scholarly journals A Novel Method to Characterise Levels of Pharmaceutical Pollution in Large-Scale Aquatic Monitoring Campaigns

2019 ◽  
Vol 9 (7) ◽  
pp. 1368 ◽  
Author(s):  
John Wilkinson ◽  
Alistair Boxall ◽  
Dana Kolpin
Keyword(s):  
Mass Spectrometry ◽  
Liquid Chromatography ◽  
Surface Water ◽  
Large Scale ◽  
Tap Water ◽  
Treatment Plant ◽  
Wwtp Effluent ◽  
Relative Standard ◽  
Novel Method ◽  
The Impact

Much of the current understanding of pharmaceutical pollution in the aquatic environment is based on research conducted in Europe, North America and other select high-income nations. One reason for this geographic disparity of data globally is the high cost and analytical intensity of the research, limiting accessibility to necessary equipment. To reduce the impact of such disparities, we present a novel method to support large-scale monitoring campaigns of pharmaceuticals at different geographical scales. The approach employs the use of a miniaturised sampling and shipping approach with a high throughput and fully validated direct-injection High-Performance Liquid Chromatography-Tandem Mass Spectrometry method for the quantification of 61 active pharmaceutical ingredients (APIs) and their metabolites in tap, surface, wastewater treatment plant (WWTP) influent and WWTP effluent water collected globally. A 7-day simulated shipping and sample stability assessment was undertaken demonstrating no significant degradation over the 1–3 days which is typical for global express shipping. Linearity (r2) was consistently ≥0.93 (median = 0.99 ± 0.02), relative standard deviation of intra- and inter-day repeatability and precision was <20% for 75% and 68% of the determinations made at three concentrations, respectively, and recovery from Liquid Chromatography Mass Spectrometry grade water, tap water, surface water and WWTP effluent were within an acceptable range of 60–130% for 87%, 76%, 77% and 63% of determination made at three concentrations respectively. Limits of detection and quantification were determined in all validated matrices and were consistently in the ng/L level needed for environmentally relevant API research. Independent validation of method results was obtained via an interlaboratory comparison of three surface-water samples and one WWTP effluent sample collected in North Liberty, Iowa (USA). Samples used for the interlaboratory validation were analysed at the University of York Centre of Excellence in Mass Spectrometry (York, UK) and the U.S. Geological Survey National Water Quality Laboratory in Denver (Colorado, USA). These results document the robustness of using this method on a global scale. Such application of this method would essentially eliminate the interlaboratory analytical variability typical of such large-scale datasets where multiple methods were used.

A Sensitive Ultra-High Performance Liquid Chromatography–Tandem Mass Spectrometry Method Based on Derivatization with 1-Nitro-2-Naphthaldehyde for Determination of Alkylhydrazines in Surface water

2021 ◽  
Author(s):  
Jin-Ah Oh ◽  
Ho-Sang Shin ◽  
Hyun-Hee Lim
Keyword(s):  
Mass Spectrometry ◽  
High Performance Liquid Chromatography ◽  
Liquid Chromatography ◽  
Surface Water ◽  
Tandem Mass Spectrometry ◽  
High Performance ◽  
Tandem Mass ◽  
Chromatography Tandem Mass Spectrometry ◽  
Relative Standard ◽  
Liquid Chromatography Tandem Mass

