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At least 73 records · Page 4

Interactions between molecular-scale biogeochemical processes and hyporheic exchange for understanding coupled Fe-S-C cycling in iron-rich riparian wetlands (Final Technical Report)

Riparian wetlands are dynamic interfaces that exert strong control over water quality, contaminant mobility, and greenhouse gas emissions. These systems are characterized by hyporheic exchange between oxic surface water and anoxic groundwater, which generates steep redox gradients and promotes spatially and temporally variable microbial activity. Despite growing recognition of tightly coupled iron (Fe), sulfur (S), and carbon (C) cycling in these environments, the mechanisms governing these interactions—particularly under low-sulfate freshwater conditions—remain poorly constrained. This project developed a mechanistic understanding of how hydrologic variability and microbial processes interact to control Fe–S–C cycling in iron-rich riparian wetlands. Using a multi-scale and multi-method approach integrating field observations, geochemical and spectroscopic analyses, metagenomics, and reactive transport modeling, we demonstrate that “cryptic” sulfur cycling—rapid sulfur transformations involving intermediate-valence species—plays a dominant and previously underrecognized role in freshwater wetlands. These processes persist despite low sulfate concentrations and significantly influence iron reduction, carbon mineralization, and methane dynamics. The results show that cryptic sulfur cycling enhances dissolved Fe 2+ production, regulates methane concentrations, and is strongly controlled by climate-driven hydrologic fluxes. By linking hydroclimate, subsurface flow, and biogeochemical reactions, this work provides a predictive framework for understanding how wetland systems respond to environmental change, with direct implications for water quality and carbon cycling.

54 ENVIRONMENTAL SCIENCES↗

Novel Remediation of Mercury-Contaminated Sediments Using Manganese Oxide and Activated Carbon Amendments - 20394

Mercury contamination in sediments poses a challenging remediation problem because of its ability to biogeochemically cycle and biomagnify in the food chain as methylmercury from low resident sediment and porewater concentrations. One mitigation approach is to lower the overall rate of net methylmercury production by creating conditions unfavorable for sulfate and iron reduction or methanogenesis, the primary pathways for methylation of inorganic mercury. Manganese oxides and other redox-active amendments are a promising and novel in situ amendment technology aimed at reducing net methylation of mercury though control of redox conditions in mercury-contaminated sediment-water systems. This paper reviews the thermodynamic and kinetic framework for this remediation technology, presents experimental and spectroscopic data illustrating the approach using solid manganese oxides, and discusses potential advantages, disadvantages, and applications. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Redox Mechanisms and Migration Tendencies in Earth-Abundant 0.7Li 2 MnO 3 ·0.3LiFeO 2 Cathodes: Coupling Spin-Resolved X-ray Absorption Near Edge and X-ray Absorption Fine Structure Spectroscopies

We report the use of iron 1s3p resonant X-ray emission processes to conduct spin-selective, high-energy resolution fluorescence detected X-ray absorption near-edge spectroscopy (HERFD-XANES) on an iron-containing, lithium- and manganese-rich, fully earth-abundant cathode material, Li 1.3 Mn 0.5 Fe 0.2 O 2 (0.7Li 2 MnO 3 ·0.3LiFeO 2 ). Coupling this technique with conventional Mn K-edge XANES and detailed extended X-ray absorption fine structure (EXAFS) analysis from both the Mn and Fe vantage points, we gain fundamental insights into the redox processes and migration tendencies of transition metals in this cathode material at the bulk level. We show that during the first charge, Fe 3+ undergoes oxidation to form Fe 4+ prior to the activation plateau. Toward the end of activation, a significant fraction of the iron is present as tetrahedral Fe 3+ . This observation reveals that iron migration from octahedral to tetrahedral sites and iron reduction are initiated during activation. Upon first discharge from the activated state, a continuous and overlapping reduction of both Fe and Mn is observed, with Fe largely restored back as an octahedrally coordinated Fe 3+ . The manganese local environment gradually changes to a distorted cooperative Jahn–Teller Mn 3+ structure during discharge, with the clear presence of two Mn–O as well as two Mn–Mn correlation distances at 2.0 V. The significant reduction of manganese in the very first discharge is distinctly different from that seen in typical nickel-based lithium-manganese-rich materials but is similar to that observed for pure Li 2 MnO 3 . In conclusion, these findings shed light on key structure–property correlations in the cathode material and point to a causative relationship between the redox mechanisms as well as structural changes endured by the material and relatively poor performance during extended electrochemical cycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Resolution XFEL Structure of the Soluble Methane Monooxygenase Hydroxylase Complex with its Regulatory Component at Ambient Temperature in Two Oxidation States

