Tifft Lecture – Sept 17, 2014 The Present Status of Regulated and Non-Regulated DBPs David A. Reckhow Department of Civil and Environmental Engineering, University of Massachusetts, Amherst, MA 01003 1 Outline What do we know about the harmful DBPs? Some favorites Halonitromethanes Iodo-DBPs Haloketones Halonitriles MX compounds Halobenzoquinones Haloaldehydes Haloamides N-haloamines Let’s make some Treatment Effects disinfection byproducts! Disinfection Scenarios Indoor factors Where do we go from here? Special interest in “indicator DBPs” 2 Formation of Cl2-driven DBPs Cl2 NaOCl The Halogenated DBPs • • • • • Br-, I- THMs HAAs and other haloacids Haloaromatics N-halo compounds Halo-nitriles, aldehydes, nitros, etc OBr-, I3NH3 ~10% The nonhalogenated DBPs NH2Cl Natural Organic Mater Anthropogenic Chemicals (PPCPs, Ag & industrial products) ~90% CO2 + Oxidized Organic Compounds • • • • Acids Aldehydes Ketones3 Nitrosamines John Rook & DBPs 1921-2010 Found DBPs and brought them to the world’s attention Brought headspace analysis from the beer industry to drinking water Found trihalomethanes (THMs) in finished water Carcinogens !?! Published in Dutch journal H2O, Aug 19, 1972 issue Deduced that they were formed as byproducts of chlorination Proposed chemical pathways Rook, 1974, Water Treat. & Exam., 23:234 4 The first, and currently regulated DBPs The THMs Br Cl Cl C Cl H C H Chloroform Bromodichloromethane Cl C Cl C Br C Cl Cl Trichloroacetic Acid COOH Dichloroacetic Acid (DCAA) H COOH Br C Br Tribromoacetic Acid Br Cl 5 COOH Chlorodibromoacetic Acid Cl H C HAA5 only Br Cl Bromodichloroacetic Acid (TCAA) Bromoform Br COOH H Br Chlorodibromomethane Br COOH Br C H Cl Cl The HAAs Br C Cl Cl Br Br C Br COOH Cl Bromochloroacetic Acid H C COOH Br Dibromoacetic 5 Acid 1300 600 20 mg/L chlorine dose pH 7.0 20oC Regulated Compounds 1200 1100 500 The are “end products” Chemically very stable Not typical of other DBPs TOX Concentration (g/L) 900 400 800 700 300 600 TCAA 500 TTHM 400 200 300 200 100 DCAA 100 (from: Reckhow & Singer, 1984) 0 0 0 20 40 60 80 100 120 Time (hrs) 140 160 300 350 6 THM, HAA Concentration (g/L) TOX 1000 Chlorine vs Chloramine Regulated DBPs NOM THMs & HAAs Oxidation & Substitution (chlorine & chloramines) Dihalo products, but little trihalo R'' O O C CCl2 C R'' R' O O C CCl2 C Hydrolysis Hydrolysis O R'' C Substitution (free chlorine only) Slow Cl2HC C OH O R'' C Hydrolysis THM O Hydrolysis & Oxidation CHCl2 OH CCl3 Oxidative Hydrolysis O TCAA CHCl3 Cl3C C OH DCAA TCAA biodegradation in lab tests Distribution system solids 8 Control of Regulated DBPs Source water management Selection of sources, watershed management Precursor Removal (mostly NOM removal) Coagulation (& settling/filtration) Biological treatment (w & w/o pre-oxidation) Adsorption, High-pressure membranes, etc. Precursor Modification Oxidation Other process changes Delayed point of chlorination, reduced dose Use of Alternative Disinfectants (e.g., chloramines) DBP Removal 9 Control of Non-Regulated DBPs We need to know what these compounds are first “I think you should be more explicit here 10 in step two” Which path? Regulatory compliance vs public health Do they end up at the same place? 