Abstract Background Alkylhydrazines are widely used in the industrial fields. An analysis of alkylhydrazines in surface water is need because these chemicals are likely to be discharged into wastewater and enter aquatic environments. Objective An ultra-high performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) method was developed to determine the levels of five alkylhydrazines (N,N-dimethylhydrazine, ethylhydrazine, 1-isopropylhydrazine, phenylhydrazine and 1-methyl-1-phenylhydrazine) in surface water. Methods This method is based on the derivatization of alkylhydrazines with 1-nitro-2-naphthaldehyde (NNA) in water. A derivatization reagent dosage of 0.5 mg of NNA, a pH of 2, and a reaction time of 30 min at 40 °C were determined to be the optimal conditions for UHPLC–MS/MS detection. The derivatives were injected into the LC system without additional extraction or purification steps. Results The proposed method was used under optimized conditions to detect alkylhydrazines in surface water, with the limit of quantification found to be 0.01–0.03 μg/L. The accuracy ranged from 91.0 to 106.0%, and the precision, expressed as the relative standard deviation, was less than 10%. Of the five alkylhydrazines, only N,N-dimethyl hydrazine was detected in the real samples at a concentration range of 0.010 to 0.041 μg/L. Conclusion The developed method can be used to confirm the presence of alkylhydrazine residues in surface water and represents an important tool for evaluating the fate of alkylhydrazines in surface water. Highlights This method to determine alkylhydrazine in surface water was developed simply and rapidly after derivatization reaction without an extraction or clean-up step in UHPLC-MS/MS.

Water matrix effect on UV photodegradation of perfluorooctanoic acid

2011 ◽  
Vol 64 (10) ◽  
pp. 1980-1986 ◽  
Author(s):  
R. R. Giri ◽  
H. Ozaki ◽  
T. Okada ◽  
S. Takikita ◽  
S. Taniguchi ◽  
...  
Keyword(s):  
Wastewater Treatment ◽  
Surface Water ◽  
Tap Water ◽  
Water Environment ◽  
Treatment Plant ◽  
Perfluorooctanoic Acid ◽  
Wastewater Effluent ◽  
Treated Wastewater ◽  
Toc Removal ◽  
The Impact

The widespread detection of perfluorinated compounds (PFCs) in the water environment has been a concern for the last several years, while effluents from wastewater treatment facilities are the major sources of these compounds. Even advanced oxidation technologies (AOTs) are not useful for mineralization of the compounds due to their very high stability. Photochemical techniques using particularly vacuum UV (VUV) have been found to be very promising in this regard. But the use of VUV in UV-based AOTs has still not progressed much. Moreover, the impact of water quality on PFCs photomineralization is unknown. This investigation aimed to assess photomineralization potentials of perfluorooctanoic acid (PFOA) in ultrapure water (UPW), tap water (TW), surface water and treated wastewater effluent using a reactor setup enabling maximum utilization of VUV emission of low pressure lamp in laboratory batch experiments. Neya River water (NRW) and the Nakahama Wastewater Treatment Plant Effluent (NWWTPE) represented surface water and treated wastewater effluent respectively. Also, tests were carried out in 50% diluted NRW and NWWTPE. PFOA photomineralization in terms of PFOA removal, defluorination and total organic carbon (TOC) removal are discussed. The usefulness of the method for PFOA mineralization in organic-rich wastewaters, and further research needs are also highlighted.

scholarly journals Toward Isolation of Palytoxins: Liquid Chromatography Coupled to Low- or High-Resolution Mass Spectrometry for the Study on the Impact of Drying Techniques, Solvents and Materials

Toxins ◽  
2021 ◽  
Vol 13 (9) ◽  
pp. 650
Author(s):  
Antonia Mazzeo ◽  
Michela Varra ◽  
Luciana Tartaglione ◽  
Patrizia Ciminiello ◽  
Zita Zendong ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Liquid Chromatography ◽  
High Resolution ◽  
Large Scale ◽  
High Resolution Mass Spectrometry ◽  
Degradation Products ◽  
Pure Water ◽  
Skin Contact ◽  
The Stability ◽  
The Impact

