The use of fluorescence spectrometry has been suggested as a simple method to determine the extent of natural organic matter humification by quantifying the red-shifting of fluorescence emission that occurs with increasing humification. Humification indices are calculated by dividing fluorescence intensity at longer wavelengths by intensity at shorter wavelengths. These indices calculated without any specific efforts to standardize dissolved organic matter (DOM) concentration will result in index values thatvary with DOM concentration due to fluorescence innerfiltering effects. This study critically evaluated the effect of DOM concentration on humification index determination using organic matter isolated from field corn extract, soil: water extract, and soil fulvic acid. The results show that humification index values are sensitive to DOM concentration of the solution and are linear with respect to transmittance of the solution at the 254 nm used as the excitation wavelength. An approximate correction for DOM is to exploit the linear nature of the regression fit and to determine index values at the extrapolated 100% transmittance value. An exact correction using explicit correction factors for both primary and secondary innerfiltration effects was shown to give humification index values that are concentration invariant when absorbance of the solution at 254 nm was less than approximately 0.3 unit. Defining the humification index as the fluorescence intensity in the 300-345 nm region divided by the sum of intensity in the 300-345 nm and 435-480 nm regions was statistically advantageous. This study suggests that for quantitative results which can be used to compare humification of natural organic matter across different studies, correction of the fluorescence emission spectra for innerfiltration effects is needed.

A sensitive method is needed to analyze soil‐water extracts that contain P at submicromolar concentrations. The proposed spectrophotometric method, based on the ionic association of malachite green with phosphomolybdate under acidic conditions, was evaluated on soil extracts. The molar absorptivity was 64641 ± 743 L mol−1 cm−1. Absorbance of the reagent blank was 0.069 ± 0.004. With 1‐cm path length cells and limiting absorbance of 0.004, the detection limit calculated from the Beer‐Lambert equation was 6.7 × 10−8 M orthophosphate P. Recovery of added P in saturated paste extracts averaged 91% with a range of 87 to 94% and averaged 101% with a range of 93 to 109% for 1:1 soil/water extract. The method was successfully applied to saturated paste extracts from soils of varied organic matter content and pH. The proposed malachite green method allows for P determination in restricted volume samples and at concentrations too low for the standard Murphy‐Riley method.

Dissolved organic matter (DOM) plays an important role in many soil ecosystem functions. Multidimensional fluorescence spectroscopy of DOM with parallel factor analysis (PARAFAC) of the resulting spectral landscape has been successful in characterizing DOM from a variety of aquatic sources. This study was conducted to assess the multiway PARAFAC approach for quantitatively characterizing the fluorescent landscapes of DOM from aqueous extracts of soils and soil amendments. The DOM was extracted from plant biomass representative of crop, wetlands, and tree species; animal manures; and soils from controlled studies of cropping systems with known histories of organic amendments. The fluorescence landscape spectra were collected in the excitation range from 240 to 400 nm and emission range from 300 to 500 nm in 3‐nm increments. The excitation and emission spectra modeled from the PARAFAC analysis showed that the plant biomass, animal manure, and soil DOM contained five fluorescing components: tryptophan‐like (peak location at excitation 270 nm, emission 354 nm), tyrosine‐like (273/309 nm), and three humic‐substance‐like components (>240/465 nm, 306/405 nm, and 315/447 nm). Principal component analysis of the concentration loading showed that the soil‐derived DOM was very similar despite the different types and quantities of organic amendments incorporated in the different cropping systems. This study shows that PARAFAC analysis of multidimensional fluorescence spectra can model the chemical profile of terrestrial DOM in a chemically meaningful way. This represents a significant advance over current approaches to interpreting the complex DOM fluorescence spectra.

