ABSTRACT
This study investigated the speciation of halogen-specific total organic halogen and disinfection byproducts (DBPs) upon chlorination of natural organic matter (NOM) in the presence of iopamidol and bromide (Br-). Experiments were conducted with low bromide source waters with different NOM characteristics from Northeast Ohio, USA and varied spiked levels of bromide (2-30 µmol/L) and iopamidol (1-5 µmol/L). Iopamidol was found to be a direct precursor to trihalomethane (THM) and haloacetic acid formation, and in the presence of Br- favored brominated analogs. The concentration and speciation of DBPs formed were impacted by iopamidol and bromide concentrations, as well as the presence of NOM. As iopamidol increased the concentration of iodinated DBPs (iodo-DBPs) and THMs increased. However, as Br- concentrations increased, the concentrations of non-brominated iodo- and chloro-DBPs decreased while brominated-DBPs increased. Regardless of the concentration of either iopamidol or bromide, bromochloroiodomethane (CHBrClI) was the most predominant iodo-DBP formed except at the lowest bromide concentration studied. At relevant concentrations of iopamidol (1 µmol/L) and bromide (2 µmol/L), significant quantities of highly toxic iodinated and brominated DBPs were formed. However, the rapid oxidation and incorporation of bromide appear to inhibit iodo-DBP formation under conditions relevant to drinking water treatment.
Subject(s)
Bromides/analysis , Disinfectants , Iopamidol/analysis , Water Pollutants, Chemical , Water Purification , Disinfection , Halogenation , Halogens , TrihalomethanesABSTRACT
Chloramines, in practice, are formed onsite by adding ammonia to chlorinated drinking water to achieve the required disinfection. While regulated disinfection byproducts (DBPs) are reduced during chloramine disinfection, other DBPs such as iodinated (iodo-) DBPs, that elicit greater toxicity are formed. The objective of this study was to investigate the impact of prechlorination time on the formation of both halogen-specific total organic halogen (TOX) and iodo/chlorinated (chloro-) DBPs during prechlorination/chloramination in source waters (SWs) containing iopamidol, an X-ray contrast medium. Barberton SW (BSW) and Cleveland SW (CSW) containing iopamidol were prechlorinated for 5-60â¯min and afterwards chloraminated for 72â¯hr with ammonium chloride. Chlorine contact time (CCT) did not significantly impact total organic iodine (TOI) concentrations after prechlorination or chloramination. Concentrations of total organic chlorine (TOCl) formed during prechlorination did not significantly change regardless of pH and prechlorination time, while TOCl appeared to decrease after 72â¯hr chloramination period. Dichloroiodomethane (CHCl2I) formation during prechlorination did not exhibit any significant trends as a function of pH or CCT, but after chloramination, significant increases were observed at pHs 6.5 and 7.5 with respect to CCT. Iodo-HAAs were not formed during prechlorination but were detected after chloramination. Significant quantities of chloroform (CHCl3) and trichloroacetic acid (TCAA) were formed during prechlorination but formation ceased upon ammonia addition. Therefore, prechlorination studies should measure TOX and DBP concentrations prior to ammonia addition to obtain data regarding the initial conditions.
Subject(s)
Chlorine/chemistry , Disinfectants/chemistry , Iopamidol/chemistry , Water Pollutants, Chemical/chemistry , Disinfection/methods , Models, Chemical , Water PurificationABSTRACT
Iodinated contrast media (ICM) are nonmutagenic agents administered for X-ray imaging of soft tissues. ICM can reach µg/L levels in surface waters because they are administered in high doses, excreted largely unmetabolized, and poorly removed by wastewater treatment. Iodinated disinfection byproducts (I-DBPs) are highly genotoxic and have been reported in disinfected waters containing ICM. We assessed the mutagenicity in Salmonella of extracts of chlorinated source water containing one of four ICM (iopamidol, iopromide, iohexol, and diatrizoate). We quantified 21 regulated and nonregulated DBPs and 11 target I-DBPs and conducted a nontarget, comprehensive broad-screen identification of I-DBPs. We detected one new iodomethane (trichloroiodomethane), three new iodoacids (dichloroiodoacetic acid, chlorodiiodoacetic acid, bromochloroiodoacetic acid), and two new nitrogenous I-DBPs (iodoacetonitrile and chloroiodoacetonitrile). Their formation depended on the presence of iopamidol as the iodine source; identities were confirmed with authentic standards when available. This is the first identification in simulated drinking water of chloroiodoacetonitrile and iodoacetonitrile, the latter of which is highly cytotoxic and genotoxic in mammalian cells. Iopamidol (5 µM) altered the concentrations and relative distribution of several DBP classes, increasing total haloacetonitriles by >10-fold. Chlorination of ICM-containing source water increased I-DBP concentrations but not mutagenicity, indicating that such I-DBPs were either not mutagenic or at concentrations too low to affect mutagenicity.