Palytoxin (PLTX) and its congeners are emerging toxins held responsible for a number of human poisonings following the inhalation of toxic aerosols, skin contact, or the ingestion of contaminated seafood. Despite the strong structural analogies, the relative toxic potencies of PLTX congeners are quite different, making it necessary to isolate them individually in sufficient amounts for toxicological and analytical purposes. Previous studies showed poor PLTX recoveries with a dramatic decrease in PLTX yield throughout each purification step. In view of a large-scale preparative work aimed at the preparation of PLTX reference material, we have investigated evaporation as a critical—although unavoidable—step that heavily affects overall recoveries. The experiments were carried out in two laboratories using different liquid chromatography-mass spectrometry (LC-MS) instruments, with either unit or high resolution. Palytoxin behaved differently when concentrated to a minimum volume rather than when evaporated to complete dryness. The recoveries strongly depended on the solubility as well as on the material of the used container. The LC-MS analyses of PLTX dissolved in aqueous organic blends proved to give a peak intensity higher then when dissolved in pure water. After drying, the PLTX adsorption appeared stronger on glass surfaces than on plastic materials. However, both the solvents used to dilute PLTX and that used for re-dissolution had an important role. A quantitative recovery (97%) was achieved when completely drying 80% aqueous EtOH solutions of PLTX under N2-stream in Teflon. The stability of PLTX in acids was also investigated. Although PLTX was quite stable in 0.2% acetic acid solutions, upon exposure to stronger acids (pH < 2.66), degradation products were observed, among which a PLTX methyl-ester was identified.

scholarly journals Polyphenol Profiling of Chestnut Pericarp, Integument and Curing Water Extracts to Qualify These Food By-Products as a Source of Antioxidants

Molecules ◽  
2021 ◽  
Vol 26 (8) ◽  
pp. 2335
Author(s):  
Gabriella Pinto ◽  
Sabrina De Pascale ◽  
Maria Aponte ◽  
Andrea Scaloni ◽  
Francesco Addeo ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Negative Impact ◽  
Tap Water ◽  
Time Of Flight ◽  
The Other ◽  
Curing Process ◽  
Flight Mass Spectrometry ◽  
Water Curing ◽  
The Impact ◽  
By Products

Plant polyphenols have beneficial antioxidant effects on human health; practices aimed at preserving their content in foods and/or reusing food by-products are encouraged. The impact of the traditional practice of the water curing procedure of chestnuts, which prevents insect/mould damage during storage, was studied to assess the release of polyphenols from the fruit. Metabolites extracted from pericarp and integument tissues or released in the medium from the water curing process were analyzed by matrix-assisted laser desorption ionization-time of flight-mass spectrometry (MALDI-TOF-MS) and electrospray-quadrupole-time of flight-mass spectrometry (ESI-qTOF-MS). This identified: (i) condensed and hydrolyzable tannins made of (epi)catechin (procyanidins) and acid ellagic units in pericarp tissues; (ii) polyphenols made of gallocatechin and catechin units condensed with gallate (prodelphinidins) in integument counterparts; (iii) metabolites resembling those reported above in the wastewater from the chestnut curing process. Comparative experiments were also performed on aqueous media recovered from fruits treated with processes involving: (i) tap water; (ii) tap water containing an antifungal Lb. pentosus strain; (iii) wastewater from a previous curing treatment. These analyses indicated that the former treatment determines a 6–7-fold higher release of polyphenols in the curing water with respect to the other ones. This event has a negative impact on the luster of treated fruits but qualifies the corresponding wastes as a source of antioxidants. Such a phenomenon does not occur in wastewater from the other curing processes, where the release of polyphenols was reduced, thus preserving the chestnut’s appearance. Polyphenol profiling measurements demonstrated that bacterial presence in water hampered the release of pericarp metabolites. This study provides a rationale to traditional processing practices on fruit appearance and qualifies the corresponding wastes as a source of bioactive compounds for other nutraceutical applications.

scholarly journals Hyperandrogenism by Liquid Chromatography Tandem Mass Spectrometry in PCOS: Focus on Testosterone and Androstenedione