Soluble methane monooxygenase (sMMO) is a multicomponent metalloenzyme that catalyzes the conversion of methane to methanol at ambient temperature using a nonheme, oxygen-bridged dinuclear iron cluster in the active site. Structural changes in the hydroxylase component (sMMOH) containing the diiron cluster caused by complex formation with a regulatory component (MMOB) and by iron reduction are important for the regulation of O 2 activation and substrate hydroxylation. Structural studies of metalloenzymes using traditional synchrotron-based X-ray crystallography are often complicated by partial X-ray-induced photoreduction of the metal center, thereby obviating determination of the structure of the enzyme in pure oxidation states. Here, microcrystals of the sMMOH:MMOB complex from Methylosinus trichosporium OB3b were serially exposed to X-ray free electron laser (XFEL) pulses, where the ≤35 fs duration of exposure of an individual crystal yields diffraction data before photoreduction-induced structural changes can manifest. Merging diffraction patterns obtained from thousands of crystals generates radiation damage-free, 1.95 Å resolution crystal structures for the fully oxidized and fully reduced states of the sMMOH:MMOB complex for the first time. The results provide new insight into the manner by which the diiron cluster and the active site environment are reorganized by the regulatory protein component in order to enhance the steps of oxygen activation and methane oxidation. Furthermore, this study also emphasizes the value of XFEL and serial femtosecond crystallography (SFX) methods for investigating the structures of metalloenzymes with radiation sensitive metal active sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Iron XANES measurements of carbonates and phyllosilicates in CM chondrites: A record of redox conditions during aqueous alteration

Multiple generations of calcite and dolomite precipitated in CM chondrites during ice melting events that led to episodes of liquid water. Models and laboratory analysis have suggested a long-term transition from oxidizing to reducing conditions during aqueous alteration on the CM parent body. We found that synchrotron X-ray absorption near edge spectroscopy (XANES) can detect relative differences in the oxidation state of trace iron within these carbonates. In CM chondrites, previous work interpreted Mn abundance in calcite as an indicator of relatively early or late formation, and dolomite is understood to form relatively late. In the CM1 chondrite Meteorite Hills 01070, XANES maps reveal that Mn-poor calcite contains more oxidized iron relative to Mn-rich calcite. While these measurements of carbonates support increasing iron reduction with progressive aqueous alteration in MET 01070, comparison among different CM chondrites suggests a complex picture of redox evolution. In addition to carbonates, we performed XANES measurements of the phyllosilicate-rich matrix of Allan Hills 83,100. Pre-edge centroid analysis indicates that this CM1/2 has an oxidation state similar to typical CM2 chondrites. While additional measurements are warranted to confirm the full span of redox trends in CM carbonates, our data do not support a correlation between redox state and petrologic type.

Bailey, Elizabeth [Univ. of California, Santa Cruz↗

Stability of a Ni/NiF 2 Reference Electrode with a Metallic Membrane for Use in Molten Fluoride Salts

In this study, an experimental high-temperature fluoride salt reference electrode (RE) developed by HiFunda LLC was tested in molten FLiNaK at 550 °C. The high-temperature reference electrode (HTRE), based on the Ni/NiF 2 redox couple, was tested over a period of 13 d for short-term stability, long-term stability, and electrochemical analysis capabilities. The HTRE was tested using open circuit potentiometry (OCP), cyclic voltammetry (CV), square wave voltammetry (SWV), and electrochemical impedance spectroscopy (EIS). The HTRE reference potential was measured against changes in salt composition by increasing FeF 2 concentrations in the melt across six additions from 0 to 0.1 mol% FeF 2 . The long-term stability of the electrode was then tested over ten days at a constant composition of 0.1 mol% FeF 2 . OCP, SWV, and CV were used to calculate an average potential drift between 7–10 mV per day. Using CV and SWV, the number of electrons transferred for iron reduction and the diffusion coefficient of Fe 2+ were measured.