Subject(s)
Disinfectants , Water Pollutants, Chemical , Water Purification , Animals , Contrast Media , Disinfection , Halogenation , Mutagens , X-RaysABSTRACT
Iopamidol is a known direct precursor to iodinated and chlorinated DBP formation; however, the influence of iopamidol on both iodo/chloro-DBP formation has yet to be fully investigated. This study investigated the effect of iopamidol on the formation and speciation of halogen-specific total organic halogen (TOX), as well as iodo/chloro-DBPs, in the presence of 3 source waters (SWs) from Northeast Ohio and chlorinated oxidants. Chlorination and chloramination of SWs were carried out at pH 6.5-9.0 and, different iopamidol and dissolved organic carbon (DOC) concentrations. Total organic iodine (TOI) loss was approximately equal (22-35%) regardless of SW. Total organic chlorine (TOCl) increased in all SWs and was substantially higher in the higher SUVA254 SWs. Iopamidol was a direct precursor to chloroform (CHCl3), trichloroacetic acid (TCAA), and dichloroiodomethane (CHCl2I) formation. While CHCl3 and TCAA exhibited different formation trends with varying iopamidol concentrations, CHCl2I increased with increasing iopamidol and DOC concentrations. Low concentrations of iodo-acids were detected without discernible trends. Total trihalomethanes (THMs), total haloacetic acids (HAAs), TOCl, and unknown TOCl (UTOCl) were correlated with fluorescence regional volumes and SUVA254. The yields of all these species showed a strong positive correlation with fulvic, humic, and combined humic and fulvic regions, as well as SUVA254. Iopamidol was then compared to the 3 SWs with respect to DBP yield. Although the SUVA254 of iopamidol was relatively high, it did not produce high yields of THMs and HAAs compared to the 3 SWs. However, chlorination of iopamidol did result in high yields of TOCl and UTOCl.
Subject(s)
Disinfectants/chemistry , Halogens/chemistry , Iopamidol/chemistry , Oxidants/chemistry , Disinfection/methods , Halogenation , Ohio , Trihalomethanes/analysis , Water Pollutants, Chemical/analysis , Water Purification/methodsABSTRACT
The presence of iodinated X-ray contrast media (ICM) in source waters is of high concern to public health because of their potential to generate highly toxic disinfection by-products (DBPs). The objective of this study was to determine the impact of ICM in source waters and the type of disinfectant on the overall toxicity of DBP mixtures and to determine which ICM and reaction conditions give rise to toxic by-products. Source waters collected from Akron, OH were treated with five different ICMs, including iopamidol, iopromide, iohexol, diatrizoate and iomeprol, with or without chlorine or chloramine disinfection. The reaction product mixtures were concentrated with XAD resins and the mammalian cell cytotoxicity and genotoxicity of the reaction mixture concentrates was measured. Water containing iopamidol generated an enhanced level of mammalian cell cytotoxicity and genotoxicity after disinfection. While chlorine disinfection with iopamidol resulted in the highest cytotoxicity overall, the relative iopamidol-mediated increase in toxicity was greater when chloramine was used as the disinfectant compared with chlorine. Four other ICMs (iopromide, iohexol, diatrizoate, and iomeprol) expressed some cytotoxicity over the control without any disinfection, and induced higher cytotoxicity when chlorinated. Only iohexol enhanced genotoxicity compared to the chlorinated source water.