11 Other Compounds The DBP Iceberg THMs, THAAs DHAAs ICR Compounds 50 MWDSC DBPs ~700 Known DBPs Susan Richardson USEPA Halobenzoquinones Halogenated Compounds Non-halogenated Compounds Stuart Krasner AWWA DBP Epidemiology Bladder Cancer DBPs linked to ~10,000 US cases every year Other Cancers Rectal, colon Basis for current EPA regulation 80 µg/L THMs 60 µg/L HAAs Reproductive & developmental effects Miscarriages & Low birth weight Birth Defects e.g., Cleft palate, neural tube defects Other Kidney & spleen disorders Immune system problems, neurotoxic effects 13 10-6 10-5 Haloacetamides Haloacetonitriles Halonitromethanes BNM DBCNM BCNM 10-4 Not Genotoxic: DCAA, TCAA, BDCAA, Dichloroacetamide, 3,3-Dibromopropenoic Acid, 3-Iodo-3-bromopropenoic Acid, 2,3,3,Tribromopropenoic Acid CNM Dichloroacetonitrile 10-3 CDBAA EMS +Control Trihloroacetamide 2-Iodo-3-bromopropenoic Acid Bromate 2,3-Dibromopropenoic Acid Chloroacetamide I > Br > Cl 2-Bromobutenedioic Acid TBAA BIAA BCAA DBAA DIAA Dibromoacetamide Trichloroacetonitrile Chloroacetonitrile DBP Chemical Class MX Tribromopyrrole DBNM DibromoacetonitrileIodoacetamide Iodoacetonitrile Bromoacetonitrile Bromoacetamide Genotoxicity Bromochloroacetonitrile 3,3-Bromochloro-4-oxopentanoic Acid CAA DCNM BAA Other DBPs BDCNM TBNM 3,3-Dibromo-4-oxopentanoic Acid TCNM Halo Acids IAA Mono-X > Di-X > Tri-X The regulated ones Haloacetic Acids 10-2 Single Cell Gel Electrophoresis Genotoxicity Potency Log Molar Concentration (4 h Exposure) From Plewa & Colleagues 14 July 2006 TOX: Known & Unknown Data from the Mills Plant (CA) August 1997 (courtesy of Stuart Krasner) Haloketones Chloropicrin Trihalomethanes 20% Regulated DBPs TTHMs But, the Bad Stuff is probably somewhere here? Haloacetonitriles 2% Unknown TOX Chloral Hydrate 1% Sum of 5 Haloacetic Acids 10% Unknown Organic Halogen 64% Bromochloroacetic Acid 3% 15 Regulated DBPs as surrogates or indicators 2D Graph 1 From: ICR Database 140 Not a perfect 120 correlation So what can we TTHM (g/L) 100 do? 80 60 40 20 0 0 100 200 Unknown TOX (g/L) Unk-TOX vs TTHMc 300 400 Maybe we need a more diverse group of surrogates Look at occurrence characteristics 16 1300 20 mg/L chlorine dose pH 7.0 20oC 1200 1100 500 TOX 1000 Regulated TOX Concentration (g/L) Byproducts 900 400 800 700 300 600 TCAA 500 TTHM 400 200 THM, HAA Concentration (g/L) Time 600 300 200 Aquatic NOM 100 DCAA 100 0 (after Reckhow & Singer, 1984) 0 0 20 40 60 80 100 120 Time (hrs) 140 160 300 350 17 Some Unregulated Byproducts 10 Chlorinated Raw Drinking Water from New Jersey (MacNeill's UMass thesis, 1994) Many decrease Biological DCAN 8 Concentration (g/L) with time Degradation Chemical 6 1,1,1-TCP 4 Not shown Chloropicrin 2 1,1-DCP 0 0 20 40 60 80 Time (hrs) 100 120 140 18 160 Chloro-Bromo-Iodo Speciation X-speciation tends to be similar for different classes of DBPs 1.2 Data from Weinberg et al., 2002 All 12 plants ClBr-THM Mole Fraction 1.0 May not hold for: CHCl3 CHBrCl2 CHBr2Cl CHBr3 • • • Hindered Precursors Strong oxidants such as O3 or ClO2 Unstable DBPs 0.8 R-Cl3 Increasing RW Bromide level 0.6 R-ClBr2 R-Cl2Br 0.4 0.2 R-Br3 Lines represent simple halogen competition model 0.0 0.0 0.1 0.2 0.3 0.4 THM Br/(Cl+Br) 0.5 0.6 19 Iodo-THMs Chlorine & Ozone produce iodate; Chloramine