High-Resolution Tandem Mass Spectrometry-Based Analysis of Model Lignin-Iron Complexes: Novel Pipeline and Complex Structures.

Understanding the chemical nature of soil organic carbon (SOC) with great potential to bind iron (Fe) minerals is critical for predicting the stability of SOC. Organic ligands of Fe are among the top candidates for SOCs able to strongly sorb on Fe minerals, but most of them are still molecularly uncharacterized. To shed insights into the chemical nature of organic ligands in soil and their fate, this study developed a protocol for identifying organic ligands using ultrahigh-performance liquid chromatography-high-resolution tandem mass spectrometry (UHPLC-HRMS/MS) and metabolomic tools. The protocol was used for investigating the Fe complexes formed by model compounds of lignin-derived organic ligands, namely, caffeic acid (CA), p-coumaric acid (CMA), vanillin (VNL), and cinnamic acid (CNA). Isotopologue analysis of 54/56Fe was used to screen out the potential UHPLC-HRMS (m/z) features for complexes formed between organic ligands and Fe, with multiple features captured for CA, CMA, VNL, and CNA when 35/37Cl isotopologue analysis was used as supplementary evidence for the complexes with Cl. MS/MS spectra, fragment analysis, and structure prediction with SIRIUS were used to annotate the structures of mono/bidentate mono/biligand complexes. The analysis determined the structures of monodentate and bidentate complexes of FeLxCly (L: organic ligand, x = 1-4, y = 0-3) formed by model compounds. The protocol developed in this study can be used to identify unknown organic ligands occurring in complex environmental samples and shed light on the molecular-level processes governing the stability of the SOC.

Relating Molecular Properties to the Persistence of Marine Dissolved Organic Matter with Liquid Chromatography-Ultrahigh-Resolution Mass Spectrometry.

Marine dissolved organic matter (DOM) contains a complex mixture of small molecules that eludes rapid biological degradation. Spatial and temporal variations in the abundance of DOM reflect the existence of fractions that are removed from the ocean over different time scales, ranging from seconds to millennia. However, it remains unknown whether the intrinsic chemical properties of these organic components relate to their persistence. Here, we elucidate and compare the molecular compositions of distinct DOM fractions with different lability along a water column in the North Atlantic Gyre. Our analysis utilized ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry at 21 T coupled to liquid chromatography and a novel data pipeline developed in CoreMS that generates molecular formula assignments and metrics of isomeric complexity. Clustering analysis binned 14 857 distinct molecular components into groups that correspond to the depth distribution of semilabile, semirefractory, and refractory fractions of DOM. The more labile fractions were concentrated near the ocean surface and contained more aliphatic, hydrophobic, and reduced molecules than the refractory fraction, which occurred uniformly throughout the water column. These findings suggest that processes that selectively remove hydrophobic compounds, such as aggregation and particle sorption, contribute to variable removal rates of marine DOM.

Quantitative Separation of Unknown Organic-Metal Complexes by Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry.

Dissolved organic matter (DOM) is widely recognized to control the solubility and reactivity of trace metals in the environment. However, the mechanisms that govern metal-DOM complexation remain elusive, primarily due to the analytical challenge of fractionating and quantifying metal-organic species within the complex mixture of organic compounds that comprise DOM. Here, we describe a quantitative method for fractionation and element-specific detection of organic-metal complexes using liquid chromatography with online inductively coupled plasma mass spectrometry (LC-ICP-MS). The method implements a post-column compensation gradient to stabilize ICP-MS elemental response across the LC solvent gradient, thereby overcoming a major barrier to achieving quantitative accuracy with LC-ICP-MS. With external calibration and internal standard correction, the method yields concentrations of organic-metal complexes that were consistently within 6% of their true values, regardless of the complex's elution time. We used the method to evaluate the effects of four stationary phases (C18, phenyl, amide, and pentafluoroylphenyl propyl) on the recovery and separation of environmentally relevant trace metals (Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb) in Suwannee River Fulvic Acid and Suwannee River Natural Organic Matter. The C18, amide, and phenyl phases generally yielded optimal metal recoveries (>75% for all metals except Pb), with the phenyl phase separating polar species to a greater extent than C18 or amide. We also fractionated organic-bound Fe, Cu, and Ni in oxidized and reduced soils, revealing divergent metal-DOM speciation across soil redox environments. By enabling quantitative fractionation of DOM-bound metals, our method offers a means for advancing a mechanistic understanding of metal-organic complexation throughout the environment.

Seasonal Oxygenation of Contaminated Floodplain Soil Releases Zn to Porewater.

Soil zinc contamination is a major threat to water quality and sensitive ecosystems. While Zn itself is not redox-active in soils, transitions in soil redox conditions may promote mobilization of Zn from common Zn hosts, including Mn(IV)/Fe(III)-(hydr)oxides and sulfide precipitates, leading to elevated concentrations of dissolved Zn in surface and groundwater and thus a potential increase in Zn transport and uptake. Here, we examined the impacts of hydrologic fluctuations and coupled redox transitions on Zn partitioning in contaminated riparian soil in a mountain watershed. We found that oxygenation of the soil profile during low water conditions caused a spike in porewater Zn concentrations, driven by oxidative dissolution of amorphous ZnS and weak partitioning of Zn to Fe(III)-(hydr)oxides, hydroxy-interlayer vermiculite, and vermiculite. In contrast to Pb, released Zn did not immediately adsorb to Fe(III)-(hydr)oxides or particulate organic matter due to less-favorable sorption of Zn than that of Pb and, further, decreased Zn sorption at slightly acidic pH. As aridification intensifies and groundwater levels decline throughout the western United States, contaminated floodplain soils in mountain watersheds may be frequently oxygenated, leading to increased mobilization of dissolved Zn, which will amplify the threat Zn poses to water quality and ecosystem health.

