Suwannee River Research Articles

Indirect photodegradation of pharmaceutical and personal care products in dissolved black carbon solution: The role of microheterogeneous distribution of hydroxyl radical and sorption

Dissolved black carbon (DBC) with a hyperconjugated structure is ubiquitous in nature, and plays a crucial role in the migration and transformation of environmental contaminants due to its prominent properties of accepting electrons and sorption. However, little is known about the DBC-induced phototransformation of pharmaceutical and personal care products (PPCPs) in natural waters. Herein, the photodegradation kinetics of PPCPs were investigated in DBC solution under simulated solar irradiation and compared with those in Suwannee River natural organic matter (SRNOM) solution. The decay rates for the positively charged PPCPs (mean 1.484 ± 0.041 h-1) were significantly higher than those for the negatively charged PPCPs (mean 0.014 ± 0.002 h-1) in DBC solution due to the charge interaction. Moreover, the decay rates for the positively charged PPCPs in DBC solution were approximately 3–16 times of those in SRNOM solution due to the discrepant sorption and ability to produce bonded HO•. Finally, a microheterogeneous photodegradation mechanism of HO•-labile PPCPs in DBC solution involving the sorption and subsequent reaction with bonded HO• in the DBC microphase was proposed, which was verified using isopropanol and isopropamide as selective HO• scavengers. This work will provide useful insights into the photochemistry of DBC and also the DBC-involved phototransformation of PPCPs in aquatic environments.

Phototransformation and photoreactivity of MPs-DOM in aqueous environment: Key role of MPs structure decoded by optical and molecular signatures

The dissolved organic matter (DOM) derived from microplastics (MPs-DOM) can be one of the photoactive components in DOM. However, information on the properties and photoreactivity of MPs-DOM during phototransformation is limited. Here, we investigated the properties and photoreactivity of MPs-DOM from polyolefins (MPs-DOM-POs), MPs-DOM derived from benzene-containing polymers (MPs-DOM-BCPs), and Suwannee River natural organic matter (SR-NOM), during a 168-hour phototransformation. After phototransformation, all examined types of DOM exhibit a decrease in concentration and molecular weight. Notably, MPs-DOM-POs display increased aromaticity and saturation, while MPs-DOM-BCPs and SR-NOM show reduced aromaticity and saturation. MPs-DOM-POs present higher steady-state concentrations of •OH but much lower steady-state concentrations of 1O2 than those of MPs-DOM-BCPs. In comparison, MPs-DOM produce more •OH but less 1O2 than SR-NOM. This study proposes that the diversification of aliphatic C─H bonds (arylation and carbonylation) by reactive intermediates (especially •OH) is the main pathway for MPs-DOM-POs phototransformation for the first time. On the other hand, the cleavage on the aromatic carboxylic acids by reactive intermediates (especially 1O2) is the main mechanism for MPs-DOM-BCPs and SR-NOM phototransformation. Our findings provide new insights into the phototransformation and photoreactivity of MPs-DOM and help to understand the potential risks of MPs in aqueous environment.

Online LC-Orbitrap MS method for the rapid molecular characterization of dissolved organic matter.

High-resolution mass spectrometry (HRMS) combined with electrospray ionization (ESI) has been the most useful technique for molecular characterization of dissolved organic matter (DOM) derived from diverse sources. However, the comprehensive detection of DOM composition was hindered by ionization suppression observed in ESI sources. HRMS coupled with liquid chromatography (LC) is a potential tool for comprehensive molecular characterization of DOM. The Suwannee River fulvic acids (SRFAs) and two DOM samples from seawater and refinery wastewater extracted by solid phase extraction (SPE) were analyzed by LC-Orbitrap MS coupled with ESI. The mobile phases, solvent composition, and gradient in the LC-Orbitrap MS analysis were optimized. The number of detected molecular formulae of SRFAs by online LC-Orbitrap MS was significantly increased by approximately 40% compared to direct injection. These additional detected compounds are mainly protein and lignin-like compounds, with a low O/C ratio and high H/C ratio. For the SRFAs, the relative standard deviations (%) of reproducibility are 5.51, 2.33, 7.97, and 1.80 for average O/C, H/C, double bond equivalent, and modified aromaticity index, respectively. This study proposed a simple and rapid method based on LC-Orbitrap MS for an in-depth analysis of the molecular composition of DOM, achieving a remarkable analysis time of only 5 min per sample. The rapid method provides a dependable and efficient approach for the molecular characterization of DOM, thereby advancing our comprehension and investigation of DOM across diverse ecosystems.

