CEE 690K ENVIRONMENTAL REACTION KINETICS Lecture #16 Case Study: - - PDF document
4/12/2008 Updated: 12 April 2008 CEE690K Lecture #16 1 Print version CEE 690K ENVIRONMENTAL REACTION KINETICS Lecture #16 Case Study: Nitrogenous Disinfection Byproducts Primary Literature as noted Introduction David A. Reckhow
CEE690K Lecture #16 1
Updated: 12 April 2008
David A. Reckhow
Primary Literature as noted
University of Massachusetts - Amherst
Junsung Kim, Guanghui Hua, Gladys MA WRRC Conference 8 April 2008 g g y Makdissy, John McClellan, Cynthia Castellon, Darlene Buttrick
Formation of N-DBPs from NOM
Occurrence Characteristics Chemistry of selected End Products DHAN DHAD NDMA Reactivity of Specific Nitrogenous Constituents Amino Acids Proteins & others Key N-DBPs and Methods to be developed
Oxidized NOM and inorganic chloride The Precursors!
Chlorinated Organics
Cl Cl Cl C H Br Cl Cl C H Br Cl Br C H Br Br Br C H Chloroform Bromodichloromethane Chlorodibromomethane Bromoform
Cl Cl Cl C COOH Br Cl Cl C COOH Br Cl Br C COOH Br Br Br C COOH Cl Cl Cl Br Trichloroacetic Bromodichloroacetic Chlorodibromoacetic Tribromoacetic Acid Acid Acid Acid
Cl H C COOH Br C COOH Br H C COOH H Cl Cl Br Dichloroacetic Bromochloroacetic Dibromoacetic Acid Acid Acid
Certain to come from N-organics when using free Certain to come from N-organics when using free
Major types: Cyanogen Halides Haloacetonitriles
Cl Cl H C C Br Cl C Br Br H C Dichloroacetonitrile Bromochloroacetonitrile Dibromoacetonitrile H N C N C N
CNCl & CNBr Halonitromethanes (DCAN) (BCAN) (DBAN)
Cl Cl Cl C C Trichloroacetonitrile
(TCAN)
N
Special focus on these compounds because of large data set
Cl Cl Cl C NO Chloropicrin
(CHP)
2
9 species
Nitrogenous organics are generally quite reactive Can be enhanced by chloramination Some evidence that they are major contributors to
Very little is known about N-DBPs Analytical chemistry is more complicated
yrrole ntrol
DBP Chemical Class
Work of Michael Plewa
8
DBNM BNM TBNM BDCNM BCNM DCNM CNM TCNM DBCNM Tribromop MX Bromate EMS +Con bromo-4-oxopentanoic Acid
bromopropenoic Acid mopropenoic Acid mobutenedioic Acid bromopropenoic Acid mo-3-methylbutenedioic Acid Bromoacetamide Dibromoacetamide Chloroacetamide Dichloroacetamide Other DBPs Haloacetamides
Trichloroacetamide Iodoacetamide Haloacetonitriles Dibromoacetonitrile Bromoacetonitrile Bromochloroacetonitrile Chloroacetonitrile romochloro-4-oxopentanoic Acid Iodoacetonitrile Dichloroacetonitrile Trichloroacetonitrile Halomethanes Iodoform Bromoform Chlorodibromomethane Chloroform
CHO Cell Cytotoxicity as %C½ Values (~LC50) Log Molar Concentration (72 h Exposure)
10-6 10-5 10-4 10-3 10-2
IAA BAA TBAA DBCAA DBAA BDCAA BCAA CAA TCAA DCAA D B T B B D C T D 3,3-Di 3-Iodo 3,3-Di Tribro 2-Brom 2,3-Di 2-Brom DIAA Haloacetic Acids Halo Acids Halonitromethanes July 2006 BIAA 2-Iodo 3,3-Br
