Rapid and Convenient Potentiometric Method for Determining Fluorosulfate, a Byproduct of the Fumigant and Greenhouse Gas Sulfuryl Fluoride.

A fluorosulfate ion (FSO3-) is a hydrolysis product of sulfuryl fluoride (SO2F2), which is widely used to fumigate buildings, soil, construction materials, and postharvest commodities, and is a potent greenhouse gas. It is a potential marker for biological exposure to SO2F2 and for monitoring the progress of reactions used to scrub SO2F2 from fumigation vent gases. Here, we report a simple and inexpensive potentiometric method for determining FSO3- using a commercial nitrate-selective electrode and discuss its application. The method is suitable for solutions between 0.0025 mM and 660 mM FSO3- at initial pH between 5 and 9. Halide interference depends on its molar ratio to FSO3- and follows the sequence, F- < Cl- < Br- ≪ I-. Halide interference can be eliminated by adding silver sulfate. Interference by bicarbonate can be eliminated by H2SO4 pretreatment, and interference by phosphate or pyrophosphate by MgSO4 addition. Sulfate does not interfere, as it does in ion chromatography. Satisfactory method detection limits for FSO3- in spiked aqueous extracts of 11 fruits were obtained. The method accurately quantified the yield of FSO3- relative to that of F- in base hydrolysis of SO2F2. This study demonstrates that the developed method is highly selective, convenient, and sensitive and thus can be of great value in practice.

Experimental and Computational Study of Pyrogenic Carbonaceous Matter Facilitated Hydrolysis of 2,4-Dinitroanisole (DNAN).

This study investigated the reaction pathway of 2,4-dinitroanisole (DNAN) on the pyrogenic carbonaceous matter (PCM) to assess the scope and mechanism of PCM-facilitated surface hydrolysis. DNAN degradation was observed at pH 11.5 and 25 °C with a model PCM, graphite, whereas no significant decay occurred without graphite. Experiments were performed at pH 11.5 due to the lack of DNAN decay at pH below 11.0, which was consistent with previous studies. Graphite exhibited a 1.78-fold enhancement toward DNAN decay at 65 °C and pH 11.5 relative to homogeneous solution by lowering the activation energy for DNAN hydrolysis by 54.3 ± 3.9%. This is supported by our results from the computational modeling using Car-Parrinello simulations by ab initio molecular dynamics/molecular mechanics (AIMD/MM) and DFT free energy simulations, which suggest that PCM effectively lowered the reaction barriers by approximately 8 kcal mol-1 compared to a homogeneous solution. Quaternary ammonium (QA)-modified activated carbon performed the best among several PCMs by reducing DNAN half-life from 185 to 2.5 days at pH 11.5 and 25 °C while maintaining its reactivity over 10 consecutive additions of DNAN. We propose that PCM can affect the thermodynamics and kinetics of hydrolysis reactions by confining the reaction species near PCM surfaces, thus making them less accessible to solvent molecules and creating an environment with a weaker dielectric constant that favors nucleophilic substitution reactions. Nitrite formation during DNAN decay confirmed a denitration pathway, whereas demethylation, the preferred pathway in homogeneous solution, produces 2,4-dinitrophenol (DNP). Denitration catalyzed by PCM is advantageous to demethylation because nitrite is less toxic than DNAN and DNP. These findings provide critical insights for reactive adsorbent design that has broad implications for catalyst design and pollutant abatement.

Analytical methods for selectively determining hydrogen peroxide, peroxymonosulfate and peroxydisulfate in their binary mixtures.