Unveiling the effects of dissolved organic matter (DOM) extracted from coastal algae and river on the photooxidation of arsenite

The coastal environment is an important ecosystem connecting land and sea, and arsenite (As(III)) in coastal seawater can seriously affect human health through the food chain. However, the effects of dissolved organic matter (DOM) extracted from coastal algae and rivers on As(III) photooxidation remain unclear. Results show that coastal algal DOM (CA-DOM) is significantly more effective than Suwannee River natural organic matter (SRNOM) in photooxidation of As(III), with a rate 8.3 times higher after correcting for light screening effects. CA-DOM accelerates As(III) photooxidation mainly through the 3DOM⁎ pathway, contributing 78.7 % to the process, whereas 3NOM⁎ contributes only 37.2 % for SRNOM. CA-DOM consists primarily of low-excited tyrosine and tryptophan-like protein substances, whereas SRNOM consists of humic and fulvic acid-like substances. Thus, CA-DOM exhibits a higher steady-state concentration of 3DOM⁎, and the 3DOM⁎ reacts much faster with As(III) than the 3NOM⁎. The increase in CA-DOM concentration can significantly accelerate the photooxidation of As(III), whereas the effect of SRNOM concentration is negligible. Increased salinity can accelerate As(III) photooxidation for all types of DOM. Our results provide new insights into the role of DOM from different sources in the photooxidation of As(III) in the natural environment or engineering applications.

Natural organic matter (NOM) can increase the uptake fluxes of three critical metals (Ga, La, Pt) in a unicellular green alga

Critical metals such as gallium, lanthanum and platinum are considered essential in a modern economy and for the required energy transition. Their relatively recent and increasing use in new technologies have led to an increase in their environmental mobility. As they reach aquatic systems, these metals can interact with organic ligands and especially Natural Organic Matter (NOM). The formation of organic complexes would be expected to reduce metal bioavailability and uptake by living cells, according to the Biotic Ligand Model (BLM). However, exceptions to this model have been determined for several critical metals in the past. The present work compared internalization kinetics of Ga, La and Pt in the green alga Chlamydomonas reinhardtii in the presence of NOMs from different origins: humic and fulvic acids from Suwannee River as well as NOMs from Ontario (Bannister Lake and Luther Marsh). Complexation was determined using a partial ultrafiltration method allowing for a normalization of data based on speciation to compare all conditions based on the concentration of the metal that was not bound to NOM. While internalization metal fluxes varied greatly from one NOM source to the other, uptake was almost always significantly higher than expected based on metal speciation. Quite often, metal internalization fluxes were even significantly increased in the presence of NOM, for the same total metal exposure concentration. For instance, Pt internalization was twice greater in the presence of Bannister Lake NOM than it was in the absence of NOM. The assumption that such exceptions could be explained by NOM characteristics was contradicted by the variable results from one metal to another. To further explore this phenomenon, internalization mechanisms for these individual metals need to be elucidated. This is a necessary step to accurately estimate the risk posed by the presence of these metals in humic aquatic systems.

Molecular weight fraction-specific transformation of natural organic matter during hydroxyl radical and sulfate radical oxidation

Aquatic natural organic matter (NOM) is one of the main scavengers of reactive species (e.g., •OH and SO4•−) during oxidation processes and undergoes complex transformations. Here, the organic content, optical properties, and redox state in various MW fractions and bulk Suwannee River NOM (SRNOM) were simultaneously evaluated during •OH and SO4•− oxidation processes for the first time. The SRNOM transformation pathways were specific to radical species and MW fractions, which was evidenced by a proportional decrease in electron-donating moieties and chromophores during •OH oxidation but a higher decrease in electron-donating moieties than chromophores during SO4•− oxidation, particularly in lower MW fractions (<3 kDa). The •OH decomposed reactive moieties mainly via aromatic ring opening or depolymerization in all MW fractions. SO4•− oxidation followed a similar pathway in higher MW fractions (>3 kDa) but mainly formed compounds with UV-absorbing properties (e.g., quinones) in lower MW fractions (<3 kDa). With competitive kinetics and depolymerization model, •OH was quantified as approximately 10 times more reactive towards MW fractions than SO4•−. However, the SO4•− concentrations were approximately 10 times those of •OH, resulting in comparable performance to •OH oxidation. SRNOM depolymerization by •OH and SO4•− resulted in formation of more precursors of disinfection byproducts than the parent constituents, especially for •OH. This work improves our understanding of the transformation of specific SRNOM fractions during radical oxidation processes.

