Direct analysis of naphthenic acids in constructed wetland samples by condensed phase membrane introduction mass spectrometry

Science of the total environment

Published On 2020/5/10

The application of direct mass spectrometry techniques to the analysis of complex samples has a number of advantages including reduced sample handling, higher sample throughput, in situ process monitoring, and the potential for adaptation to on-site analysis. We report the application of a semi-permeable capillary hollow fibre membrane probe (immersed directly into an aqueous sample) coupled to a triple quadrupole mass spectrometer by a continuously flowing methanol acceptor phase for the rapid analysis of naphthenic acids with unit mass resolution. The intensity of the naphthenic acid-associated peaks in the mass spectrum are normalized to an internal standard in the acceptor phase for quantitation and the relative abundance of the peaks in the mass spectrum are employed to monitor compositional changes in the naphthenic acid mixture using principle component analysis. We demonstrate the direct …

Journal

Science of the total environment

Published On

2020/5/10

Volume

716

Page

137063

Authors

Dena McMartin, PhD, PEng, PAg

Dena McMartin, PhD, PEng, PAg

University of Saskatchewan

Position

Professor of Environmental Engineering

H-Index(all)

27

H-Index(since 2020)

19

I-10 Index(all)

0

I-10 Index(since 2020)

0

Citation(all)

0

Citation(since 2020)

0

Cited By

0

Research Interests

watershed management

water quality

oilsands tailings waters

climate extremes

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

Joseph Monaghan

Joseph Monaghan

Vancouver Island University

Position

H-Index(all)

6

H-Index(since 2020)

6

I-10 Index(all)

0

I-10 Index(since 2020)

0

Citation(all)

0

Citation(since 2020)

0

Cited By

0

Research Interests

Direct Mass Spectrometry

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 …

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 …

Dena McMartin, PhD, PEng, PAg

Dena McMartin, PhD, PEng, PAg

University of Saskatchewan

Chemosphere

Low adsorption affinity of Athabasca oil sands naphthenic acid fraction compounds to a peat-mineral mixture

Much of the toxicity in oil sands process-affected water in Athabasca oil sands tailings has been attributed to naphthenic acids (NAs) and associated naphthenic acid fraction compounds (NAFCs). Previous work has characterized the environmental behaviour and fate of these compounds, particularly in the context of constructed treatment wetlands. There is evidence that wetlands can attenuate NAFCs in natural and engineered contexts, but relative contributions of chemical, biotic, and physical adsorption with sequestration require deconvolution. In this work, the objective was to evaluate the extent to which prospective wetland substrate material may adsorb NAFCs using a peat-mineral mix (PMM) sourced from the Athabasca Oil Sands Region (AOSR). The PMM and NAFCs were first mixed and then equilibrated across a range of NAFC concentrations (5 to 500 mg/L) with moderate ionic strength and hardness …

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.

Dena McMartin, PhD, PEng, PAg

Dena McMartin, PhD, PEng, PAg

University of Saskatchewan

Energy & Fuels

Evaluations of Weathering of Polar and Nonpolar Petroleum Components in a Simulated Freshwater–Oil Spill by Orbitrap and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

The comprehensive chemical characterization of crude oil is important for the evaluation of the transformation and fate of components in the environment. Molecular-level speciation of naphthenic acid fraction compounds (NAFCs) was investigated in a mesoscale spill tank using both negative-ion electrospray ionization (ESI) Orbitrap mass spectrometry (MS) and positive-ion atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry (APPI-FT-ICR-MS). Both ionization techniques are coupled to high-resolution mass spectrometric detectors (ESI: Orbitrap MS; APPI: FT-ICR-MS at 9.4 T), enabling insight into the behavior and fate of petrogenic compounds during a simulated freshwater crude oil spill. Negative-ion ESI Orbitrap-MS reveals that oxygen-containing (Ox) classes are detected early in the spill, whereby species with more oxygen per molecule evolve later in the …

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 …

Dena McMartin, PhD, PEng, PAg

Dena McMartin, PhD, PEng, PAg

University of Saskatchewan

Separations

Cross-Contamination of Ignitable Liquid Residues on Wildfire Debris—Effects of Packaging and Storage on Detection and Characterization

