Water monitoring with an automated smart sensor supported with solar power for real-time and long range detection of ferrous iron.

Low-power and smart sensing systems for iron detection are necessary for in situ monitoring of water quality. Here, a potentiometric Fe2+-selective electrode (ISE) was fabricated based on cyanomethyl N-methyl-N-phenyl dithiocarbamate for the first time as an ionophore. Under optimal conditions, the ISE showed a Nernstian slope of 29.76 ± 0.6 mV per decade for Fe2+ ions over a wide concentration range from 1.0 × 10-1 to 1.0 × 10-5 M with a lower detection limit (LOD) of 1.0 × 10-6 M. The ISE interference of various cations on the potentiometric response was also investigated. The ISE had a response time less than 3 s and the lifetime was two months. Also, an automated, long-range (LoRa), wireless enabled sampling microfluidic device powered with a solar panel as an autonomous power source was developed for a continuous sampling and sensing process. The sensing platform was employed in the determination of Fe2+ in acid mine drainage and spiked water samples with an average recovery of 100.7%. This simple, inexpensive (below $350), portable sensing platform will allow for rapid real-time monitoring of ground-, drinking-, and industrial waters contaminated with iron.

Multitask Deep Learning Enabling a Synergy for Cadmium and Methane Mitigation with Biochar Amendments in Paddy Soils.

Biochar has demonstrated significant promise in addressing heavy metal contamination and methane (CH4) emissions in paddy soils; however, achieving a synergy between these two goals is challenging due to various variables, including the characteristics of biochar and soil properties that influence biochar's performance. Here, we successfully developed an interpretable multitask deep learning (MTDL) model by employing a tensor tracking paradigm to facilitate parameter sharing between two separate data sets, enabling a synergy between Cd and CH4 mitigation with biochar amendments. The characteristics of biochar contribute similar weightings of 67.9% and 62.5% to Cd and CH4 mitigation, respectively, but their relative importance in determining biochar's performance varies significantly. Notably, this MTDL model excels in custom-tailoring biochar to synergistically mitigate Cd and CH4 in paddy soils across a wide geographic range, surpassing traditional machine learning models. Our findings deepen our understanding of the interactive effects of Cd and CH4 mitigation with biochar amendments in paddy soils, and they also potentially extend the application of artificial intelligence in sustainable environmental remediation, especially when dealing with multiple objectives.

Fire Impacts on the Soil Metabolome and Organic Matter Biodegradability.

Global wildfire activity has increased since the 1970s and is projected to intensify throughout the 21st century. Wildfires change the composition and biodegradability of soil organic matter (SOM) which contains nutrients that fuel microbial metabolism. Though persistent forms of SOM often increase postfire, the response of more biodegradable SOM remains unclear. Here we simulated severe wildfires through a controlled "pyrocosm" approach to identify biodegradable sources of SOM and characterize the soil metabolome immediately postfire. Using microbial amplicon (16S/ITS) sequencing and gas chromatography-mass spectrometry, heterotrophic microbes (Actinobacteria, Firmicutes, and Protobacteria) and specific metabolites (glycine, protocatechuate, citric cycle intermediates) were enriched in burned soils, indicating that burned soils contain a variety of substrates that support microbial metabolism. Molecular formulas assigned by 21 T Fourier transform ion cyclotron resonance mass spectrometry showed that SOM in burned soil was lower in molecular weight and featured 20 to 43% more nitrogen-containing molecular formulas than unburned soil. We also measured higher water extractable organic carbon concentrations and higher CO2 efflux in burned soils. The observed enrichment of biodegradable SOM and microbial heterotrophs demonstrates the resilience of these soils to severe burning, providing important implications for postfire soil microbial and plant recolonization and ecosystem recovery.

Determination of Soil Contamination at the Wildland-Urban Interface after the 2021 Marshall Fire in Colorado, USA.