A Simple Model of Flow Reversals in Florida’s Karst Springs

AbstractNorth Florida's karst springs are among the largest and most abundant in the world. Despite relatively stable spring discharges, flow reversals can episodically occur in some springs when river waters backflow into the aquifer during flood events. Reversals are normal features of the springs along the Suwanee River, but the changing incidence of these reversals in response to anthropogenic activities or climate change remains unclear and the mechanisms responsible for these reversals remain poorly described. Here we develop a reduced‐complexity hydrogeological model of the Suwannee River catchment to explore conditions needed to induce spring flow reversals. Our model demonstrates that reversals require two conditions: (a) a hydrogeological setting that combines an upstream catchment with rapid hydrological responses to meteorological drivers, which freely drains to a downstream catchment containing the karst aquifer (i.e., the spring‐fed river segment); and (b) meteorological conditions that create sufficient temporal variability in recharge. Given both conditions, recharge events can propagate from the upstream catchment and fill the downstream river segment faster than it can drain, causing river stage to rise above the aquifer head, resulting in temporary spring flow reversal (or bank storage). Our model accurately predicts significant post‐flood increases in spring flow as bank storage recedes, and using measured electrical conductivity at a major river‐adjacent spring we also quantify the enhancement of limestone dissolution (cave enlargement) due to reversal events. A comprehensive assessment of the incidence and duration of reversal events shows a predominant influence of climate and vegetation changes over that of groundwater pumping.

Humic acid changes effect of naturally occurring oxidants on the environmental transformation of molybdenum disulfide nanosheets

2H-phase molybdenum disulfide (2H-MoS2) has been considered to be a chemically stable two-dimensional (2D) nanomaterial. Nonetheless, the persistence of 2H-MoS2 in the presence of environmental redox-active matrices, such as naturally occurring oxidants (e.g., manganese dioxide (MnO2)) and natural organic matter (NOM), remains largely unknown. Herein, we examined the interplay between 2H-MoS2, MnO2 (a common natural oxidant), and NOM species (i.e., Aldrich humic acid (ALHA) and Suwannee River natural organic matter (SRNOM)). The results show that MnO2 accelerates the oxidative dissolution of 2H-MoS2, regardless of the presence of dissolved oxygen. The effect of NOM on the MnO2-induced fate of 2H-MoS2 was found to depend on its affinity for 2H-MoS2 and the functionality of NOM. ALHA preferentially adsorbed on hydrophobic 2H-MoS2 nanosheets due to the enrichment of reductive polycyclic aromatics and polyphenolic constituents. The preferential ALHA adsorption counteracted the MnO2-triggered oxidative transformation of 2H-MoS2, as revealed by the cathodic response of 2H-MoS2 (i.e., decreased the open circuit potential by 0.0338 V) and the emergence of reductive Mo‒C bonds at 228.8 and 231.9 eV upon the addition of ALHA. This work evaluated the persistence of 2H-MoS2, illustrating its susceptibility to decomposition by naturally occurring oxidants and the influence of NOM on it. These findings are crucial for revealing the fate and transport of MoS2 in aquatic environments and provide guidelines for related applications in natural or engineered systems for MoS2 and potentially other 2D materials.

Molecular characterization of nontarget brominated disinfection byproducts formed during the ozonation in the presence of bromide and ammonium and their potential toxicity implications

