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      Ferrate(VI) pre-treatment and subsequent chlorination of blue-green algae: Quantification of disinfection byproducts

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          Abstract

          Algal organic matter (AOM) from seasonal algal blooms may be an important precursor of disinfection byproducts (DBPs) in drinking water. This paper presents the effect of ferrate(VI) treatment on two blue-green algae, Chlorella sp. and Pseudanabaena limnetica, in eutrophic water. The results demonstrated that Fe(VI) removed the algal cells by causing cell death, apoptosis, and lost integrity, and decreased AOM (in terms of total organic carbon) in water via oxidation and coagulation. Chlorination of the Fe(VI) pre-oxidized algal water samples generated halogenated DBPs (including trihalomethanes, haloacetic acids, haloketones, chloral hydrate, haloacetonitriles, and trichloronitromethane), but the concentrations of DBPs were lower than those formed in the chlorinated samples without pre-treatment by Fe(VI). Higher Fe(VI) dose, longer oxidation time, and alkaline pH were beneficial in controlling DBPs. In bromide-containing algal solutions, negligible amount of bromo-DBPs were generated in the Fe(VI) pre-oxidation, and halogenated DBPs were mainly formed in the subsequent chlorination.

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          Fluorescence excitation-emission matrix regional integration to quantify spectra for dissolved organic matter.

          Wen Wei Chen, Paul Westerhoff, Jerry Leenheer … (2003)
          Excitation-emission matrix (EEM) fluorescence spectroscopy has been widely used to characterize dissolved organic matter (DOM) in water and soil. However, interpreting the > 10,000 wavelength-dependent fluorescence intensity data points represented in EEMs has posed a significant challenge. Fluorescence regional integration, a quantitative technique that integrates the volume beneath an EEM, was developed to analyze EEMs. EEMs were delineated into five excitation-emission regions based on fluorescence of model compounds, DOM fractions, and marine waters or freshwaters. Volumetric integration under the EEM within each region, normalized to the projected excitation-emission area within that region and dissolved organic carbon concentration, resulted in a normalized region-specific EEM volume (phi(i,n)). Solid-state carbon nuclear magnetic resonance (13C NMR), Fourier transform infrared (FTIR) analysis, ultraviolet-visible absorption spectra, and EEMs were obtained for standard Suwannee River fulvic acid and 15 hydrophobic or hydrophilic acid, neutral, and base DOM fractions plus nonfractionated DOM from wastewater effluents and rivers in the southwestern United States. DOM fractions fluoresced in one or more EEM regions. The highest cumulative EEM volume (phi(T,n) = sigma phi(i,n)) was observed for hydrophobic neutral DOM fractions, followed by lower phi(T,n) values for hydrophobic acid, base, and hydrophilic acid DOM fractions, respectively. An extracted wastewater biomass DOM sample contained aromatic protein- and humic-like material and was characteristic of bacterial-soluble microbial products. Aromatic carbon and the presence of specific aromatic compounds (as indicated by solid-state 13C NMR and FTIR data) resulted in EEMs that aided in differentiating wastewater effluent DOM from drinking water DOM.
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            Occurrence, genotoxicity, and carcinogenicity of regulated and emerging disinfection by-products in drinking water: a review and roadmap for research.

            S. Richardson, M. Plewa, E. Wagner … (2007)
            Disinfection by-products (DBPs) are formed when disinfectants (chlorine, ozone, chlorine dioxide, or chloramines) react with naturally occurring organic matter, anthropogenic contaminants, bromide, and iodide during the production of drinking water. Here we review 30 years of research on the occurrence, genotoxicity, and carcinogenicity of 85 DBPs, 11 of which are currently regulated by the U.S., and 74 of which are considered emerging DBPs due to their moderate occurrence levels and/or toxicological properties. These 74 include halonitromethanes, iodo-acids and other unregulated halo-acids, iodo-trihalomethanes (THMs), and other unregulated halomethanes, halofuranones (MX [3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone] and brominated MX DBPs), haloamides, haloacetonitriles, tribromopyrrole, aldehydes, and N-nitrosodimethylamine (NDMA) and other nitrosamines. Alternative disinfection practices result in drinking water from which extracted organic material is less mutagenic than extracts of chlorinated water. However, the levels of many emerging DBPs are increased by alternative disinfectants (primarily ozone or chloramines) compared to chlorination, and many emerging DBPs are more genotoxic than some of the regulated DBPs. Our analysis identified three categories of DBPs of particular interest. Category 1 contains eight DBPs with some or all of the toxicologic characteristics of human carcinogens: four regulated (bromodichloromethane, dichloroacetic acid, dibromoacetic acid, and bromate) and four unregulated DBPs (formaldehyde, acetaldehyde, MX, and NDMA). Categories 2 and 3 contain 43 emerging DBPs that are present at moderate levels (sub- to low-mug/L): category 2 contains 29 of these that are genotoxic (including chloral hydrate and chloroacetaldehyde, which are also a rodent carcinogens); category 3 contains the remaining 14 for which little or no toxicological data are available. In general, the brominated DBPs are both more genotoxic and carcinogenic than are chlorinated compounds, and iodinated DBPs were the most genotoxic of all but have not been tested for carcinogenicity. There were toxicological data gaps for even some of the 11 regulated DBPs, as well as for most of the 74 emerging DBPs. A systematic assessment of DBPs for genotoxicity has been performed for approximately 60 DBPs for DNA damage in mammalian cells and 16 for mutagenicity in Salmonella. A recent epidemiologic study found that much of the risk for bladder cancer associated with drinking water was associated with three factors: THM levels, showering/bathing/swimming (i.e., dermal/inhalation exposure), and genotype (having the GSTT1-1 gene). This finding, along with mechanistic studies, highlights the emerging importance of dermal/inhalation exposure to the THMs, or possibly other DBPs, and the role of genotype for risk for drinking-water-associated bladder cancer. More than 50% of the total organic halogen (TOX) formed by chlorination and more than 50% of the assimilable organic carbon (AOC) formed by ozonation has not been identified chemically. The potential interactions among the 600 identified DBPs in the complex mixture of drinking water to which we are exposed by various routes is not reflected in any of the toxicology studies of individual DBPs. The categories of DBPs described here, the identified data gaps, and the emerging role of dermal/inhalation exposure provide guidance for drinking water and public health research.
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              Role of Ferrate(IV) and Ferrate(V) in Activating Ferrate(VI) by Calcium Sulfite for Enhanced Oxidation of Organic Contaminants