Subject(s)
Contrast Media/analysis , Disinfectants/analysis , Drinking Water/chemistry , Water Pollutants, Chemical/analysis , Water Purification/methods , Contrast Media/chemistry , Disinfectants/toxicity , Disinfection/methods , Halogenation , Iohexol/analogs & derivatives , Iohexol/analysis , Iohexol/chemistry , Iopamidol/analogs & derivatives , Iopamidol/analysis , Iopamidol/chemistry , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/toxicity , X-RaysABSTRACT
The transformation of the iodinated X-ray contrast media (ICM) iopamidol, iopromide, iohexol, iomeprol, and diatrizoate was examined in purified water over the pH range from 6.5 to 8.5 in the presence of sodium hypochlorite, monochloramine, and chlorine dioxide. In the presence of aqueous chlorine, only iopamidol was transformed. All other ICM did not show significant reactivity, regardless of the oxidant used. Chlorination of iopamidol followed a second order reaction, with an observed rate constant of up to 0.87 M(-1) s(-1) (±0.021 M(-1) s(-1)) at pH 8.5. The hypochlorite anion was identified to be the reactive chlorine species. Iodine was released during the transformation of iopamidol, and was mainly oxidized to iodate. Only a small percentage (less than 2% after 24 h) was transformed to known organic iodinated disinfection byproducts (DBPs) of low molecular weight. Some of the iodine was still present in high-molecular weight DBPs. The chemical structures of these DBPs were elucidated via MSn fragmentation and NMR. Side chain cleavage was observed as well as the exchange of iodine by chlorine. An overall transformation pathway was proposed for the degradation of iopamidol. CHO cell chronic cytotoxicity tests indicate that chlorination of iopamidol generates a toxic mixture of high molecular weight DBPs (LC50 332 ng/µL).
Subject(s)
Halogenation , Iopamidol/chemistry , Animals , CHO Cells , Chlorine/chemistry , Cricetinae , Cricetulus , Disinfection , Hydrogen-Ion Concentration , Iodine/chemistry , Iopamidol/toxicity , Kinetics , Models, Theoretical , Molecular Weight , Time Factors , Water Pollutants, Chemical/analysisABSTRACT
This work demonstrates the ability of an acetylcholinesterase-inspired biomimetic sensor to accurately predict the toxicity of acetylcholinesterase (AChE) inhibitors. In surface waters used for municipal drinking water supplies, numerous pesticides and other anthropogenic chemicals have been found that inhibit AChE; however, there is currently no portable toxicity assay capable of determining the potential neurotoxicity of water samples and complex mixtures. Biological assays have been developed to determine the toxicity of unknown samples, but the short shelf-life of cells and other biological materials often make them undesirable for use in portable assays. Chemical methods and structure-activity-relationships, on the other hand, require prior knowledge on the compounds of interest that is often unavailable when analyzing environmental samples. In the toxicity assay presented here, the acetylcholinesterase enzyme has been replaced with 1-phenyl-1,2,3-butanetrione 2-oxime (PBO) a biomimetic compound that is structurally similar to the AChE active site. Using a biomimetic compound in place of the native enzyme allows for a longer shelf-life while maintaining the selective and kinetic ability of the enzyme itself. Previous work has shown the success of oxime-based sensors in the selective detection of AChE inhibitors and this work highlights the ability of an AChE-inspired biomimetic sensor to accurately predict the toxicity (LD50 and LC50) for a range of AChE inhibitors. The biomimetic assay shows strong linear correlations to LD50 (oral, rat) and LC50 (fish) values. Using a test set of eight AChE inhibitors, the biomimetic assay accurately predicted the LC50 value for 75% of the inhibitors within one order of magnitude.
Subject(s)
Acetylcholinesterase/metabolism , Cholinesterase Inhibitors/toxicity , Environmental Pollutants/toxicity , Toxicity Tests/methods , Animals , Biomarkers/metabolism , Biomimetics , Pesticides/toxicity , Risk Assessment/methods , Structure-Activity RelationshipABSTRACT
The goal of this study was to develop a robust method capable of quantifying taste and odor compounds (i.e., geosmin and 2-methylisoborneol) at very low aqueous concentrations in the presence of wastewater and algal derived contaminants. A polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber was used to perform headspace-solid phase microextraction (HS-SPME) to extract and analyze taste and odor compounds from model, source water, and finished drinking water samples. Gas chromatography coupled with mass spectrometery (GC/MS) in full scan mode was used to analyze the compounds desorbed from the fiber in the GC inlet. The following parameters were optimized in order to enhance analyte recovery: extraction temperature, extraction time, desorption time, sonication temperature, sonication time and GC/MS configuration/temperature program. After optimization, the method provided a linear response from 1 to 300 ng L(-1) and yielded limit of detections (LODs) of 1 ng L(-1) for both 2-MIB and geosmin. In MS full scan mode, wastewater contaminants and other algal derived volatile organic compounds (ADVOCs) relevant to cyanobacterial bloom dynamics were detected and monitored in real source water samples. In the presence of known interferents with similar mass/charge fragments and elution times, the optimized method yielded low detection limits as well as exact molecular confirmation for taste and odor compounds in impacted source water samples. This method could be used as a tool to aid in the development of source water protection plans by identifying potential sources of anthropogenic and algal derived contamination in drinking water sources.
