Gregory Korshin | University of Washington (original) (raw)

Papers by Gregory Korshin

Degradation products and pathways Effluent organic matter Absorbance a b s t r a c t This study a... more Degradation products and pathways Effluent organic matter Absorbance a b s t r a c t This study addressed the formation and properties of degradation products of ciprofloxacin, norfloxacin and lomefloxacin formed during ozonation of secondary wastewater effluent containing these fluoroquinolone antibiotics. The generation of the degradation products was interpreted in the context of transformations of effluent organic matter (EfOM) tracked via absorbance measurements. The structures of 20 degradation products were elucidated for ciprofloxacin and norfloxacin, respectively. 27 degradation products were identified for lomefloxacin. The prevalent oxidation pathways were suggested based on the structures of the identified products formed in the absence and presence of the hydroxyl radical scavenger t-butanol. These pathways were largely similar for all studied fluoroquinolones and involved attacks on the piperazine ring and the quinolone structure.

... Organic Matter in Drinking Water Prepared by: Jean-Phillipe Croue Laboratoire de Chimie de I&... more ... Organic Matter in Drinking Water Prepared by: Jean-Phillipe Croue Laboratoire de Chimie de I'Eau et de I'Environnement, Ecole Superieure d'lngenieurs de Poitiers, Universite de Poitiers, 86022 Poitiers Cedex, France Gregory V. Korshin and Mark Benjamin Department of ...

Journal of hazardous materials, Jan 20, 2015

This study examined the degradation behavior of polycyclic musks (PMs) and antineoplastic drugs (... more This study examined the degradation behavior of polycyclic musks (PMs) and antineoplastic drugs (ADs) and the absorbance spectra of effluent organic matter (EfOM) in municipal wastewater by ozone. Specific ozone doses used in the experiments ranged from 0 to 1mg O3/mg dissolved organic matter (DOC). The examined PMs included galaxolide, tonalide, celestolide, traseolide and phantolide. ADs included busulfan, chlorambucil, cyclophosphamide, dacarbazine, flutamide, ifosfamide, tamoxifen and methotrexate. Strong monotonic albeit nonlinear correlations were found to exist between relative changes of EfOM absorbance at 254nm (i.e. ΔA254/A(0)254) and the degradation of the selected PMs and ADs. This result was interpreted based on the concept of the simultaneous oxidation of EfOM and, on the other hand, PMs and ADs. This interpretation showed that PMs were degraded primarily via OH radical attack, with tonalide and phantolide being less reactive compared with the other PMs. ADs such as cy...

Environmental science & technology, Jan 5, 2015

This study examined the electrochemical (EC) reduction of monoiodoacetic acid (MIAA) and iodoform... more This study examined the electrochemical (EC) reduction of monoiodoacetic acid (MIAA) and iodoform (CHI3), which are typical iodine-containing disinfection byproducts (I-DBPs). Experiments carried out using the method of a rotating ring-disk electrode (RRDE) with a gold working electrode showed that the reduction of CHI3 and MIAA is diffusion-controlled. The MIAA diffusion coefficient was determined to be (1.86 ± 0.24)·10(-5) cm(2) s(-1). The yield of the iodide ion formed as a result of MIAA or CHI3 reduction was affected by the presence of dissolved organic matter (DOM) and resorcinol. Increasing concentrations of DOM or resorcinol did not affect the EC reduction of the examined I-DBPs, but the formation of iodide was suppressed. This indicated that free iodine, ·I, was formed as a result of the first step in the EC reduction of MIAA and CHI3. This also indicated that the pathway of the EC reduction of MIAA and CHI3 was different from that typical for the reduction of Br- and Cl-co...

Water Research, 2015

The binding of Ca(2+) and Cu(2+) by dissolved organic matter (DOM) exemplified by Suwannee River ... more The binding of Ca(2+) and Cu(2+) by dissolved organic matter (DOM) exemplified by Suwannee River Humic Acid (SRHA) was examined in this study. Metal-DOM interactions were quantified using linear and log-transformed DOM absorbance spectra acquired at varying pHs and total Ca(2+) and Cu(2+) concentrations. The binding of Cu(2+) by DOM was examined in the presence of three different Ca(2+) concentrations. Interactions of Ca(2+) with DOM chromophores were accompanied by the emergence of features in the differential spectra that were dissimilar from those characteristic for the binding of Cu(2+). The amount of Ca(2+) and Cu(2+) bound by DOM was ascertained using changes of the slopes of log-transformed absorbance spectra in the range of wavelength 350-400 nm (denoted as S350-400) and comparing the data with model predictions. The observed effects indicated the occurrence of the replacement of a characteristic number of protons by the bound Ca(2+) and Cu(2+) ions.