Producing defensible data for legal proceedings requires strict monitoring of sample integrity. In fire debris analysis, various approved packaging and storage solutions are designed to achieve this by preventing cross-contamination. This study examines the efficiency of current practices at preventing cross-contamination in the presence of a sample matrix (charred wood) via analysis by comprehensive multidimensional gas chromatography coupled with time-of-flight mass spectrometry (GC×GC-ToF MS). The transfer of ignitable liquid residue (ILR) was assessed by comparing percentages of the target ILR area relative to the total chromatogram area and applying chemometric tools developed to detect cross-contamination. All practices reduced cross-contamination in comparison to faulty packaging. Individual practices varied in their performance. Nylon-based packaging performed best, whereas commercial polyethylene-based packaging performed worst due to interfering compounds emitted from the material and sealing mechanism. Heat-sealing was the best sealing mechanism when applied correctly, followed by press-fit connections, and lastly, adhesive sealing. Refrigerated storage offered several advantages, with elevated impact for polyethylene-based packaging and adhesive sealing mechanisms. Triple-layer packaging practices did not show significant benefits over double-layers. The recommended packaging approach based on these findings is mixed-material packaging (metal quart can in a heat-sealed nylon bag), offering advanced prevention of cross-contamination and practical advantages with continued refrigeration during …

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 …

Dena McMartin, PhD, PEng, PAg

Dena McMartin, PhD, PEng, PAg

University of Saskatchewan

PLOS Water

Shifting formal education toward hydrosocial and hydrorelational learning

The way that freshwater is accessed, used, consumed, and managed in highly industrialized countries demonstrates our lack of value or respect of water. Consider the adage,“show me your budget and I’ll tell you your priorities” and put it in terms of freshwater: show me how you use water and I’ll tell you how you value it. Show me where and how freshwater is incorporated into your formal education curriculum, and I’ll show you how your society respects freshwater.Understanding and managing water resources is a social responsibility and activity. However, many societies view water as political power, an economic tool, an engineering exercise. Most peer-reviewed research speaks to water from a scientific perspective, placing humans either outside the problem or as the primary beneficiaries or deterrents of the outcomes [1]. We argue that water research and understandings come from interconnections and should be analyzed through the lens of relationships rather than in selected isolation. Interpretations of data must include a holistic approach, incorporating humans, rather than having humans viewed as a consumer or manipulator of nature and natural resources. The necessity of bringing to bear the benefits of multidisciplinary critical thinking and problem solving is clear in terms of identifying meaningful and successful approaches to informing societies about the intersecting and interconnected complexities of changing climate, extreme weather events like floods and droughts, and equitable water use and resource management. However, Western approaches to water are human-centric, resource-based approaches that do not consider …

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 …

Joseph Monaghan

Joseph Monaghan

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 …

Dena McMartin, PhD, PEng, PAg

Dena McMartin, PhD, PEng, PAg

University of Saskatchewan

Environmental Pollution

Site-specific spatiotemporal occurrence and molecular congener distributions of naphthenic acids in Athabasca oil sands wetlands of Alberta, Canada

The Athabasca oil sands region (AOSR) of Alberta, Canada is notable for its considerable unconventional petroleum extraction projects, where bitumen is extracted from naturally-occurring oil sands ore. The large scale of these heavy crude oil developments raises concerns because of their potential to distribute and/or otherwise influence the occurrence, behaviour, and fate of environmental contaminants. Naphthenic acids (NAs) are one such contaminant class of concern in the AOSR, so studies have examined the occurrence and molecular profiles of NAs in the region. We catalogued the spatiotemporal occurrence and characteristics of NAs in boreal wetlands in the AOSR over a 7-year period, using derivatized liquid chromatography-tandem mass spectrometry (LC-MS/MS). Comparing median concentrations of NAs across these wetlands revealed a pattern of NAs suggesting NAs in surface waters derived …

CG Gill

CG Gill

Vancouver Island University

Separations

Online membrane sampling for the mass spectrometric analysis of oil sands process affected water-derived naphthenic acids in real-world samples

