Comparison of calibration strategies for accurate quantitation by isotope dilution mass spectrometry: a case study of ochratoxin A in flour.

Analysis of low-level organic contaminants in complex matrices is essential for monitoring global food safety. However, balancing sample throughput with complex experimental designs and/or sample clean-up to best reduce matrix effects is a constant challenge. Multiple strategies exist to mitigate these effects, with internal standard-based methods such as isotope dilution mass spectrometry (IDMS) being the most advantageous. Here, multiple internal calibration strategies were investigated for the quantification of ochratoxin A (OTA) in wheat samples by liquid chromatography-mass spectrometry (LC-MS). Internal standard-based quantitation methods such as single (ID1MS), double (ID2MS), and quintuple (ID5MS) isotope dilution mass spectrometry, as well as external standard calibration, were explored and compared. A certified reference material (CRM) of OTA in flour, MYCO-1, was used to evaluate the accuracy of each method. External calibration generated results 18-38% lower than the certified value for MYCO-1, largely due to matrix suppression effects. Concurrently, consistently lower OTA mass fractions were obtained for the wheat samples upon quantitation by external calibration as opposed to ID1MS, ID2MS, and ID5MS. All isotope dilution methods produced results that fell within the expected range for MYCO-1 (3.17-4.93 µg/kg), validating their accuracy. However, an average 6% decrease in the OTA mass fraction was observed from results obtained by ID1MS compared to those by ID2MS and ID5MS. Upon scrutiny, these differences were attributed to an isotopic enrichment bias in the isotopically labelled internal standard [13C6]-OTA that was used for ID1MS, the OTAL-1 CRM. The advantages and limitations of each isotopic method are illustrated.

Marine environment pollution: The contribution of mass spectrometry to the study of seawater.

The study of marine pollution has been traditionally addressed to persistent chemicals, generally known as priority pollutants; a current trend in environmental analysis is a shift toward "emerging pollutants," defined as newly identified or previously unrecognized contaminants. The present review is focused on the peculiar contribution of mass spectrometry (MS) to the study of pollutants in the seawater compartment. The work is organized in five paragraphs where the most relevant groups of pollutants, both "classical" and "emerging," are presented and discussed, highlighting the relative data obtained by the means of different MS techniques. The hyphenation of MS and separative techniques, together with the development of different ion sources, makes MS and tandem MS the analytical tool of choice for the determination of trace organic contaminants in seawater. © 2016 Wiley Periodicals, Inc. Mass Spec Rev 37:492-512, 2018.

Multiple names for multi-scope analytical methods, more than a semantic issue.

The use of multiple names for multi-scope analytical methods is often confusing. More precise classification to better accommodate the scope of analytical validation and application is needed.

Unique hepatic maternal transfer pattern of trace metals and perfluoroalkyl substances (PFAS) in a bluntnose sixgill shark (Hexanchus griseus).

The fate and distribution of environmental contaminants includes bioaccumulation within marine organisms. A deceased 4-m long adult female bluntnose sixgill shark, pregnant with 72 pups, was recovered from Coles Bay on Vancouver Island, BC, Canada in 2019. This specimen provided a unique opportunity to examine maternal transfer of contaminants in a yolk-sac viviparous shark species. Liver subsamples of the adult and offspring were analyzed for 18 targeted inorganic elements by inductively coupled plasma optical emission spectroscopy (ICP-OES) and 21 targeted perfluoroalkyl substances (PFAS) by liquid chromatography-electrospray ionization-high resolution mass spectrometry (LC-ESI-Orbitrap MS). The maternal-offspring transfer efficiencies in liver tissue were subsequently examined for both contaminant classes. Concentrations of all detectable metals apart from calcium and magnesium were found to be higher in the mother compared to the offspring, including substantial levels of toxic cadmium (6 ± 2 mg kg-1 dw) and lead (7 ± 3 mg kg-1 dw). Conversely, high maternal transfer efficiencies were observed for PFAS (i.e., ΣPFAS = 71 ± 9 ng g-1 ww in offspring compared to 13 ± 9 ng g-1 ww in the mother). This study highlighted the unique maternal transfer characteristics of PFAS in bluntnose sixgill sharks depending on the structure of the polar head group, with greater liver-to-liver transfer efficiencies observed for perfluorocarboxylic acids (PFCAs) than perfluorosulfonic acids (PFSAs) of the same fluorocarbon chain length.