Subject(s)
Drinking Water/analysis , Environmental Monitoring/methods , Gas Chromatography-Mass Spectrometry/methods , Solid Phase Microextraction/methods , Water Pollutants, Chemical/analysis , Camphanes/analysis , Dimethylpolysiloxanes/chemistry , Naphthols/analysis , Odorants/analysis , Ohio , Polyvinyls/chemistry , Volatile Organic Compounds/chemistryABSTRACT
The transformation of two benzophenone UV filters (Oxybenzone and Dioxybenzone) was examined over the pH range 6-11 in the presence of excess aqueous chlorine. Under these conditions, both UV filters were rapidly transformed by aqueous chlorine just above circumneutral pH while transformation rates were significantly lower near the extremes of the pH range investigated. Observed first-order rate coefficients (k(obs)) were obtained at each pH for aqueous chlorine concentrations ranging from 10 to 75 µM. The k(obs) were used to determine the apparent second-order rate coefficient (k(app)) at each pH investigated as well as determine the reaction order of aqueous chlorine with each UV filter. The reaction of aqueous chlorine with either UV filter was found to be an overall second-order reaction, first-order with respect to each reactant. Assuming elemental stoichiometry described the reaction between aqueous chlorine and each UV filter, models were developed to determine intrinsic rate coefficients (k(int)) from the k(app) as a function of pH for both UV filters. The rate coefficients for the reaction of HOCl with 3-methoxyphenol moieties of oxybenzone (OXY) and dioxybenzone (DiOXY) were k(1,OxY) = 306 ± 81 M⻹s⻹ and k(1,DiOxY) = 154 ± 76 M⻹s⻹, respectively. The k(int) for the reaction of aqueous chlorine with the 3-methoxyphenolate forms were orders of magnitude greater than the un-ionized species, k(2,OxY) = 1.03(±0.52) × 106 M⻹s⻹ and k(2_1,DiOxY) = 4.14(±0.68) × 105 M⻹s⻹. Also, k(int) for the reaction of aqueous chlorine with the DiOXY ortho-substituted phenolate moiety was k(2_2,DiOxY) = 2.17(±0.30) × 10³ M⻹s⻹. Finally, chloroform formation potential for OXY and DiOXY was assessed over the pH range 6-10. While chloroform formation decreased as pH increased for OXY, chloroform formation increased as pH increased from 6 to 10 for DiOXY. Ultimate molar yields of chloroform per mole of UV filter were pH dependent; however, chloroform to UV filter molar yields at pH 8 were 0.221 CHCl3/OXY and 0.212 CHCl3/DiOXY.
Subject(s)
Benzophenones/chemistry , Chlorine/chemistry , Chloroform/chemistry , Disinfectants/chemistry , Sunscreening Agents/chemistry , Water Pollutants, Chemical/chemistry , Water Purification , Benzophenones/adverse effects , Benzophenones/analysis , Chloroform/analysis , Chloroform/toxicity , Consumer Product Safety , Hydrogen-Ion Concentration , Hypochlorous Acid/analysis , Hypochlorous Acid/chemistry , Kinetics , Models, Chemical , Osmolar Concentration , Solubility , Sunscreening Agents/adverse effects , Sunscreening Agents/analysis , Ultraviolet Rays/adverse effects , Water Pollutants, Chemical/adverse effects , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/toxicityABSTRACT
Iodinated X-ray contrast media (ICM) were investigated as a source of iodine in the formation of iodo-trihalomethane (iodo-THM) and iodo-acid disinfection byproducts (DBPs), both of which are highly genotoxic and/or cytotoxic in mammalian cells. ICM are widely used at medical centers to enable imaging of soft tissues (e.g., organs, veins, blood vessels) and are designed to be inert substances, with 95% eliminated in urine and feces unmetabolized within 24 h. ICM are not well removed in wastewater treatment plants, such that they have been found at elevated concentrations in rivers and streams (up to 100 µg/L). Naturally occurring iodide in source waters is believed to be a primary source of iodine in the formation of iodo-DBPs, but a previous 23-city iodo-DBP