2020 ◽  
Vol 10 (1) ◽  
pp. 119
Author(s):  
Giorgia Grassi ◽  
Elisa Polledri ◽  
Silvia Fustinoni ◽  
Iacopo Chiodini ◽  
Ferruccio Ceriotti ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Liquid Chromatography ◽  
Polycystic Ovary ◽  
Free Testosterone ◽  
Reference Intervals ◽  
Model Assessment ◽  
Homeostatic Model Assessment ◽  
Liquid Chromatography Tandem Mass ◽  
And Control ◽  
The Impact

The identification of hyperandrogenism in polycystic ovary syndrome (PCOS) is concerning because of the poor accuracy of the androgen immunoassays (IA) and controversies regarding which androgens should be measured. The aim of our study was to evaluate the impact of the assessment of testosterone (T) and androstenedione (A) by liquid chromatography in tandem with mass spectrometry (LC/MS-MS), in the diagnosis of PCOS. We evaluated 131 patients referred for suspected PCOS. Fourteen patients in total were excluded, some because of other diagnosis (n = 7) or incomplete diagnostic workup (n = 7). We measured T and A both by IA and LC-MS/MS in the 117 subjects included. We calculated free T (fT) by the Vermeulen formula and recorded clinical and metabolic data. 73 healthy females served as controls to derive immunoassays (IA) and LC-MS/MS reference intervals for T, fT and A. PCOS was confirmed in 90 subjects by IA and in 93 (+3.3%) by LC-MS/MS. The prevalence of biochemical hyperandrogenism in PCOS by LC-MS/MS increased from 81.7% to 89.2% if A was also considered. The most frequently elevated androgens were fT (73.1%) and A (64.5%) and they had similar levels of accuracy in differentiating PCOS and controls (0.34 ng/dL, Sn 91% Sp 89%; 1.16 ng/mL, Sn 91% Sp 88%, respectively). Free testosterone correlated with body mass index (BMI), homeostatic model assessment (HOMA)-index, glycated hemoglobin (HbA1c), and sex-binding globulin (SHBG). The results confirm that LC-MS/MS is slightly more sensitive than IA in the diagnosis of PCOS with LC-MS/MS detecting higher levels of fT and A. Moreover, assessment of fT and A by LC-MS/MS had a similar level of accuracy in discriminating between PCOs and control subjects. Lastly, fT by LC-MS/MS correlates with adverse metabolic parameters.

scholarly journals Monitoring Lipophilic Toxins in Seawater Using Dispersive Liquid—Liquid Microextraction and Liquid Chromatography with Triple Quadrupole Mass Spectrometry

Toxins ◽  
2021 ◽  
Vol 13 (1) ◽  
pp. 57
Author(s):  
Ainhoa Oller-Ruiz ◽  
Natalia Campillo ◽  
Manuel Hernández-Córdoba ◽  
Javier Gilabert ◽  
Pilar Viñas
Keyword(s):  
Mass Spectrometry ◽  
Liquid Chromatography ◽  
Reversed Phase ◽  
Triple Quadrupole ◽  
Relative Standard ◽  
Mar Menor Lagoon ◽  
Lipophilic Toxins ◽  
Seawater Samples ◽  
Dispersive Liquid Liquid Microextraction ◽  
Liquid Microextraction

The use of dispersive liquid–liquid microextraction (DLLME) is proposed for the preconcentration of thirteen lipophilic marine toxins in seawater samples. For this purpose, 0.5 mL of methanol and 440 µL of chloroform were injected into 12 mL of sample. The enriched organic phase, once evaporated and reconstituted in methanol, was analyzed by reversed-phase liquid chromatography with triple-quadrupole tandem mass spectrometry. A central composite design multivariate method was used to optimize the interrelated parameters affecting DLLME efficiency. The absence of any matrix effect in the samples allowed them to be quantified against aqueous standards. The optimized procedure was validated by recovery studies, which provided values in the 82–123% range. The detection limits varied between 0.2 and 5.7 ng L−1, depending on the analyte, and the intraday precision values were in the 0.1–7.5% range in terms of relative standard deviation. Ten water samples taken from different points of the Mar Menor lagoon were analyzed and were found to be free of the studied toxins.

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