Where should Fenton go for the degradation of refractory organic contaminants in wastewater?

Fenton process has become a research hotspot due to the nonselective and efficient degradation of dissolved organic matter (DOM) by ·OH. However, there are still many challenges and bottlenecks for conventional Fenton (CF). This study provides the first comprehensive insight into the mechanisms of DOM degradation by the Fenton process, including the various subcategories of humic substances, emerging trace contaminants, including persistent organic pollutants, endocrine disrupting chemicals, and pharmaceuticals and personal care products, and the interference of humus and low molecular weight organic acids on the removal of trace contaminants. In addition, a statistical comparison of the economics of CF and three types of Fenton-like technologies (Photo-Fenton, Electro-Fenton, and Ultrasonic-Fenton) is conducted based on existing studies, which can be used as a reference for engineering applications. Moreover, a brief overview of the categories and characteristics of heterogeneous Fenton, which have been extensively studied in recent years, and a comparison of their catalysts are presented. In the end, the paper advances a possible future research direction.

Enzymatic post-treatment of ozonation: laccase-mediated removal of the by-products of acetaminophen ozonation.

Ozonation is a powerful technique to remove micropollutants from wastewater. As chemical oxidation of wastewater comes with the formation of varying, possibly persistent and toxic by-products, post-treatment of the ozonated effluent is routinely suggested. This study explored an enzymatic treatment of ozonation products using the laccase from Trametes versicolor. A high-performance liquid chromatography coupled with high-resolution mass spectrometry (HPLC-HRMS) analysis revealed that the major by-products were effectively degraded by the enzymatic post-treatment. The enzymatic removal of the by-products reduced the ecotoxicity of the ozonation effluent, as monitored by the inhibition of Aliivibrio fischeri. The ecotoxicity was more effectively reduced by enzymatic post-oxidation at pH 7 than at the activity maximum of the laccase at pH 5. A mechanistic HPLC-HRMS and UV/Vis spectroscopic analysis revealed that acidic conditions favored rapid conversion of the phenolic by-products to dead-end products in the absence of nucleophiles. In contrast, the polymerization to harmless insoluble polymers was favored at neutral conditions. Hence, coupling ozonation with laccase-catalyzed post-oxidation at neutral conditions, which are present in wastewater effluents, is suggested as a new resource-efficient method to remove persistent micropollutants while excluding the emission of potentially harmful by-products.

Narrowing the analytical gap for water-soluble polymers: A novel trace-analytical method and first quantitative occurrence data for polyethylene oxide in surface and wastewater.

Water-soluble polymers (WSPs) like polyethylene oxide (PEO) have annual production volumes ranging from thousands to millions of tonnes and are used in a wide variety of applications that enable a release into the aquatic environment. Despite these facts, a lack of quantitative trace-analytical methods for WSPs prevents the comprehensive study of their environmental occurrence. Here, size exclusion chromatography was hyphenated with electrospray ionization high-resolution mass spectrometry. An all-ion fragmentation approach for the formation of diagnostic fragments independent of molecular weight, charge state, and ion species was used to quantify PEO and its derivatives in wastewater treatment plants (WWTPs) and surface water samples. Despite its inherent biodegradability, PEO concentrations found in the samples analysed ranged from 1 µg/L) and reached up to 20 µg/L (effluent) and 400 µg/L (influent) for WWTPs. A substantial shift in molecular weight ranges was observed between influent and effluent, pointing towards a molecular weight fraction between 1.3 and 4 kDa being dominant in the effluent. Due to an assumed size exclusion during sample enrichment, information on the MW-distribution of PEO is limited to MW < 55 kDa. The high concentrations widely detected for a readily biodegradable WSP such as PEO, raise strong concerns about the occurrence and fate of recalcitrant WSPs in the aquatic environment. The method presented herein may provide the tools necessary to assess the burden of these high production volume chemicals and the risk they may pose.

Micropollutant concentration fluctuations in combined sewer overflows require short sampling intervals.