occurrence study also revealed appreciable levels of iodo-DBPs in some drinking waters that had very low or no detectable iodide in their source waters. When 10 of the original 23 cities' source waters were resampled, four ICM were found--iopamidol, iopromide, iohexol, and diatrizoate--with iopamidol most frequently detected, in 6 of the 10 plants sampled, with concentrations up to 2700 ng/L. Subsequent controlled laboratory reactions of iopamidol with aqueous chlorine and monochloramine in the absence of natural organic matter (NOM) produced only trace levels of iodo-DBPs; however, when reacted in real source waters (containing NOM), chlorine and monochloramine produced significant levels of iodo-THMs and iodo-acids, up to 212 nM for dichloroiodomethane and 3.0 nM for iodoacetic acid, respectively, for chlorination. The pH behavior was different for chlorine and monochloramine, such that iodo-DBP concentrations maximized at higher pH (8.5) for chlorine, but at lower pH (6.5) for monochloramine. Extracts from chloraminated source waters with and without iopamidol, as well as from chlorinated source waters with iopamidol, were the most cytotoxic samples in mammalian cells. Source waters with iopamidol but no disinfectant added were the least cytotoxic. While extracts from chlorinated and chloraminated source waters were genotoxic, the addition of iopamidol enhanced their genotoxicity. Therefore, while ICM are not toxic in themselves, their presence in source waters may be a source of concern because of the formation of highly toxic iodo-DBPs in chlorinated and chloraminated drinking water.
Subject(s)
Contrast Media/toxicity , Diagnostic Imaging , Disinfection , Halogenation/drug effects , Iodine Compounds/toxicity , Animals , CHO Cells , Cell Death/drug effects , Contrast Media/chemistry , Cricetinae , Cricetulus , DNA Damage , Drinking Water/chemistry , Iodides/chemistry , Iodine Compounds/chemistry , Iothalamic Acid/chemistry , Iothalamic Acid/toxicity , Mutagenicity Tests , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/isolation & purification , Water Pollutants, Chemical/toxicity , Water Pollution/analysisABSTRACT
The degradation of commonly detected organophosphorus (OP) pesticides, in drinking water sources, was investigated under simulated chloramination conditions. Due to monochloramine autodecomposition, it is difficult to observe the direct reaction of monochloramine with each OP pesticide. Therefore, a model was developed to examine the reaction of monochloramine (NH(2)Cl) and dichloramine (NHCl(2)) with chlorpyrifos (CP), diazinon (DZ), and malathion (MA). Monochloramine was found not to be very reactive with each OP pesticides, (k)NH(2)Cl,OP = 11-21 M(-1)h(-1). While, dichloramine (NHCl(2)) was found to be 2 orders of magnitude more reactive with each of the OP pesticides than monochloramine, (k)NHCl(2),OP = 2000-2900 M(-1)h(-1), which is still three orders of magnitude less than the hypochlorous acid reaction rate coefficient with each OP pesticide. For each pesticide, the reactivity of the three chlorinated oxidants was then found to correlate with half-wave potentials (E(1/2)) of each oxidant. With reaction rate coefficients for the three chlorinated oxidations as well as neutral and alkaline hydrolysis rate coefficients for the pesticides, the model was used to determine the dominant reaction pathways as a function of pH. At pH 6.5, OP pesticide transformation was mostly due to the reaction of hypochlorous acid and dichloramine. Above pH 8, alkaline hydrolysis or the direct reaction with monochloramine was the primary degradation pathway responsible for the transformation of OP pesticides. This demonstrates the ability of models to be used as tools to elucidate degradation pathways and parameterize critical reaction parameters when used with select yet comprehensive data sets.