Environmental Science & Technology, 2015

Natural organic matter (NOM) generated in all niches of the environment constitutes a large fract... more Natural organic matter (NOM) generated in all niches of the environment constitutes a large fraction of the global pool of organic carbon while magnesium is one of the most abundant elements that has multiple roles in both biotic and abiotic processes. Although interactions between Mg2+ and NOM have been recognized to affect many environmental processes, little is understood about relevant mechanisms and equilibria. This study addressed this deficiency and quantified Mg2+-NOM interactions using differential absorbance spectroscopy (DAS) in combination with the NICA-Donnan speciation model. DAS data were obtained for varying total Mg concentrations, pHs from 5.0 to 11.0 and ionic strengths from 0.001 to 0.3 mol L-1. DAS results demonstrated the existence of strong interactions between magnesium and NOM at all examined conditions and demonstrated that the binding of Mg2+ by NOM was accompanied by the replacement of protons in the protonation-active phenolic and carboxylic groups. The slope of the log-transformed absorbance spectra of NOM in the range of wavelength 350-400 nm was found to be indicative of the extent of Mg2+-NOM binding. The differential and absolute values of the spectral slopes were strongly correlated with the amount of NOM-bound Mg2+ ions and with the concentrations of NOM-bound protons.

$Research paper thumbnail of Characterization of dissolved organic matter from Australian and Chinese source waters by combined fractionation techniques$

Water Science & Technology, 2011

Water Research, 2006

Diethylstilbestrol Endocrine disruptor Chlorination Electrochemical treatment By-products A B S T... more Diethylstilbestrol Endocrine disruptor Chlorination Electrochemical treatment By-products A B S T R A C T Transformations of diethylstilbestrol (DES) and bisphenol A (BPA) in conventional chlorination and electrochemically (EC) treated solutions were examined using spectrophotometry and chromatographic analyses. EC treatment was carried out using an undivided EC cell with a PbO 2 anode and a stainless steel cathode. EC-treatment and conventional chlorination caused DES and BPA to undergo a rapid degradation accompanied by the generation of low molecular weight chlorinated organic species indicative of the breakdown of DES and BPA. The identified compounds were predominated by chloroacetic acids (HAAs), but approximately 80% of the total organic halogen (TOX) was comprised by unidentified species. For EC treatment, the HAA yields were lower and HAAs were predominated by monochloroacetic acid (MCAA), while in the case of conventional chlorination, trichloroacetic acid (TCAA) was predominant and MCAA was virtually absent.

Ozone: Science & Engineering, 2008

Water Research, 2005

Treatment of solutions of nonylphenol (NP), Triton X-100 (TrX) and phenol in a flow-through undiv... more Treatment of solutions of nonylphenol (NP), Triton X-100 (TrX) and phenol in a flow-through undivided EC reactor equipped with a Co 2+ -promoted PbO 2 anode and a stainless steel cathode was accompanied by consistent changes of absorbance, fluorescence and mass spectra of the effluents, and formation of aldehydes ranging from formaldehyde to decyl aldehyde. Deconvolution of the absorbance spectra of EC-treated NP, TrX and phenol and examination of their fluorescence indicated that the compounds are rapidly degraded in the reactor. For NP, the degradation of the target proceeded via the generation (at current densities o25 mA/cm 2 ) of benzoquinone intermediates that yielded peaks with m=z ratios 223, 227, 235, and 241 D in the mass spectra. Their breakdown at current densities 410 mA/cm 2 was accompanied by the release of aldehydes that were predominated by acetaldehyde and formaldehyde. The total yield of aldehydes increased with the current density, but their speciation showed little sensitivity to it. Deconvolution of the absorbance spectra of NP solutions subjected to ozonation, and analysis for reaction by-products formed in these conditions showed the reaction pathway in the latter case was likely to be similar to that observed for the EC treatment. r

Chemosphere, 2015

This study examined the formation of aldehydes and carboxylic acids in ozonated surface water and... more This study examined the formation of aldehydes and carboxylic acids in ozonated surface water and municipal wastewater secondary effluent and addressed correlations between the generation of these compounds and concurrent changes of the fluorescence of natural/effluent organic matter (NOM/EfOM) substrates. Ozonation was effective in removing fluorophores in all excitation/emission matrix (EEM) regions, with those operationally assigned to humic- and protein-like species showing relatively higher reactivity than fulvic-like species. Examination of HO exposures and attendant changes of fluorescence-based parameters allows establishing strong linear relationships between formation of the aldehydes and carboxylic acids and the relative changes of integrated fluorescence (ΔIF/IF0). This demonstrates the feasibility of surrogate monitoring of the formation of biodegradable ozonation by-products via online measurements of water/wastewater EEM fluorescence.

'This report describes progress through May, 1998, which is a little past mid-way through... more 'This report describes progress through May, 1998, which is a little past mid-way through the second year of a three-year project. The goal of the research is to develop a treatment system for the separation of contaminants in low-organic Hanford tank wastes into various sub-groups that are relatively easy to treat further to yield products that are amenable to final

ACS Symposium Series, 1996

Page 1. Chapter 12 Use of UV Spectroscopy To Study Chlorination of Natural Organic Matter Gregory... more Page 1. Chapter 12 Use of UV Spectroscopy To Study Chlorination of Natural Organic Matter Gregory V. Korshin, Chi-Wang Li, and Mark M. Benjamin Department of Civil Engineering, Box 352700, University of Washington, Seattle, WA 98195-2700 ...