Large volumes of oil sands process-affected waters (OSPW) result from heavy oil extraction in Alberta, Canada. Currently, a toxic legacy of ca. 500 Mm3 is stored in tailings ponds under a zero-discharge policy. OSPW is a complex mixture of suspended and dissolved materials including a wide range of inorganic and organic contaminants. Classically defined naphthenic acids (NAs; CnH2n+ZO2) are one of the primary toxic fractions in OSPW and have therefore been the subject of considerable research interest. Most studies employ considerable sample cleanup followed by liquid chromatography and/or high-resolution mass spectrometry (HRMS) for the characterization of these complex mixtures. However, these strategies can be time- and cost-intensive, limiting the scope of research and adoption for regulatory purposes. Condensed phase membrane introduction mass spectrometry (CP-MIMS) is emerging as a “fit-for-purpose” approach for the analysis of NAs. This technique directly interfaces the mass spectrometer with an aqueous sample using a hydrophobic semi-permeable membrane, requiring only pH adjustment to convert NAs to a membrane-permeable form. Here, we examine the perm-selectivity of classical NAs (O2) relative to their more oxidized counterparts (O3–O7) and heteroatomic (N, S) species collectively termed naphthenic acid fraction compounds (NAFCs). The investigation of 14 model compounds revealed that classically defined NAs are greater than 50-fold more membrane permeable than their oxidized/heteroatomic analogs. HRMS analysis of real OSPW extracts with and without membrane clean-up further supported …

CG Gill

CG Gill

Vancouver Island University

Drug Testing and Analysis

A strategy for the detection of benzodiazepine drugs using low‐resolution paper‐spray mass spectrometry for harm reduction drug checking

The ability to detect newly emerging substances is of great importance in reducing harms for people who use drugs. New psychoactive substances including novel benzodiazepines in the illicit drug supply have been linked to high rates of overdose deaths while complicating drug checking as an overdose prevention strategy. Paper‐spray mass spectrometry (PS‐MS) has emerged as a novel strategy to rapidly detect trace components in street drug samples. While targeted, low‐resolution PS‐MS methods have proven effective, newly emerging substances are often missed. To address this, a method was applied to low‐resolution full‐scan PS‐MS data to aid in the early detection and identification of novel benzodiazepines in the unregulated drug supply. Using the developed method, true positives rates of 0.89 and 0.75 were achieved for bromazolam and etizolam in street samples obtained in a community drug …

2023/12/25

Article Details
Joseph Monaghan

Joseph Monaghan

Vancouver Island University

Separations

Online membrane sampling for the mass spectrometric analysis of oil sands process affected water-derived naphthenic acids in real-world samples

Large volumes of oil sands process-affected waters (OSPW) result from heavy oil extraction in Alberta, Canada. Currently, a toxic legacy of ca. 500 Mm3 is stored in tailings ponds under a zero-discharge policy. OSPW is a complex mixture of suspended and dissolved materials including a wide range of inorganic and organic contaminants. Classically defined naphthenic acids (NAs; CnH2n+ZO2) are one of the primary toxic fractions in OSPW and have therefore been the subject of considerable research interest. Most studies employ considerable sample cleanup followed by liquid chromatography and/or high-resolution mass spectrometry (HRMS) for the characterization of these complex mixtures. However, these strategies can be time- and cost-intensive, limiting the scope of research and adoption for regulatory purposes. Condensed phase membrane introduction mass spectrometry (CP-MIMS) is emerging as a “fit-for-purpose” approach for the analysis of NAs. This technique directly interfaces the mass spectrometer with an aqueous sample using a hydrophobic semi-permeable membrane, requiring only pH adjustment to convert NAs to a membrane-permeable form. Here, we examine the perm-selectivity of classical NAs (O2) relative to their more oxidized counterparts (O3–O7) and heteroatomic (N, S) species collectively termed naphthenic acid fraction compounds (NAFCs). The investigation of 14 model compounds revealed that classically defined NAs are greater than 50-fold more membrane permeable than their oxidized/heteroatomic analogs. HRMS analysis of real OSPW extracts with and without membrane clean-up further supported …

CG Gill

CG Gill

Vancouver Island University

Investigating Impacts of Ultraviolet Filters on the Cowichan River Ecosystem

Ultraviolet filters (UVFs) are compounds added to chemical sunscreens, personal care products, and plastics to block or absorb ultraviolet radiation from the sun, protecting human skin or extending the usable life of a product. However, several different UVFs have been found to disrupt normal hormonal and genetic function in aquatic organisms at high doses. Scientific evidence also suggests that several UVFs bioaccumulate and can biomagnify within aquatic and terrestrial ecosystems at higher concentrations than found in ambient water.The British Columbia Conservation Foundation (BCCF) oversaw collection of river and lake water, sediment, benthic macroinvertebrates, mussels, juvenile fish and adult fish from the Cowichan watershed over 3.5 years (2019-2022) as part of an investigation into the status of UVF contamination in the watershed. The purpose was to develop a baseline of information against which to compare future mitigation efforts. This monitoring was completed with the valuable assistance of community streamkeepers, volunteers, and angling guides.