Wildfires at the wildland-urban interface (WUI) are increasingly common. The impacts of such events are likely distinct from those that occur strictly in wildland areas, as we would expect an elevated likelihood of soil contamination due to the combustion of anthropogenic materials. We evaluated the impacts of a wildfire at the WUI on soil contamination, sampling soils from residential and nonresidential areas located inside and outside the perimeter of the 2021 Marshall Fire in Colorado, USA. We found that fire-affected residential properties had elevated concentrations of some heavy metals (including Zn, Cu, Cr, and Pb), but the concentrations were still below levels of likely concern, and we observed no corresponding increases in concentrations of polycyclic aromatic hydrocarbons (PAHs). The postfire increases in metal concentrations were not generally observed in the nonresidential soils, highlighting the importance of combustion of anthropogenic materials for potential soil contamination from wildfires at the WUI. While soil contamination from the 2021 Marshall Fire was lower than expected, and likely below the threshold of concern for human health, our study highlights some of the challenges that need to be considered when assessing soil contamination after such fires.

Iron Vacancy Accelerates Fe(II)-Induced Anoxic As(III) Oxidation Coupled to Iron Reduction.

Chemical oxidation of As(III) by iron (Fe) oxyhydroxides has been proposed to occur under anoxic conditions and may play an important role in stabilization and detoxification of As in subsurface environments. However, this reaction remains controversial due to lack of direct evidence and poorly understood mechanisms. In this study, we show that As(III) oxidation can be facilitated by Fe oxyhydroxides (i.e., goethite) under anoxic conditions coupled with the reduction of structural Fe(III). An excellent electron balance between As(V) production and Fe(III) reduction is obtained. The formation of an active metastable Fe(III) phase at the defective surface of goethite due to atom exchange is responsible for the oxidation of As(III). Furthermore, the presence of defects (i.e., Fe vacancies) in goethite can noticeably enhance the electron transfer (ET) and atom exchange between the surface-bound Fe(II) and the structural Fe(III) resulting in a two time increase in As(III) oxidation. Atom exchange-induced regeneration of active goethite sites is likely to facilitate As(III) coordination and ET with structural Fe(III) based on electrochemical analysis and theoretical calculations showing that this reaction pathway is thermodynamically and kinetically favorable. Our findings highlight the synergetic effects of defects in the Fe crystal structure and Fe(II)-induced catalytic processes on anoxic As(III) oxidation, shedding a new light on As risk management in soils and subsurface environments.

Incorporation of Cu into Goethite Stimulates Oxygen Activation by Surface-Bound Fe(II) for Enhanced As(III) Oxidative Transformation.

The dark production of reactive oxygen species (ROS) coupled to biogeochemical cycling of iron (Fe) plays a pivotal role in controlling arsenic transformation and detoxification. However, the effect of secondary atom incorporation into Fe(III) oxyhydroxides on this process is poorly understood. Here, we show that the presence of oxygen vacancy (OV) as a result of Cu incorporation in goethite substantially enhances the As(III) oxidation by Fe(II) under oxic conditions. Electrochemical and density functional theory (DFT) evidence reveals that the electron transfer (ET) rate constant is enhanced from 0.023 to 0.197 s-1, improving the electron efficiency of the surface-bound Fe(II) on OV defective surfaces. The cascade charge transfer from the surface-bound Fe(II) to O2 mediated by Fe(III) oxyhydroxides leads to the O-O bond of O2 stretching to 1.46-1.48 Šequivalent to that of superoxide (•O2-), and •O2- is the predominant ROS responsible for As(III) oxidation. Our findings highlight the significant role of atom incorporation in changing the ET process on Fe(III) oxyhydroxides for ROS production. Thus, such an effect must be considered when evaluating Fe mineral reactivity toward changing their surface chemistry, such as those noted here for Cu incorporation, which likely determines the fates of arsenic and other redox sensitive pollutants in the environments with oscillating redox conditions.