Electrochemistry↗

Safety Review of the Hydrogen Components of a Reference Design of the Wind-H2-Green Steel/Ammonia Project

The Department of Energy Hydrogen Fuel Cell Technology Office and Wind Energy Technologies Office’s Wind-H2-Green Steel/Ammonia project is an initiative to demonstrate the feasibility and efficacy of GW-scale integrated energy systems. The team designed reference facilities that utilize wind- and solar-produced hydrogen for industrial steel and ammonia production. This novel concept warranted review of safety codes and standards as they apply to the designs and the identification of codes and standards as they apply to the designs and the identification of codes and standards gaps. This report reviews hydrogen production and storage codes and standards using reference design specifications from a Minnesota steel plant. Requirements, recommendations, and exclusions for the system were identified. Observed gaps included non-specific salt cavern storage requirements, electrolyzer capacity beyond regulated ranges, and lack of requirements for iron reduction via hydrogen. This report will aide future project design efforts and may provide a basis for safety reviews in new designs for industrial facilities with hydrogen production integration.

08 HYDROGEN↗

Safety Review of the Hydrogen Components of a Reference Design of the Wind-H2-Green Steel/Ammonia Project

The Department of Energy Hydrogen Fuel Cell Technology Office and Wind Energy Technologies Office's Wind-H2-Green Steel/Ammonia project is an initiative to demonstrate the feasibility and efficacy of GW-scale integrated energy systems. The team designed reference facilities that utilize wind- and solar-produced hydrogen for industrial steel and ammonia production. This novel concept warranted review of safety codes and standards as they apply to the designs and the identification of codes and standards gaps. This report reviews hydrogen production and storage codes and standards using reference design specifications from a Minnesota steel plant. Requirements, recommendations, and exclusions for the system were identified. Observed gaps included non-specific salt cavern storage requirements, electrolyzer capacity beyond regulated ranges, and lack of requirements for iron reduction via hydrogen. This report will aide future project design efforts and may provide a basis for safety reviews in new designs for industrial facilities with hydrogen production integration.

08 HYDROGEN↗

Demand and supply of hydrogen as chemical feedstock in USA

Projections are made for the demand and supply of hydrogen as chemical feedstock in USA. Industrial sectors considered are petroleum refining, ammonia synthesis, methanol production, isocyanate manufacture, edible oil processing, coal liquefaction, fuel cell electricity generation, and direct iron reduction. Presently, almost all the hydrogen required is produced by reforming of natural gas or petroleum fractions. Specific needs and emphases are recommended for future research and development to produce hydrogen from other sources to meet the requirements of these industrial sectors. The data and the recommendations summarized in this paper are based on the Workshop 'Supply and Demand of Hydrogen as Chemical Feedstock' held at the University of Houston on December 12-14, 1977.

Huang, C. J.↗

The Stable Isotope Fractionation of Abiotic Reactions: A Benchmark in the Detection of Life