doesn’t O3 O3 IO3- CHCl2I 40 CHClI2 400 30 300 CHBrI2 CHI3 20 200 10 100 0 IO3- (g/L) I-THM (g/L) CHBrClI CHBr2I 0 Cl2 O3/Cl2 NH2Cl O3/NH2Cl ClO2 Cambridge MA Water, DOC: 4.2 mg/L, I: 200 g/L 20 Hua & Reckhow, 2007 Iodo-DBP Occurrence Iodo-THM Occurrence Concentrations Percentile 50% 0.4 75% 2 90% From 12 systems in NA Up to 25 µg/L for direct chloramination Relative Prevalence Conc (µg/L) 2% of THM4 at 50%ile; 7% at 75%ile? Iodo-THMs ≈ 0.1* Bromo-THMs 4 From: Weinberg, Krasner, et al., 2002 Iodo-HAA Occurrence Little or no triHAAs containing iodine?? 21 Many Iodo-acids decompose Decarboxylation rates of THAAs in water From Zhang and Minear, 2002; expanded by UMass HAA TCAA BDCAA DBCAA TBAA DCIAA BCIAA DBIAA CDIAA BDIAA TIAA Half-life (hr) % Remaining @ 24 hr 20C 55C 20C 55C 99000 130 100.0% 88.0% 21600 36 99.9% 63.0% 4400 8 99.6% 12.5% 620 3 97.4% 0.4% 2414 3.2 99.3% 0.5% 479 0.63 96.6% 0.0% 95 0.12 84.0% 0.0% 62 0.08 76.5% 0.0% 12 0.02 26.0% 0.0% 2 0.00 0.0% 0.0% Distribution System degradation product (THM) chloroform bromodichloromethane chlorodibromomethane bromoform dichloroiodomethane bromochloroiodomethane dibromoiodomethane chlorodiiodomethane bromodiiodomethane triiodomethane Water Heater 22 An Example: Dichloropropanone Doesn’t track Dichloropropanone vs TTHM4 THMs or HAAs Like most DBPs More with Chloramines Pre-ozonation? Utility #1 (Cl2/NH2Cl) Utility #2 (Cl2/Cl2) 4 Dichloropropanone (ug/L) 5 Utility #1 (Cl2/Cl2) Utility #3 (O3/Cl2) Utility #4 (Cl2/NH2Cl) 3 Utility #5 (ClO2/Cl2) Utility #6 (O3/NH2Cl) 2 1 0 0 50 100 TTHM4(ug/L) 150 23 200 1,1,1-trichloropropanone More with free chlorine Also pre-O3 and ClO2 24 Nitrogenous DBPs Special Toxicological Concerns Compounds Br Cl H C C N H C Br C N Nitrosamines Cl Cl Dichloroacetonitrile Bromochloroacetonitrile Halonitriles (DCAN) (BCAN) Haloamides Cyanogen halides (CNCl, CNBr) Halonitroalkanes N-Halo amines Sources: algae could be very important High nitrogen content H C C N Br Dibromoacetonitrile (DBAN) Cl NO Cl C 2 Cl Chloropicrin (CHP) 25 Organic Nitrogen Abundance Ratio to carbon Redrawn from Westerhoff & Mash, 2002 60 Terrestrial Plant dominated DOC/DON (mg-C/mg-N) 50 40 30 27 20 15 8.2 10 Algal dominated 0 0 10 20 30 40 50 Percentile 5.7 mg-C/mg-N (Redfield Ratio) 60 70 80 90 100 26 12.0 11.0 11.0 10.0 10.0 Tunnel #1 Tunnel #2 Tunnel #3 Cannonsville Pepacton Neversink Rondout Ashokan Schoharie Kensico: Del Kensico: Cat 8.0 7.0 6.0 5.5 7.0 6.0 5.5 5.0 4.5 1.0 1.0 0.5 0.5 0.0 0.0 20 07 /1 / 20 0 10 9/ 1/ 20 0 8/ 1/ 20 0 7/ 1/ 20 0 6/ 1/ 20 0 5/ 1/ 4/ 1/ 20 0 3/ 1/ 20 0 2/ 1/ 1/ 1/ /1 / 12 /1 / 20 0 Date 7 1.5 7 1.5 7 2.0 7 2.0 7 2.5 7 2.5 7 3.0 7 3.0 7 3.5 20 06 3.5 20 06 4.0 20 06 4.0 11 Amanda Keyes Measuring Org-N 8.0 NYC Reservoirs 4.5 /1 / From Amino acids? Algal activity Dichloroacetonitrile FP (g/L) 5.0 10 Dichloroacetonitrile 9.0 27 Dichloroacetonitrile FP (g/L) 9.0 20 0 HAN example 12.0 DHAN - Algal Source? Algal-N release Proteins Some free AAs 28 H Cl Continued Rxn Key intermediates DHAMs N-halo species C Cl C N OCl Cl OH k4 k2 k1 H Cl C DCAN H H2O N Cl C C fast OH H fast H2O Cl C C Cl OH C Cl NCl C OH Cl Final product DHAAs H NH N C O Cl N-Cl-DCAD anion fast pKa = 3.7 DCAD Concentrations Cl are well known N-Cl-DCAD H H NH2 