Hydrogen peroxide (H2O2), peroxymonosulfate (PMS), and peroxydisulfate (PDS) are key bulk oxidants in many advanced oxidation processes (AOPs) for treating chemically contaminated water. In some systems these peroxides may coexist in solution either through intentional co-addition or their inadvertent formation (especially H2O2) due to reaction chemistry. While many analytical methods to determine these peroxides individually have been established, mutual interference among the peroxides in such methods has seldom been evaluated, and new methods or variants of established methods to selectively determine peroxides in binary mixtures are lacking. We re-examined five established colorimetric methods-the Permanganate, Titanium Oxalate (Ti-oxalate), Iodide, N.N­diethyl-p-phenylenediamine (DPD), and 2,20-azino-bis(3-ethylbenzothiazoline-6-sulfonate (ABTS) methods-for mutual interference among peroxides and devised variants of these methods for selectively quantifying one peroxide in the presence of another. Hydrogen peroxide can be selectively determined by the Permanganate method at short reaction time; by the Ti-oxalate method; by the DPD method with added peroxidase (POD); or by the ABTS method with added POD. PMS can be selectively determined by the Iodide method; by the DPD or ABTS methods with added iodide ion as catalyst; or by the DPD method with added catalase (CAT) (with co-existing H2O2 but not PDS). The DPD method can be used to determine PDS without interference by H2O2 and-provided the sample is pretreated with l-histidine-without interference by PMS. The recommended methods were successfully applied to binary peroxide mixtures in complex waters, including a tap water and a synthetic water. Overall, the new selective methods will assist mechanistic investigation of AOPs based on these peroxides and support efforts to apply them commercially.

Peroxymonosulfate Activation by Fe(III)-Picolinate Complexes for Efficient Water Treatment at Circumneutral pH: Fe(III)/Fe(IV) Cycle and Generation of Oxyl Radicals.

Improving the reactivity of Fe(III) for activating peroxymonosulfate (PMS) at circumneutral pH is critical to propel the iron-activated PMS processes toward practical wastewater treatment but is yet challenging. Here we employed the complexes of Fe(III) with the biodegradable picolinic acid (PICA) to activate PMS for degradation of selected chlorinated phenols, antibiotics, pharmaceuticals, herbicides, and industrial compounds at pH 4.0-6.0. The FeIII-PICA complexes greatly outperformed the ligand-free Fe(III) and other Fe(III) complexes of common aminopolycarboxylate ligands. In the main activation pathway, the key intermediate is a peroxymonosulfate complex, tentatively identified as PICA-FeIII-OOSO3-, which undergoes O-O homolysis or reacts with FeIII-PICA and PMS to yield FeIV=O and SO4•- without the involvement of commonly invoked Fe(II). PICA-FeIII-OOSO3- can also react directly with certain compounds (chlorophenols and sulfamethoxazole). The relative contributions of PICA-FeIII-OOSO3-, FeIV=O, and SO4•- depend on the structure of target compounds. This work sets an eligible example to enhance the reactivity of Fe(III) toward PMS activation by ligands and sheds light on the previously unrecognized role of the metal-PMS complexes in directing the catalytic cycle and decontamination as well.

Engineered Nanoparticles, Natural Nanoclay and Biochar, as Carriers of Plant-Growth Promoting Bacteria.

The potential of biochar and nanoparticles to serve as effective delivery agents for beneficial bacteria to crops was investigated. Application of nanoparticles and biochar as carriers for beneficial bacteria improved not only the amount of nitrogen-fixing and phosphorus-solubilizing bacteria in soil, but also improved chlorophyll content (1.2-1.3 times), cell viability (1.1-1.5 times), and antioxidative properties (1.1-1.4 times) compared to control plants. Treatments also improved content of phosphorus (P) (1.1-1.6 times) and nitrogen (N) (1.1-1.4 times higher) in both tomato and watermelon plants. However, the effect of biochars and nanoparticles were species-specific. For example, chitosan-coated mesoporous silica nanoparticles with adsorbed bacteria increased the phosphorus content in tomato by 1.2 times compared to a 1.1-fold increase when nanoclay with adsorbed bacteria was applied. In watermelon, the situation was reversed: 1.1-fold increase in the case of chitosan-coated mesoporous silica nanoparticles and 1.2 times in case of nanoclay with adsorbed bacteria. Our findings demonstrate that use of nanoparticles and biochar as carriers for beneficial bacteria significantly improved plant growth and health. These findings are useful for design and synthesis of novel and sustainable biofertilizer formulations.

Computational Predictions of the Hydrolysis of 2,4,6-Trinitrotoluene (TNT) and 2,4-Dinitroanisole (DNAN).