Agricultural Sulfur Applications Alter the Quantity and Composition of Dissolved Organic Matter from Field-to-Watershed Scales.

Over the past several decades, agricultural sulfur (S) use has dramatically increased. Excess S in the environment can cause several biogeochemical and ecologic consequences, including methylmercury production. This study investigated agriculturally associated changes to organic S─the most dominant form of S within soils─from field-to-watershed scales. Using a novel complementary suite of analytical methods, we combined Fourier transform ion cyclotron resonance mass spectrometry, δ34S-DOS, and S X-ray absorption spectroscopy to characterize dissolved organic S (DOS) in soil porewater and surface water samples from vineyard agriculture (S addition) and forest/grassland areas (no S addition) within the Napa River watershed (California, U.S.). Vineyard soil porewater dissolved organic matter samples had two-fold higher S content compared to forest/grasslands and had unique CHOS2 chemical formulas─the latter also found in tributary and Napa River surface water. The isotopic difference between δ34S-DOS and δ34S-SO42- values provided insights into the likely dominant microbial S processes by land use/land cover (LULC), whereas the S oxidation state did not strongly differ by LULC. The results add to our understanding of the modern S cycle and point to upland agricultural areas as S sources with the potential for rapid S transformations in downgradient environments.

Persisting Effects in Daphnia magna Following an Acute Exposure to Flowback and Produced Waters from the Montney Formation.

Hydraulic fracturing extracts oil and gas through the injection of water and proppants into subterranean formations. These injected fluids mix with the host rock formation and return to the surface as a complex wastewater containing salts, metals, and organic compounds, termed flowback and produced water (FPW). Previous research indicates that FPW is toxic to Daphnia magna (D. magna), impairing reproduction, molting, and maturation time; however, recovery from FPW has not been extensively studied. Species unable to recover have drastic impacts on populations on the ecological scale; thus, this study sought to understand if recovery from an acute 48 h FPW exposure was possible in the freshwater invertebrate, D. magna by using a combination of physiological and molecular analyses. FPW (0.75%) reduced reproduction by 30% and survivorship to 32% compared to controls. System-level quantitative proteomic analyses demonstrate extensive perturbation of metabolism and protein transport in both 0.25 and 0.75% FPW treatments after a 48 h FPW exposure. Collectively, our data indicate that D. magna are unable to recover from acute 48 h exposures to ≥0.25% FPW, as evidence of toxicity persists for at least 19 days post-exposure. This study highlights the importance of considering persisting effects following FPW remediation when modeling potential spill scenarios.

Improved Dynamic Range, Resolving Power, and Sensitivity Achievable with FT-ICR Mass Spectrometry at 21 T Reveals the Hidden Complexity of Natural Organic Matter.

Fourier transform ion-cyclotron resonance mass spectrometry (FT-ICR MS) is the only mass analyzer that can resolve the molecular complexity of natural organic matter at the level of elemental composition assignment. Here, we leverage the high dynamic range, resolving power, resistance to peak coalescence, and maximum ion number and ion trapping duration in a custom built, 21 tesla hybrid linear ion trap /FT-ICR mass spectrometer for a dissolved organic matter standard (Suwanne River Fulvic Acid). We compare the effect of peak-picking threshold (3σ, 4σ, 5σ, and 6σ) on number of elemental composition assignments, mass measurement accuracy, and dynamic range for a 6.3 s transient across the mass range of m/z 200-1200 that comprises the highest achieved resolving power broadband FT-ICR mass spectrum collected to date. More than 36 000 species are assigned with signal magnitude greater than 3σ at root-mean-square mass error of 36 ppb, the most species identified reported to date for dissolved organic matter. We identify 18O and 17O isotopologues and resolve isobaric overlaps on the order of a few electrons across a wide mass range (up to m/z 1000) leveraging mass resolving powers (3 000 000 at m/z 200) only achievable by 21 T FT-ICR MS and increased by ∼30% through absorption mode data processing. Elemental compositions unique to the 3σ span a wide compositional range of aromaticity not detected at higher peak-picking thresholds. Furthermore, we leverage the high dynamic range at 21 T FT-ICR MS to provide a molecular catalogue of a widely utilized reference standard (SRFA) to the analytical community collected on the highest performing mass analyzer for complex mixture analysis to date. This instrument is available free of charge to scientists worldwide.

