A study of the reaction of ferrate with pentachlorophenol - kinetics and degradation products.

Pentachlorophenol (PCP) is a persistent pollutant which has been widely used as a pesticide and a wood preservative. As PCP is toxic and is present in significant quantities in the environment, there is considerable interest in elimination of PCP from waters. One of the promising methods is the application of ferrate. Ferrate is an oxidant and coagulant. It can be applied as a multi-purpose chemical for water and wastewater treatment as it degrades a wide range of environmental pollutants. Moreover, ferrate is considered a green oxidant and disinfectant. This study focuses on the kinetics of PCP degradation by ferrate under different pH conditions. The formation of degradation products is also considered. The second-order rate constants of the PCP reaction with ferrate increased from 23 M-1 s-1 to 4,948 M-1 s-1 with a decrease in pH from 9 to 6. At neutral pH the degradation was fast, indicating that ferrate could be used for rapid removal of PCP. The total degradation of PCP was confirmed by comparing the initial PCP molarity with the molarity of chloride ions released. We conclude no harmful products are formed during ferrate treatment as all PCP chlorine was released as chloride. Specifically, no polychlorinated dibenzo-p-dioxins and dibenzofurans were detected.

Degradability of chlorophenols using ferrate(VI) in contaminated groundwater.

The production and use of chlorophenolic compounds in industry has led to the introduction of many xenobiotics, among them chlorophenols (CPs), into the environment. Five CPs are listed in the priority pollutant list of the U.S. EPA, with pentachlorophenol (PCP) even being proposed for listing under the Stockholm Convention as a persistent organic pollutant (POP). A green procedure for degrading such pollutants is greatly needed. The use of ferrate could be such a process. This paper studies the degradation of CPs (with an emphasis on PCP) in the presence of ferrate both in a spiked demineralized water system as well as in real contaminated groundwater. Results proved that ferrate was able to completely remove PCP from both water systems. Investigation of the effect of ferrate purity showed that even less pure and thus much cheaper ferrate was applicable. However, with decreasing ferrate purity, the degradability of CPs may be lower.

Degradability of hexachlorocyclohexanes in water using ferrate (VI).

Regarding environmental pollution, the greatest public and scientific concern is aimed at the pollutants listed under the Stockholm Convention. These pollutants are not only persistent but also highly toxic with a high bioaccumulation potential. One of these pollutants, γ-hexachlorocyclohexane (γ-HCH), has been widely used in agriculture, which has resulted in wide dispersion in the environment. Remediation of this persistent and hazardous pollutant is difficult and remains unresolved. Of the many different approaches tested, to date, none has used ferrates. This is unexpected as ferrates are generally believed to be an ideal chemical reagent for water treatment due to their strong oxidation potential and the absence of harmful by-products. In this paper, the degradation/transformation of HCHs by ferrates under laboratory conditions was studied. HCH was degraded during this reaction, producing trichlorobenzenes and pentachlorocyclohexenes as by-products. A detailed investigation of pH conditions during Fe(VI) application identified pH as the main factor affecting degradation. We conclude that ferrate itself is unreactive with HCH and that high pH values, produced by K2O impurity and the reaction of ferrate with water, are responsible for HCH transformation. Finally, a comparison of Fe(VI) with Fe(0) is provided in order to suggest their environmental applicability for HCH degradation.

Field emission scanning electron microscopy (FE-SEM) as an approach for nanoparticle detection inside cells.

When developing new nanoparticles for bio-applications, it is important to fully characterize the nanoparticle's behavior in biological systems. The most common techniques employed for mapping nanoparticles inside cells include transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM). These techniques entail passing an electron beam through a thin specimen. STEM or TEM imaging is often used for the detection of nanoparticles inside cellular organelles. However, lengthy sample preparation is required (i.e., fixation, dehydration, drying, resin embedding, and cutting). In the present work, a new matrix (FTO glass) for biological samples was used and characterized by field emission scanning electron microscopy (FE-SEM) to generate images comparable to those obtained by TEM. Using FE-SEM, nanoparticle images were acquired inside endo/lysosomes without disruption of the cellular shape. Furthermore, the initial steps of nanoparticle incorporation into the cells were captured. In addition, the conductive FTO glass endowed the sample with high stability under the required accelerating voltage. Owing to these features of the sample, further analyses could be performed (material contrast and energy-dispersive X-ray spectroscopy (EDS)), which confirmed the presence of nanoparticles inside the cells. The results showed that FE-SEM can enable detailed characterization of nanoparticles in endosomes without the need for contrast staining or metal coating of the sample. Images showing the intracellular distribution of nanoparticles together with cellular morphology can give important information on the biocompatibility and demonstrate the potential of nanoparticle utilization in medicine.