Hydrolysis is a common transformation reaction that can affect the environmental fate of many organic compounds. In this study, three proposed mechanisms of alkaline hydrolysis of 2,4,6-trinitrotoluene (TNT) and 2,4-dinitroaniline (DNAN) were investigated with plane-wave density functional theory (DFT) combined with ab initio and classical molecular dynamics (AIMD/MM) free energy simulations, Gaussian basis set DFT calculations, and correlated molecular orbital theory calculations. Most of the computations in this study were carried out using the Arrows web-based tools. For each mechanism, Meisenheimer complex formation, nucleophilic aromatic substitution, and proton abstraction reaction energies and activation barriers were calculated for the reaction at each relevant site. For TNT, it was found that the most kinetically favorable first hydrolysis steps involve Meisenheimer complex formation by attachment of OH- at the C1 and C3 arene carbons and proton abstraction from the methyl group. The nucleophilic aromatic substitution reactions at the C2 and C4 arene carbons were found to be thermodynamically favorable. However, the calculated activation barriers were slightly lower than in previous studies, but still found to be ΔG‡ ≈ 18 kcal/mol using PBE0 AIMD/MM free energy simulations, suggesting that the reactions are not kinetically significant. For DNAN, the barriers of nucleophilic aromatic substitution were even greater (ΔG‡ > 29 kcal/mol PBE0 AIMD/MM). The most favorable hydrolysis reaction for DNAN was found to be a two-step process in which the hydroxyl first attacks the C1 carbon to form a Meisenheimer complex at the C1 arene carbon C1-(OCH3)OH-, and subsequently, the methoxy anion (-OCH3) at the C1 arene carbon dissociates and the proton shuttles from the C1-OH to the dissociated methoxy group, resulting in methanol and an aryloxy anion.

Mn(II) Acceleration of the Picolinic Acid-Assisted Fenton Reaction: New Insight into the Role of Manganese in Homogeneous Fenton AOPs.

The homogeneous Fe-catalyzed Fenton reaction remains an attractive advanced oxidation process for wastewater treatment, but sustaining the Fe(III)/Fe(II) redox cycle at a convenient pH without the costly input of energy or reductants remains a challenge. Mn(II) is known to accelerate the Fenton reaction, yet the mechanism has never been confidently established. We report a systematic kinetic and spectroscopic investigation into Mn(II) acceleration of atrazine or 2,4,6-trichlorophenol degradation by the picolinic acid (PICA)-assisted Fenton reaction at pH 4.5-6.0. Mn(II) accelerates Fe(III) reduction, superoxide radical (HO2•/O2•-) formation, and hydroxyl radical (HO•) formation. A Mn(II/III)-H2O2 redox cycle as an independent source of reactive oxygen species, as proposed in the literature, is shown to be insignificant. Rather, Mn(II) assists by participating directly and catalytically in the Fe(III)/Fe(II) redox cycle. Initially, Mn(II) (as MnII(PICA)+) complexes with a ferric hydroperoxo species, PICA-FeIII-OOH. The resulting binuclear complex undergoes intramolecular electron transfer to give Fe(II), which later generates HO• from H2O2, plus MnO2+, which later decomposes to HO2•/O2•- (an Fe(III) reductant) and Mn(II), completing the catalytic cycle. This scheme may apply to other Fenton-type systems that go through an FeIII-OOH intermediate. The findings here will inform the design of practical and sustainable Fenton-based AOPs employing Mn(II) in combination with chelating agents.

Sorption and Mobility of Charged Organic Compounds: How to Confront and Overcome Limitations in Their Assessment.