Enhanced Speciation of Pyrogenic Organic Matter from Wildfires Enabled by 21 T FT-ICR Mass Spectrometry.

Wildfires affect soils through the formation of pyrogenic organic matter (pyOM) (e.g., char and soot). While many studies examine the connection between pyOM persistence and carbon (C) composition, nitrogen (N) transformation in wildfire-impacted systems remains poorly understood. Thermal reactions in wildfires transform biomass into a highly complex, polyfunctional, and polydisperse organic mixture that challenges most mass analyzers. High-field Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is the only mass analyzer that achieves resolving powers sufficient to separate species that differ in mass by the mass of an electron across a wide molecular weight range (m/z 150-1500). We report enhanced speciation of organic N by positive-ion electrospray ionization (ESI) that leverages ultrahigh resolving power (m/Δm50% = 1 800 000 at m/z 400) and mass accuracy (<10-100 ppb) achieved by FT-ICR MS at 21 T. Isobaric overlaps, roughly the mass of an electron (Me- = 548 µDa), are resolved across a wide molecular weight range and are more prevalent in positive ESI than negative ESI. The custom-built 21 T FT-ICR MS instrument identifies previously unresolved mass differences in CcHhNnOoSs formulas and assigns more than 30 000 peaks in a pyOM sample. This is the first molecular catalogue of pyOM by positive-ion ESI 21 T FT-ICR MS and presents a method to provide new insight into terrestrial cycling of organic carbon and nitrogen in wildfire impacted ecosystems.

Nitrogen Enrichment during Soil Organic Matter Burning and Molecular Evidence of Maillard Reactions.

Wildfires in forested watersheds dramatically alter stored and labile soil organic matter (SOM) pools and the export of dissolved organic matter (DOM). Ecosystem recovery after wildfires depends on soil microbial communities and revegetation and therefore is limited by the availability of nutrients, such as nitrogen-containing and labile, water-soluble compounds. However, SOM byproducts produced at different wildfire intensities are poorly understood, leading to difficulties in assessing wildfire severity and predicting ecosystem recovery. In this work, water-extractable organic matter (WEOM) from laboratory microcosms of soil burned at discrete temperatures was characterized by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry to study the impacts of fire temperature on SOM and DOM composition. The molecular composition derived from different burn temperatures indicated that nitrogen-containing byproducts were enriched with heating and composed of a wide range of aromatic features and oxidation states. Mass difference-based analysis also suggested that products formed during heating could be modeled using transformations along the Maillard reaction pathway. The enrichment of N-containing SOM and DOM at different soil burning intensities has important implications for ecosystem recovery and downstream water quality.

PFAS Analysis with Ultrahigh Resolution 21T FT-ICR MS: Suspect and Nontargeted Screening with Unrivaled Mass Resolving Power and Accuracy.

Per- and polyfluoroalkyl substances (PFASs) are a large family of thousands of chemicals, many of which have been identified using nontargeted time-of-flight and Orbitrap mass spectrometry methods. Comprehensive characterization of complex PFAS mixtures is critical to assess their environmental transport, transformation, exposure, and uptake. Because 21 tesla (T) Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) offers the highest available mass resolving power and sub-ppm mass errors across a wide molecular weight range, we developed a nontargeted 21 T FT-ICR MS method to screen for PFASs in an aqueous film-forming foam (AFFF) using suspect screening, a targeted formula database (C, H, Cl, F, N, O, P, S; ≤865 Da), isotopologues, and Kendrick-analogous mass difference networks (KAMDNs). False-positive PFAS identifications in a natural organic matter (NOM) sample, which served as the negative control, suggested that a minimum length of 3 should be imposed when annotating CF2-homologous series with positive mass defects. We putatively identified 163 known PFASs during suspect screening, as well as 134 novel PFASs during nontargeted screening, including a suspected polyethoxylated perfluoroalkane sulfonamide series. This study shows that 21 T FT-ICR MS analysis can provide unique insights into complex PFAS composition and expand our understanding of PFAS chemistries in impacted matrices.