While there is extensive literature covering byproducts formed during various water treatment processes, there is limited research focusing on the generation of brominated disinfection byproducts (Br-DBPs) specifically during ozonation in the presence of bromide (Br−) and ammonium (NH4+). This study used Orbitrap mass spectrometry and a custom halogen extraction code to selectively pinpoint 109 Br-DBPs generated during the ozonation of Suwannee River natural organic matter (SRNOM) containing Br− and NH4+. The Br-DBPs are predominantly distributed ranging from m/z 190 to 320, with elemental compositions consisting of CHOBr and CHONBr. They mainly fell within the H/C (0.5–1.5) and O/C (0.2–1.0) zones, with 16 % being aromatic compounds. NH4+ suppressed Br-DBP formation in CHOBr1-2 subgroups but promoted it in CHONBr1-2 subgroups compared to Br−-containing SRNOM ozonation. Kendrick mass defect diagram revealed 64 identical Br-DBP formulas in the CHOBr1-2 subgroups in both systems, and among them, 13 brominated carboxylic acids were identified, whose formation was suppressed by the addition of NH4+. Moreover, bromonitrophenol and bromobenzonitrile were identified in CHONBr1-2 subgroups, and their formation pathways were proposed. Nitrogen-containing Br-DBPs, especially the aromatic nitrogen-containing ones, exhibited higher toxicity. Caution is necessary to minimize toxic Br-DBPs formation during Br− and NH4+-involved ozonation. This study offers insights into Br-DBP characterization, formation mechanisms and toxicity, guiding enhanced water treatment strategies.

Nontargeted Analysis of Reactive Nitrogenous Compounds in Suwannee River Standard Reference Materials and Authentic River Water Samples.

Concerns over toxic nitrogenous disinfection byproducts (N-DBPs) necessitate identifying their precursors in source water. Natural organic amino compounds are known precursors to N-DBPs. Three Suwannee River (SR) standard reference materials (SRMs), humic acids (HA), fulvic acids (FA), and natural organic matter (NOM), are commonly used to study DBP formation, but the chemical makeup of amino compounds in SRSRMs remains largely unknown. To address this, we combined stable hydrogen/deuterium isotope labeling, HDPairFinder bioinformatics, and nontargeted high-performance liquid chromatography-high-resolution mass spectrometry (HPLC-HRMS) to characterize these compounds in SRSRMs. This method classifies reactive amines, provides accurate masses and MS/MS spectra, and quantifies intensities. We identified 2707 high-quality features with primary and/or secondary amines in SRSRMs and 75% of them having an m/z < 300. Across all three SRSRMs, 327 amino features were detected, while 856, 794, and 200 unique features were found in SRNOM, SRHA, and SRFA, respectively. In North Saskatchewan River (NSR) samples, a total of 6449 amino features were detected, 818 of them matched those in SRSRMs, and 87% of them were different between the two rivers. Using chemical standards, we confirmed 10 compounds and tentatively identified 5 more. This study highlights similarities and differences in reactive N-precursors in SRSRMs and local river water, enhancing the understanding of geo-differences in reactive N-precursors in different source waters.

Photolytic Mass Loss of Humic Substances Measured with a Quartz Crystal Microbalance.

Laboratory studies have shown that photolytic mass loss can be a significant sink for secondary organic aerosol (SOA). Here, we use a quartz crystal microbalance to measure mass loss of Suwannee River Humic Acid (SRHA) and Suwannee River Fulvic Acid (SRFA), surrogates for SOA, exposed to 254, 300, and 405 nm radiation over the course of 24 h. We find that the photolytic mass loss rates of these materials are comparable to those for laboratory-generated limonene and toluene SOA material from the study of Baboomian et al, ACS Earth Space Chem. 2020, 4, 1078. Scaling our results to ambient conditions, we estimate that humic substances in aerosols can lose as much as 8% by mass in the first day of exposure in the atmosphere, equivalent to 0.025% of J NO2 , the photolysis rate of nitrogen dioxide. By using zero air instead of nitrogen, we also find that the presence of oxygen accelerates the photolytic mass loss rate by a factor of 2 to 4 at all wavelengths suggesting a potential role for reactive oxygen species. UV photolysis of an aqueous SRFA solution demonstrated both photobleaching at UV wavelengths and photoenhancement at visible wavelengths. Ultrahigh-resolution mass spectrometric analysis showed that condensed-phase SRFA photolysis led to decreased intensity in the 100-300 m/z range while aqueous SRFA photolysis resulted in an increase in intensity in the same range. This work reaffirms that photolytic mass loss is a potentially significant sink for SOA, but only on the time scale of a day or two and demonstrates that SRHA and SRFA are suitable surrogates for atmospheric SOA with respect to photolytic mass loss.