C k1-1 H Cl C Cl Cl C C C S (+IV) O Cl NHCl Cl(+II) k1-2 OH OH O HOCl H NH2 C O Cl Cl fast fast NH3 Cl H O C C Cl DCAA C Cl NHCl C OCl OH NHCl2 OH 29 OCl Dichloroacetonitrile half-life DCAN Halflife At 20 C From Reckhow, 100 1 Hour 8 Hours Chlorine Residual (mg/L) 10 Minutes Platt, MacNeill & McClellan, 2001 1 Day OCl- 10 3 Days Degradation in DS observed to increase with increasing pH 1 Week 1 OH- H2O Aqua 50:1:113 ICR data: Obolensky & Frey, 2002 0.1 3 Weeks 6 7 8 9 pH 10 11 30 DCAN→DCAM→DCAA Formation and degradation of dichloroacetonitrile, dichloroacetamide, and dichloroacetic acid in Utility # 11 slurry samples (left) and DI samples (right) 31 Organic Chloramines – an example Stable N-chloroaldimine from amino acids Pathway favored at lower pHs Half-life of 35-60 hrs @pH 7-8 phenylalanine N-chlorophenylacetaldimine 32 Conyers & Scully, 1993 [ES&T 27:261] TOX pie revised Median C/N ratio (15) NX 0.5 TON Organic Chloramines NX 0.2 TON THMs 20% Unknown organic Halogen 63% GAC reduces N-X in TOX analysis Haloacetonitriles 2% HAA5 10% Chloral Hydrate 1% Bromochloroacetic Acid 3% Halonitromethanes Haloketones 33 Halonitromethanes Mechanisms and Treatment Highest levels with pre-O3 followed by chlorine/chloramines Greatly enhanced by UV (medium pressure) Some nitration reactions (e.g., Choi & Richardson, 2004) Probably some activation of pre-existing N-organics Photonitration Postulated for nitrification hot spots (Thibaud et al., 1987) Ammonia nitrite nitrating species nitro-organicCP Occurrence 0.1-3 µg/L for individual species 0.28 and 0.43 µg/L were median values in PE & DS 12 plant national study (Weinberg, Krasner et al., 2002) 8 plants from NC (Singer et al., 1995) 0.5 and 0.9 µg/L were 75 and 90%ile in DS from ICR 34 Trichloronitromethane (Chloropicrin) Sometimes Chloropicrin vs TTHM4 greater formation with Chloramines Pre-ozone Utility #1 (Cl2/NH2Cl) Utility #2 (Cl2/Cl2) 6 Utility #1 (Cl2/Cl2) Utility #3 (O3/Cl2) Utility #4 (Cl2/NH2Cl) 5 Chloropicrin (ug/L) 7 Utility #5 (ClO2/Cl2) Utility #6 (O3/NH2Cl) 4 3 2 1 0 0 50 100 TTHM4(ug/L) 150 35 200 Chloramines vs Free Chlorine 2011 study of a large US utility Chloramines Free Chlorine 6 6 Concentration(ug/L) 5 5 4 4 3 3 2 2 1 1 0 Concentration(ug/L) DCP CP TCP 0 1 2 3 4 5 6 7 8 9 10 11 12 13 sample location 1 2 3 4 5 6 7 8 9 10 11 12 13 sample location 36 Chloramines vs Free Chlorine DBPs Lower levels of trihalogenated byproducts Less impact on dihalogenated compound Easier to meet current DBP regulations Some are higher with chloramines More of some types of N-DBPs Organic chloramines, nitriles, amides, nitro compds Other concerns Growth of ammonia oxidizing bacteria Loss of residual, formation of reactive intermediates Reduction of Lead (IV) Public perception & direct health effects 37 Chloramines: with pipe reactions N2O NO3X2 H2N2O2 Chemical Reduction Chemical Oxidation HNO NH2Cl Biodegradation AMO ClNHOH X1 N2 Pb+2 Pb(IV) NO2- NH2OH NH3 AMO HAO AOB NOB 38 Moving Indoors Where the “exposure” is More time for reaction Abiotic Biodegradation Temperature changes Especially water heater: accelerated decomposition/reaction Phase changes Contact with food and related home products New precursors, continued reaction 39 City Water Major Routes