High Spatial Resolution Fluorescence Imagery for Optimized Pest Management in a Huanglongbing-Infected Citrus Grove.

Huanglongbing (HLB), or citrus greening disease, has significantly decreased citrus production all over the world. The disease management currently depends on the efficient application and adequate distribution of insecticides to reduce the density of the disease vector, the Asian citrus psyllid. Here, we use a novel fluorescent-based method to evaluate insecticide distribution in an HLB-infected citrus grove in Florida. Specifically, we evaluated six different locations within citrus trees, the top and bottom sides of leaves, the effect of application approach (tractor versus airplane), and different application rates. We found that despite the insecticide distribution being highly variable among the different locations within a tree, the top of the leaves received an average increase of 21 times more than the bottom of the leaves. Application by tractor also resulted in a 4- to 87-fold increase in insecticide coverage compared with aerial application, depending on the location in the tree and side of the leaf. When taken to context with the type of insecticide that is applied (systemic vs. contact), these results can be used to optimize a pest management strategy to effectively target psyllids and other pests while minimizing the time and money spent on insecticide application and reducing risk to the environment.

Expanding the Analytical Window for Biochar Speciation: Molecular Comparison of Solvent Extraction and Water-Soluble Fractions of Biochar by FT-ICR Mass Spectrometry.

Biochar, a low-density yet carbon-rich material derived from different organic materials pyrolyzed under low or no oxygen conditions, has been widely studied as a soil amendment, for greenhouse gas mitigation and in remediation of trace element-contaminated soils. Molecular speciation of biochar compounds has been challenging due to low solubility, aggregation, and immense compositional polydispersity that challenges nearly all mass spectrometry methods routinely applied to carbon-based organic materials. Through a combined technique approach that applies advanced analytical strategies, we provide bulk and molecular characterization of Kentucky bluegrass biochar that can be applied to any biomass or biochar sample. First, we characterize Kentucky bluegrass biochar chemical functional groups by solid-state magic-angle spinning dynamic nuclear polarization NMR (MAS-DNP NMR) and resolve aromatic and aliphatic signals from the pyrogenic material and intact plant material. Next, we isolate water-soluble biochar species by solid-phase extraction followed by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and identify highly polar, oxygen species across a wide carbon number range. Solvent fractionation of biochar further expands the compositional range and identifies condensed polycyclic aromatic species across nonpolar and polar classes detected by two ionization modes (-ESI and +APPI) by FT-ICR MS. Plotting biochar species with DBE versus carbon number highlights the pericondensed molecular structural motif that persists across numerous heteroatom classes and ionization modes. To the best of our knowledge, this is the first molecular level identification of nonfunctionalized PAHs in biochar extracts by APPI FT-ICR MS. Thus, we identify biochar species that span the same compositional space as coal, heavy oil asphaltenes, and coal tar and correspond to condensed ring PAHs.

Soil Organic Matter Characterization by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR MS): A Critical Review of Sample Preparation, Analysis, and Data Interpretation.