Participation of strong charge-assisted hydrogen bonds in interactions of dissolved organic matter represented by Suwannee River Humic Acid

Terrestrial dissolved organic matter (DOM) plays critical roles in many biotic and abiotic environmental reactions as well as in water treatment. Its structure is therefore of great interest. We examined dissolved Suwannee River Humic Acid (HA) to probe the potential participation of exceptionally strong, negative charge-assisted hydrogen bonds, (−)CAHB, in DOM cohesion and interaction with small weak acids using high performance size exclusion chromatography (HPSEC), transmission electron microscopy, zeta-pH curves, and pH drift experiments. The results support a previously proposed two-tier state of aggregation, in which tightly-knit primary particles (≤ ∼10 kDa) form larger secondary aggregates (up to micrometer in size). Evidence for (−)CAHB is gained through zeta potential changes and pH drift experiments. The primary particles interact with (−)CAHB-capable solutes (simple carboxylic acids and phosphate) but not (−)CAHB-incapable solutes. We identified disruption of intra-segmental and inter-molecular (−)CAHB leading to swelling and disaggregation, as well as formation of nouveau (−)CAHB with free groups on HA. The effects were solute-concentration dependent and greater at pH 5 than pH 6, consistent with CAHB theory. Phosphate induced the greatest shifts in the HPSEC molecular size distribution curves. The shifts were unaffected by prior stripping of innate polyvalent metals. We conclude that the (−)CAHB contributes to the cohesion of DOM, affecting its size and charge, and provides a means by which weak acid pollutants, nutrients, and natural compounds can interact with DOM. Such interactions have implications for the behavior of DOM in the environment, the fate and transport of anthropogenic pollutants, and the roles DOM play in water treatment technologies.

Competitive Binding Kinetics of Methylmercury-Cysteine with Dissolved Organic Matter: Critical Impacts of Thiols on Adsorption and Uptake of Methylmercury by Algae.

Complexes with low-molecular-weight thiols are crucial species of methylmercury (MeHg) excreted by anaerobic Hg-methylating microbes, notably, MeHg-cysteine (MeHg-Cys). As MeHg-Cys diffuses into surface water, it would undergo a ligand exchange process with dissolved organic matter (DOM) under nonsulfidic conditions, inevitably altering MeHg speciation and bioavailability to phytoplankton. In this study, we investigated the competitive binding kinetics between MeHg-Cys and Suwannee River natural organic matter, and their influence on the adsorption and uptake of MeHg by the cyanobacterium, Synechocystis sp. PCC6803. Liquid chromatography-inductively coupled plasma mass spectrometry was employed to monitor the kinetics processes involving competition of DOM with Cys for MeHg binding, which revealed that competitive binding kinetics were dictated by the abundance of thiol moieties in DOM. Thiol concentrations of 0.97 and 49.34 μmol of thiol (g C)-1 resulted in competitive binding rate constant (k values) of 0.30 and 3.47 h-1, respectively. Furthermore, the time-dependent competitive binding of DOM toward MeHg-Cys significantly inhibited MeHg adsorption and uptake by cyanobacteria, an effect that was amplified by an increased thiol abundance in DOM. These findings offer valuable insights into the kinetic characteristics of MeHg's fate and transport, as well as their impact on bioconcentration in aquatic organisms within natural aquatic ecosystems.

Characterization of Low-Molecular-Weight Dissolved Organic Matter Using Optional Dialysis and Orbitrap Mass Spectrometry.

Low-molecular-weight (LMW, <1000 Da) dissolved organic matter (DOM) plays a significant role in metal/organic pollutant complexation, as well as photochemical/microbiological processes in freshwater ecosystems. The micro size and high reactivity of LMW-DOM hinder its precise characterization. In this study, Suwannee River fulvic acid (SRFA), a commonly used reference material for aquatic DOM, was applied to examine the optical features and molecular composition of LMW-DOM by combining membrane separation, ultraviolet-visible absorption and Orbitrap mass spectrometry (MS) characterization. The 100-500 Da molecular weight cut-off (MWCO) membrane had a better performance in regard to separating the tested LMW-DOM relative to the 500-1000 Da MWCO membrane. The ultraviolet-visible absorbance decreased dramatically for the retentates, whereas it increased for the dialysates. Specifically, carbohydrates, lipids and peptides exhibited high selectivity to the 100-500 Da MWCO membrane in early dialysis. Lignins, tannins and condensed aromatic molecules displayed high permeability to the 500-1000 Da MWCO membrane in late dialysis. Overall, the retentates were dominated by aromatic rings and phenolic hydroxyls with high O/Cwa (weighted average of O/C) and low H/Cwa. Conversely, such dialysates had numerous aliphatic chains with high H/Cwa and low O/Cwa compared to SRFA. In particular, LMW-DOM below 200 Da was identified by Orbitrap MS. This work provides an operational program for identifying LMW-DOM based on the SRFA standard and MS analysis.