Lowest Observed Adverse Effect Level
100 200 f halogenated DBPs 5 10 15 er of halonitriles
All Halo DBPs Halonitriles
AWWARF report by Bull et al., 2007
>1000 >100-1000 >10-100 >1-10 >0.1-1 >0.01-1 Distribution of estimated chronic LOAELs, mg/kg day-1 Number of 5 Numbe
5 5 6.0 6.5
Surface Water
hloroacetonitrile (μg/L)
2 0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
Time (hrs)
20 40 60 80 100 120
Dich
0.0 0.5 1.0 1.5 2.0 10 mg/L 5 mg/L 2.5 mg/L Loss of Residual Chlorine Dose
C N C H Cl Cl C C H Cl Cl N OH H NH C C H Cl Cl N OCl H NCl
H2O
fast fast k2 k1 k4
DCAN OCl OH
Key intermediate Concentrations are
C C Cl Cl OH C C H Cl Cl NH2 O C C H Cl Cl NHCl O H2O
Cl(+II) S (+IV)
C C Cl Cl O
pKa = 3.7
fast k1-2 k1-1
DCAD HOCl OH OH N-Cl-DCAD N-Cl-DCAD anion
C C H Cl Cl O OH NHCl2 NH3 C C H Cl Cl NHCl OCl OH C C H Cl Cl NH2 OH O fast fast
DCAA
Hydrolysis and oxidation
Hydrolysis and oxidation k1 = 1.78 x10-7 ±0.35 x10-7 (s-1)
−
1 2 3
k2 = 3.42 ±0.31 (M-1s-1) k3 = 1.30 x 10-1 ±0.08 x 10-1 (M-1s-1)
100 1 Hour
Platt, MacNeill & McClellan, 2001
Aqua 50:1:1-13
increase with increasing pH
ICR data:
rine Residual (mg/L)
1 10
10 Minutes 1 Hour 8 Hours 1 Day 3 Days 1 Week
Obolensky & Frey, 2002
pH
6 7 8 9 10 11
Chlor
0.1
3 Weeks
Compounds Compounds Monohaloacetamides
Chloroacetamide, Bromoacetamide
Dihaloacetamides
Dichloroacetamide (DCAD) Bromochloracetamide (BCAD) Dibromoacetamide (DBAD)
T ih l
Trihaloacetamides
trichloroacetamide & analogues
Chlorination byproducts Probably a bit less prevalent with chloramines Pre-oxidation will probably reduce subsequent formation
Measureable by GC
Mostly from HANs:
N-Halogenated Forms Free (f) Chlorine Sulfite Combined (c ) Total (t)
ual (mg/L)
10 100 DCAD Halflife 1 Hour 8 Hours 1 Day 10 Minutes
Chlorine Residu
0.1 1 3 Weeks 1 Day 3 Days 1 Week
6 7 8 9 10 11
pH
6 7 8 9 10 11
3 Weeks 1 Hour 8 Hours 1 Day 3 Days 1 Week Reducing Conditions
NDMA: typically formed at greater levels with
Continues to form across DS?
Levels and mechanisms Earlier work: Valentine & Weinberg Earlier work: Valentine & Weinberg New mechanism: Mitch
Role of Dichloramine and oxygen Role of Dichloramine and oxygen
N
Cl Cl H
N
CH3 CH3 R
N N
H Cl CH3 CH3
R Cl Dichloramine Dimethyl(xx)amine Monochloro Unsymmetric Dimethylhydrazine (UDMH-Cl) O
O
O N
Cl Cl H
PRODUCTS Nitrosodimethylamine (NDMA) Oxygen N N
CH3 CH3 O
Based on recent work by Bill Mitch and colleagues
19
Ranitidine (Zantac) 63% conversion to NDMA
Schmidt et al., 2006 [WQTC]
Introduced in 1981, largest selling prescription drug by 1988
Stomach ulcers and esophageal reflux
Mean concentration of 3000 ng/L estimated for raw municipal
WW (national average) WW (national average)
Sedlak 2005 AWWARF report
450 ng/L formation in raw WW expected Unknowns: how much does this persist in treatment and in the
environment?