The biogeochemical cycling of soil organic matter (SOM) plays a central role in regulating soil health, water quality, carbon storage, and greenhouse gas emissions. Thus, many studies have been conducted to reveal how anthropogenic and climate variables affect carbon sequestration and nutrient cycling. Among the analytical techniques used to better understand the speciation and transformation of SOM, Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) is the only technique that has sufficient mass resolving power to separate and accurately assign elemental compositions to individual SOM molecules. The global increase in the application of FTICR MS to address SOM complexity has highlighted the many challenges and opportunities associated with SOM sample preparation, FTICR MS analysis, and mass spectral interpretation. Here, we provide a critical review of recent strategies for SOM characterization by FTICR MS with emphasis on SOM sample collection, preparation, analysis, and data interpretation. Data processing and visualization methods are presented with suggested workflows that detail the considerations needed for the application of molecular information derived from FTICR MS. Finally, we highlight current research gaps, biases, and future directions needed to improve our understanding of organic matter chemistry and cycling within terrestrial ecosystems.

Sensors for detecting per- and polyfluoroalkyl substances (PFAS): A critical review of development challenges, current sensors, and commercialization obstacles.

Per- and polyfluoroalkyl substances (PFAS) are a class of compounds that have become environmental contaminants of emerging concern. They are highly persistent, toxic, bioaccumulative, and ubiquitous which makes them important to detect to ensure environmental and human health. Multiple instrument-based methods exist for sensitive and selective detection of PFAS in a variety of matrices, but these methods suffer from expensive costs and the need for a laboratory and highly trained personnel. There is a big need for fast, inexpensive, robust, and portable methods to detect PFAS in the field. This would allow environmental laboratories and other agencies to perform more frequent testing to comply with regulations. In addition, the general public would benefit from a fast method to evaluate the drinking water in their homes for PFAS contamination. A PFAS sensor would provide almost real-time data on PFAS concentrations that can also provide actionable information for water quality managers and consumers around the planet. In this review, we discuss the sensors that have been developed up to this point for PFAS detection by their molecular detection mechanism as well as the goals that should be considered during sensor development. Future research needs and commercialization challenges are also highlighted.

The Mechanism of C-H Bond Oxidation by Aqueous Permanganate.

The permanganate ion (MnO4-) has been widely used as a reagent for water treatment for over a century. It is a strong enough oxidant to activate carbon-hydrogen bonds, one of the most important reactions in biological and chemical systems. Our current textbook understanding of the oxidation mechanism in aqueous solution involves an initial, rate-limiting hydride abstraction by permanganate followed by reaction of the carbocation with bulk water to form an alcohol. This mechanism fits well into the classic oxidation sequence of alkane → alcohol → aldehyde → carboxylate, the central paradigm for both abiotic and biotic alkane oxidation in aqueous environments. In this study, we provide three lines of evidence through (1) a broken-symmetry density functional theory approach, (2) isotope labeling experiments, and (3) kinetic network modeling to demonstrate that aqueous permanganate can circumvent prior alcohol formation and produce aldehydes directly via a reaction path that bifurcates after the initial transition state. In contrast to classic transition state theory, the rate-limiting step is found to not determine product distribution, bearing critical implications for pathway and rate predictions. This complex reaction network provides new insights into the oxidation mechanisms of organic compounds involving transition metal complexes as well as enzyme or metal oxide surface active sites.

Oxidation of Fe(II)-Organic Matter Complexes in the Presence of the Mixotrophic Nitrate-Reducing Fe(II)-Oxidizing Bacterium Acidovorax sp. BoFeN1.

