John D Sivey

Towson University, تاوسن، مریلند, Maryland, United States

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Publications (9)35 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: Safeners are included in many commercial herbicide formulations to selectively protect crops from injury induced by active ingredients. Despite their bioactivity, safeners are classified as inert from a regulatory perspective, and as such, safeners have received minimal attention in the peer-reviewed literature regarding their environmental fate and effects. Herein, we review what is known about the uses, physicochemical properties, environmental transformations, and (eco)toxicological effects of dichloroacetamide safeners, which represent one of the most commonly used safener classes (estimated use of >2 x 10(6) kg/year in the United States). We particularly highlight transformation pathways that may enhance biological activity and/or persistence; for example, limited studies suggest dichloroacetamides can transform via dechlorination into products with increased bioactivity. We also identify several research needs to improve our understanding of the environmental fate and potential risks of this overlooked agrochemical class, which in turn will enhance the efficacy and safety of future herbicide safener formulations.
    No preview · Article · Sep 2015
  • John D Sivey · Mark A Bickley · Daniel A Victor
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    ABSTRACT: When bromide-containing waters are chlorinated, conventional wisdom typically assumes HOBr is the only active brominating agent. Several additional and often-overlooked brominating agents (including BrCl, Br2, BrOCl, Br2O) can form in chlorinated waters, albeit at generally lower concentrations than HOBr. The extent to which these additional brominating agents influence bromination rates of disinfection by-product precursors is, however, poorly understood. Herein, the influence of BrCl, Br2, BrOCl, Br2O, and HOBr toward rates of sequential bromination of anisole was quantified. Conditions affecting bromine speciation (e.g., pH, concentrations of chloride, bromide, and chlorine) were varied, and regiospecific second-order rate constants were calculated for reactions of each brominating agent with anisole, 2-bromoanisole, and 4-bromoanisole. The regioselectivity of anisole bromination changed with pH, consistent with the participation of more than one brominating agent. Under conditions representative of chlorinated drinking water, contributions to bromination rates decreased as: BrCl>BrOCl>HOBr>Br2O (Br2 negligible). The second-order rate constant determined for net bromination of anisole by HOBr is up to 3000-times less than reported in previous studies (which assumed HOBr was the only active brominating agent). Accordingly, models that assume HOBr is the only kinetically-relevant brominating agent in solutions of free bromine may be insufficient for reactions involving modestly nucleophilic organic compounds.
    No preview · Article · Mar 2015 · Environmental Science & Technology
  • John D. Sivey · Mark A. Bickley · Daniel A. Victor