One very important tool in the analysis of biogenic, and potentially biogenic, samples is the study of their stable isotope distributions. The isotope distribution of a sample depends on the process(es) that created it. One important application of the analysis of C & N stable isotope ratios has been in the determination of whether organic matter in a sample is of biological origin or was produced abiotically. For example, the delta C-13 of organic material found embedded in phosphate grains was cited as a critical part of the evidence for life in 3.8 billion year old samples. The importance of such analysis in establishing biogenicity was highlighted again by the role this issue played in the recent debate over the validity of what had been accepted as the Earth s earliest microfossils. These kinds of analysis imply a comparison with the fractionation that one would have seen if the organic material had been produced by alternative, abiotic, pathways. Could abiotic reactions account for the same level of fractionation? Additionally, since the fractionation can vary between different abiotic reactions, understanding their fractionations can be important in distinguishing what reactions may have been significant in the formation of different abiological samples (such as extraterrestrial samples). There is however, a scarcity of data on the fractionation of carbon and nitrogen by abiotic reactions. In order to interpret properly what the stable isotope ratios of samples tell us about their biotic or abiotic nature, more needs to be known about how abiotic reactions fractionate C and N. Carbon isotope fractionations have been studied for a few abiotic processes. These studies presumed the presence of a reducing atmosphere, focusing on reactions involving spark discharge, W photolysis of reducing gas mixtures, and cyanide polymerization in the presence of ammonia. They did find that the initial products showed a depletion in I3C with values in the range of a few per mil to as low as -60 % (potentially comparable to that which accompanies the biosynthesis of organic matter). We need to understand what kind of fractionations are observed with reactions under the non-reducing or mildly reducing conditions now thought to be present on the early Earth. While nitrogen is receiving increased attention as a tool for these kinds of analyses, almost nothing is known about the isotope fractionation that one would expect for abiotic sources of fixed/reduced nitrogen. This project will measure the fixation from a series of abiotic reactions that may have been present on the early Earth (and other terrestrial planets) and produced organic material that could have ended up in the rock record. The work will look at a number of reactions, under a non- reducing, or mildly reducing, atmosphere, covering sources of prebiotic organic C & N from shock heating, to photochemistry, to hydrothermal reactions. Some reactions that we plan to study are; Shock heating of a non-reducing atmosphere to produce CO and NO (in collaboration with Chris McKay), formation of formaldehyde (and related compounds) from COY the formation of ammonia from nitrogen oxides (ultimately from NO) by ferrous iron reduction, and the hydrothermal synthesis of compounds including the hydrocarboxylation/hydrocarbonylation reaction (in collaboration with George Cody), reactions of oxalate to form hydrocarbons and other oxygenated compounds and the formation of lipids from oxalic/formic acid (in collaboration with Tom McCollom), and reactions of carbon monoxide & carbon dioxide with N2, ammonia or nitritehitrate to form hydrogen cyanide, nitriles, ammonia/amines and nitrous

Summers, David P.↗

Small molecule dye for molecular imaging and photothermal therapy

Disclosed is a small molecule dye for use in imaging in the near-infrared window, namely between 1000 nm-1700 nm wavelength. The present dyes are also useful for photoacoustic imaging and photothermal therapy. The dyes have a structure of a D-A-D (donor-acceptor-donor) fluorescent compound core and side chains rendering the compounds water soluble and easily conjugated to hydrophilic polymers and/or targeting ligands. Further disclosed is compound, CH1055 that can be PEGylated, conjugated to a targeting ligand, or conjugated to taurine. Key steps utilized to assemble the core structure of the target included a cross-Suzuki coupling reaction, iron reduction and N-thionylaniline induced ring closure. Four carboxylic acid groups were introduced into the donor-acceptor-donor (D-A-D) type fluorescent compound to impart a certain aqueous solubility and to allow facile conjugation to targeting ligands.

Cheng, Zhen↗

Templating Bicarbonate in the Second Coordination Sphere Enhances Electrochemical CO 2 Reduction Catalyzed by Iron Porphyrins

Bicarbonate-based electrolytes are ubiquitous in aqueous electrochemical CO 2 reduction, particularly in heterogenous catalysis, where they demonstrate improved catalytic performance relative to other buffers. In contrast, the presence of bicarbonate in organic electrolytes and its roles in homogeneous electrocatalysis remain underexplored. Here, we investigate the influence of bicarbonate on iron porphyrin-catalyzed electrochemical CO 2 reduction. In this work, we show that bicarbonate is a viable proton donor in organic electrolyte (p K a = 20.8 in dimethyl sulfoxide) and that urea pendants in the second coordination sphere can be used to template bicarbonate in the vicinity of a molecular iron porphyrin catalyst. The templated binding of bicarbonate increases its acidity, resulting in a 1500-fold enhancement in catalytic rates relative to unmodified parent iron porphyrin. This work emphasizes the importance of bicarbonate speciation in wet organic electrolytes and establishes second-sphere bicarbonate templating as a design strategy to harness this adventitious acid and enhance CO 2 reduction catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reduction of iron-bearing lunar minerals for the production of oxygen