Permanently charged and ionizable organic compounds (IOC) are a large and diverse group of compounds belonging to many contaminant classes, including pharmaceuticals, pesticides, industrial chemicals, and natural toxins. Sorption and mobility of IOCs are distinctively different from those of neutral compounds. Due to electrostatic interactions with natural sorbents, existing concepts for describing neutral organic contaminant sorption, and by extension mobility, are inadequate for IOC. Predictive models developed for neutral compounds are based on octanol-water partitioning of compounds (Kow) and organic-carbon content of soil/sediment, which is used to normalize sorption measurements (KOC). We revisit those concepts and their translation to IOC (Dow and DOC) and discuss compound and soil properties determining sorption of IOC under water saturated conditions. Highlighting possible complementary and/or alternative approaches to better assess IOC mobility, we discuss implications on their regulation and risk assessment. The development of better models for IOC mobility needs consistent and reliable sorption measurements at well-defined chemical conditions in natural porewater, better IOC-, as well as sorbent characterization. Such models should be complemented by monitoring data from the natural environment. The state of knowledge presented here may guide urgently needed future investigations in this field for researchers, engineers, and regulators.

Surface-catalyzed hydrolysis by pyrogenic carbonaceous matter and model polymers: An experimental and computational study on functional group and pore characteristics.

We employed a polymer network to understand what properties of pyrogenic carbonaceous matter (PCM; e.g., activated carbon) confer its reactivity, which we hereinafter referred to as PCM-like polymers (PLP). This approach allows us to delineate the role of functional groups and micropore characteristics using 2,4,6-trinitrotoluene (TNT) as a model contaminant. Six PLP were synthesized via cross-coupling chemistry with specific functionality (-OH, -NH2, -N(CH3)2, or -N(CH3)3+) and pore characteristics (mesopore, micropore). Results suggest that PCM functionality catalyzed the reaction by: (1) serving as a weak base (-OH, -NH2) to attack TNT, or (2) accumulating OH- near PCM surfaces (-N(CH3)3+). Additionally, TNT hydrolysis rates, pH and co-ion effects, and products were monitored. Microporous PLP accelerated TNT decay compared to its mesoporous counterpart, as further supported by molecular dynamics modeling results. We also demonstrated that quaternary ammonium-modified activated carbon enhanced TNT hydrolysis. These findings have broad implications for pollutant abatement and catalyst design.

Physicochemical Changes in Biomass Chars by Thermal Oxidation or Ambient Weathering and Their Impacts on Sorption of a Hydrophobic and a Cationic Compound.

This study examined conditions that mimic oxidative processes of biomass chars during formation and weathering in the environment. A maple char prepared at the single heat treatment temperature of 500 °C for 2 h was exposed to different thermal oxidation conditions or accelerated oxidative aging conditions prior to sorption of naphthalene or the dication paraquat. Strong chemical oxidation (SCO) was included for comparison. Thermal oxidation caused micropore reaming, with ambient oxidation and SCO much less so. All oxidative treatments incorporated O, acidity, and cation exchange capacity (CEC). Thermal incorporation of O was a function of headspace O2 concentration and reached a maximum at 350 °C due to the opposing process of burn-off. The CEC was linearly correlated with O/C, but the positive intercept together with nuclear magnetic resonance data signifies that, compared to O groups derived by anoxic pyrolysis, O acquired through oxidation by thermal or ambient routes contributes more to the CEC. Thermal oxidation increased the naphthalene sorption coefficient, the characteristic energy of sorption, and the uptake rate due to pore reaming. By contrast, ambient oxidation (and SCO) suppressed naphthalene sorption by creating a more hydrophilic surface. Paraquat sorption capacity was predicted by an equation that includes a CEC2 term due to bidentate interaction with pairs of charges, predominating over monodentate interaction, plus a term for the capacity of naphthalene as a reference representing nonspecific driving forces.

The Fenton Reaction in Water Assisted by Picolinic Acid: Accelerated Iron Cycling and Co-generation of a Selective Fe-Based Oxidant.