    No preview · Chapter · Jan 2015
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    ABSTRACT: HOBr, formed via oxidation of bromide by free available chlorine (FAC), is frequently assumed to be the sole species responsible for generating brominated disinfection byproducts (DBPs). Our studies reveal that BrCl, Br2, BrOCl, and Br2O can also serve as brominating agents of the herbicide dimethenamid in solutions of bromide to which FAC was added. Conditions affecting bromine speciation (pH, total free bromine concentration ([HOBr]T), [Cl–], and [FAC]o) were systematically varied, and rates of dimethenamid bromination were measured. Reaction orders in [HOBr]T ranged from 1.09 (±0.17) to 1.67 (±0.16), reaching a maximum near the pKa of HOBr. This complex dependence on [HOBr]T implicates Br2O as an active brominating agent. That bromination rates increased with increasing [Cl–], [FAC]o (at constant [HOBr]T), and excess bromide (where [Br–]o>[FAC]o) implicate BrCl, BrOCl, and Br2, respectively, as brominating agents. As equilibrium constants for the formation of Br2O and BrOCl (aq) have not been previously reported, we have calculated these values (and their gas-phase analogues) using benchmark-quality quantum chemical methods [CCSD(T) up to CCSDTQ calculations plus solvation effects]. The results allow us to compute bromine speciation and hence second-order rate constants. Intrinsic brominating reactivity increased in the order: HOBr Br2O < BrOCl ≈ Br2 < BrCl. Our results indicate that species other than HOBr can influence bromination rates under conditions typical of drinking water and wastewater chlorination.
    No preview · Article · Jul 2013 · Environmental Science & Technology
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    ABSTRACT: Although protein degradation by neutrophil-derived hypochlorous acid (HOCl) and eosinophil-derived hypobromous acid (HOBr) can contribute to inactivation of pathogens, collateral damage to host proteins can also occur and has been associated with inflammatory diseases ranging from arthritis to atherosclerosis. Though previous research suggested halotyrosines as biomarkers of protein damage and lysine as a mediator of halogen transfer to tyrosine, these reactions within whole proteins are poorly understood. Herein, reactions of HOCl and HOBr with three well-characterized proteins [adenylate kinase (ADK), ribose binding protein (RBP), and bovine serum albumin (BSA)] were characterized. Three assessments of oxidative modifications were evaluated for each of the proteins: (1) covalent modification of electron-rich amino acids (assessed via liquid chromatography/tandem mass spectrometry), (2) attenuation of secondary structure (via circular dichroism), and (3) fragmentation of protein backbones (via SDS-PAGE). In addition to forming halotyrosines, HOCl and HOBr converted lysine into lysine nitrile (2-amino-5-cyanopentanoic acid), a relatively stable and largely overlooked product, in yields up to 80%. At uniform oxidant levels, fragmentation and loss of secondary structure correlated with protein size. To further examine the role of lysine, a lysine-free ADK variant was rationally designed. The absence of lysine increased yields of chlorinated tyrosines and decreased yields of brominated tyrosines following treatments with HOCl and HOBr respectively, without influencing the susceptibility of ADK toward HOX-mediated losses of secondary structure. These findings suggest that lysine serves predominantly as a sacrificial antioxidant (via formation of lysine nitrile) toward HOCl and as a halogen-transfer mediator (via reactions involving ε-N-(di)haloamines) with HOBr.
    No preview · Article · Jan 2013 · Biochemistry
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    ABSTRACT: HOBr, formed via oxidation of bromide by free available chlorine (FAC), is frequently assumed to be the sole species responsible for generating brominated disinfection byproducts (DBPs). Our studies reveal that BrCl, Br(2), BrOCl, and Br(2)O can also serve as brominating agents of the herbicide dimethenamid in solutions of bromide to which FAC was added. Conditions affecting bromine speciation (pH, total free bromine concentration ([HOBr](T)), [Cl(-)], and [FAC](o)) were systematically varied, and rates of dimethenamid bromination were measured. Reaction orders in [HOBr](T) ranged from 1.09 (±0.17) to 1.67 (±0.16), reaching a maximum near the pK(a) of HOBr. This complex dependence on [HOBr](T) implicates Br(2)O as an active brominating agent. That bromination rates increased with increasing [Cl(-)], [FAC](o) (at constant [HOBr](T)), and excess bromide (where [Br(-)](o)>[FAC](o)) implicate BrCl, BrOCl, and Br(2), respectively, as brominating agents. As equilibrium constants for the formation of Br(2)O and BrOCl (aq) have not been previously reported, we have calculated these values (and their gas-phase analogues) using benchmark-quality quantum chemical methods [CCSD(T) up to CCSDTQ calculations plus solvation effects]. The results allow us to compute bromine speciation and hence second-order rate constants. Intrinsic brominating reactivity increased in the order: HOBr ≪ Br(2)O < BrOCl ≈ Br(2) < BrCl. Our results indicate that species other than HOBr can influence bromination rates under conditions typical of drinking water and wastewater chlorination.
    Preview · Article · Jan 2013 · Environmental Science & Technology
  • John D Sivey · A Lynn Roberts