The kinetics and mechanism of the reduction of simulants of the iron-bearing lunar minerals olivine ((Fe,Mg)2SiO4), pyroxene ((Fe,Mg,Ca)SiO3), and ilmenite (FeTiO3) are investigated, extending previous work with ilmenite. Fayalite is reduced by H2 at 1070 K to 1480 K. A layer of mixed silica glass and iron forms around an unreacted core. Reaction kinetics are influenced by permeation of hydrogen through this layer and a reaction step involving dissociated hydrogen. Reaction mechanisms are independent of Mg content. Augite, hypersthene, and hedenbergite are reduced in H2 at the same temperatures. The products are iron metal and lower iron silicates mixed throughout the mineral. Activation energy rises with calcium content. Ilmenite and fayalite are reduced with carbon deposited on partially reduced minerals via the CO disproportionation reaction. Reduction with carbon is rapid, showing the carbothermal reduction of lunar minerals is possible.

Massieon, Charles↗

Stable, Efficient Iron Electrodeposition via Anion-Directed Control of Fe(II) Coordination

Traditional steelmaking processes consume about 7% of the world’s energy supply, with reduction of iron oxides into iron via blast furnaces representing the most energy-demanding and capital-intensive step. To economize and modularize iron reduction processes, we aim to develop an electrodeposition technique to reduce aqueous iron ions to metallic iron. However, the hydrogen reduction reaction (HER) occurs at a more positive standard reduction potential than the iron reduction reaction. In addition, aqueous Fe(II) cations easily precipitate at mildly acidic conditions (pH ≥ 3), which limits the deposition efficiency and degrades deposit quality. To address these challenges, we first search for anions that have intermediate coordination strength with Fe(II) based on the hard-soft acid-base theory, trading a slightly more negative Fe(II) reduction potential for a considerably broader pH stability range. We select citrate with predicted intermediate coordination strength, in combination with more weakly coordinating anions (e.g., SO 4 2- , Cl - ) to control the coordination structure of Fe 2+ for improved electrolyte stability and electrodeposition behavior. We find that citrate coordination stabilizes Fe 2+ -based electrolytes at higher pH conditions (4.8–5.5), significantly extending their shelf life while also suppressing HER during Fe electrodeposition by orders of magnitude. To measure Faradaic efficiencies (FE), we developed a straightforward, titration-based methodology to quantify the amount of deposited iron regardless of the rate of concurrent HER. Although coordination between citrate and Fe 2+ decreases the reduction potential of Fe(II), high FE (≥98%) was achieved at 10 mA cm -2 . FE and achievable deposition rates are tunable by both concentration and the ratio of Fe 2+ to citrate. In all cases, Raman spectroscopy and X-ray diffraction (XRD) reveal that iron deposition in citrate-containing electrolytes suppresses iron oxide/hydroxide precipitation, in contrast to deposits generated in citrate-free electrolytes. Altogether, this work demonstrates that citrate-mediated anion coordination enables high-purity iron electrodeposition with increased FE, high current density, and improved electrolyte stability. This multi-anion coordination strategy provides a versatile framework for designing stable electrolyte and efficient metal electrodeposition.

coordination↗

Selective Electrocatalytic Reduction of Nitrous Oxide to Dinitrogen with an Iron Porphyrin Complex

Nitrous oxide (N 2 O) is the third largest contributor to anthropogenic greenhouse gas emissions and plays a detrimental role in the depletion of ozone. Despite the contribution of N 2 O as an atmospheric pollutant, there are currently only a few examples of electrochemical N 2 O remediation to N 2 . Herein we report the electrocatalytic deoxygenation of N 2 O by iron tetraphenylporphyrin (FeTPP) to form N 2 with quantitative Faradaic efficiency and an observed rate of 1.91 s –1 . No degradation was observed after controlled potential electrolysis. Mechanistic investigation of the proposed catalytic steps determined that hydrogen-bond donors are critical for accelerating N 2 O activation and that proton transfer is involved in the rate-determining step.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Inhibition of Chromium(III) Oxidation through Manganese(IV) Oxide Passivation and Iron(II) Abiotic Reduction