The Fenton reaction is limited by a narrow acidic pH range, the slow reduction of Fe(III), and susceptibility of the nonselective hydroxyl radical (HO•) to scavenging by water constituents. Here, we employed the biodegradable chelating agent picolinic acid (PICA) to address these concerns. Compared to the classical Fenton reaction at pH 3.0, PICA greatly accelerated the degradation of atrazine, sulfamethazine, and various substituted phenols at pH 5.0 in a reaction with autocatalytic characteristics. Although HO• served as the principal oxidant, a high-spin, end-on hydroperoxo intermediate, tentatively identified as PICA-FeIII-OOH, also exhibited reactivity toward several test compounds. Chloride release from the oxidation of 2,4,6-trichlorophenol and the positive slope of the Hammett correlation for a series of halogenated phenols were consistent with PICA-FeIII-OOH reacting as a nucleophilic oxidant. Compared to HO•, PICA-FeIII-OOH is less sensitive to potential scavengers in environmental water samples. Kinetic analysis reveals that PICA facilitates Fe(III)/Fe(II) transformation by accelerating Fe(III) reduction by H2O2. Autocatalysis is ascribed to the buildup of Fe(II) from the reduction of Fe(III) by H2O2 as well as PICA oxidation products. PICA assistance in the Fenton reaction may be beneficial to wastewater treatment because it favors iron cycling, extends the pH range, and balances oxidation universality with selectivity.

Adsorption of Organic Compounds by Biomass Chars: Direct Role of Aromatic Condensation (Ring Cluster Size) Revealed by Experimental and Theoretical Studies.

Biomass chars are a major component of the soil environmental black carbon pool and prepared forms are a potentially useful tool in remediation. A function critical to the roles of both environmental and prepared chars is sorption of organic compounds. Char properties known to control sorption include surface area, porosity, functional group composition, and percent aromatic carbon. Here, we show that sorption affinity (but not maximum capacity) of organic compounds is directly related to the degree of condensation of the aromatic fraction. The Dubinin-Ashtakov characteristic sorption energy (EDA, kJ mol-1) of 22 compounds on a thermoseries of bamboo chars correlates strongly with the DP/MAS-13C NMR-determined bridgehead aromatic carbon fraction (χb), which relates to the mean ring cluster size. Density functional theory-computed binding energy (Ebd) for five of the compounds on a representative series of polybenzenoid hydrocarbon open-face sheets also correlates positively with χb, leveling off for rings larger than ∼C55. The Ebd, in turn, correlates strongly with EDA. An increase in Ebd with cluster size is also found for sorption, both monolayer and bilayer, between parallel sheets representing slit micropores. The increasing sorption energy with cluster size is shown to be due to increasing cluster polarizability, which strengthens dispersion forces with the sorbate. The findings underscore a previously overlooked explicit role of aromatic condensation in sorption energy, and illustrate the utility of EDA-Ebd comparison for predicting sorption.

Reaction of Substituted Phenols with Lignin Char: Dual Oxidative and Reductive Pathways Depending on Substituents and Conditions.

Biomass chars are known to be intrinsically redox-reactive toward some organic compounds, but the mechanisms are still unclear. To address this, a char made anoxically at 500 °C from dealkaline lignin was reacted either in the fresh state or after 180-day aging in air with p-nitrophenol (NO2-P), p-hydroxybenzaldehyde (CHO-P), phenol (H-P), or p-methoxyphenol (MeO-P). The reactions were carried out under oxic or anoxic conditions. Degradation occurred in all cases. Both oxidation and reduction products were identified, with yields dependent on the presence or absence of air during reaction or storage. They included oligomers, amines, and ring-hydroxylated compounds, among others. Exposure to air suppressed sorption, annihilated reducing sites, and provided a source of reactive oxygen species that assisted degradation. Sorption suppression was due to the incorporation of hydrophilic groups by chemisorption of oxygen, and possibly blockage of sites by products. Fresh char has comparable electron-donating and accepting capacity, whereas there is a preponderance of electron-accepting over donating capacity in aged char. Under anoxic conditions, both oxidation and reduction occurred. Under oxic conditions or after aging in air, oxidation predominated, and linear free energy relationships were found between the rate constant and the Hammett or Brown substituent electronic parameter or the standard electrode potential of the phenol. The results demonstrate that chars possess heterogeneous redox activities depending on reaction pairs, reaction conditions, and aging.

Modification of pyrogenic carbons for phosphate sorption through binding of a cationic polymer.