Subject(s)
Chloramines/chemistry , Drinking , Organophosphorus Compounds/chemistry , Pesticides/chemistry , Water Supply/analysis , Chlorpyrifos/chemistry , Diazinon/chemistry , Humans , Hydrogen-Ion Concentration , Hydrolysis , Hypochlorous Acid/chemistry , Kinetics , Malathion/chemistry , Models, Chemical , Oxidation-Reduction , Structure-Activity RelationshipABSTRACT
The fate of organophosphorus (OP) pesticides in the presence of aqueous chlorine was investigated under simulated drinking water treatment conditions. Intrinsic rate coefficients were found for the reaction of hypochlorous acid (k(HOCl,OP)) and hypochlorite ion (k(OCl,OP) for several OP pesticides. The reaction of hypochlorous acid (HOCl) with each OP pesticide was relatively rapid near neutral pH, k(HOCl,OP) = 0.86 - 3.56 x 10(6) M(-1)h(-1). HOCI reacts at the thiophosphate (P = S) moiety of the OP pesticide resulting in the formation of the corresponding oxon (P=0), which is more toxic than the parent pesticide. Hypochlorite ion (OCl-) was found not to oxidize OP pesticides but act like a nucleophile accelerating hydrolysis, k(OCl,OP) = 37.3-15910 M(-1)h(-1). Both the k(HOCl,OP) and the k(OCl,OP) were found to correlate well with molecular descriptors within each subgroup of the OP pesticide class. A model was developed to predict the transformation of OP pesticides in the presence of aqueous chlorine. With hydrolysis rate coefficients, the transformation of OP pesticides under drinking water treatment conditions was found to be adequately predicted. The structure-activity relationships and model developed here could be used by risk assessors to determine exposure to OP pesticides and their transformation products in potable water.
Subject(s)
Chlorine/chemistry , Organophosphorus Compounds/chemistry , Pesticides/chemistry , Hydrolysis , Kinetics , Structure-Activity Relationship , WaterABSTRACT
The aqueous chlorination of chlorpyrifos (CP) was investigated in the presence of bromide and natural organic matter (NOM), which were identified as naturally occurring aqueous constituents that could affect CP transformation rates to the toxic product chlorpyrifos oxon (CPO). Bromide can be oxidized by chlorine to form hypobromous acid (HOBr), which was found to oxidize CP at a rate that was 3 orders of magnitude faster than was the case with chlorine: k HOBr,CP=1.14 (+/-0.21)x10(9) M(-1) h(-1) and k HOCl,CP=1.72x10(6) M(-1) h(-1), respectively. Similar to previous findings with the hypochlorite ion, hypobromite (OBr-) was found to accelerate the hydrolysis of CP and CPO: kOBr,CP=965 (+/-110) M(-1) h(-1) and kOBr,CPO=1390 (+/-160) M(-1) h(-1), respectively. Treated water from the Athens-Clarke County (ACC) water treatment plant in Athens, GA, was used in some of the experiments as a NOM source. A mechanistic model was used to adequately predict the loss of CP as well as the formation of CPO and the hydrolysis product 3,5,6-trichloro-2-pyridinol (TCP) in the presence of the ACC water.
Subject(s)
Bromides/chemistry , Chlorine/chemistry , Chlorpyrifos/chemistry , Insecticides/chemistry , Models, Chemical , Chlorpyrifos/metabolism , Hydrolysis , Insecticides/metabolism , Kinetics , Oxidation-Reduction , Solutions , Water/chemistryABSTRACT
A comprehensive reaction model was developed that incorporates the effect of bromide on monochloramine loss and formation of bromine and chlorine containing dihaloacetic acids (DHAAs) in the presence of natural organic matter (NOM). Reaction pathways accounted for the oxidation of bromide to active bromine (Br(l)) species, catalyzed monochloramine autodecomposition, NOM oxidation, and halogen incorporation into DHAAs. The reaction scheme incorporates a simplified reaction pathway describing the formation and termination of Br(l). In the absence of NOM, the model adequately predicted bromide catalyzed monochloramine autodecomposition. The Br(l) reaction rate coefficients are 4 orders of magnitude greater than HOCl for the same NOM sources under chloramination conditions. Surprisingly, the rate of NOM oxidation by Br(l) was faster than bromide catalyzed monochloramine autodecomposition by Br(l) so that the latter reactions could largely be ignored in the presence of NOM. Incorporation of bromine and chlorine into DHAAs was proportional to the amount of NOM oxidized by each halogen and modeled using simple bromine (alpha(Br)) and chlorine (alpha(Cl)) incorporation coefficients. Both coefficients were found to be independent of each other and alpha(Br) was one-half the value of alpha(Cl). This indicates that chlorine incorporates itself into DHAA precursors more effectivelythan bromine. Model predictions compared well with DHAA measurements in the presence of increasing bromide concentrations and is attributable to the increased rate of NOM oxidation, which is rate limited by the oxidation of bromide ion in chloraminated systems.