Combined sewer overflows (CSOs) are an important pathway of organic micropollutants from urban areas to open water bodies. Understanding the temporal dynamics of these micropollutants during overflow events is crucial for applying appropriate sampling methods and implementing effective management strategies. Yet, little is known about the dynamics of micropollutants in CSOs, because most studies report concentrations from single grab samples or event mean concentrations (EMCs). With unique high temporal resolution measurements (3 min), we show the real dynamics of polar organic micropollutants in CSOs of one small (2,700 people: P) and one large (159,000 P) urban catchment, for two micropollutant categories: (i) 33 micropollutants in municipal wastewater and (ii) 13 micropollutants from urban surface runoff. The concentration dynamics depend on the substance source and the catchment size. Indoor substances such as pharmaceuticals show high temporal dynamics with changes of 1 to 2 orders of magnitude within 9 min in the CSO of the small catchment. In contrast, outdoor substances at the small catchment and all substances at the large catchment display considerably lower variation. We tested various time-proportional sampling strategies to assess the range of error when estimating EMCs. We recommend an interval of 3 min to capture the dynamics of indoor substances in CSOs from small catchments. The results highlight that both future monitoring campaigns and the planning and management of urban wet-weather treatment systems will benefit from high temporal sampling resolutions, not only to understand dynamics but also to minimize errors of estimated EMCs.

A decade of monitoring micropollutants in urban wet-weather flows: What did we learn?

Urban wet-weather discharges from combined sewer overflows (CSO) and stormwater outlets (SWO) are a potential pathway for micropollutants (trace contaminants) to surface waters, posing a threat to the environment and possible water reuse applications. Despite large efforts to monitor micropollutants in the last decade, the gained information is still limited and scattered. In a metastudy we performed a data-driven analysis of measurements collected at 77 sites (683 events, 297 detected micropollutants) over the last decade to investigate which micropollutants are most relevant in terms of 1) occurrence and 2) potential risk for the aquatic environment, 3) estimate the minimum number of data to be collected in monitoring studies to reliably obtain concentration estimates, and 4) provide recommendations for future monitoring campaigns. We highlight micropollutants to be prioritized due to their high occurrence and critical concentration levels compared to environmental quality standards. These top-listed micropollutants include contaminants from all chemical classes (pesticides, heavy metals, polycyclic aromatic hydrocarbons, personal care products, pharmaceuticals, and industrial and household chemicals). Analysis of over 30,000 event mean concentrations shows a large fraction of measurements (> 50%) were below the limit of quantification, stressing the need for reliable, standard monitoring procedures. High variability was observed among events and sites, with differences between micropollutant classes. The number of events required for a reliable estimate of site mean concentrations (error bandwidth of 1 around the "true" value) depends on the individual micropollutant. The median minimum number of events is 7 for CSO (2 to 31, 80%-interquantile) and 6 for SWO (1 to 25 events, 80%-interquantile). Our analysis indicates the minimum number of sites needed to assess global pollution levels and our data collection and analysis can be used to estimate the required number of sites for an urban catchment. Our data-driven analysis demonstrates how future wet-weather monitoring programs will be more effective if the consequences of high variability inherent in urban wet-weather discharges are considered.

Mechanistic insights for efficient inactivation of antibiotic resistance genes: a synergistic interfacial adsorption and photocatalytic-oxidation process.

Advanced oxidation processes (AOPs) have been applied to address multiple environmental concerns including antibiotic resistance genes (ARGs). ARGs have shown an increasing threat to human health, and they are either harbored by antibiotic-resistant bacteria (ARB) or free in the environment. However, the control of ARGs has been substantially limited by their low concentration and the limited knowledge about their interfacial behavior. Herein, a novel AOP catalyst, Ag/TiO2/graphene oxide (GO), combined with a polyvinylidene fluoride (PVDF) ultrafiltration membrane was designed with a synergistic interfacial adsorption and oxidation function to inactivate ARGs with high efficiency in both model solutions and in secondary wastewater effluent, especially when the residue concentration was low. Further analysis showed that the mineralization of bases and phosphodiesters mainly caused the inactivation of ARGs. Moreover, the interfacial adsorption and oxidation processes of ARGs were studied at the molecular level. The results showed that GO was rich in sp2 backbones and functional oxygen groups, which efficiently captured and enriched the ARGs via π-π interactions and hydrogen bonds. Therefore, the photogenerated active oxygen species attack the ARGs by partially overcoming the kinetic problems in this process. The Ag/TiO2/GO catalyst was further combined with a PVDF membrane to test its potential in wastewater treatment applications. This work offers an efficient method and a corresponding material for the inactivation and mineralization of intra/extracellular ARGs. Moreover, the molecular-level understanding of ARG behaviors on a solid-liquid interface will inspire further control strategies of ARGs in the future.