This study reports on the development of modified pyrogenic carbonaceous materials (PCMs) for recovering orthophosphate (PO4-P). The PCMs include softwood and hardwood biochars and a commercial granular activated carbon (GAC) that were modified by irreversible adsorption of the quaternary ammonium polymer, poly(diallyldimethylammonium) chloride (pDADMAC), which reverses electrokinetic charge and increases PO4-P sorption. MgO-doped biochars were prepared by a literature method for comparison. Imaging and spectroscopic analyses characterize pDADMAC coverage, MgO doping, and binding of PO4-P. At environmentally relevant concentrations, PO4-P sorption by the pDADMAC-treated biochars was ~100 times greater than that of the corresponding unmodified biochars, and was comparable to that of the corresponding MgO-doped biochars on a coating content basis. The pDADMAC-coated carbons bind PO4-P by ion exchange, while the MgO-doped biochars bind PO4-P principally by forming an amorphous Mg phosphate species. Susceptibility to competition from other relevant anions (Cl-, NO3-, HCO3-/CO32-, SO42-) and poultry and dairy manure extracts was moderate and comparable for the two types of modified softwood biochars. Sorption to the pDADMAC-treated biochars appears to be more reversible than to the MgO-doped biochars using stepwise water extraction. Greater reversibility may be advantageous for trapping and recycling phosphate.

Biochar amendment as a remediation strategy for surface soils impacted by crude oil.

The impact of organic bulking agents on the biodegradation of petroleum hydrocarbons in crude oil impacted soils was evaluated in batch laboratory experiments. Crude oil impacted soils from three separate locations were amended with fertilizer and bulking agents consisting of biochars derived from walnut shells or ponderosa pine wood chips produced at 900 °C. The batch reactors were incubated at 25 °C and sampled at pre-determined intervals to measure changes in total petroleum hydrocarbons (TPH) over time. For the duration of the incubation, the soil moisture content was adjusted to 75% of the maximum water holding capacity (MWHC) and prior to each sampling event, the sample was manually stirred. Results show that the addition of fertilizer and bulking agents increased biodegradation rates of TPH. Soil samples amended with ponderosa pine wood biochar achieved the highest biodegradation rate, whereas the walnut shell biochar was inhibitory to TPH biodegradation. The beneficial impact of biochars on TPH biodegredation was more pronounced for a soil impacted with lighter hydrocarbons compared to a soil impacted with heavier hydrocarbons. This study demonstrates that some biochars, in combination with fertilizer, have the potential to be a low-technology and eco-friendly remediation strategy for crude oil impacted soils.

Peroxymonosulfate Oxidizes Amino Acids in Water without Activation.

A variety of peptidic and proteinaceous contaminants (e.g., proteins, toxins, pathogens) present in the environment may pose risk to human health and wildlife. Peroxymonosulfate is a strong oxidant (EH0 = 1.82 V for HSO5-, the predominant species at environmental pH values) that may hold promise for the deactivation of proteinaceous contaminants. Relatively little quantitative information exists on the rates of peroxymonosulfate reactions with free amino acids. Here, we studied the oxidation of 19 of the 20 standard proteinogenic amino acids (all except cysteine) by peroxymonosulfate without explicit activation. Reaction half-lives at pH 7 ranged from milliseconds to hours. Amino acids possessing sulfur-containing, heteroaromatic, or substituted aromatic side chains were the most susceptible to oxidation by peroxymonosulfate, with rates of transformation decreasing in the order methionine > tryptophan > tyrosine > histidine. The rate of tryptophan oxidation did not decrease in the presence of an aquatic natural organic matter. Singlet oxygen resulting from peroxymonosulfate self-decomposition, while detected by electron paramagnetic resonance spectroscopy, was unlikely to be the principal reactive species. Our results demonstrate that peroxymonosulfate is capable of oxidizing 19 amino acids without explicit activation and that solvent-exposed methionine and tryptophan residues are likely initial targets of oxidation in peptides and proteins.

Adsorption and desorption of nitrous oxide by raw and thermally air-oxidized chars.

