular microenvironments and provide molecular evidence for cancer cell dysfunction and proliferation. Mass spectrometry imaging (MSI) is a label-free technique that can be used to map biomolecules in tumors in situ. Here, we discuss current progress in applying MSI to uncover molecular heterogeneity in tumors. First, the analytical strategies to profile small molecules and proteins are outlined, and current methods for multimodal imaging to maximize biological information are highlighted. Second, we present and summarize biological insights obtained by MSI of tumor tissue. Finally, we discuss important considerations for …

Kyle Duncan

Kyle Duncan

Vancouver Island University

Advances in Prostaglandin

Advances in Prostaglandin

Prostaglandins (PG) are a group of physiologically active lipid compounds called eicosanoids having diverse hormone-like effects in animals. Prostaglandins have been found in almost every tissue in humans and other animals. They are derived enzymatically from the fatty acid arachidonic acid.Every prostaglandin contains 20 carbon atoms, including a 5-carbon ring. They are a subclass of eicosanoids and of the prostanoid class of fatty acid derivatives. In the present book, twelve typical literatures about prostaglandin published on international authoritative journals were selected to introduce the worldwide newest progress, which contains reviews or original researches on prostaglandin. We hope this book can demonstrate advances in prostaglandin as well as give references to the researchers, students and other related people.

Jonas Bergquist

Jonas Bergquist

Uppsala Universitet

Iscience

Toward ovarian cancer screening with protein biomarkers using dried, self-sampled cervico-vaginal fluid

Early detection is key for increased survival in ovarian cancer, but no general screening program exists today due to lack of biomarkers and overall cost versus benefit over traditional clinical methods. Here, we used dried cervico-vaginal fluid (CVF) as sampling matrix coupled with mass spectrometry for detection of protein biomarkers. We find that self-collected CVF on paper cards yields robust results and is suitable for high-throughput proteomics. Artificial intelligence–based methods were used to identify an 11-protein panel that separates cases from controls. In validation data, the panel achieved a sensitivity of 0.97 (95% CI 0.91–1.00) at a specificity of 0.67 (0.40–0.87). Analyses of samples collected prior to development of symptoms indicate that the panel is informative also of future risk of disease. Dried CVF is used in cervical cancer screening, and our results opens the possibility for a screening program also …

CG Gill

CG Gill

Vancouver Island University

Analyst

Paper spray mass spectrometry combined with machine learning as a rapid diagnostic for chronic kidney disease

A new analytical method for chronic kidney disease (CKD) detection utilizing paper spray mass spectrometry (PS-MS) combined with machine learning is presented. The analytical protocol is rapid and simple, based on metabolic profile alterations in urine. Anonymized raw urine samples were deposited (10 μL each) onto pointed PS-MS sample strips. Without waiting for the sample to dry, 75 μL of acetonitrile and high voltage were applied to the strips, using high resolution mass spectrometry measurement (15 s per sample) with polarity switching to detect a wide range of metabolites. Random forest machine learning was used to classify the resulting data. The diagnostic performance for the potential diagnosis of CKD was evaluated for accuracy, sensitivity, and specificity, achieving results >96% for the training data and >91% for validation and test data sets. Metabolites selected by the classification model as up- or …

Jeffrey Hawkes

Jeffrey Hawkes

Uppsala Universitet

Environmental Science & Technology

Preparation of Simple Bicyclic Carboxylate-Rich Alicyclic Molecules for the Investigation of Dissolved Organic Matter

Dissolved organic matter (DOM) is a vast and complex chemical mixture that plays a key role in the mediation of the global carbon cycle. Fundamental understanding of the source and fate of oceanic organic matter is obscured due to poor definition of the key molecular contributors to DOM, which limits accurate sample analysis and prediction of the Earth’s carbon cycle. Previous work has attempted to define the components of the DOM through a variety of chromatographic and spectral techniques. However, modern preparative and analytical methods have not isolated or unambiguously identified molecules from DOM. Therefore, previously proposed structures are based solely on the mixture’s aggregate properties and do not accurately describe any true individual molecular component. In addition to this, there is a lack of appropriate analogues of the individual chemical classes within DOM, limiting the scope of …

