Implications of sample treatment on characterization of riverine dissolved organic matter

Aj, Nelson; Toyoda, Jason; Chu, Rosalie K.; Tolić, Nikola; Garayburu‐Caruso, Vanessa; Saup, Casey M.; Renteria, Lupita; Wells, Jacqueline; Stegen, James C.; Wilkins, Michael J.; Danczak, Robert E.

doi:10.1039/d2em00044j

Cited by 8 publications

(10 citation statements)

References 45 publications

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“…MS is consequently sub-optimal for investigating bulk DOM and its biodegradability. SPE is highly important prior to ESI-MS analysis, and cannot be removed as a preparation stepindeed, fewer molecular formulas may be assigned in this case due to lower sample concentrations and competition for electrospray from salts . Studies that aim to characterize biodegradable DOM may require alternative preparative and analytical techniques, for example, focusing on sugar and protein compound classes after ultrafiltration, as this has been successful previously, , and such efforts could be combined with PPL ESI-MS approaches for more complete sample coverage.…”

Section: Resultsmentioning

confidence: 99%

Hydrophilic Species Are the Most Biodegradable Components of Freshwater Dissolved Organic Matter

Grasset,

Groeneveld,

Tranvik

et al. 2023

Environ. Sci. Technol.

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Aquatic dissolved organic matter (DOM) is a crucial component of the global carbon cycle, and the extent to which DOM escapes mineralization is important for the transport of organic carbon from the continents to the ocean. DOM persistence strongly depends on its molecular properties, but little is known about which specific properties cause the continuum in reactivity among different dissolved molecules. We investigated how DOM fractions, separated according to their hydrophobicity, differ in biodegradability across three different inland water systems. We found a strong negative relationship between hydrophobicity and biodegradability, consistent for the three systems. The most hydrophilic fraction was poorly recovered by solid-phase extraction (SPE) (3–28% DOC recovery) and was thus selectively missed by mass spectrometry analysis during SPE. The change in DOM composition after incubation was very low according to SPE–ESI (electrospray ionization)–mass spectrometry (14% change, while replicates had 11% change), revealing that this method is sub-optimal to assess DOM biodegradability, regardless of fraction hydrophobicity. Our results demonstrate that SPE–ESI mass spectrometry does not detect the most hydrophilic and most biodegradable species. Hence, they question our current understanding of the relationships between DOM biodegradability and its molecular composition, which is built on the use of this method.

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Section: Resultsmentioning

confidence: 99%

Hydrophilic Species Are the Most Biodegradable Components of Freshwater Dissolved Organic Matter

Grasset,

Groeneveld,

Tranvik

et al. 2023

Environ. Sci. Technol.

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“…Finally, ionization potential among molecules via ESI is always subjective across a range of DOM sources and matrices, for which we highlight a few key points. First, our study did not compare directly to whole water FTICR-MS as the ability to obtain comparable peak information to SPE samples is limited by additional interferences that impact compound ionization (Nelson et al 2022). As our goal was to extract SPE-based FTICR-MS information across optical signals, the absence of comparable whole water FTICR-MS data does not impede the primary findings of this study.…”

Section: Discussionmentioning

confidence: 99%

“…Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) is another powerful tool capable of resolving thousands of individual molecular formulae in complex DOM mixtures. In this case, direct injection analyses require desalting and extraction of DOM from the original sample matrix (Kujawinski 2002), which can introduce potential biases in the types of DOM identified (Li et al 2016(Li et al , 2017Bahureksa et al 2021;Nelson et al 2022).…”

mentioning

confidence: 99%

Investigating the impacts of solid phase extraction on dissolved organic matter optical signatures and the pairing with high‐resolution mass spectrometry data across a freshwater stream network

Roebuck Jr,

Myers‐Pigg,

Garayburu‐Caruso

et al. 2024

Limnology & Ocean Methods

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Advancing our understanding of dissolved organic matter (DOM) chemistry in aquatic systems necessitates the integration of data streams from multiple analytical platforms. Some measurements require pretreatment with solid phase extraction (SPE), while others are performed directly on whole water samples. Evidence has suggested that SPE will be biased against select DOM fractions, leading to concerns over the ability to establish data linkages across platforms with variable needs for SPE pretreatment, such as those from optical measurements and those that provide high‐resolution molecular information. Here, we directly addressed this concern by assessing the impact of SPE on DOM optical properties through excitation–emission matrices with parallel factor analysis (PARAFAC) for 47 samples across a stream network within a single watershed reflective of variable DOM sources. PARAFAC data was further paired with molecular information obtained by Fourier transform ion cyclotron resonance mass spectrometry (FTICR‐MS). A comparison of PARAFAC models first revealed no systematic qualitative differences in major components between whole water DOM and DOM isolated by SPE (SPE‐DOM); however, quantitative biases against select components were observed. Further linkages with FTICR‐MS data revealed that the molecular fingerprint associated with each PARAFAC component was consistent between the whole water DOM and SPE‐DOM. Our results suggest that bulk scale linkages across these analytical platforms could be inferred irrespective of the observed quantitative biases resulting from SPE for samples within this example watershed. This work represents a key step toward the systematic evaluation of linkages between optical and high‐resolution mass spectrometry datasets in freshwater lotic environments.