Ingestion Water Heater Drinking Showering & Washing Beverage Preparation Food Preparation Dermal & Inhalation Ingestion & Inhalation Ingestion & Inhalation Clothes Washing Dermal & Inhalation Dish Washing Dermal & Inhalation Human Exposure Activity 40 Hot vs Cold: THMs 50 Heavy Hot Water Use Water Heater is Flushed 40 Cold Tap Hot Tap Plant Effluent 30 20 Hwang's level of concern 10 0 16 :0 18 0 :0 20 0 :0 22 0 :0 00 0 :0 02 0 :0 04 0 :0 06 0 :0 08 0 :0 10 0 :0 12 0 :0 14 0 :0 16 0 :0 18 0 :0 20 0 :0 22 0 :0 00 0 :0 02 0 :0 04 0 :0 06 0 :0 08 0 :0 0 TTHM Concentration ( g/L) Utility # 14 Monday Tuesday Wednesday 41 Day and Time Hot vs Cold: Dichloroacetonitrile Utility #14 Heavy Hot Water Use Water Heater is Flushed 2.0 Cold Tap Hot Tap Plant Effluent 1.5 1.0 0.5 0.0 16 :0 18 0 :0 20 0 :0 22 0 :0 00 0 :0 02 0 :0 04 0 :0 06 0 :0 08 0 :0 10 0 :0 12 0 :0 14 0 :0 16 0 :0 18 0 :0 20 0 :0 22 0 :0 00 0 :0 02 0 :0 04 0 :0 06 0 :0 08 0 :0 0 Dichloroacetontrile Concentration ( g/L) 2.5 Monday Tuesday Wednesday 42 Day and Time 16 :0 18 0 :0 20 0 :0 22 0 :0 00 0 :0 02 0 :0 04 0 :0 06 0 :0 08 0 :0 10 0 :0 12 0 :0 14 0 :0 16 0 :0 18 0 :0 20 0 :0 22 0 :0 00 0 :0 02 0 :0 04 0 :0 06 0 :0 08 0 :0 0 Chloropicrin Concentration ( g/L) Hot vs Cold: Chloropicrin Utility #14 Heavy Hot Water Use Water Heater is Flushed 0.6 0.4 Cold Tap Hot Tap Plant Effluent 0.2 0.0 Monday Tuesday Day and Time Wednesday 43 THMs: Hot vs Cold pH 7 120 Dermal and inhalation exposure 80 Heating Chloroform (g/L) 100 60 No heating 6 hrs ambient+subsequent heating 24 hrs ambient+subsequent heating 48 hrs ambient+subsequent heating 72 hrs ambient+subsequent heating 96 hrs ambient+subsequent heating 40 20 0 Ingestion exposure 0 20 40 60 80 Total Reaction Time (hr) System Water Age 100 120 Precursors & Behavior General Trends Removal by: Mono & DihaloDBPs Trihalo-DBPs Precursor Origins Coag. or Oxidation Biodregradation Haloacids (DCAA) THMs General NOM Average Average Aldehydes Aldehydes Oxidized NOM Poor (Chloral Hydrate) (bacterial, solar, ozone) Ketones Ketones (Dichloropropanone) (Trichloropropanone) Nitroalkanes Nitroalkanes (Chloropicrin) reactive Nitrogen species Nitriles Nitriles Algal (Dichloroacetonitrile) (Trichloroacetonitrile) (autochthonous) Amides Amides (Dichloroacetamide) (Trichloroacetamide) Good Average Average Good Poor Cyanogen Halides (CNCl, CNBr) Halobenzoquinones? Haloacids (TCAA) Terrestrial Lignin (allochthonous) Preferentially formed by Chloramination 45 Driven by Regulations DBP control with DS management Notes: Parameter THM TriDiHAAs HAAs HANs TCP DCP CP IodoDBPs Time Cl2 Dose ~ pH ~ Cl2 to NH2Cl ~ ~ ~ Temp ~ HANs: haloacetontriles, including DCAN TCP: trichloropropanone, a haloketone DCP: dichloropropanone: a haloketone CP: chloropicrin: a halonitromethane Iodo-DBPs: include iodinated THMs, HAAs, etc 46 Conclusions I Chlorination brings overwhelming public health benefits However some of its risks are still poorly understood Which are the most toxic DBPs and what is their origin? Some may come from terrestrial precursors Others may come from algal precursors Haloquinones? Halonitriles, haloamides, N-chloro DBPs We really don’t know the answer Conventional approaches may not be effective at reducing these “metastable” byproducts