Jonas Bergquist

Jonas Bergquist

Uppsala Universitet

Scientific reports

A metabolomics perspective on 2 years of high-intensity training in horses

The plasma metabolomic profile of elite harness horses subjected to different training programmes was explored. All horses had the same training programme from 1.5 until 2 years of age and then high-intensity training was introduced, with horses divided into high and low training groups. Morning blood samples were collected at 1.5, 2, 2.5 and 3.5 years of age. The plasma was analysed using targeted absolute quantitative analysis and a combination of tandem mass spectrometry, flow-injection analysis and liquid chromatography. Differences between the two training groups were observed at 2 years of age, when 161 metabolites and sums and ratios were lower (e.g. ceramide and several triglycerides) and 51 were higher (e.g. aconitic acid, anserine, sum of PUFA cholesteryl esters and solely ketogenic AAs) in High compared with low horses. The metabolites aconitic acid, anserine, leucine, HArg synthesis and …

CG Gill

CG Gill

Vancouver Island University

Analyst

Simultaneous quantitation of urinary albumin and creatinine for rapid clinical albuminuria diagnostics using high-throughput paper spray mass spectrometry

Albuminuria is a clinical condition associated with poor kidney function, diagnosed by determining the ratio of albumin to creatinine concentrations in patient urine samples. We present a high-throughput paper spray mass spectrometry (PS-MS) method for simultaneous quantitation of urinary albumin and creatinine for potential diagnosis of albuminuria. Minimal (urine dilution) or no sample preparation is required. The analytical performance of the method was evaluated, achieving linear calibration curves (R2 > 0.99) with little inter-day variability in the slope (N = 5 days), exhibiting coefficient of variation (CV) of 8% and 3% for albumin and creatinine, respectively. LOD and LOQ for albumin were 2.1 and 7.0 mg L−1, and for creatinine were 0.01 and 0.03 mmol L−1, respectively. Intra- and inter-day (N = 5) precisions (%CV) and accuracies (%bias) were <10% and ±11%, respectively, for both analytes. The method was …

Jonas Bergquist

Jonas Bergquist

Uppsala Universitet

Hearing loss and its association with the proteome of perilymph, cerebrospinal fluid, and tumor tissue in patients with vestibular schwannoma

This study examined the association between hearing loss in sporadic vestibular schwannoma patients and the proteome of perilymph (PL), cerebrospinal fluid (CSF), and vestibular schwannoma. Intraoperative sampling of PL and of CSF, and biopsy of vestibular schwannoma tissue, was performed in 32, 32, and 20 patients with vestibular schwannoma, respectively. Perilymph and CSF in three patients with meningioma and normal hearing were also sampled.

Jonas Bergquist

Jonas Bergquist

Uppsala Universitet

bioRxiv

Multi-omics analysis of aggregative multicellularity

The extent to which mRNA and protein levels or their regulation correlate remains obscure, especially during development. In particular, this is true for organisms that exhibit aggregative multicellularity, such as the social amoeba Dictyostelium discoideum. The transcriptome of D. discoideum has been thoroughly studied during multicellular development, however the proteome and the correlation to the transcriptome during transition from uni- to multicellular life have not been analyzed in detail. Here, we present the first paired transcriptomics and proteomics developmental time series during aggregative multicellularity. The dataset reveals that mRNA and protein levels correlate highly during growth, but decrease when multicellular development is initiated. This accentuates that transcripts alone cannot accurately describe gene expression. This dataset can therefore be an important resource to study gene expression during aggregative multicellular development, in particular in D. discoideum.

Jonas Bergquist

Jonas Bergquist

Uppsala Universitet

Journal of Chromatography B

A fast ultra performance supercritical fluid chromatography-tandem mass spectrometric method for profiling of targeted phytosterols

Phytosterols are essential structural components of plant cell membranes and possess health-related benefits, including lowering blood cholesterol levels in humans. Numerous analytical methods are being used to profile plant and animal sterols. Chromatography hyphenated to tandem mass spectrometry, is a better option due to its specificity, selectivity, and sensitivity. An ultra-performance supercritical fluid chromatography hyphenated with atmospheric pressure chemical ionization (APCI) tandem mass spectrometric method was developed and evaluated for fingerprint analysis of seven phytosterols. Mass spectrometry fragmentation behavior was used for phytosterol identification, and multiple reaction monitoring scanning was utilized for phytosterol confirmation, where APCI outperformed superiority in terms of ion intensity, particularly in the production of [M + H-H2O]+ ions rather than [M + H]+ ions. The …