CG Gill

CG Gill

Vancouver Island University

ACS ES&T Water

Automated, High-Throughput Analysis of Tire-Derived p-Phenylenediamine Quinones (PPDQs) in Water by Online Membrane Sampling Coupled to MS/MS

The tire-derived contaminant N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine quinone (6-PPDQ) was recently identified as a potent toxin to coho salmon (Oncorhynchus kisutch). Studies investigating 6-PPDQ have employed solid-phase extraction (SPE) or liquid–liquid extraction (LLE) with liquid chromatography–mass spectrometry (LC-MS), providing excellent sensitivity and selectivity. However, cleanup and pre-enrichment steps (SPE/LLE) followed by chromatographic separation can be time- and cost-intensive, limiting sample throughput. The ubiquitous distribution of 6-PPDQ necessitates numerous measurements to identify hotspots for targeted mitigation. We recently developed condensed phase membrane introduction mass spectrometry (CP-MIMS) for rapid 6-PPDQ analysis (2.5 min/sample), with a simple workflow and low limit of detection (8 ng/L). Here, we describe improved quantitation using …

Other articles from Science of the total environment journal

Hamada Abdelrahman

Hamada Abdelrahman

Cairo University

Science of The Total Environment

Mitigation of the mobilization and accumulation of toxic metal (loid) s in ryegrass using sodium sulfide

Remediation of soils contaminated with toxic metal(loid)s (TMs) and mitigation of the associated ecological and human health risks are of great concern. Sodium sulfide (Na2S) can be used as an amendment for the immobilization of TMs in contaminated soils; however, the effects of Na2S on the leachability, bioavailability, and uptake of TMs in highly-contaminated soils under field conditions have not been investigated yet. This is the first field-scale research study investigating the effect of Na2S application on soils with Hg, Pb and Cu contents 70-to-7000-fold higher than background values and also polluted with As, Cd, Ni, and Zn. An ex situ remediation project including soil replacement, immobilization with Na2S, and safe landfilling was conducted at Daiziying and Anle (China) with soils contaminated with As, Cd, Cu, Hg, Ni, Pb and Zn. Notably, Na2S application significantly lowered the sulfuric-nitric acid …

Wei Guo

Wei Guo

University of Massachusetts Lowell

Science of The Total Environment

A new assessment framework to forecast land use and carbon storage under different SSP-RCP scenarios in China

The vision of achieving “carbon neutrality” has created new requirements for the projection of land use and land cover (LULC), as well as the carbon storage (CS) of terrestrial ecosystem. Global-scale LULC scenario assessments with coarser resolution introduces uncertainties to national and regional-scale studies, which in turn has a negative impact on CS analysis based on land use perspective. Therefore, we proposed a new framework for scenario-based assessment that integrates the global-scale Land Use Harmonization (LUH2) dataset, Patch-generating Land Use Simulation (PLUS) model, and Integrated Valuation of Ecosystem Services and Trade-offs (InVEST) model, which we called LUH2-PLUS-InVEST (LPI) model. Our aim is to investigate the potential impacts of the combinations of Shared Socioeconomic Pathways (SSPs) and Representative Concentration Pathways (RCPs) on China's future LULC …

Wei Guo

Wei Guo

University of Massachusetts Lowell

Science of The Total Environment

Bio-organic fertilizer facilitated phytoremediation of heavy metal (loid) s-contaminated saline soil by mediating the plant-soil-rhizomicrobiota interactions