Subject(s)
Acetates/chemistry , Bromides/chemistry , Chloramines/chemistry , Water/chemistry , Oxidation-ReductionABSTRACT
Perfluorocarboxylic acids (PFCAs), namely perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA), have been identified as persistent, bioaccumulative and potentially toxic compounds. The structural analog, 8-2 fluorotelomer alcohol (8-2 fTOH) is considered the probable precursor of these stable metabolites. Because simultaneous quantification is needed for volatile and non-volatile perfluorinated chemicals (PFCs) in complex matrices, a GC/MS method was developed and tested based on selected ion monitoring of perfluorinated alkyl parent chain fragment ions. Although the method requires a derivatization step, combined GC/MS analysis of PFCA-me's and FTOHs increases analytical efficiency and decreases sample analysis time. The method instrument detection limits are between 7.1 and 24.5 ng/mL extract (MTBE), and the method quantification limits are below 50 ng/mL serum or ng/g liver for all PFCs investigated. Recoveries from mouse serum and liver homogenates, which were spiked with FTOHs and PFCAs at levels of 25 and 200 ng/mL or ng/g, ranged from 81 to 101%. Finally, the utility of the method was demonstrated by dosing male CD-1 mice with 30 mg/kg-BW of 8-2 fTOH and quantifying PFCs 6h post-treatment. The advantages of this method are (1) the simultaneous detection of both volatile and non-volatile fluorotelomer-based chemicals in complex matrices, such as mammalian tissues, (2) as a confirmatory method to LC-MS/MS, and (3) as an alternative method of analysis for laboratories without access to LC-MS/MS.
Subject(s)
Fluorocarbons/analysis , Gas Chromatography-Mass Spectrometry/methods , Animals , Calibration , Fluorocarbons/blood , Liver/chemistry , Male , Mice , Reference Standards , Sensitivity and SpecificityABSTRACT
The speciation of aqueous free chlorine above pH 5 is a well-understood equilibrium of H2O + HOCl <==> OCl- + H3O+ with a pKa of 7.5. However, the identity of another very potent oxidant present at low pH (below 5) has been attributed by some researchers to Cl2(aq) and by others to H2OCl+. We have conducted a series of experiments designed to ascertain which of these two species is correct. First, using Raman spectroscopy, we found that an equilibrium of H2O + H2OCl+ <==> HOCl + H3O+ is unlikely because the "apparent pKa" increases monotonically from 1.25 to 2.11 as the analytical concentration is increased from 6.6 to 26.2 mM. Second, we found that significantly reducing the chloride ion concentration changed the Raman spectrum and also dramatically reduced the oxidation potency of the low-pH solution (as compared to solutions at the same pH that contained equimolar concentrations of Cl- and HOCl). The chloride ion concentration was not expected to impact an equilibrium of H2O + H2OCl+ <==> HOCl + H3O+, if it existed. These observations supported the following equilibrium as pH is decreased: Cl2(aq) + 2H2O <==> HOCl + Cl- + H3O+. The concentration-based equilibrium constant was estimated to be approximately 2.56 x 10(-4) M2 in solutions whose ionic strengths were approximately 0.01 M. The oxidative potency of the species in low pH solutions was investigated by monitoring the oxidation of secondary alcohols to ketones. These and other results reported here argue strongly that Cl2(aq) is the correct form of the potent low-pH oxidant in aqueous free-chlorine solutions.
Subject(s)
Chlorine/chemistry , Oxidants/chemistry , Spectrum Analysis, Raman , Water Supply , Water/chemistry , Alcohols/chemistry , Hydrogen-Ion Concentration , Hypochlorous Acid/chemistry , Ketones/chemistryABSTRACT
A kinetic model was developed to predict dichloroacetic acid (DCAA) formation in chloraminated systems. Equations describing DCAA formation were incorporated into an established comprehensive monochloramine-natural organic matter (NOM) reaction model. DCAA formation was theorized to be proportional to the amount of NOM oxidized by monochloramine and described by a single dimensionless DCAA formation coefficient, theta(DCAA) (M(DCAA)/M(DOC(ox)). The applicability of the model to describe DCAA formation in the presence of six different NOM sources was evaluated. DCAA formation could be described by considering a single NOM source-specific value for theta(DCAA) over a wide range of experimental conditions (i.e., pH, NOM, free ammonia, and monochloramine concentrations). DCAA formation appears to be directly proportional to the amount of active chlorine (monochloramine and free chlorine) that reacted with the NOM under these experimental conditions. Values of theta(DCAA) for all six NOM sources, determined by nonlinear regression analysis, varied from 6.51 x 10(-3) to 1.15 x 10(-2) and were linearly correlated with specific ultraviolet absorbance at 280 nm (SUVA(280)). The ability to model monochloramine loss and DCAA formation in the presence of NOM provides insight into disinfection by-product (DBP) formation pathways under chloramination conditions. The subsequent model and correlations to SUVA has the potential to aid the water treatment industry as a tool in developing strategies that minimize DBP formation while maintaining the microbial integrity of the water distribution system.