Abbreviations DMD: dimethyldiazene
TMT: tetramethyltetrazene FMMH: formaldehyde
monomethylhydrazone
FDMH: formaldehyde
dimethylhydrazone
DMC: dimethylcyanamide DMF: dimethylformamide
From: Mitch & Sedlak, 2002 [ES&T, 36:588]
ICR Compounds ICR Compounds
THMs, THAAs DHAAs
ICR Compounds ICR Compounds
50 MWDSC DBPs 50 MWDSC DBPs ~700 Known DBPs ~700 Known DBPs
Stuart Krasner Susan Richardson
Halogenated Compounds Non Non-
halogenated Compounds Compounds
Ratio to carbon
mg-C/mg-N)
30 40 50 60
27
Ratio to carbon Redrawn from Westerhoff & Mash, 2002
Percentile
10 20 30 40 50 60 70 80 90 100
DOC/DON (m
10 20 30
27 15 8.2
Estimates from literature surveys
Classification 50%ile 90%ile 99%ile DON 350 800 2000 Free AA 20 50 200 Combined AA 40 100 400 Order of magnitude estimates for organic nitrogen in surface waters (all values in µg-N/L) Combined AA 40 100 400 Nucleic acids 20 50 200 Amino Sugars 40 100 400 Humic-N 25 200 1000 Others
Simple Amino Acids
f M d AN
H2C C H COOH NH2
NH 2
some form THMs and HANs Highest reactivity for activated
AAs
Tyrosine & Tryptophan: activated
aromatic
Cysteine: sulfhydryl group Proteins
Alanine Alanine
HO C H2 C H COOH
Tyrosine Tyrosine
many linked AAs; relatively
unreactive polypeptide bonds
Reactions with proteins occurs
most readily on AA side chains
rine Demand (mg/mg-C)
4 6 8 10 12
Aquatic NOM Fractions
Selected Amino Acids
More reactive than
Precursor
W h
e W a t e r s F u l v i c A c i d H u m i c A c i d W e a k H y d r
h
i c A c i d s H y d r
h
i c N e u t r a l H y d r
h
i c B a s e s H y d r
h i l i c A c i d s H y d r
h i l i c N e u t r a l s H y d r
h i l i c B a s e s M e t h i
i n e A s p a r t i c a c i d L y s i n e A r g i n i n e H i s t i d i n e A s p a r a g i n e G l u t a m i n e T r y p t
h a n P h e n y l a l a n i n e T y r
i n e C y s t e i n e C y s t i n e
Chlor
2
ethane Formation (μg/mg-C)
35 40 45 50 55 60 65 70 80 100 120 140
Aquatic NOM Fractions
Selected Amino Acids
113 147
Minor except
Tryptophan Tyrosine
Precursor
W h
e W a t e r s F u l v i c A c i d H u m i c A c i d W e a k H y d r
h
i c A c i d s H y d r
h
i c N e u t r a l H y d r
h
i c B a s e s H y d r
h i l i c A c i d s H y d r
h i l i c N e u t r a l s H y d r
h i l i c B a s e s M e t h i
i n e A s p a r t i c a c i d L y s i n e A r g i n i n e H i s t i d i n e A s p a r a g i n e G l u t a m i n e T r y p t
h a n P h e n y l a l a n i n e T y r
i n e C y s t e i n e C y s t i n e
Trihalome
5 10 15 20 25 30
Like THMs Tryptophan Tyrosine
etic Acid Formation (μg/mg-C)
30 35 40 45 50 55 60 80 100 120 140
Aquatic NOM Fractions
Selected Amino Acids
107 137 105
Precursor
W h
e W a t e r s F u l v i c A c i d H u m i c A c i d W e a k H y d r
h
i c A c i d s H y d r