Redox Properties of Solid Phase Electron Acceptors Affect Anaerobic Microbial Respiration under Oxygen-Limited Conditions in Floodplain Soils.

Mountain floodplain soils often show spatiotemporal variations in redox conditions that arise due to changing hydrology and resulting biogeochemistry. Under oxygen-depleted conditions, solid phase terminal electron acceptors (TEAs) can be used in anaerobic respiration. However, it remains unclear to what degree the redox properties of solid phases limit respiration rates and hence organic matter degradation. Here, we assess such limitations in soils collected across a gradient in native redox states from the Slate River floodplain (Colorado, U.S.A.). We incubated soils under anoxic conditions and quantified CO2 production and microbial Fe(III) reduction, the main microbial metabolic pathway, as well as the reactivity of whole-soil solid phase TEAs toward mediated electrochemical reduction. Fe(III) reduction occurred together with CO2 production in native oxic soils, while neither Fe(II) nor CO2 production was observed in native anoxic soils. Initial CO2 production rates increased with increasing TEA redox reactivity toward mediated electrochemical reduction across all soil depths. Low TEA redox reactivity appears to be caused by elevated Fe(II) concentrations rather than crystallinity of Fe(III) phases. Our findings illustrate that the buildup of Fe(II) in systems with long residence times limits the thermodynamic viability of dissimilatory Fe(III) reduction and thereby limits the mineralization of organic carbon.

Porewater Lead Concentrations Limited by Particulate Organic Matter Coupled With Ephemeral Iron(III) and Sulfide Phases during Redox Cycles Within Contaminated Floodplain Soils.

Lead contamination in soils and sediments is a major threat to water quality. In surface and near-surface environments, Pb is not redox active; however, common Pb hosts, including Fe(III)-(hydr)oxides and sulfides, dissolve and precipitate as redox conditions change. Dissolution of Pb hosts may release Pb to porewater, leading to spikes in dissolved Pb concentrations and potential transport into surface or groundwater. Here, we examine the impacts of hydrologically coupled redox transitions on Pb partitioning in contaminated floodplain soils. We find that the affinity of Pb for particulate organic matter (POM), inclusive of mineral-associated organic matter, ensures that across redox transitions Pb is retained in the solid phase, despite host-phase (Fe(III)-(hydr)oxide and sulfide) dissolution. As seasonal hydrologic dynamics shift porewater redox conditions, Pb-bearing Fe(III)-(hydr)oxides (Pb-HFO) and sulfides (PbS) are dissolved and (re)precipitated. However, despite these shifts in redox conditions and associated host-phase transformations, Pb retention on POM, coupled with the formation of PbS and Pb-HFO, maintains dissolved Pb concentrations below 17 µg L-1. Importantly, the predominance of Pb adsorbed on POM alongside low dissolved Pb concentrations indicates that Pb released from HFO and PbS is retained by POM. Thus, despite host-phase dissolution during redox transitions, partitioning of Pb to the aqueous phase is minimal and, therefore, transport of dissolved Pb is unlikely.

Calcium-Uranyl-Carbonato Species Kinetically Limit U(VI) Reduction by Fe(II) and Lead to U(V)-Bearing Ferrihydrite.

Reaction conditions and mechanisms promoting or inhibiting U reduction exert a central control on U solubility and, therefore, U transport and its associated risks. Here, we vary and track common aqueous uranium species to show that a kinetic restriction inhibits homogeneous reduction of the calcium-uranyl-carbonato species (CaUO2(CO3)32- and Ca2UO2(CO3)3) by Fe(II)(aq), while ferrihydrite surface-catalyzed reduction of all aqueous uranyl by Fe(II) proceeds. Using U L3 high energy resolution fluorescence detection (HERFD) X-ray absorption near edge structure (XANES) spectroscopy, U L3 extended X-ray absorption fine structure (EXAFS) spectroscopy, and transmission electron microscopy (TEM), we also show that U(V) is generated and incorporated into ferrihydrite formed from homogeneous U(VI) reduction by Fe(II)(aq). Through elucidation of the mechanisms that inhibit reduction of the calcium-uranyl-carbonato species and promote stabilization of U(V), we advance our understanding of the controls on U solubility and thus improve prediction of U transport in surface and subsurface systems.

Beaver dams overshadow climate extremes in controlling riparian hydrology and water quality.

Hydrologic extremes dominate chemical exports from riparian zones and dictate water quality in major river systems. Yet, changes in land use and ecosystem services alongside growing climate variability are altering hydrologic extremes and their coupled impacts on riverine water quality. In the western U.S., warming temperatures and intensified aridification are increasingly paired with the expanding range of the American beaver-and their dams, which transform hydrologic and biogeochemical cycles in riparian systems. Here, we show that beaver dams overshadow climatic hydrologic extremes in their effects on water residence time and oxygen and nitrogen fluxes in the riparian subsurface. In a mountainous watershed in Colorado, U.S.A., we find that the increase in riparian hydraulic gradients imposed by a beaver dam is 10.7-13.3 times greater than seasonal hydrologic extremes. The massive hydraulic gradient increases hyporheic nitrate removal by 44.2% relative to seasonal extremes alone. A drier, hotter climate in the western U.S. will further expand the range of beavers and magnify their impacts on watershed hydrology and biogeochemistry, illustrating that ecosystem feedbacks to climate change will alter water quality in river systems.