Permanganate Oxidation of Organic Contaminants and Model Compounds.

Permanganate oxidation is an attractive environmental remediation strategy due to its low cost, ease of use, and wide range in reactivity. Here, permanganate reactivity trends are investigated for model organic compounds and organic contaminants. Second-order permanganate reaction rate constants were compiled for 215 compounds from 82 references (journal articles, conference proceedings, master's theses, and dissertations). Additionally, we validated some phenol rate constants and contribute a few additional phenol rate constants. Commonalities between contaminant oxidation products are also discussed, and we tentatively identify several model compound oxidation products. Aromatic rings, alcohols, and ether groups had low reaction rate constants with permanganate. Alkene reaction sites had the highest reaction rate constants, followed by phenols, anilines, and benzylic carbon-hydrogen bonds. Generally, permanganate reactivity follows electrophilic substitution trends at the reaction site where electron donating groups increase the rate of reaction, while electron withdrawing groups decrease the rate of reaction. Solution conditions, specifically, buffer type and concentration, may impact the rate of reaction, which could be due to either an ionic strength effect or the buffer ions acting as ligands. The impact of these solution conditions, unfortunately, precludes the development of a quantitative structure-activity relationship for permanganate reaction rate constants with the currently available data. We note that critical experimental details are often missing in the literature, which posed a challenge when comparing rate constants between studies. Future research directions on permanganate oxidation should seek to improve our understanding of buffer effects and to identify oxidation products for model compounds so that extrapolations can be made to more complex contaminant structures.

Chemical Alterations of Dissolved Organic Matter by Permanganate Oxidation.

Dissolved organic matter (DOM) is ubiquitous in raw drinking water and can efficiently scavenge oxidants, such as permanganate. Here, changes to DOM induced by permanganate oxidation under typical drinking water treatment conditions (6 µM, 1 h) to bulk DOM properties, DOM functional groups, and DOM chemical formulae were examined for two DOM isolate types (terrestrial and microbial). Permanganate oxidation did not mineralize DOM, rather changes were compositional in nature. Optical properties suggest that permanganate oxidation decreased DOM aromaticity (decreased SUVA-254), decreased DOM electron-donating capacity, and decreased DOM average molecular weight (increased E2/E3 ratios). Fourier-transform-infrared spectroscopy second derivative analyses revealed that permanganate does not oxidize DOM alkene groups, suggesting permanganate access to functional groups may be important. Four ionization techniques were used with ultrahigh-resolution mass spectrometry: negative and positive ion mode electrospray ionization and negative and positive ion mode laser/desorption ionization. The results from all four techniques were combined to understand changes in DOM chemical formulae. It was concluded that nitrogen-containing aromatic compounds and alkylbenzenes were oxidized by permanganate to form nitrogen-containing aliphatic compounds and benzoic acid-containing compounds. This work highlights how multiple ionization techniques coupled with UHR-MS can enable a more detailed characterization of DOM.

Data-Based Chemical Class Regions for Van Krevelen Diagrams.

Ultrahigh resolution mass spectrometry (UHR-MS) is commonly used to characterize natural organic matter (NOM). The complexity of both NOM and the data set produced make data visualization challenging. Van Krevelen diagrams─plots of component hydrogen/carbon (H/C) against oxygen/carbon (O/C) elemental ratios─have become a popular way to visualize the chemical formulas identified by UHR-MS. Different regions on the van Krevelen diagram have been attributed to different chemical classes; however, the classifications vary between studies and the regions lack standard definitions. Here, chemical formulas were obtained from public databases to create H/C and O/C ranges for amino sugar, carbohydrate, lignin, lipid, peptide, and tannin chemical classes on van Krevelen diagrams. The recommended H/C and O/C ranges are presented in a table and can be adapted to any data analysis software programs. The regions recommended here agreed reasonably well with previous literature for amino sugar, carbohydrate, lignin, lipid, and peptide regions. However, the recommended tannin region appears at lower H/C ratio values and with a wider range of O/C ratio values compared to previous studies. The regions presented herein are strongly recommended for use as consistent reference points in future NOM characterization studies to aid in the discussion of data and to readily compare studies.

Removal of cyanotoxins by potassium permanganate: Incorporating competition from natural water constituents.

In recent years, harmful algal blooms capable of producing toxins including microcystins, cylindrospermopsin, and saxitoxin have increased in occurrence and severity. These toxins can enter drinking water treatment plants and, if not effectively removed, pose a serious threat to human health. The work here investigated the efficacy of permanganate oxidation as a treatment strategy, with a focus on incorporating competition by cyanobacterial cells and dissolved organic matter (DOM). We report rate constants of 272 ±â€¯23 M-1 s-1 for the reaction between permanganate and microcystin-LR, 0.26 ±â€¯0.05 M-1 s-1 for the reaction between permanganate and cylindrospermopsin, and, using chemical analogs, estimate a maximum rate constant of 2.7 ±â€¯0.2 M-1 s-1 for the reaction between permanganate and saxitoxin. We conclude that permanganate only shows potential to remove microcystins. No pH (6-10) or alkalinity (0-50 mM) dependence was observed for the rate of reaction between microcystin-LR and permanganate; however, a temperature dependence was observed and can be characterized by an activation energy of 16 ±â€¯5 kJ mol-1. The competition posed by cyanobacterial cells was quantified by an apparent second order rate constant of 2.5 ±â€¯0.3 × 10-6 L µg chl-a-1 s-1. From this apparent second order rate constant, it was concluded that cyanobacterial cells are not efficient scavengers of permanganate within typical contact times but this second order rate constant can be used to accurately predict microcystin degradation in algal-impacted waters. The competition posed by DOM depended on both the amount of DOM present (as measured by TOC) and its electron donating capacity (as predicted by SUVA-254 or E2/E3 ratio). DOM was concluded to scavenge permanganate efficiently and we forward that this should be considered in permanganate dosing calculations.

Diethyl phenylene diamine (DPD) oxidation to measure low concentration permanganate in environmental systems.

Permanganate has been used traditionally in drinking water treatment for its oxidation properties and ease of use. The concentration of permanganate in treatment conditions is low and difficult to detect. A colorimetric method using diethylphenylene diamine (DPD) oxidation to measure low levels (i.e., less than 6 µM) of permanganate in water was developed and applied to quantify permanganate scavenging by dissolved organic matter (DOM). Manganese dioxide (MnO2) particles were shown to interfere with DPD oxidation; however, particles were removed effectively using 0.1 µm PVDF filters prior to reaction with DPD. DOM and complexed-Mn(III) were concluded to not interfere with the DPD reaction. The DPD method was validated by obtaining the second-order rate constant for permanganate reaction with phenol (1.7 ±â€¯0.2 M-1 s-1), and comparing to the rate constant obtained independently by monitoring phenol degradation (i.e., UPLC-UV) (1.6 ±â€¯0.2 M-1 s-1). Permanganate reaction with DOM isolate samples did not follow pseudo-first order kinetics. Faster reaction rates were observed with higher ionic strength (1 mM versus 5 mM carbonate). No change in reaction rates with pH was observed at lower ionic strength (1 mM); while at higher ionic strength, the reaction rate was faster at pH 7 than at pH 10. In contrast, linear kinetics were observed for permanganate reaction with DOM in filtered whole water samples. These samples showed similar trends with pH and ionic strength as for DOM isolates. The presented method is valid to quantify permanganate reaction rates with organic contaminants or with natural scavengers.