Iron (Fe)-bearing mineral phases contribute disproportionately to adsorption of soil organic matter (SOM) due to their elevated chemical reactivity and specific surface area (SSA). However, the spectrum of Fe solid-phase speciation present in oxidation-reduction-active soils challenges analysis of SOM-mineral interactions and may induce differential molecular fractionation of dissolved organic matter (DOM). This work used paired selective dissolution experiments and batch sorption of postextraction residues to (1) quantify the contributions of Fe-bearing minerals of varying crystallinity to DOM sorption, and (2) characterize molecular fractionation using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). A substantial proportion of soil SSA was derived from extracted Fe-bearing phases, and FT-ICR-MS analysis of extracted DOM revealed distinct chemical signatures across Fe-OM associations. Sorbed carbon (C) was highly correlated with Fe concentrations, suggesting that Fe-bearing phases are strong drivers of sorption in these soils. Molecular fractionation was observed across treatments, particularly those dominated by short-range-order (SRO) mineral phases, which preferentially adsorbed aromatic and lignin-like formulas, and higher-crystallinity phases, associated with aliphatic DOM. These findings suggest Fe speciation-mediated complexation acts as a physicochemical filter of DOM moving through the critical zone, an important observation as predicted changes in precipitation may dynamically alter Fe crystallinity and C stability.

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The chemical properties of organic matter affect important soil processes such as speciation, solubilization, and transport of plant nutrients and metals. This work uses ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry to determine the molecular composition of three organic matter fractions of soils and aqueous extracts of crop biomass. Comparison of the van Krevelen plots allowed tracking the changes in organic matter with increasing humification. Aqueous plant biomass extracts contain a diverse mixture of lipids, proteins, and lignins. Soil aqueous extracts were marked by increases in lignin and carbohydrate components and decrease in the protein component as compared to the plant extract. Refractory humic acid fractions were marked by decrease in the lignin component and increases in the lipid and condensed aromatic components. The multivariate indicator species analysis was used to identify marker components of the four organic matter types investigated. The plant extract group had 772 marker components compared to 237 for soil aqueous extract, 92 for mobile humic acid, and 418 for calcium humic acid. This study demonstrates that ultrahigh resolution mass spectrometry and multivariate methods can be used to identify marker components to gain a molecular-scale description and understanding of C dynamics.

Organic matter-metal complexes in soil solution and aquatic systems are involved in important environmental and ecological processes such as plant nutrient availability and the solubilization and transport of metals. Our work presented here extends the use of fluorescence spectrometry for determining conditional stability constants for such complexes. We combine the use of excitation-emission matrix (EEM) fluorescence spectrometry and parallel factor analysis (PARAFAC) to determine the stability constants of the chemically meaningful components modeled by PARAFAC. Water-soluble organic matter (WSOM) from O-horizon soils of deciduous and coniferous forest stands were extracted and titrated at pH = 4.7 with iron(lll) (Fe) and aluminum (Al) which are important metals in acid soil systems. The EEM spectra were then recorded and PARAFAC analysis showed that the WSOM contained three humic-substance-like components. Fe titration led to fluorescence quenching of the three components, while Al titration enhanced fluorescence for two components and quenched one of the components. The average Ryan-Weber stability constants at pH 4.7 ranged from log K of 4.28 to 4.91 for Fe and 4.84 to 5.96 for Al. The conditional stability constants were similar for Fe binding for deciduous and coniferous stand-derived WSOM, while they were stronger for Al binding with coniferous stand-derived WSOM. This difference in binding strengths for Al may affect the chemical behavior of Al in soil and aquatic systems. Determining the individual binding parameters of organic matter components with metals represents a significant advance over current approaches that utilize fluorescence quenching at a single excitation-emission wavelength pair to characterize organic matter-metal interactions.

While the importance of organic matter adsorption onto reactive iron-bearing mineral surfaces to carbon stabilization in soils and sediments has been wellestablished, fundamental understanding of how compounds assemble at the mineral interface remains elusive. Organic matter is thought to layer sequentially onto the mineral surface, forming molecular architecture stratified by bond strength and compound polarity. However, prominent complexation models lack experimental backing, despite the role of such architecture in fractionated, compound-dependent persistence of organic matter and modulating future perturbations in mineral stabilization capacity. Here, we use kinetic assays and ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry under high temporal frequency to directly detect the molecular partitioning of organic matter onto an iron oxyhydroxide during adsorption. We observed three sequential intervals of discrete molecular composition throughout the adsorption reaction, in which rapid primary adsorption of aromatic compounds was followed by secondary lignin-like and tertiary aliphatic compounds. These findings, paired with observed differential fractionation along formulas nitrogen and oxygen content and decreasing selective sorption with reaction time, support "zonal" assembly models. This work presents direct detection of sequential molecular assembly of organic matter at the mineral interface, an important yet abstruse regulator of carbon stabilization and composition across temporal and spatial scales.