CG Gill

CG Gill

Vancouver Island University

Analytical Chemistry

PAMAM-functionalized paper as a new substrate for the paper spray mass spectrometry measurement of proteins

Paper surface functionalization with polyamidoamine (PAMAM) dendrimers has been developed for increased sensitivity analysis of proteins by paper spray mass spectrometry (PS-MS). PAMAM is a branched polymeric compound with an ethylenediamine core linked to repeating PAMAM units that generates an outer surface rich in primary amines. These positively charged amine groups can interact electrostatically with negatively charged residues (e.g., aspartate, glutamate) on the protein surface. PAMAM inner amide moieties can also promote hydrogen bonding with protein surface oxygens, making PAMAM a useful material for protein extraction. PAMAM-functionalized PS-MS paper strips were used to extract proteins from biofluids, dipped in acetonitrile to remove unbound constituents, dried, and then measured with PS-MS. The use of this strategy was optimized and compared with unmodified paper strips …

Jonas Bergquist

Jonas Bergquist

Uppsala Universitet

International Journal of Molecular Sciences

Silencing DTX3L inhibits the progression of cervical carcinoma by regulating PI3K/AKT/mTOR signaling pathway

Cervical carcinoma (CC) is the second most prevalent gynecologic cancer in females across the world. To obtain a better understanding of the mechanisms underlying the development of CC, high-resolution label-free mass spectrometry was performed on CC and adjacent normal tissues from eight patients. A total of 2631 proteins were identified, and 46 significant differently expressed proteins (DEPs) were found between CC and normal tissues (p < 0.01, fold change >10 or <0.1). Ingenuity pathway analysis revealed that the majority of the proteins were involved in the regulation of eIF4 and p70S6K signaling and mTOR signaling. Among 46 DEPs, Integrinβ6 (ITGB6), PPP1CB, TMPO, PTGES3 (P23) and DTX3L were significantly upregulated, while Desmin (DES) was significantly downregulated in CC tissues compared with the adjacent normal tissues. In in vivo and in vitro experiments, DTX3L knockdown suppressed CC cell proliferation, migration, invasion and xenograft tumorigenesis, and enhanced cell apoptosis. Combination of silencing DTX3L and cisplatin treatment induced higher apoptosis percentage compared to cisplatin treatment alone. Moreover, DTX3L silencing inhibited the PI3K/AKT/mTOR signal pathway. Thus, our results suggested DTX3L could regulate CC progression through the PI3K/AKT/mTOR signal pathway and is potentially a novel biomarker and therapeutic target for CC.

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Environmental Science & Technology

Interspecies Mobility of Organohalide Respiration Gene Clusters Enables Genetic Bioaugmentation

Anthropogenic organohalide pollutants pose a severe threat to public health and ecosystems. In situ bioremediation using organohalide respiring bacteria (OHRB) offers an environmentally friendly and cost-efficient strategy for decontaminating organohalide-polluted sites. The genomic structures of many OHRB suggest that dehalogenation traits can be horizontally transferred among microbial populations, but their occurrence among anaerobic OHRB has not yet been demonstrated experimentally. This study isolates and characterizes a novel tetrachloroethene (PCE)-dechlorinating Sulfurospirillum sp. strain SP, distinguishing itself among anaerobic OHRB by showcasing a mechanism essential for horizontal dissemination of reductive dehalogenation capabilities within microbial populations. Its genetic characterization identifies a unique plasmid (pSULSP), harboring reductive dehalogenase and de novo …

Yuanchao Hu(胡元超)

Yuanchao Hu(胡元超)

Wuhan University

Environmental Science & Technology

Mitigation Measures Could Aggravate Unbalanced Nitrogen and Phosphorus Emissions from Land-Use Activities

Socioeconomic factors and mitigation potentials are essential drivers of the dynamics of nutrient emissions, yet these drivers are rarely examined at broad spatiotemporal scales. Here, we combine material flow analysis and geospatial analysis to examine the past and future changes of nitrogen and phosphorus emissions in China. Results show that anthropogenic nitrogen and phosphorus emissions increased by 17% and 32% during 2000–2019, respectively. Meanwhile, many regions witnessed decreasing nitrogen emissions but rising phosphorus discharged to waterbody, leading to a 20% decrease in the nitrogen/phosphorus ratio. In addition to many prominent factors like fertilizer use, the increasing impervious land area around cities is a notable factor driving the emissions, indicating the urgency to limit building expansion, especially in North China Plain and other less-developed regions. Improving land …