Bio-organic fertilizer (BOF) was effective to promote the phytoremediation efficiency of heavy metal(loid)s-contaminated saline soil (HCSS) by improving rhizosphere soil properties, especially microbiome. However, there existed unclear impacts of BOF on plant metabolome and plant-driven manipulation on rhizosphere soil microbiota in HCSS, which were pivotal contributors to stress defense of plants trapped in adverse conditions. Here, a pot experiment was conducted to explore the mechanisms of BOF in improving alfalfa (Medicago sativa)-performing phytoremediation of HCSS. BOF application significantly increased the biomass (150.87–401.58 %) to support the augments of accumulation regarding heavy metal(loid)s (87.50 %–410.54 %) and salts (38.27 %–271.04 %) in alfalfa. BOF promoted nutrients and aggregates stability but declined pH of rhizosphere soil, accompanied by the boosts of rhizomicrobiota …

Lei Shi

Lei Shi

Xi'an Jiaotong University

Science of The Total Environment

How do the growth forms of macrophytes affect the homogeneity of nearshore and open water areas?

Macrophytes with different growth forms exhibit diverse functional traits and ecological functions. In natural sub-deep lakes, there are often large differences in water quality between nearshore areas with macrophytes and open water areas. However, it remains unclear whether this phenomenon can be attributed to differences in plant growth forms. Therefore, we conducted continuous monitoring for four years, both before and after the implementation of an ecological restoration project, to explore whether the change in plant growth forms caused differences in water quality between the nearshore and open water areas. The results showed that implementing ecological restoration projects proved highly effective in improving the local environment, including water physicochemical properties and biological components, in the implementation area. First, the ecological restoration project greatly altered the plant …

Brian Graham

Brian Graham

University of Colorado Denver

Science of The Total Environment

Hypobaric hypoxia drives selection of altitude-associated adaptative alleles in the Himalayan population

Genetic variants play a crucial role in shaping the adaptive phenotypes associated with high-altitude populations. Nevertheless, a comprehensive understanding of the specific impacts of different environments associated with increasing altitudes on the natural selection of these genetic variants remains undetermined. Hence, this study aimed to identify genetic markers responsible for high-altitude adaptation with specific reference to different altitudes, majorly focussing on an altitude elevation range of ∼1500 m and a corresponding decrease of ≥5 % in ambient oxygen availability. We conducted a comprehensive genome-wide investigation (n = 192) followed by a validation study (n = 514) in low-altitude and three high-altitude populations (>2400 m) of Nubra village (NU) (3048 m), Sakti village (SKT) (3812 m), and Tso Moriri village (TK) (4522 m). Extensive genetic analysis identified 86 SNPs that showed …

Geoffroy Séré

Geoffroy Séré

Université de Lorraine

Science of The Total Environment

Selection of soil health indicators for modelling soil functions to promote smart urban planning

The contribution of soil health to global health receives a growing interest, especially in urban environment. Therefore, there is a true need to develop methods to evaluate ecological functions provided by urban soils in order to promote smart urban planning. This work aims first at identifying relevant soil indicators based either on in situ description, in situ measurement or lab analysis. Then, 9 soil functions and sub-functions were selected to meet the main expectations regarding soil health in urban contexts. A crucial step of the present research was then to select adequate indicators for each soil function and then to create adapted reference frameworks; they were in the form of 4 classes with scores ranging from 0 to 3. All the reference frameworks were developed to evaluate soil indicators in order to score soil functions, either by using existing scientific or technical standards or references or based on the …

Timothy Coggan

Timothy Coggan

RMIT University

Science of The Total Environment

Per-and polyfluoroalkyl substances (PFAS) in little penguins and associations with urbanisation and health parameters

Per- and Polyfluoroalkyl substances (PFAS) are increasingly detected in wildlife and present concerning and unknown health risks. While there is a growing body of literature describing PFAS in seabird species, knowledge from temperate Southern Hemisphere regions is lacking. Little penguins (Eudyptula minor) can nest and forage within heavily urbanised coastal environments and hence may be at risk of exposure to pollutants. We analysed scat contaminated nesting soils (n = 50) from 17 colonies in lutruwita/Tasmania for 16 PFAS, plasma samples (n = 45) from nine colonies, and three eggs for 49 PFAS. We detected 14 PFAS across the sample types, with perfluorooctanesulfonic acid (PFOS) and perfluorohexanesulfonic acid (PFHxS) most commonly detected. Mean concentration of PFOS in plasma was 2.56 ± 4.3 ng/mL (<LOD–22.3), soil was 2.92 ± 5.39 μg/kg (<LOD–29.8) and eggs were 11.89 ± 11.30 μg …