h
i c N e u t r a l H y d r
h
i c B a s e s H y d r
h i l i c A c i d s H y d r
h i l i c N e u t r a l s H y d r
h i l i c B a s e s M e t h i
i n e A s p a r t i c a c i d L y s i n e A r g i n i n e H i s t i d i n e A s p a r a g i n e G l u t a m i n e T r y p t
h a n P h e n y l a l a n i n e T y r
i n e C y s t e i n e C y s t i n e
Trihaloace
5 10 15 20 25
Aspartic acid
etic Acid Formation (μg/mg-C)
25 30 35 40 45 50 55 60 100 150 200 250 300 350 400
Aquatic NOM Fractions
Selected Amino Acids
387 89 115
Aspartic acid Histidine
Precursor
W h
e W a t e r s F u l v i c A c i d H u m i c A c i d W e a k H y d r
h
i c A c i d s H y d r
h
i c N e u t r a l H y d r
h
i c B a s e s H y d r
h i l i c A c i d s H y d r
h i l i c N e u t r a l s H y d r
h i l i c B a s e s M e t h i
i n e A s p a r t i c a c i d L y s i n e A r g i n i n e H i s t i d i n e A s p a r a g i n e G l u t a m i n e T r y p t
h a n P h e n y l a l a n i n e T y r
i n e C y s t e i n e C y s t i n e
Dihaloace
5 10 15 20 25
Asparagine
Aspartic acid
etonitrile Formation (μg/mg-C)
7 8 9 10 11 12 13 14 15 50 100 150 200 250
Aquatic NOM Fractions
Selected Amino Acids
255 85
Histidine
Precursor
W h
e W a t e r s F u l v i c A c i d H u m i c A c i d W e a k H y d r
h
i c A c i d s H y d r
h
i c N e u t r a l H y d r
h
i c B a s e s H y d r
h i l i c A c i d s H y d r
h i l i c N e u t r a l s H y d r
h i l i c B a s e s M e t h i
i n e A s p a r t i c a c i d L y s i n e A r g i n i n e H i s t i d i n e A s p a r a g i n e G l u t a m i n e T r y p t
h a n P h e n y l a l a n i n e T y r
i n e C y s t e i n e C y s t i n e
Dihaloace
1 2 3 4 5 6
30
From: Perdue & Ritchie, 2004
Amino AA conc
Cl2 Cons.
DBP Formation (µg/mg-C) Acid
(µM/mg-C)
(mg/mg-C)
TOX THM TCAA DCAA HANs Unkn TOX Glycine 0.030 0.0072 0.002 0.000 0.000 0.000 0.000 0.001 Alanine 0.030 0.0046 0.007 0.000 0.000 0.002 0.000 0.006 Valine 0.013 0.0022 0.009 0.002 0.001 0.002 0.000 0.005 Isoleucine 0.011 0.0018 0.004 0.000 0.000 0.002 0.000 0.001 Leucine 0.015 0.0022 0.000 0.000 0.000 0.002 0.000
Serine 0.028 0.0083 0.001 0.000 0.000 0.000 0.000 0.001 Threonine 0.018 0.0068 0.012 0.000 0.000 0.000 0.000 0.011 Methionine 0.003 0.0010 0.004 0.001 0.000 0.001 0.000 0.003 Aspartic acid 0.026 0.0083 0.849 0.002 0.002 0.491 0.323 0.367 Glutamic acid 0.026 0.0036 0.004 0.000 0.002 0.002 0.000 0.001 Lysine 0.004 0.0013 0.001 0.000 0.000 0.001 0.000 0.000 Ornithine 0.005 0.0017 0.011 0.002 0.000 0.000 0.000 0.009 Arginine 0.019 0.0104 0.032 0.000 0.000 0.003 0.001 0.030 Histidine 0.007 0.0040 0.153 0.002 0.021 0.042 0.040 0.084 Asparagine 0.001 0.0004 0.012 0.000 0.000 0.005 0.000 0.009 Glutamine 0.001 0.0004 0.000 0.000 0.000 0.000 0.000 0.000 Tryptophan 0.006 0.0068 0.432 0.124 0.115 0.050 0.013 0.193 Phenylalanine 0.009 0.0017 0.000 0.000 0.000 0.003 0.001