Solomon Bililign

Solomon Bililign

North Carolina Agricultural and Technical State University

Environmental Science & Technology

Quantifying the Light-Absorption Properties and Molecular Composition of Brown Carbon Aerosol from Sub-Saharan African Biomass Combustion

Sub-Saharan Africa is a hotspot for biomass burning (BB)-derived carbonaceous aerosols, including light-absorbing organic (brown) carbon (BrC). However, the chemically complex nature of BrC in BB aerosols from this region is not fully understood. We generated smoke in a chamber through smoldering combustion of common sub-Saharan African biomass fuels (hardwoods, cow dung, savanna grass, and leaves). We quantified aethalometer-based, real-time light-absorption properties of BrC-containing organic-rich BB aerosols, accounting for variations in wavelength, fuel type, relative humidity, and photochemical aging conditions. In filter samples collected from the chamber and Botswana in the winter, we identified 182 BrC species, classified into lignin pyrolysis products, nitroaromatics, coumarins, stilbenes, and flavonoids. Using an extensive set of standards, we determined species-specific mass and …

William Pomerantz

William Pomerantz

University of Minnesota-Twin Cities

Environmental Science & Technology

Fluorinated Pharmaceutical and Pesticide Photolysis: Investigating Reactivity and Identifying Fluorinated Products by Combining Computational Chemistry,19F …

Fluorinated breakdown products from photolysis of pharmaceuticals and pesticides are of environmental concern due to their potential persistence and toxicity. While mass spectrometry workflows have been shown to be useful in identifying products, they fall short for fluorinated products and may miss up to 90% of products. Studies have shown that 19F NMR measurements assist in identifying and quantifying reaction products, but this protocol can be further developed by incorporating computations. Density functional theory was used to compute 19F NMR shifts for parent and product structures in photolysis reactions. Computations predicted NMR spectra of compounds with an R2 of 0.98. Computed shifts for several isolated product structures from LC-HRMS matched the experimental shifts with <0.7 ppm error. Multiple products including products that share the same shift that were not previously reported were …

naji milad bassil

naji milad bassil

Manchester University

Environmental Science & Technology

Ammonium-Enhanced Arsenic Mobilization from Aquifer Sediments

Ammonium-related pathways are important for groundwater arsenic (As) enrichment, especially via microbial Fe(III) reduction coupled with anaerobic ammonium oxidation; however, the key pathways (and microorganisms) underpinning ammonium-induced Fe(III) reduction and their contributions to As mobilization in groundwater are still unknown. To address this gap, aquifer sediments hosting high As groundwater from the western Hetao Basin were incubated with 15N-labeled ammonium and external organic carbon sources (including glucose, lactate, and lactate/acetate). Decreases in ammonium concentrations were positively correlated with increases in the total produced Fe(II) (Fe(II)tot) and released As. The molar ratios of Fe(II)tot to oxidized ammonium ranged from 3.1 to 3.7 for all incubations, and the δ15N values of N2 from the headspace increased in 15N-labeled ammonium-treated series, suggesting N …

Zhongyang Zhang

Zhongyang Zhang

Icahn School of Medicine at Mount Sinai

Environmental Science & Technology

Exposure to Airborne PM2.5 Water-Soluble Inorganic Ions Induces a Wide Array of Reproductive Toxicity

Water-soluble inorganic ions (WSIIs, primarily NH4+, SO42–, and NO3–) are major components in ambient PM2.5, but their reproductive toxicity remains largely unknown. An animal study was conducted where parental mice were exposed to PM2.5 WSIIs or clean air during preconception and the gestational period. After delivery, all maternal and offspring mice lived in a clean air environment. We assessed reproductive organs, gestation outcome, birth weight, and growth trajectory of the offspring mice. In parallel, we collected birth weight and placenta transcriptome data from 150 mother-infant pairs from the Rhode Island Child Health Study. We found that PM2.5 WSIIs induced a broad range of adverse reproductive outcomes in mice. PM2.5 NH4+, SO42–, and NO3– exposure reduced ovary weight by 24.22% (p = 0.005), 14.45% (p = 0.048), and 16.64% (p = 0.022) relative to the clean air controls. PM2.5 SO42 …

Ruoyu Wang (王若宇)