              Binbin Shao, Hongyu Dong, Bo K. Sun … (2018)
              Although the Fe(VI)-sulfite process has shown great potential for the rapid removal of organic contaminants, the major active oxidants (Fe(IV)/Fe(V) versus SO4•-/•OH) involved in this process are still under debate. By employing sparingly soluble CaSO3 as a slow-releasing source of SO32-, this study evaluated the oxidation performance of the Fe(VI)-CaSO3 process and identified the active oxidants involved in this process. The process exhibited efficient oxidation of a variety of compounds, including antibiotics, pharmaceuticals, and pesticides, at rates that were 6.1-173.7-fold faster than those measured for Fe(VI) alone, depending on pH, CaSO3 dosage, and the properties of organic contaminants. Many lines of evidence verified that neither SO4•- nor •OH was the active species in the Fe(VI)-CaSO3 process. The accelerating effect of CaSO3 was ascribed to the direct generation of Fe(IV)/Fe(V) species from the reaction of Fe(VI) with soluble SO32- via one-electron steps as well as the indirect generation of Fe(IV)/Fe(V) species from the self-decay of Fe(VI) and Fe(VI) reaction with H2O2, which could be catalyzed by uncomplexed Fe(III). Besides, the Fe(VI)-CaSO3 process exhibited satisfactory removal of organic contaminants in real water, and inorganic anions showed negligible effects on organic contaminant decomposition in this process. Thus, the Fe(VI)-CaSO3 process with Fe(IV)/Fe(V) as reactive oxidants may be a promising method for abating various micropollutants in water treatment.
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                Author and article information

                Journal
                Journal ID (nlm-journal-id): 7807270
                Journal ID (pubmed-jr-id): 22115
                Journal ID (nlm-ta): Environ Int
                Journal ID (iso-abbrev): Environ Int
                Title: Environment international
                ISSN (Print): 0160-4120
                ISSN (Electronic): 1873-6750
                Publication date Nihms-submitted: 25 November 2020
                Publication date (Electronic): 22 October 2019
                Publication date (Print): December 2019
                Publication date PMC-release: 03 December 2020
                Volume: 133
                Issue: Pt B
                Page: 105195
                Affiliations
                [a ]College of Civil Engineering and Architecture, Zhejiang University, Hangzhou 310027, China
                [b ]School of Environment and Architecture, University of Shanghai for Science and Technology, Shanghai 200433, China
                [c ]Department of Environmental and Occupational Health, School of Public Health, Texas A&M University, College Station, TX 77843, USA
                Author notes
                [* ]Corresponding authors. congil@ 123456aliyun.com (C. Li), vsharma@ 123456tamu.edu (V.K. Sharma).
                Article
                Manuscript ID: NIHMS1648458
                DOI: 10.1016/j.envint.2019.105195
                PMC ID: 7711035
                PubMed ID: 31654918
                SO-VID: aec78cb2-85ef-4fa5-bae1-092f749a7416
                License:

                This is an open access article under the CC BY-NC-ND license ( http://creativecommons.org/licenses/BY-NC-ND/4.0/).

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                Subject: Article

                Keywords: algal organic matter,ferrate(vi),chlorination,disinfection byproducts
                Data availability:
                Keywords: algal organic matter, ferrate(vi), chlorination, disinfection byproducts

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