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“…Subsequently, the obvious low mass error formula [C 14 H 24 O 4 Na] + was assigned to this peak (mass error = 74 ppb) with this assignment supported by the significantly higher (p < 0.05) intensity deviation of 13 C-isotopic peaks (Figure S3). Therefore, in addition to the isotopic refining (using 13 C, 34 S, 41 K, 18 O, and 15 N patterns) and the empirical rule of selecting a formula with a lower number of N + S + P for natural organic matter, 12 the minimum mass error is important in assigning optimal formulae for ESI(+)-FT-ICR MS peaks and has been considered in this adduct analysis algorithm (the fifth selection in Figure 1).…”

Section: Si Si Intenmentioning

confidence: 99%

“…The FT-ICR MS technique operated in both ESI(−) and ESI(+) modes has been employed to characterize DOM from soils, aerosol, lignin products, and surface water. ,,− However, there is a paucity of comparative characterization by UHR-MS in both ionization modes for DOM from groundwater, which is one of the most DOM-rich ecosystems and contributes 13 Tg carbon to the surface water system . Additionally, as one of the most ubiquitous components in aquatic systems, DOM impacts the fate and transformation of some inorganic contaminants coexisting in the same environments, such as halogen and heavy metal species.…”

Section: Introductionmentioning

confidence: 99%

Complementary Elucidation of the Molecular Characteristics of Groundwater Dissolved Organic Matter Using Ultrahigh-Resolution Mass Spectrometry Coupled with Negative- and Positive-Ion Electrospray Ionization

Zhou

Fujii

et al. 2023

Environ. Sci. Technol.

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The formula assignment of the Fourier transform ion cyclotron resonance mass spectrometry coupled with positive-ion electrospray ionization [ESI(+)-FT-ICR MS] is challenging because of the extensive occurrence of adducts. However, there is a paucity of automated formula assignment methods for ESI(+)-FT-ICR MS spectra. The novel automated formula assignment algorithm for ESI(+)-FT-ICR MS spectra developed herein has been applied to elucidate the composition of dissolved organic matter (DOM) in groundwater during air-induced ferrous [Fe(II)] oxidation. The ESI(+)-FT-ICR MS spectra of groundwater DOM were profoundly impacted by [M + Na]+ adducts and, to a lesser extent, [M + K]+ adducts. Oxygen-poor and N-containing compounds were frequently detected when the FT-ICR MS was operated in the ESI(+) mode, while the components with higher carbon oxidation states were preferentially ionized in the negative-ion electrospray ionization [ESI(−)] mode. Values for the difference between double-bond equivalents and the number of oxygen atoms from −13 to 13 are proposed for the formula assignment of the ESI(+)-FT-ICR MS spectra of aquatic DOM. Furthermore, for the first time, the Fe(II)-mediated formation of highly toxic organic iodine species was reported in groundwater rich in Fe(II), iodide, and DOM. The results of this study not only shed light on the further algorithm development for comprehensive characterization of DOM by ESI(−)-FT-ICR MS and ESI(+)-FT-ICR MS but also highlight the importance of appropriate treatment of specific groundwater prior to use.

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Implications of sample treatment on characterization of riverine dissolved organic matter

Abstract: High-resolution mass spectrometry techniques are widely used in the environmental sciences to characterize natural organic matter and, when utilizing these instruments, researchers must make multiple decisions regarding sample pre-treatment and...

Cited by 8 publications

References 45 publications

Hydrophilic Species Are the Most Biodegradable Components of Freshwater Dissolved Organic Matter

Hydrophilic Species Are the Most Biodegradable Components of Freshwater Dissolved Organic Matter

Investigating the impacts of solid phase extraction on dissolved organic matter optical signatures and the pairing with high‐resolution mass spectrometry data across a freshwater stream network

Complementary Elucidation of the Molecular Characteristics of Groundwater Dissolved Organic Matter Using Ultrahigh-Resolution Mass Spectrometry Coupled with Negative- and Positive-Ion Electrospray Ionization

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