Manganese (Mn) oxides are strong oxidants that are ubiquitous in soils and can oxidize redox-active metals, including chromium (Cr). In soil environments, trivalent chromium (Cr(III)) is a benign, immobile micronutrient, whereas the hexavalent Cr(VI) form is present as a highly mobile, toxic chromate oxyanion. Although many studies have characterized the capacity of Mn(III/IV) oxides to oxidize Cr(III) to toxic Cr(VI), the oxidative capacity of Mn oxides in the presence of potentially passivating soil constituents, specifically reduced soluble iron (Fe(II) aq ), remains unresolved. We hypothesized that chemical processes at redox interfaces, such as diffusion-limited environments within soil aggregates, can lead to decreased Cr(VI) production from Mn oxide-driven oxidation due to passivation by Fe(II) aq . A multichamber diffusion-limited reactor was used to simulate transport at soil redox interfaces and investigate the capacity of poorly crystalline and crystalline Mn oxides to oxidize solid Cr(III) minerals to Cr(VI) in the presence of Fe(II) aq . As predicted, Cr(VI) was produced through the Mn oxide-catalyzed oxidation of Cr(III) at a rate controlled by the solubility of Cr(OH) 3 . However, in the presence of Fe(II) aq , the concentration of aqueous Cr(VI) decreased as a function of the Fe(II) aq concentration, where high concentrations of Fe(II) aq completely inhibited Cr(VI) production, likely through both the passivation of the Mn oxide and the direct reduction of Cr(VI) by Fe(II). At both low (14 μM) and high (100 μM) Fe(II) aq concentrations, the iron oxide minerals hematite (Fe 2 O 3 ) and goethite (α-FeOOH) were associated with the Mn oxides, which can cause surface passivation, a likely role that decreases Cr(III) oxidation. Additionally, the Cr(III) oxidation rate decreased with increasing crystallinity of the Mn oxides whether or not Fe(II) was present.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Time dependent zero valent iron oxidation and the reductive removal of pertechnetate at variable pH

Elemental iron Fe 0 is a promising reductant for removal of radioactive technetium-99 (Tc) from complex aqueous waste streams that contain sulfate, halides, and other inorganic anions generated during processing of legacy radioactive waste. The impact of sulfate on the kinetics of oxidation and reduction capacity of Fe 0 in the presence of Tc has not been examined. We investigated the oxidative transformation of Fe 0 and reductive removal of TcO 4 - in 0.1 M Na 2 SO 4 as a function of initial pH (i.e., pH i 4, 7, and 10) under aerobic conditions up to 30 days. Tc reduction was the fastest at pH i 7 and slowest at pHi 10 (Tc reduction rate pHi 7 > 4 > 10). Aqueous fraction of Tc was measured at 0.4% at pH i 7 within 6 h, whereas ≥ 97% of Tc was removed from solutions at pH i of 4 and 10 within 24 h. Solid phase characterization showed that magnetite was the only oxidized crystalline phase for the first 6 h regardless of initial pH. Lepidocrocite was the most abundant oxidized product for pH i 10 after 5 days, but was not observed at pH of 4 or 7.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Unexpected mechanism for glucose-primed soil organic carbon mineralization under an anaerobic–aerobic transition

Redox reactions are important for cycling of carbon (C) in soils frequently subject to fluctuations in redox conditions, such as wetland soils, which contribute around one third of the global terrestrial C reservoir. Priming effects (PE), induction of changes in C mineralization due to additions of energy-rich organic carbon (OC) substrates, have been largely ignored during redox transitions in current modelling and experimental efforts for evaluating C cycles. In this study, we investigated the effects of glucose input on the mineralization of soil OC during an anaerobic-aerobic transition. Substantially more soil OC was mineralized under aerobic conditions in samples that received glucose under preceding anaerobic conditions compared to controls that did not receive glucose and to samples that received glucose under aerobic-only conditions. Our results reveal a novel PE by which glucose indirectly primes the mineralization of soil OC by increasing the reductive release of iron oxide-associated OC under anaerobic conditions, followed by a dramatic positive PE when aerobic conditions are reestablished. Inclusion of this novel indirect priming mechanism is crucial for accurately predicting the contribution of atmospheric greenhouse gases from soils experiencing redox fluctuations (e.g.,wetlands).

54 ENVIRONMENTAL SCIENCES↗