Ruoyu Wang (王若宇)

Vanderbilt University

Environmental Science & Technology

Membrane Design Principles for Ion-Selective Electrodialysis: An Analysis for Li/Mg Separation

Selective electrodialysis (ED) is a promising membrane-based process to separate Li+ from Mg2+, which is the most critical step for Li extraction from brine lakes. This study theoretically compares the ED-based Li/Mg separation performance of different monovalent selective cation exchange membranes (CEMs) and nanofiltration (NF) membranes at the coupon scale using a unified mass transport model, i.e., a solution-friction model. We demonstrated that monovalent selective CEMs with a dense surface thin film like a polyamide film are more effective in enhancing the Li/Mg separation performance than those with a loose but highly charged thin film. Polyamide film-coated CEMs when used in ED have a performance similar to that of polyamide-based NF membranes when used in NF. NF membranes, when expected to replace monovalent selective CEMs in ED for Li/Mg separation, will require a thin support layer …

Lucas Gonçalves Queiroz

Lucas Gonçalves Queiroz

Universidade de São Paulo

Environmental Science & Technology

Biofragmentation of Polystyrene Microplastics: A Silent Process Performed by Chironomus sancticaroli Larvae

Polystyrene (PS) is one of the main synthetic polymers produced around the world, and it is present in the composition of a wide variety of single-use objects. When released into the environment, these materials are degraded by environmental factors, resulting in microplastics. We investigated the ability of Chironomus sancticaroli (Diptera, Chironomidae) to promote the fragmentation of PS microspheres (24.5 ± 2.9 μm) and the toxic effects associated with exposure to this polymer. C. sancticaroli larvae were exposed to 3 different concentrations of PS (67.5, 135, and 270 particles g–1 of dry sediment) for 144 h. Significant lethality was observed only at the highest concentration. A significant reduction in PS particle size as well as evidence of deterioration on the surface of the spheres, such as grooves and cracks, was observed. In addition, changes in oxidative stress biomarkers (SOD, CAT, MDA, and GST) were …

Reza Deevsalar

Reza Deevsalar

University of Tehran

Environmental Science & Technology

Local Structure and Crystallization Transformation of Hydrous Ferric Arsenate in Acidic H2O–Fe(III)–As(V)–SO42– Systems: Implications for Acid Mine Drainage …

Hydrous ferric arsenate (HFA) is a common thermodynamically metastable phase in acid mine drainage (AMD). However, little is known regarding the structural forms and transformation mechanism of HFA. We investigated the local atomic structures and the crystallization transformation of HFA at various Fe(III)/As(V) ratios (2, 1, 0.5, 0.33, and 0.25) in acidic solutions (pH 1.2 and 1.8). The results show that the Fe(III)/As(V) in HFA decreases with decreasing initial Fe(III)/As(V) at acidic pHs. The degree of protonation of As(V) in HFA increases with increasing As(V) concentrations. The Fe K-edge extended X-ray absorption fine structure and X-ray absorption near-edge structure results reveal that each FeO6 is linked to more than two AsO4 in HFA precipitated at Fe(III)/As(V) < 1. Furthermore, the formation of scorodite (FeAsO4·2H2O) is greatly accelerated by decreasing the initial Fe(III)/As(V). The release of As(V) from …

Pan Meilan

Pan Meilan

Nanyang Technological University

Environmental Science & Technology

Pioneering Piezoelectric-Driven Atomic Hydrogen for Efficient Dehalogenation of Halogenated Organic Pollutants

The electrocatalytic hydrodehalogenation (EHDH) process mediated by atomic hydrogen (H*) is recognized as an efficient method for degrading halogenated organic pollutants (HOPs). However, a significant challenge is the excessive energy consumption resulting from the recombination of H* to H2 production in the EHDH process. In this study, a promising strategy was proposed to generate piezo-induced atomic H*, without external energy input or chemical consumption, for the degradation and dehalogenation of HOPs. Specifically, sub-5 nm Ni nanoparticles were subtly dotted on an N-doped carbon layer coating on BaTiO3 cube, and the resulted hybrid nanocomposite (Ni-NC@BTO) can effectively break C-X (X = Cl and F) bonds under ultrasonic vibration or mechanical stirring, demonstrating high piezoelectric driven dehalogenation efficiencies toward various HOPs. Mechanistic studies revealed that the …