This study introduces graphited nanodiamond (G-ND) as an environmentally friendly, easy-to-regenerate, and cost-effective alternative catalyst to activate persulfate (i.e., peroxymonosulfate (PMS) and peroxydisulfate (PDS)) and oxidize organic compounds in water. The G-ND was found to be superior for persulfate activation to other benchmark carbon materials such as graphite, graphene, fullerene, and carbon nanotubes. The G-ND/persulfate showed selective reactivity toward phenolic compounds and some pharmaceuticals, and the degradation kinetics were not inhibited by the presence of oxidant scavengers and natural organic matter. These results indicate that radical intermediates such as sulfate radical anion and hydroxyl radical are not majorly responsible for this persulfate-driven oxidation of organic compounds. The findings from linear sweep voltammetry, thermogravimetric analysis, Fourier transform infrared spectroscopy, and electron paramagnetic resonance spectroscopy analyses suggest that the both persulfate and phenol effectively bind to G-ND surface and are likely to form charge transfer complex, in which G-ND plays a critical role in mediating facile electron transfer from phenol to persulfate.
This study reports that the combination of Cu(II) with hydroxylamine (HA) (referred to herein as Cu(II)/HA system) in situ generates H2O2 by reducing dissolved oxygen, subsequently producing reactive oxidants through the reaction of Cu(I) with H2O2. The external supply of H2O2 to the Cu(II)/HA system (i.e., the Cu(II)/H2O2/HA system) was found to further enhance the production of reactive oxidants. Both the Cu(II)/HA and Cu(II)/H2O2/HA systems effectively oxidized benzoate (BA) at pH between 4 and 8, yielding a hydroxylated product, p-hydroxybenzoate (pHBA). The addition of a radical scavenger, tert-butyl alcohol, inhibited the BA oxidation in both systems. However, electron paramagnetic resonance (EPR) spectroscopy analysis indicated that (•)OH was not produced under either acidic or neutral pH conditions, suggesting that the alternative oxidant, cupryl ion (Cu(III)), is likely a dominant oxidant.
Pointer invalidation has been a popular approach adopted in many recent studies to mitigate use-after-free errors. The approach can be divided largely into two different schemes: explicit invalidation and implicit invalidation. The former aims to eradicate the root cause of use-after-free errors by explicitly invalidating every dangling pointer. In contrast, the latter aims to prevent dangling pointers by freeing an object only if there is no pointer referring to it. A downside of the explicit scheme is that it is expensive, as it demands high-cost algorithms or a large amount of space to maintain up-to-date lists of pointer locations linking to each object. Implicit invalidation is more efficient in that even without any explicit effort, it can eliminate dangling pointers by leaving objects undeleted until all the links between the objects and their referring pointers vanish by themselves during program execution. However, such an argument only holds if the scheme knows exactly when each link is created and deleted. Reference counting is a traditional method to determine the existence of reference links between objects and pointers. Unfortunately, impeccable reference counting for legacy C/C++ code is very difficult and expensive to achieve in practice, mainly because of the type unsafe operations in the code. In this paper, we present a solution, called CRCount, to the use-after-free problem in legacy C/C++. For effective and efficient problem solving, CRCount is armed with the pointer footprinting technique that enables us to compute, with high accuracy, the reference count of every object referred to by the pointers in the legacy code. Our experiments demonstrate that CRCount mitigates the useafter-free errors with a lower performance-wise and space-wise overhead than the existing pointer invalidation solutions.
Oxidative degradation of six representative microcystins (MCs) (MC-RR, -LR, -YR, -LF, -LW, and -LA) by potassium permanganate (KMnO; Mn(VII)) was investigated, focusing on the temperature- and pH-dependent reaction kinetics, the effect of dissolved organic matter (DOM), and the oxidation mechanisms. Second-order rate constants for the reactions of the six MCs with Mn(VII) ( k) were determined to be 160.4-520.1 M s (MC-RR > -LR ≈ -YR > -LF ≈ -LW > -LA) at pH 7.2 and 21 °C. The k values exhibited activation energies ranging from 15.1 to 22.4 kJ mol. With increasing pH from 2 to 11, the k values decreased until pH 5, and plateaued over the pH range of 5-11, except for that of MC-YR (which increased at pH > 8). Species-specific second-order rate constants were calculated using predicted p K values of MCs. The oxidation of MCs in natural waters was accurately predicted by the kinetic model using k and Mn(VII) exposure (∫[Mn(VII)]dt) values. Among different characteristics of DOM in natural waters, UV, SUVA, and the abundance of humic-like substances characterized by fluorescence spectroscopy exhibited good correlation with ∫[Mn(VII)]dt. A thorough product study of MC-LR oxidation by Mn(VII) was performed using liquid chromatography-mass spectrometry.
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