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    ABSTRACT: Safeners are so-called "inert" constituents of herbicide formulations added to protect crops from the toxic effects of herbicides. We examined the reactivity of three dichloroacetamide safeners and 12 structural analogues [all neutral compounds of the form Cl(2)CXC(═O)NRR'; X = H, Cl; R-groups include alkyl, branched alkyl, n-allyl, and cyclic moieties] in one homogeneous and two heterogeneous reductant systems: solutions of Cr(H(2)O)(6)(2+), suspensions of Fe(II)-amended goethite, and suspensions of Fe(II)-amended hematite. Analyses of reaction products indicate each safener can undergo stepwise hydrogenolysis (replacement of chlorine by hydrogen) in each system at near-neutral pH. The first hydrogenolysis step generates compounds similar (in one case, identical) to herbicide active ingredients. Rates of product formation and (when reactions were sufficiently fast) parent loss were quantified; reaction rates in heterogeneous systems spanned 2 orders of magnitude and were strongly influenced by R-group structure. The length of n-alkyl R-groups exerted opposite effects on hydrogenolysis rates in homogeneous versus heterogeneous systems: as R-group size increased, reduction rates in heterogeneous systems increased, whereas reduction rates in the homogeneous system decreased. Branched alkyl R-groups decreased hydrogenolysis rates relative to their straight-chain homologues in both homogeneous and heterogeneous systems. Reaction rates in heterogeneous systems can be described via polyparameter linear free energy relationships employing molecular parameters likely to influence dichloroacetamide adsorption. The propensity of dichloroacetamide safeners to undergo reductive transformations into herbicide-like products challenges their classification as "inert" agrochemical ingredients.
    No preview · Article · Feb 2012 · Environmental Science & Technology
  • John D Sivey · A Lynn Roberts
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    ABSTRACT: Cl(2) and Cl(2)O are highly reactive electrophiles capable of influencing rates of disinfection byproduct (DBP) precursor chlorination in solutions of free available chlorine (FAC). The current work examines how organic compound structure influences susceptibility toward chlorination by Cl(2) and Cl(2)O relative to the more abundant (but less reactive) electrophile HOCl. Chlorination rates and products were determined for three aromatic ethers, whose reactivities with FAC increased in the order: 3-methylanisole <1,3-dimethoxybenzene <1,3,5-trimethoxybenzene. Varying solution conditions (pH, [FAC], [Cl(-)]) permitted quantification of regiospecific second-order rate constants for formation of each product by Cl(2), Cl(2)O, and HOCl. Our results indicate that as the reactivity of methoxybenzenes decreases, the importance of Cl(2) and Cl(2)O (relative to HOCl) increases. Accordingly, Cl(2) and Cl(2)O are likely to play important roles in generating DBPs that originate from natural organic matter (NOM) constituents of somewhat moderate reactivity. As [Cl(2)] is proportional to [Cl(-)] and [Cl(2)O] is proportional to [HOCl](2), ramifications for DBP control measures may differ significantly for these precursors compared to more reactive NOM moieties likely to react predominantly with HOCl. In particular, the role of chloride as a chlorination catalyst challenges its traditional classification as an "inert" electrolyte in water treatment processes.
    No preview · Article · Jan 2012 · Environmental Science & Technology
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    John D Sivey · Corey E McCullough · A Lynn Roberts
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    ABSTRACT: HOCl is often assumed to represent the active oxidant in solutions of free available chlorine (FAC). We present evidence that Cl(2)O and Cl(2) can play a greater role than HOCl during chlorination of the herbicide dimethenamid. Reaction orders in [FAC] were determined at various solution conditions and ranged from 1.10 +/- 0.13 to 1.78 +/- 0.22, consistent with the concurrent existence of reactions that appear first-order and second-order in [FAC]. Solution pH, [Cl(-)], [FAC], and temperature were systematically varied so that the reactivity and activation parameters of each FAC species could be delineated. Modeling of kinetic data afforded calculation of second-order rate constants (units: M(-1) s(-1)) at 25 degrees C: k(Cl2O) = (1.37 +/- 0.17) x 10(6), k(Cl2) = (1.21 +/- 0.06) x 10(6), and k(HOCl) = 0.18 +/- 0.10. Under conditions typical of drinking water chlorination, Cl(2)O is the predominant chlorinating agent of dimethenamid. To the extent that Cl(2)O represents the active species in reactions with other disinfection byproduct (DBP) precursors, the influence of [FAC] and pH on DBP precursor reaction rates is different than if HOCl were the principal oxidant. Moreover, these findings call into question the validity of apparent rate constants (k(app)) commonly reported in the chlorination literature.
    Preview · Article · Mar 2010 · Environmental Science and Technology

Publication Stats

76 Citations
35.00 Total Impact Points

Institutions

  • 2015
    • Towson University
      • Department of Chemistry
      تاوسن، مریلند, Maryland, United States
  • 2013
    • Yale University
      • Department of Chemical & Environmental Engineering
      New Haven, Connecticut, United States
  • 2010-2013
    • Johns Hopkins University
      • Department of Geography Environmental Engineering
      Baltimore, Maryland, United States