Conrad A Pilditch

Conrad A Pilditch

University of Waikato

Science of The Total Environment

Scaling up benthic primary productivity estimates in a large intertidal estuary using remote sensing

As two main primary producers in temperate intertidal regions, seagrass and microphytobenthos (MPB) support estuarine ecosystem functions in multiple ways including stabilizing food webs and regulating sediment resuspension among others. Monitoring estuary productivity at large scales can inform ecosystem scale responses to environmental stressors (climate change, pollution and habitat degradation). Here we use a case study to show how Sentinel-2 data can be used to estimate estuary-wide emerged and submerged gross primary productivity (GPP) on intertidal flats by coupling a new machine learning model to map seagrass and unvegetated habitats with literature-derived photosynthesis-irradiance (P – I) relationships. The model consisted of (1) supervised classification with random forest to delineate seagrass and unvegetated areas and (2) artificial neural network (ANN) regression to predict …

Manogaran Lakshmikandan

Manogaran Lakshmikandan

Jiangsu University

Science of The Total Environment

Comparing the removal efficiency of diisobutyl phthalate by Bacillariophyta, Cyanophyta and Chlorophyta

The utilization of microalgae for both removing phthalate esters (PAEs) from wastewater and producing bioenergy has become a popular research topic. However, there is a lack of studies comparing the effectiveness of different types of microalgae in removing these harmful compounds. Therefore, the present study aimed to evaluate and compare the efficiency of various processes, such as hydrolysis, photolysis, adsorption, and biodegradation, in removing diisobutyl phthalate (DiBP) using six different species of microalgae. The study indicated that the average removal efficiency of DiBP (initial concentrations of 5, 0.5, and 0.05 mg L−1) by all six microalgae (initial cell density of 1 × 106 cells mL−1) was in the order of Scenedesmus obliquus (95.39 %) > Chlorella vulgaris (94.78 %) > Chroococcus sp. (91.16 %) > Cyclotella sp. (89.32 %) > Nitzschia sp. (88.38 %) > Nostoc sp. (84.33 %). The results of both …

Roland I. Hall

Roland I. Hall

University of Waterloo

Science of the Total Environment

‘Paleofloodscapes’: Application of sediment source fingerprinting to track flood regime change over space and time at the Peace-Athabasca Delta, Canada

Deltas are hydrologically dynamic landscapes where river floodwaters create a mosaic of productive ecosystems that provide important services. The flood regime, however, is vulnerable to upstream anthropogenic activities, climate change and geomorphic processes. Deciphering the roles of multiple potential stressors on flood regime change is critical for developing appropriate adaptive and mitigative strategies but requires knowledge of hydrological variability at broader scales of space and time than is typically available from instrumental and observational records. At the globally recognized Peace-Athabasca Delta (Canada), the timing, magnitude and causes of reduced flooding and drawdown of perched basin water levels remain an intense focus of investigation. Here we employ novel ‘paleofloodscapes’, generated from geospatial interpolation of Bayesian mixing model fingerprinting of sediment elemental …

Adriano Gonçalves dos Reis

Adriano Gonçalves dos Reis

Universidade Estadual Paulista

Science of The Total Environment

Machine learning framework for modeling flocculation kinetics using non-intrusive dynamic image analysis

The implementation of a machine learning (ML) model to improve both the effectiveness and sustainability of the water treatment system is a significant challenge in the water sector, with the optimization of flocculation processes being a major setback. The objective of this study was to develop a ML model for predicting flocs evolution of the flocculation process in water treatment. Furthermore, we have devised a framework for its potential adoption in large-scale water treatment. Therefore, the paper can be split into two parts. In the first one, flocculation evolution has been studied from an experimental setup, using a non-intrusive image acquisition method. Subsequently, the ML framework has been implemented. Batch assay data of two velocity gradients (Gf 20 and 60 s−1) and flocculation time of three hours were partitioned into five groups for flocs length range 0.27–3.5 mm and upscaled using linear method …

Amin Abbasi

Amin Abbasi

Universiti Teknologi Petronas

Science of the Total Environment

The predictive machine learning model of a hydrated inverse vulcanized copolymer for effective mercury sequestration from wastewater