Fe(II)-organic matter (Fe(II)-OM) complexes are abundant in the environment and may play a key role for the behavior of Fe and pollutants. Mixotrophic nitrate-reducing Fe(II)-oxidizing bacteria (NRFeOx) reduce nitrate coupled to the oxidation of organic compounds and Fe(II). Fe(II) oxidation may occur enzymatically or abiotically by reaction with nitrite that forms during heterotrophic denitrification. However, it is unknown whether Fe(II)-OM complexes can be oxidized by NRFeOx. We used cell-suspension experiments with the mixotrophic nitrate-reducing Fe(II)-oxidizing bacterium Acidovorax sp. strain BoFeN1 to reveal the role of nonorganically bound Fe(II) (aqueous Fe(II)) and nitrite for the rates and extent of oxidation of Fe(II)-OM complexes (Fe(II)-citrate, Fe(II)-EDTA, Fe(II)-humic acid, and Fe(II)-fulvic acid). We found that Fe(II)-OM complexation inhibited microbial nitrate-reducing Fe(II) oxidation; large colloidal and negatively charged complexes showed lower oxidation rates than aqueous Fe(II). Accumulation of nitrite and fast abiotic oxidation of Fe(II)-OM complexes only happened in the presence of aqueous Fe(II) that probably interacted with (nitrite-reducing) enzymes in the periplasm causing nitrite accumulation in the periplasm and outside of the cells, whereas Fe(II)-OM complexes probably could not enter the periplasm and cause nitrite accumulation. These results suggest that Fe(II) oxidation by mixotrophic nitrate reducers in the environment depends on Fe(II) speciation, and that aqueous Fe(II) potentially plays a critical role in regulating microbial denitrification processes.

Fe(II)-Catalyzed Transformation of Organic Matter-Ferrihydrite Coprecipitates: A Closer Look Using Fe Isotopes.

Ferrihydrite is a common Fe mineral in soils and sediments that rapidly transforms to secondary minerals in the presence of Fe(II). Both the rate and products of Fe(II)-catalyzed ferrihydrite transformation have been shown to be significantly influenced by natural organic matter (NOM). Here, we used enriched Fe isotope experiments and 57Fe Mössbauer spectroscopy to track the formation of secondary minerals, as well as electron transfer and Fe mixing between aqueous Fe(II) and ferrihydrite coprecipitated with several types of NOM. Ferrihydrite coprecipitated with humic acids transformed primarily to goethite after reaction with Fe(II). In contrast, ferrihydrite coprecipitated with fulvic acids and Suwannee River NOM (SRNOM) resulted in no measurable formation of secondary minerals. Despite no secondary mineral transformation, Mössbauer spectra indicated electron transfer still occurred between Fe(II) and ferrihydrite coprecipitated with fulvic acid and SRNOM. In addition, isotope tracer experiments revealed that a significant fraction of structural Fe in the ferrihydrite mixed with the aqueous phase Fe(II) (∼85%). After reaction with Fe(II), Mössbauer spectroscopy indicated some subtle changes in the crystallinity, particle size, or particle interactions in the coprecipitate. Our observations suggest that ferrihydrite coprecipitated with fulvic acid and SRNOM remains a highly dynamic phase even without ferrihydrite transformation.

Ammonia Emissions from Subalpine Forest and Mountain Grassland Soils in Rocky Mountain National Park.

Atmospheric deposition of NH and NH contributes to eutrophication within sensitive subalpine ecosystems of Rocky Mountain National Park (RMNP) in the United States. However, little is known about the local contribution of NH from soils within the park. Thus, the goal of this study was to quantify and compare NH emissions from intact soil cores sampled from a subalpine grassland and forest within RMNP. Cores were collected at 2-wk intervals from 20 June 2011 to 12 Sept. 2011 and transferred to a laboratory chamber system for NH flux measurements. Additionally, N wet deposition was monitored at the sampling location to investigate possible impacts on NH soil emissions. The average quantifiable NH emissions (with SDs) from intact soil cores analyzed in the laboratory (23°C) were 0.42 ± 0.30 mg NH-N m d for grassland soil and 0.21 ± 0.03 mg NH-N m d for forest soil ( < 0.001). A mechanistic model was developed to estimate the impact of temperature on soil emissions using the chamber data and field-site air temperatures. Average estimated NH emissions from the field site over the study period were 0.21 and 0.082 mg NH-N m d for grasslands and forests, respectively. Ammonium wet deposition was not correlated to short term reemission of NH based on N isotope analysis. This work provides new information on the magnitude of NH emissions from native subalpine soils, indicating that natural emissions are not likely major sources of NH in the RMNP airshed.