A Gated TIMS FTICR MS Instrument to Decipher Isomeric Content of Complex Organic Mixtures.

Modern research faces increasingly complex materials with a constant need for new analytical strategies that can provide deeper levels of chemical insight. Ultrahigh resolution mass spectrometry (MS), particularly Fourier transform ion cyclotron resonance (FTICR) MS, has provided a robust analytical foundation. However, MS alone offers limited structural information. Here, we present the first implementation and results from an FTICR MS with fully integrated dual accumulation analysis with gated trapped ion mobility spectrometry (gTIMS) capability. The drastically extended charge capacity and parallel accumulation facilitate the analysis of complex mixtures. We achieved a high dynamic range of 4 orders of magnitude within a single FTICR acquisition event. Simultaneously, the valuable linear relationship between the TIMS elution voltage and reduced mobility was retained over a wide mobility range. Benchmarking the instrument performance with Suwannee River fulvic acid (SRFA) by variable ramp gTIMS analysis allowed separation and unambiguous assignment of different charge state distributions. Application to bio-oils has proven the capability to distinguish the isomeric diversity in these ultracomplex samples, while maintaining the expected FTICR MS resolving power and mass accuracy. Valuable information about the molecular distribution, isomeric diversity, and main molecular differences could directly be extracted within the analysis time of a classical "dilute and shoot" direct infusion experiment. The development of this fully integrated and flexible gTIMS with FTICR MS analysis possesses the potential to significantly change the current landscape of high-resolution mass spectrometric analysis of complex mixtures through the added insight of isomeric complexity afforded by TIMS. The exploration of the added IMS dimension promises transformative effects across diverse fields including energy transition, environmental studies, and biological research.

Influence of Iron and Magnesium on Fouling Properties of Organic Matter Solution in Membrane Process.

Organic matter has been identified as a significant type of foulant in membrane processes for water treatment. Its fouling tendency is highly affected by the presence of ions and inorganics. While the effects of ions addition on organic fouling have been extensively researched in the past, studies on the effect of positively-charged inorganics, such as Fe2+ and Mg2+, on organic fouling are limited. This study investigates the influence of Fe2+ and Mg2+ addition on fouling properties of the Suwannee River Organic Matter (SROM) solution in the MF process, with and without Ca2+ ions. Results showed that increasing the concentration of Fe2+ and Mg2+ from 0-5 mM promoted SROM fouling, and resulted in an increased flux decline up to 33% and 58%, respectively. Cake layer resistance became more dominant with the addition of Fe2+ and Mg2+, and was counted for more than 60% of the fouling. Mg2+, however, caused higher internal pore blocking, and facilitated the formation of a less permeable cake layer, compared to Fe2+. This was evident in the analysis of the cake layer properties and the visualization of the fouling layer. In all cases, SROM fouling with Fe2+ and Mg2+ worsened with the addition of Ca2+ ions. The results of the study indicated the importance of understanding the interaction between organic matter and Fe2+ and Mg2+, which would provide useful insights on their fouling mechanism and control.

Picky Eaters: Carbon Isotopic Evidence for the Uniform Bioavailability of Riverine Dissolved Organic Matter to a Model Marine Microorganism

AbstractDissolved organic matter (DOM) is a key component of the global carbon cycle, with rivers delivering significant amounts of DOM to oceans. Urbanization and agricultural land‐use alter the age and chemical composition of riverine DOM, which likely impact the downstream bioavailability of riverine DOM. Here, we use bioreactor incubations of a marine bacterium (Pseudoalteromonas sp. 3D05) to investigate DOM bioavailability from two distinct rivers: the Suwannee River (natural, non‐urbanized), and the Upper Mississippi River Basin (anthropogenically influenced). We measured rates of microbial CO2 production and radiocarbon ages (as Δ14C) to assess DOM remineralization. We observed nearly identical cell densities and degradation patterns for both riverine DOM incubations. Respired DOM Δ14C values were also similar and decreased over time indicative of preferential utilization of recently synthesized “modern” substrates. These findings reveal unexpected similarities in riverine DOM bioavailability, indicating similar short term biological reactivity despite large DOM compositional differences.