Inverse vulcanized polysulfides (IVP) are promising sulfur-enriched copolymers with unconventional properties irresistible for diverse applications like Hg2+ remediation. Nevertheless, due to their inherent hydrophobic nature, these copolymers still offer low Hg2+ uptake capacity. Herein, we reported the synthesis of IVP by reacting molten sulfur with 4-vinyl benzyl chloride, followed by their functionalization using N-methyl D-glucamine (NMDG) to increase the hydration of the developed IVP. The chemical composition and structure of the functionalized IVP were proposed based on FTIR and XPS analysis. The functionalized IVP demonstrated a high mercury adsorption capacity of 608 mg/g (compared to <26 mg/g for common IVP) because of rich sulfur and hydrophilic regions. NMDG functionalized IVP removed 100 % Hg2+ from a low feed concentration (10–50 mg/l). A predictive machine learning model was also …

Ji-Qin Ni

Ji-Qin Ni

Purdue University

Science of the Total Environment

Effect of municipal sludge-based biochar produced at different pyrolysis temperatures on humification and oxytetracycline degradation of pig manure composting

This study explored the influence of pyrolysis temperatures on the properties of municipal sludge-based biochar (MSB) and evaluated the impact of MSB on humification and oxytetracycline (OTC, a broad-spectrum antibiotic) degradation in pig manure composting. Three types of MSB were produced from sewage sludge pyrolyzed at 300 °C, 500 °C, and 700 °C, respectively. Results indicated that pyrolysis temperature adjusted the formation sequence of the functional groups in MSB, and higher pyrolysis temperatures enriched the aromaticity of the biochar and augmented the concentrations of humic precursor compounds. The MSB addition to pig manure composting enhanced the peak temperature and prolonged the thermophilic phase. Moreover, the MSB addition significantly increased the HI (humic acid/fulvic acid) values (1.6–2.57) compared with the control (1.28), with a more pronounced effect observed at …

Senchao Lai

Senchao Lai

South China University of Technology

Science of The Total Environment

Origin and transformation of volatile organic compounds at a regional background site in Hong Kong: Varied photochemical processes from different source regions

Volatile organic compounds (VOCs) are important gaseous constituents in the troposphere, impacting local and regional air quality, human health, and climate. Oxidation of VOCs, with the participation of nitrogen oxides (NOx), leads to the formation of tropospheric ozone (O3). Accurately apportioning the emission sources and transformation processes of ambient VOCs, and effectively estimation of OH reactivity and ozone formation potential (OFP) will play an important role in reducing O3 pollution in the atmosphere and improving public health. In this study, field measurements were conducted at a regional background site (Hok Tsui; HT) in Hong Kong from October to November 2020 with proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF-MS). VOC data coupled with air mass back trajectory cluster analysis and receptor modelling were applied to reveal the pollution pattern, emission sources and …

Senchao Lai

Senchao Lai

South China University of Technology

Science of The Total Environment

Multiphase reactions of proteins in the air: Oligomerization, nitration and degradation of bovine serum albumin upon ambient exposure

Proteins in atmospheric aerosol can react with atmospheric pollutants such as ozone (O3) and nitrogen dioxide (NO2) in the atmosphere via the reactions of oxidation, nitration, and cross-linking etc. Currently, the reactions have been more thoroughly studied in the laboratory but rarely investigated in the ambient environment. In this study, we used bovine serum albumin (BSA) as the model protein to conduct the exposure experiment in the ambient environment in southern China, an area with increasing oxidative capacity, to investigate the reactions of proteins in the atmosphere. We observed the occurrence of oligomerization, nitration and degradation of BSA upon exposure. The mass fraction of BSA monomer decreased by 5.86 ± 1.61% after exposure and those of dimers, trimers and higher oligomers increased by 1.04 ± 0.49%, 1.37 ± 0.74% and 3.40 ± 1.06%, respectively. Simultaneously, the nitration degrees …

Coline Boonman

Coline Boonman

Radboud Universiteit

Science of The Total Environment

Drainage effects on carbon budgets of degraded peatlands in the north of the Netherlands

Peatlands store vast amounts of carbon (C). However, land-use-driven drainage causes peat oxidation, resulting in CO 2 emission. There is a growing need for ground-truthing CO 2 emission and its potential drivers to better quantify long-term emission trends in peatlands. This will help improve National Inventory Reporting and ultimately aid the design and verification of mitigation measures. To investigate regional drivers of CO 2 emission, we estimated C budgets using custom-made automated chamber systems measuring CO 2 concentrations corrected for carbon export and import. Chamber systems were rotated among thirteen degraded peatland pastures in Friesland (the Netherlands). These peatlands varied in water table depth (WTD), drainage-irrigation management (fixed regulated ditch water level (DWL), subsurface irrigation, furrow irrigation, or dynamic regulated DWL), and soil moisture. We …