Tyrosine 0.006 0.0053 0.257 0.069 0.065 0.021 0.006 0.138 Total FAA 0.259 0.0780 1.789 0.201 0.207 0.626 0.385 0.856 Upper Limit 3.454 1.0403 23.855 2.677 2.765 8.340 5.131 11.418 Whole Waters 1.89 185 48.2 60 33.1 1.8 129.7 Total FAA 4.1% 1.0% 0.4% 0.3% 1.9% 21.4% 0.7% Upper Limit 55.0% 12.9% 5.6% 4.6% 25.2% 285.0% 8.8% N
C R1 H R4 R3 R2
N
C R1 X R4 R3 R2
N
C X X R4 R3 R2 R1=H X+ Nu X+ Nu
R2=H or COOH R4=H HX (CO2) R2=H or COOH
C
N R3 X R4
I II III IV C
N R3 R1 R4 NH2X R1=H X+ Nu HX (CO2) General scheme for carbonyl
and cyano formation from chlorination of amines and amino acids
C
O R4 R3
R1NH2 C
N R3
V VI
NH2X HX
Monohalamine Pathway Dihalamine Pathway
amino acids
Scully, 1989, and Armesto et al., 1998).
Reactions of chlorine with organic amines
Primary amines Secondary amines Inorganic chloramines can transfer their active 2 2
HOCl HOCl
HOCl
2 2
HOCl (M-1s-1)
6 7 8 9 Amino Acids 1o Amines 2o Amines 3o Amines Polypeptides Relationship between
basicity and 2nd order rate constants for reaction of HOCl with N-compounds
al., 1972; Isaac et al., 1983; Armesto et al., 1993; Armesto et al., 1994; Antelo et al., 1995; Abia et al., 1998 pKa
7 8 9 10 11 12
Log kH
2 3 4 5
1
Alanine 1.3E-04 86 Glycine 1.4E-06 8400 Histidine 2.7E-04 43 Leucine 1.6E-04 72 Phenylalanine 2.2E-04 52 Serine 2.4E-04 49 Creatinine 3.5E-06 3300 Glycine N acetyl 6.0E-07 19000 Glycine ethyl ester 2.3E-04 50 Glycylglycine 1.0E-05 1100 Sarcosine 5.3E-05 210
Approach
Seems well suited to LC Prior efforts with GC were not very successful e.g., tosyl derivatization Proposal Fast analysis with UPLC Parallel detection and analysis by Post-column reaction with I and absorbance LC/MS/MS
Group Example Occurrence Toxicology Haloquinones 2,6-dichloro-3-methyl-1,2- benzoquinone (DMBQ) 1 2 Organic N- haloamines Prioritize on range of stabilities and mutagenic activity 2 1 Alkaloidal nitrosamines N-nitrosonornicotine 1-N-
1 2 Cyclopentenoic acids & MX-related 3,5-dichloro—1-hydroxy-4- ketocyclopent-2-enoic acid CMCF 1 2 2 1 Halonitriles 2,3-Dichloropropenal (Carc) 2,3-dibromopropionitrile (DT) 1 1
There is a broad range of nitrogenous organic compounds in natural waters There is a broad range of nitrogenous organic compounds in natural waters
that are reactive with chlorine and produce both regulated and non- regulated DBPs
Amino acids are generally reactive High Chlorine demand Very high DHAN formation Moderate to high DiHAAs; low to moderate THMs & TriHAAs Proteins
Toxic compounds that may be regulated could include
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David A. Reckhow
CEE690K Lecture #16