Biomedical subjects

Mark M Benjamin

Publications and source records attributed to Mark M Benjamin.

5 recordsLinked to original sources

PubMed2004

Reactions of the flavonoid hesperetin with chlorine: a spectroscopic study of the reaction pathways.

The flavonoid hesperetin (Hsp) contains aromatic rings substituted with hydroxyl and methoxyl groups, which activate it toward electrophilic attack and hence make it a potential surrogate for natural organic matter with respect to reactions with chlorine. This paper describes the chlorination pathway of Hsp, based on a combination of electrospray tandem mass spectrometry (MS/MS) and absorbance spectroscopy. When a solution containing Hsp is dosed with NaOCl at pH 7, chlorine substitution into Hsp occurs exclusively into the meta-dihydroxy substituted ring. The first two Cl atoms to enter the ring do so at the highly activated carbons that are each ortho to two oxygenated carbon atoms. These substitutions make the molecule more acidic, but do not change its primary structure or aromaticity. The third Cl atom that substitutes into the molecule does so at one of the previously chlorinated sites, destroying the aromaticity of the ring and altering the molecular properties more dramatically than do the first two. The absorbance spectra of Hsp and mono- and di-chlorinated Hsp are all very similar and are very distinct from that of trichlorinated Hsp. In particular, the latter is the only one of those species that absorbs visible light (in a characteristic band centered at approximately 422nm). Di- and trichloroHsp form even at low molar Cl/Hsp ratios, and can coexist with Hsp and monochloroHsp in neutral, aqueous solutions for at least 24 h in the absence of free chlorine. If free chlorine is present, the less-chlorinated species continue to acquire Cl, and trichloroHsp undergoes further reaction, until either the free chlorine or the trichloroHsp is fully depleted. The appearance of di- and trichloroHsp while substantial amounts of Hsp remain unreacted indicates that substitution of one or two Cl atoms into the ring facilitates the incorporation of yet more Cl into the ring. This autoacceleration of the chlorination process is hypothesized to be induced by the increase in acidity that accompanies Cl incorporation. Specifically, the increase in the acidity of the phenolic groups shifts the equilibrium toward the enolate anion, which is considered to be much more amenable to electrophilic attack than the enol.

Chlorine↗

PubMed2003

Fouling and natural organic matter removal in adsorbent/membrane systems for drinking water treatment.

Adsorbent particles added to ultrafiltration (UF) systems treating drinking water can remove natural organic matter (NOM) and some other contaminants from the water, but their effect on membrane fouling is inconsistent-in some cases, fouling is reduced, and in others, it is exacerbated. This research investigated the behavior of UF systems to which powdered activated carbon (PAC), heated iron oxide particles (HIOPs), or (nonadsorbent) SiO2 particles were added. On a mass basis, the PAC removed the most NOM from solution, the HIOPs removed less, and the SiO2 removed essentially none. However, in the case of both PAC and SiO2, increasing the dose of solids led to a steady increase in fouling, whereas the opposite trend applied when HIOPs were added. In the absence of NOM, none of the solids fouled the membrane significantly. Thus, even though NOM is a causative agent for fouling, removing it from solution does not necessarily reduce fouling; the mechanism of removal can be just as important as the absolute amount removed, if the removal occurs in a cake layer near the membrane surface. Scanning electron microscopy images of the cake layers formed in the three systems suggest that the NOM binds PAC or SiO2 particles to one another and to the membrane surface, so that the particles become part of the foulant in the system. By contrast, the NOM appears to bind HIOPs to one another but not to the membrane. This process leaves enough pore space in the cake layer for water to reach the membrane with minimal resistance, and it reduces the tendency for either the NOM or the HIOPs to foul the membrane surface.

Adsorption↗

PubMed2002

Modeling the mass-action expression for bidentate adsorption.

The number of bidentate binding sites on a pristine surface (i.e., sites comprising two adjacent monodentate sites plus the space between them) can be substantially larger than the maximum number of bidentate molecules that can adsorb to the surface. When bidentate sorption occurs, the number of available bidentate sites decreases in response to direct occupation of some sites, but an even more significant loss results from the fact that several unoccupied sites immediately surrounding each adsorbed molecule can also become unavailable. Recognition of this phenomenon allows development of a model for the adsorption process that matches simulated data from Monte Carlo (MC) modeling extremely well. The model also explains the observation that, on a given surface with a given fractional occupation, the number of available bidentate sites depends on whether the occupied sites are populated by monodentate or bidentate adsorbed species. A model developed more than 60 years ago but not widely recognized by modern adsorption modelers also fits the MC simulations very well. The simulated data are also reasonably approximated by assuming that the number of available bidentate sites on a surface is proportional to the square of the number of available monodentate sites, although the fit is not as good as with the models mentioned above. By contrast, approximating the number of available sites as proportional to the number of monodentate sites to the first power yields predictions that do not match the simulations. The results have implications for modeling of both multidentate adsorption reactions and monovalent-divalent ion exchange.

Adsorption↗

PubMed2002

The relationship between TOX formation and spectral changes accompanying chlorination of pre-concentrated or fractionated NOM.

The change in the absorbance upon chlorination (the differential absorbance, AA) of natural organic matter (NOM) that has been concentrated, isolated, and/or fractionated from five sources was explored as a possible indicator of the formation of total organic halogen (TOX) in the samples. The results demonstrate that concentration and isolation of NOM using techniques that are currently in widespread use does not significantly alter the TOX-deltaA272 relationship that applies to the unprocessed NOM. However, when such samples are fractionated, the TOX-deltaA272 relationships for the different fractions are not identical. In particular, when the hydrophobic and hydrophilic neutral fractions of NOM are chlorinated, the amount of TOX formed per unit of A272 destroyed is significantly larger than the corresponding value for other NOM fractions. This observation might reflect the relatively high content of proteins and other amino acid structures that can be disinfection by-product precursors but that absorb little or no light at 272 nm.

Amino Acids↗

PubMed2002

Correlations between differential absorbance and the formation of individual DBPs.

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 unstable at pH 7 and 8, but at pH 6 linear correlations between their concentrations and -deltaA272 were as strong as those for the more stable DBPs. The threshold -deltaA272 value is approximately the same for many of the DBPs studied, supporting the hypothesis that individual DBPs are released following the formation of a common intermediate, or at least a small group of similar intermediates. The DBP vs. -deltaA272 correlations may have practical value since they provide an alternative approach for monitoring the formation of individual DBP species on-line, but the generality of the relationships needs to be further examined.

Absorption↗