Ramesh Kumar

Ramesh Kumar

Sharda University

Science of the Total Environment

Integrating satellite and model data to explore spatial-temporal changes in aerosol optical properties and their meteorological relationships in northwest India

This study aims to analyze the temporal and spatial distribution of Aerosol Optical Properties across Northwest India using aerosol data from MODIS (Moderate Resolution Imaging Spectroradiometer) and OMI (Ozone Monitoring Instrument) sensors from 2003 to 2022. Therefore, this study investigated the decadal, interannual, and seasonal changes in aerosol optical properties, vegetation index, and meteorological parameters in the northwest Indian region (8 boxes). Using GIOVANNI (Goddard Earth Sciences Data and Information Services Center (GES DISC) Online Visualization and Analysis Infrastructure), we retrieved daily and monthly Aqua and Terra MODIS products of aerosol optical depth (AOD), Angstrom exponent (AE), normalized difference vegetation index (NDVI), and OMI aerosol index (AI) to examine the spatiotemporal variations by using statistical approaches. The results demonstrated that the …

Kourosh Behzadian

Kourosh Behzadian

University of West London

Science of the Total Environment

Analysis of environmental factors influencing endemic cholera risks in sub-Saharan Africa

The recurring cholera outbreaks in sub-Saharan Africa are of growing concern, especially considering the potential acceleration in the global trend of larger and more lethal cholera outbreaks due to the impacts of climate change. However, there is a scarcity of evidence-based research addressing the environmental and infrastructure factors that sustain cholera recurrence in Africa. This study adopts a statistical approach to investigate over two decades of endemic cholera outbreaks and their relationship with five environmental factors: water provision, sanitation provision, raising temperatures, increased rainfall and GDP. The analysis covers thirteen of the forty-two countries in the mainland sub-Saharan region, collectively representing one-third of the region’s territory and half of its population. This breadth enables the findings to be generalised at a regional level. Results from all analyses consistently associate …

Divina M. Amalin

Divina M. Amalin

De La Salle University

Science of The Total Environment

Detection of SARS-CoV-2 and Omicron variant RNA in wastewater samples from Manila, Philippines

Manila, a highly urbanized city, is listed as one of the top cities with the highest recorded number of coronavirus disease 2019 (COVID-19) cases in the Philippines. This study aimed to detect and quantify the RNA of the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and the Omicron variant in 51 wastewater samples collected from three locations in Manila, namely Estero de Santa Clara, Estero de Pandacan, which are open drainages, and a sewage treatment plant (STP) at De La Salle University–Manila, between July 2022 and February 2023. Using one-step reverse transcription-quantitative polymerase chain reaction, SARS-CoV-2 and Omicron variant RNA were detected in 78 % (40/51; 4.9 ± 0.5 log10 copies/L) and 60 % (24/40; 4.4 ± 0.3 log10 copies/L) of wastewater samples collected from all sampling sites, respectively. SARS-CoV-2 RNA was detected frequently at Estero de Santa Clara …

Sarian Kosten

Sarian Kosten

Radboud Universiteit

Science of The Total Environment

Experimental warming promotes CO2 uptake but hinders carbon incorporation toward higher trophic levels in cyanobacteria-dominated freshwater communities

Shallow freshwaters can exchange large amounts of carbon dioxide (CO2) with the atmosphere and also store significant quantities of carbon (C) in their sediments. Current warming and eutrophication pressures might alter the role of shallow freshwater ecosystems in the C cycle. Although eutrophication has been widely associated to an increase in total phytoplankton biomass and particularly of cyanobacteria, it is still poorly understood how warming may affect ecosystem metabolism under contrasting phytoplankton community composition. We studied the effects of experimental warming on CO2 fluxes and C allocation on two contrasting natural phytoplankton communities: chlorophytes-dominated versus cyanobacteria-dominated, both with a similar zooplankton community with a potentially high grazing capacity (i.e., standardized density of large-bodied cladocerans). The microcosms were subject to two …