Characterizing Macroporous Ion Exchange Membrane Adsorbers for Natural Organic Matter (NOM) Removal-Adsorption and Regeneration Behavior.

Addressing the characterization of Natural Organic Matter (NOM) removal by functionalized membranes in water treatment, this study evaluates the effectiveness of two commercial ion-exchange membrane adsorbers: Sartobind® Q (with quaternary amines) and D (with tertiary amines). Using Suwannee River NOM (SRNOM) as a surrogate, Langmuir adsorption isotherms revealed maximum capacities (Qmax) of 2966 ± 153 mg C/m2 and 2888 ± 112 mg C/m2, respectively. Variations in flux from 50 to 500 LMH had a minimal impact on breakthrough times, proving low diffusion limitations. The macroporous (3-5 µm) functionalized cellulose-based membranes exhibited high permeabilities of 10,800 L/(h m2 bar). Q maintained positive zeta potential vs. pH, while D's zeta potential decreased above pH 7 due to amine deprotonation and turning negative above an isoelectric point of 9.1. Regeneration with 0.01 M NaOH achieved over 95% DOC regeneration for Sartobind® D, characterizing reversibility through a pH-swing. Cyclic adsorption showed that Q maintained its capacity with over 99% DOC regeneration, while D required acidic conditioning after the first regeneration cycle to mitigate capacity reduction and re-deprotonate the adsorber. These results have demonstrated the potential suitability of adsorber membranes, designed originally for biotechnological purposes, for the possible removal of disinfection byproduct precursors in drinking water treatment.

Inferring the Molecular Basis for Dissolved Organic Matter Photochemical and Optical Properties.

Despite the widespread use of photochemical and optical properties to characterize dissolved organic matter (DOM), a significant gap persists in our understanding of the relationship among these properties. This study infers the molecular basis for the optical and photochemical properties of DOM using a comprehensive framework and known structural moieties within DOM. Utilizing Suwannee River Fulvic Acid (SRFA) as a model DOM, carboxylated aromatics, phenols, and quinones were identified as dominant contributors to the absorbance spectra, and phenols, quinones, aldehydes, and ketones were identified as major contributors to radiative energy pathways. It was estimated that chromophores constitute ∼63% w/w of dissolved organic carbon in SRFA and ∼47% w/w of overall SRFA. Notably, estimations indicate the pool of fluorescent compounds and photosensitizing compounds in SRFA are likely distinct from each other at wavelengths below 400 nm. This perspective offers a practical tool to aid in the identification of probable chemical groups when interpreting optical and photochemical data and challenges the current "black box" thinking. Instead, DOM photochemical and optical properties can be closely estimated by assuming the DOM is composed of a mixture of individual compounds.

Resolving Uncertainties in the Quantification of Trace Elements within Organic-Rich Boreal Rivers for AF4-UV-ICP-MS Analysis.

Over the past few decades, asymmetric flow field-flow fractionation (AF4) has emerged as a robust technique for the separation of colloid-associated trace elements (TEs) in aqueous samples. Nevertheless, little is known about potential artifacts and how to control them when measuring the concentrations of colloid-associated elements at low (μg L-1) or ultralow concentrations (ng L-1) using AF4-UV-ICP-MS. Water from a boreal river was selected as a challenging test material due to its high concentrations of dissolved organic matter (DOM) and Fe-rich colloids. These colloids are expected to be significant contributors to artifact occurrence, even in a metal-free, ultraclean laboratory. The results show that the adsorption of Mn, Co, Ni, Cu, and Pb onto acid-cleaned, non-channel surfaces (such as connection tubing and autosampler) accounted for up to 48% of TE loss. These losses on non-channel surfaces also represent potential sources of cross-contamination for Co, Ni, Cu, and Pb. New, uncleaned poly(ether sulfone) membranes are also sources of contamination for Ni and Cu. Analytical bias may exist in the measured concentrations of TEs, primarily due to the potential carryover of weakly adsorbed TEs (e.g., Ni and Cu) on the system surfaces by colloids in the samples (e.g., DOM). On the other hand, colloids in the samples can also act to gradually remove contaminants from the surfaces. For these types of DOM-rich waters, preconditioning the AF4 system using 40 mg C L-1 of Suwannee River Natural Organic Matter (SRNOM, pH = 7) is recommended to mitigate the impact of membrane fouling and carryover. A comprehensive strategy for minimizing instrumental artifacts is presented and discussed.