Chloramines, short chlorine contact time, low pH 47 Conclusions II Exposure may not be proportional to concentrations in the main Water Heaters substantially change the DBP levels and character Some increase many fold Some show little change TriHAAs Some decrease THMs, DiHAAs, Chloropicrin Dichloroacetonitrile, Trichloropropanone For most, we simply don’t know The best solution may be to: Minimize reactive NOM by removal & oxidation Use free chlorine, minimizing residual 48 Recommendations Above all, maintain good disinfection practice Minimize harmful DBPs by: Reducing “reactive” TOC Avoiding N-DBP precursors Possible regulatory strategy Eliminate HAA reg & monitoring requirement If it must be kept, separate DiHAAs and TriHAAs Make better use of THM monitoring Expand analyte list to include other Neutrals (NE) Develop guidelines for other NE compounds 49 Acknowledgements Richard Bull UMass Colleagues & Researchers John Tobiason & Jim Edzwald Chen Wu, Boning Liu, Guanghui Hua & JS Kim Sponsors AWWA Research Foundation (now WRF) Project #2867, #4089 and #4242 NSF, EPA Utility Partners ~30 across the US and Canada 50 Press Release: Sept 9, 2014 51 U.S. EPA STAR NATIONAL CENTERS FOR INNOVATION IN SMALL DRINKING WATER SYSTEMS Water Innovation Network for Sustainable Small Systems (WINSSS) Center University of Massachusetts Amherst Design of Risk Reducing, Innovative Implementable Small System Knowledge (DeRISK) Center University of Colorado Boulder WINSSS Center Team University of Massachusetts (Amherst) Dave Reckhow (PI), John Tobiason, Caitlyn Butler, Chul Park and Prashant Shenoy (Co-PIs) University of Texas (Austin) Desmond Lawler, Lynn Katz, Mary Jo Kirisits, Kerry Kinney (Co-PIs), Navid Saleh, Gerald Speitel University of Nebraska (Lincoln) Bruce Dvorak (Co-PI), Rebecca Lai, Chittaranjan Ray University of Florida (Gainesville) Treavor Boyer (Co-PI) University of Illinois (Urbana-Champaign) Steven Wilson (Co-PI) University of South Florida Jane Zhang (Co-PI) Carollo Engineers Jess Brown (Co-PI) 16 Projects A1: Implementing ferrate treatment of drinking water in the US A2: Simultaneous removal of inorganic contaminants, DBP precursors, and particles in alum and ferric coagulation A3: Contaminant reduction, life cycle impacts, and life cycle costs of ion exchange treatment and regeneration A4: Natural filtration impacts on post disinfection water quality in small systems A5: Intermittent treatment plant operation: understanding and minimization of detrimental impacts A6: Coagulant selection and dosing control for particle and NOM removal A7: Effect of climate change on water treatment practice at small systems B1: Developing a standardized approach for state acceptance of innovative technologies B2: Simplified data entry system for asset management built off existing software B3: A distributed sensing and monitoring system: application to SWTR compliance and POU devices C1: Electrodialysis coupled with RO and NF membranes C2: Peroxide oxidative coupling linked with a super-hydrophilic hollow-fiber membrane system C3: Hollow fiber membrane air stripping D1: Nitrification D2: Denitrification D3: Biological Treatment and Nitrogenous DBPs
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