Environmental science & technology, Jan 21, 2015

This study examined effects of variations of the ionic strength (IS) on the absorbance of dissolv... more This study examined effects of variations of the ionic strength (IS) on the absorbance of dissolved organic matter (DOM). The measurements performed for DOM of allochthonous (Suwannee River humic and fulvic acids, SRHA and SRFA) and autochthonous (Pony Lake fulvic acid, PLFA) origin showed that increases of IS (which was controlled by additions of sodium perchlorate) from 0.001 to 0.3 mol/L were accompanied by increases of the absorbance of DOM. The extent of the increase of DOM absorbance observed at increasing IS was consistently greater at higher pHs, and it followed the order of PLFA<SRFA<SRHA. The absolute values of the spectral slopes of the log-processed absorbance spectra of DOM calculated for a 350 to 400 nm wavelength range decreased proportionally to the logarithm of IS values. This result was hypothesized to be indicative of the deprotonation of the DOM chromophores at increasing IS values, which was supported by model calculations showing that values of the spectr...

Water research, 2014

This study examined the behavior of corrosion potential (Ecorr) of iron exposed to drinking water... more This study examined the behavior of corrosion potential (Ecorr) of iron exposed to drinking water during episodes of stagnation and flow. These measurements showed that during stagnation episodes, Ecorr values decrease prominently and consistently. This decrease is initially rapid but it becomes slower as the stagnation time increases. During flow episodes, the Ecorr values increase and reach a quasi-steady state. Experiments with varying concentrations of dissolved oxygen showed that the decrease of Ecorr values characteristic for stagnation is likely to be associated with the consumption of dissolved oxygen by the exposed metal. The corrosion potential of iron and its changes during stagnation were sensitive to the concentrations of sulfate and chloride ions. Measurements of iron release showed that both the absolute values of Ecorr measured prior to or after stagnation episodes were well correlated with the logarithms of concentrations of total iron. The slope of this dependence ...

Water research, 2002

This study examined correlations between the differential absorbance at 272nm (deltaA272) and the... more This study examined correlations between the differential absorbance at 272nm (deltaA272) and the formation of disinfection by-products (DBPs) in chlorinated water from the Tolt River, a water source for Seattle, WA. The DBPs investigated included chloroform (CHCl3), dichlorobromomethane (CHCl2Br), mono-, di- and trichloroacetic acids (MCAA, DCAA, and TCAA, respectively), chloral hydrate (CH), dichloroacetonitrile (DCAN) and 1,1,1-trichloropropanone (TCP). Whereas the kinetics of DBP formation are complex and are non-linear, the same DBP data represented as a function of deltaA272 are quite simple. Absorbance decreases when the water is chlorinated, i.e., deltaA272 is always negative. The DBP vs. -deltaA272 correlations can almost always be quantified by linear equations, at least above some threshold value of -deltaA272, with R2 values > 0.95. The only DBP that did not follow this trend was CH, for which an exponential relationship better described the data. TCP and DCAN were un...

Water research, 2015

This study utilized the methods of fluorescence quenching and differential absorbance to probe in... more This study utilized the methods of fluorescence quenching and differential absorbance to probe in situ the extent and the nature of the interactions between rare earth ions (REIs) and humic substances. Experiments were conducted with the standard Suwannee river humic acid (SRHA) in the presence of varying amount of lanthanum, europium and terbium. The data of differential absorbance showed that the mechanism of SRHA-metal complexation was largely the same for all the examined REIs. In all cases several discrete bands whose properties were discerned via numerical decomposition of the differential spectra absorbance were observed. Their nature was examined based on the comparison of the experimental data and those of NICA-Donnan modeling carried out for Eu³⁺. The observed effects suggested that the changes of SRHA absorbance induced by REIs binding are likely to be caused by a bathochromic shift of the absorbance bands associated with such chromophores. The intensity of the Gaussian b...

Journal of hazardous materials, Jan 23, 2015

This study examined the degradation of the widely used antineoplastic drug 5-fluorouracil (5FU) b... more This study examined the degradation of the widely used antineoplastic drug 5-fluorouracil (5FU) by chlorine and bromine. 5FU was determined to interact readily with free chlorine and bromine but was stable in the presence of chloramine. The removal of 5FU followed a second-order kinetic pattern. Apparent rates (kapp) of 5FU removal by chlorine and bromine were strongly pH dependent and had maximum 14.8M(-1)s(-1) and 1.9×10(3)M(-1)s(-1)kapp values, respectively at pH 7. Modeling of the dependence of the kapp values vs. pH indicated the presence of a relatively acidic (pK 6.4 vs. 8.5 of 5FU per se) 5FU intermediate generated in the presence of halogen species. Spectrophotometric measurements confirmed the increased acidity of 5FU chlorination products and allowed proposing a degradation pathway of 5FU by chlorine. This pathway suggests that 5FU chlorination proceeds via chlorine incorporation at the 6th carbon in the heterocyclic ring of 5FU.