Graphene Oxide Membranes for Trace Hydrocarbon Contaminant Removal from Aqueous Solution.

The aim of this paper is to shed light on the application of graphene oxide (GO) membranes for the selective removal of benzene, toluene, and xylene (BTX) from wastewater. These molecules are present in traces in the water produced from oil and gas plants and are treated now with complex filtration systems. GO membranes are obtained by a simple, fast, and scalable method. The focus of this work is to prove the possibility of employing GO membranes for the filtration of organic contaminants present in traces in oil and gas wastewater, which has never been reported. The stability of GO membranes is analyzed in water solutions with different pH and salinity. Details of the membrane preparation are provided, resulting in a crucial step to achieve a good filtration performance. Material characterization techniques such as electron microscopy, x-ray diffraction, and infrared spectroscopy are employed to study the physical and chemical structure of GO membranes, while gas chromatography, UV-visible spectroscopy, and gravimetric techniques allow the quantification of their filtration performance. An impressive rejection of about 90% was achieved for 1 ppm of toluene and other pollutants in water, demonstrating the excellent performance of GO membranes in the oil and gas field.

Untargeted approach for the evaluation of anthropic impact on the sheltered marine area of Portofino (Italy).

Seawater passive sampling with Polar Organic Chemical Integrative Samplers (POCIS) combined with Gaschromatography-Mass Spectrometry analysis were employed as a tool for screening unknown contaminants in a complex Ligurian marine coastal area. The untargeted approach allowed recognizing different classes of compounds, mainly hydrocarbons from C20 to C30. Besides, two chemicals, deriving from anthropic activities, N-butylbenzenesulfonamide (NBBS) and diphenyl sulfone (DPS), were identified and quantified in all samples. Both analytes showed decreasing concentrations from the more confined site to the outer one. The oceanographic characterization of the area performed with multiparametric probes provided useful information, in agreement with chemical analyses. The presence of NBBS and DPS in the site presenting lower continental inputs demonstrated the usefulness of the integrative sampling approach for temporal and spatial monitoring, especially for low level and/or short-term pollution events that traditional monitoring can fail to detect.

Assessment of chemical and material contamination in waste wood fuels--A case study ranging over nine years.

The increased demand for waste wood (WW) as fuel in Swedish co-combustion facilities during the last years has increased the import of this material. Each country has different laws governing the use of chemicals and therefore the composition of the fuel will likely change when combining WW from different origins. To cope with this, enhanced knowledge is needed on WW composition and the performance of pre-treatment techniques for reduction of its contaminants. In this study, the chemical and physical characteristics of 500 WW samples collected at a co-combustion facility in Sweden between 2004 and 2013 were investigated to determine the variation of contaminant content over time. Multivariate data analysis was used for the interpretation of the data. The concentrations of all the studied contaminants varied widely between sampling occasions, demonstrating the highly variable composition of WW fuels. The efficiency of sieving as a pre-treatment measure to reduce the levels of contaminants was not sufficient, revealing that sieving should be used in combination with other pre-treatment methods. The results from this case study provide knowledge on waste wood composition that may benefit its management. This knowledge can be applied for selection of the most suitable pre-treatments to obtain high quality sustainable WW fuels.

Comparing graphene, carbon nanotubes, and superfine powdered activated carbon as adsorptive coating materials for microfiltration membranes.

Multi-walled carbon nanotubes (MWCNTs), nano-graphene platelets (NGPs), and superfine powdered activated carbon (S-PAC) were comparatively evaluated for their applicability as adsorptive coatings on microfiltration membranes. The objective was to determine which materials were capable of contaminant removal while causing minimal flux reduction. Methylene blue and atrazine were the model contaminants. When applied as membrane coatings, MWCNTs had minimal retention capabilities for the model contaminants, and S-PAC had the fastest removal. The membrane coating approach was also compared with a stirred vessel configuration, in which the adsorbent was added to a stirred flask preceding the membrane cell. Direct application of the adsorbent to the membrane constituted a greater initial reduction in permeate concentrations of the model contaminants than with the stirred flask setup. All adsorbents except S-PAC showed flux reductions less than 5% after application as thin-layer membrane coatings, and flux recovery after membrane backwashing was greater than 90% for all materials and masses tested.