Subject(s)
Chloramines/chemistry , Dichloroacetic Acid/chemistry , Models, Chemical , Nonlinear DynamicsABSTRACT
Chlorpyrifos (CP) was used as a model compound to develop experimental methods and prototype modeling tools to forecast the fate of organophosphate (OP) pesticides under drinking water treatment conditions. CP was found to rapidly oxidize to chlorpyrifos oxon (CPO) in the presence of free chlorine. The primary oxidant is hypochlorous acid (HOCl), kr = 1.72 (+/-0.68) x 10(6) M(-1)h(-1). Thus, oxidation is more rapid at lower pH (i.e., below the pKa of HOCl at 7.5). At elevated pH, both CP and CPO are susceptible to alkaline hydrolysis and degrade to 3,5,6-trichloro-2-pyridinol (TCP), a stable end product. Furthermore, hydrolysis of both CP and CPO to TCP was shown to be accelerated in the presence of free chlorine by OCl-, kOCl,CP = 990 (+/-200) M(-1)h(-1) and kOCl,CPO = 1340 (+/-110) M(-1)h(-1). These observations regarding oxidation and hydrolysis are relevant to common drinking water disinfection processes. In this work, intrinsic rate coefficients for these processes were determined, and a simple mechanistic model was developed that accurately predicts the temporal concentrations of CP, CPO, and TCP as a function of pH, chlorine dose, and CP concentration.
Subject(s)
Chlorine/chemistry , Chlorpyrifos/chemistry , Models, Chemical , Kinetics , Solutions , Water/chemistryABSTRACT
A comprehensive model describing monochloramine loss in the presence of natural organic matter (NOM) is presented. The model incorporates simultaneous monochloramine autodecomposition and reaction pathways resulting in NOM oxidation. These competing pathways were resolved numerically using an iterative process evaluating hypothesized reactions describing NOM oxidation by monochloramine under various experimental conditions. The reaction of monochloramine with NOM was described as biphasic using four NOM specific reaction parameters. NOM pathway 1 involves a direct reaction of monochloramine with NOM (k(doc1) = 1.05 x 10(4)-3.45 x 10(4) M(-1) h(-1)). NOM pathway 2 is slower in terms of monochloramine loss and attributable to free chlorine (HOCl) derived from monochloramine hydrolysis (k(doc2) = 5.72 x 10(5)-6.98 x 10(5) M(-1) h(-1)), which accounted for the majority of monochloramine loss. Also, the free chlorine reactive site fraction in the NOM structure was found to correlate to specific ultraviolet absorbance at 280 nm (SUVA280). Modeling monochloramine loss allowed for insight into disinfectant reaction pathways involving NOM oxidation. This knowledge is of value in assessing monochloramine stability in distribution systems and reaction pathways leading to disinfection by-product (DBP) formation.
Subject(s)
Chloramines/analysis , Disinfection , Models, Chemical , Organic Chemicals/analysis , Water Purification/methods , Chloramines/chemistry , Chlorine/chemistry , Disinfectants/chemistry , Hydrolysis , Organic Chemicals/chemistry , Oxidation-Reduction , Spectrophotometry, Ultraviolet , Time Factors , Water Pollutants, Chemical/analysis , Water SupplyABSTRACT
Studies were conducted to investigate the hypothesis that N-nitrosodimethylamine (NDMA) is a potential disinfection by-product specifically produced during chlorination or chloramination. Experiments were conducted using dimethylamine (DMA) as a model precursor. NDMA was formed by the reaction of DMA with free chlorine in the presence of ammonia and also with monochloramine. We proposed a mechanism for NDMA formation in chlorinated or chloraminated water, which does not require nitrite as in N-nitrosation. The critical NDMA formation reactions consist of (i) the formation of monochloramine by combination of free chlorine with ammonia, (ii) the formation of 1,1-dimethylhydrazine (UDMH) intermediate from the reaction of DMA with monochloramine followed by, (iii) the oxidation of UDMH by monochloramine to NDMA, and (iv) the reversible chlorine transfer reaction between free chlorine/monochloramine and DMA which is parallel with (i) and (ii). A kinetic model was also developed to validate the proposed mechanism.