Addition of biomass chars (biochar) to soil reportedly suppresses emissions of nitrous oxide (N2O), a potent greenhouse and ozone-depleting gas, but the causes and endurance of the effect are unclear. To determine whether adsorption may play a role, adsorption isotherms of N2O were constructed at 273 K on outgassed samples of anoxically-prepared wood-derived chars (300-700 °C) and on a subset briefly reheated in air at 400 °C. Sorption by the chars was greater and more reversible than sorption by soils or soil mineral phases. Adsorption by chars increased with pyrolysis temperature and upon post-pyrolysis air oxidation. The Langmuir maximum capacity correlates well with the CO2-determined (but not N2-B.E.T.-determined) surface area. At environmentally realistic partial pressures in soil, N2O adsorption correlates with CO2 adsorption, and is found to predominate in the micropores (<1.5 nm), especially ultramicropores (<0.7 nm). Neither adsorption nor adsorption reversibility was affected by coating the char with soil organic matter extract. It is concluded that char added at levels above 1% in soil would act as a strong and reversible sink for N2O, and could be responsible for the temporary nature of N2O emission suppression observed in some cases.

Charge-assisted hydrogen bonding as a cohesive force in soil organic matter: water solubility enhancement by addition of simple carboxylic acids.

Weak bonds between molecular segments and between separate molecules of natural organic matter (OM) govern OM solubility, adsorption, supramolecular association in solution, and complexation with metal ions and oxides. We tested the hypothesis that especially strong hydrogen bonds, known as (negative) charge-assisted hydrogen bonds, (-)CAHB, contribute significantly to OM cohesion and play a role in the water solubility of solid-phase OM. The (-)CAHB, exemplified by structures such as (-CO2HO2C-)- and (-CO2HO-)-, may form between weak acids with similar proton affinity, and is shorter, more covalent, and much stronger than ordinary hydrogen bonds. Using a high-organic reference soil, we show that (-)CAHBs within the solid OM phase (intra-OM) are disrupted by solutions of aliphatic and aromatic acids, resulting in enhanced solubility of OM. The aromatic acids included naturally occurring plant exudate compounds. At constant pH and ionic strength, OM solubility increased with added organic acid concentration and molecular weight. Polar compounds incapable of forming (-)CAHBs, such as alkanols, acetonitrile, and dimethyl sulfoxide, were ineffective. Solubility enhancement showed behavior consistent with (-)CAHB theory and published observations-namely, (i) that formate is more effective than acetate due to its tendency to form stronger (-)CAHBs; (ii) that solubility enhancement peaks at pH ∼5-6, where the product of the concentration of the interacting carboxylate ions reaches a maximum; and (iii) that elution of acetate or formate through soil columns releases hydroxide ion, consistent with formation of (-)CAHBs between added acid and free weak acid groups on the solid OM. The results support the hypothesis that the (-)CAHB contributes to the cohesion of OM in the solid state.

Oxidation of Organic Compounds in Water by Unactivated Peroxymonosulfate.

Peroxymonosulfate (HSO5- and PMS) is an optional bulk oxidant in advanced oxidation processes (AOPs) for treating wastewaters. Normally, PMS is activated by the input of energy or reducing agent to generate sulfate or hydroxyl radicals or both. This study shows that PMS without explicit activation undergoes direct reaction with a variety of compounds, including antibiotics, pharmaceuticals, phenolics, and commonly used singlet-oxygen (1O2) traps and quenchers, specifically furfuryl alcohol (FFA), azide, and histidine. Reaction time frames varied from minutes to a few hours at pH 9. With the use of a test compound with intermediate reactivity (FFA), electron paramagnetic resonance (EPR) and scavenging experiments ruled out sulfate and hydroxyl radicals. Although 1O2 was detected by EPR and is produced stoichiometrically through PMS self-decomposition, 1O2 plays only a minor role due to its efficient quenching by water, as confirmed by experiments manipulating the 1O2 formation rate (addition of H2O2) or lifetime (deuterium solvent isotope effect). Direct reactions with PMS are highly pH- and ionic-strength-sensitive and can be accelerated by (bi)carbonate, borate, and pyrophosphate (although not phosphate) via non-radical pathways. The findings indicate that direct reaction with PMS may steer degradation pathways and must be considered in AOPs and other applications. They also signal caution to researchers when choosing buffers as well as 1O2 traps and quenchers.