Adam Mickiewicz University
Faculty of Chemistry
Department of Water Treatment Technology
Adam Mickiewicz University,
University, Poznań
THE SCOPE OF THE LECTURE
1. Water treatment – aims and methods.
2. Disinfection – the most important stage of water
treatment.
3. Chlorine, ClO2 and ozone disinfection by-products.
4. Methods of analysis of chlorination by-products.
5. Chlorine dioxide disinfection by-products: chlorities and
chlorates.
6. Ozonation by-products: aldehydes and carboxylic acids.
7. Biodegradable organic matter –importance and methods
of determination.
ANALYSIS OF WATER
DISINFECTION BYBY-PRODUCTS
Jacek Nawrocki
Gdańsk 2003
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WATER TREATMENT – AIMS AND METHODS
WATER TREATMENT – AIMS AND METHODS
WATER QUALITY PARAMETRS
UNIT PROCESSES IN WATER TREATMENT
¾ MIKCROBIOLOGICAL
¾ PHYSICAL PROCESSES
¾ CHEMICAL
¾ CHEMICAL PROCESSES
¾ PHYSICAL (taste,
taste, flavor,
flavor, turbidity,
turbidity, color)
color)
¾ BIOLOGICAL PROCESSES
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WATER TREATMENT – AIMS AND METHODS
WATER TREATMENT – AIMS AND METHODS
UNIT PROCESSES IN WATER TREATMENT
POLISH DRINIKIG WATER ACT
D. Disinfection by-produts [µg/l]
¾Single person uses 130130-200l/day
200l/day
¾Of that only 2l for consumption
¾Only 1-1,5% of the water produced
is used for consumption
46
Bromate
25
46a
Bromate
105)
47
Bromodichloromethane
15
48
Chloramine
500
49
Chlorate
200
50
Chlorite
200
51
Formaldehyde
50
52
Tetrachloromethane
2
53
Chloral hydrate
10
54
Trichloromethane (chloroform)
30
55
2,4,6-trichlorophenol
200
56
Σ THM
150
56a
Σ THM
1005)
5)
Zakresy wartości stosuje się zgodnie z § 12 rozporządzenia.
§ 12. W załączniku nr 2 do rozporządzenia określone:
3) w lp. 46a dopuszczalne zakresy wartości dla bromianów stosuje się od dnia 1 stycznia 2008 r.;
4) w lp. 56a dopuszczalne zakresy wartości dla Σ THM stosuje się od dnia 1 stycznia 2008 r.
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Adam Mickiewicz University,
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DISINFECTION
The most important stage of water treatment
DISINFECTION
The most important stage of water treatment
¾ PHISICAL METHODS
THE MOST IMPORTANT AIM OF WATER
TREATMENT IS WATER
MICROBIOLOGICAL SAFETY.
¾ UV irradiation
¾ Ultrasounds
¾ Thermal
¾ CHEMICAL (Strong
Although disinfection leads to the formation of
many chemical byby-products mic
microbiological
robiological
¾ Chloroamines
¾ Ozone
¾ Potassium permanganate
quality of water cannot be compromised.
compromised.
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Liczba ludzi korzystających z wody uzdatnionej [mln]
Liczba przypadków zachorowań na dur brzuszny/100 000 osób
umie
ra ln
oś ć
na d
ur
brzu
s
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DISINFECTION
The most important stage of water treatment
40
oxidants)
oxidants)
¾ Chlorine
¾ Chlorine dioxide
DISINFECTION
The most important stage of water treatment
zny
30
20
10
0
1900
1905
1910
1915
1920
Rok
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DISINFECTION
Tragic results of nondesinfected water in Peru
¾ Late 1980s in Peru: decision to stop water chlorination
DEZYNFEKCJA
¾ January 1991, Chancay (Peru): beginning of cholera epidemy
SKUTKI WSTRZYMANIA
¾ 1991: Equador,
Equador, Columbia, Brasil
¾ September 1991 : Boliwia
¾ By the end of 1992 (23 months after first case):
case):
¾ cases in South and Central America
(from Mexico to Argentina)
Argentina)
¾ 731 312 cholera cases with 6 323 deaths (Peru 2 720 deaths)
deaths)
3
140
¾ By the end of 1995:
¾ Over 1000 000 cholera cases with 11 000 deaths)
deaths)
1
0
0
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10
20
30
40
50
60
70
80
90 100 110 120 130 140 150
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DISINFECTION BYBY-PRODUCTS
CHLORINATION BYBY-PRODUCTS
STRONG OXIDANTS USED AS DISINFECTANTS
REACTIONS OF CHLORINE WITH WATER
%
100
ClO
BrO -
HBrO
HClO
At pH>2
pH>2 :
Cl2 + H2O → H+ + HOCl + Cl-
75
¾ CHLORINE
Br2
¾ CHLORINE DIOXIDE
At pH>7.5
pH>7.5 :
HOCl
50
→ H+ + ClO-
Cl reacts with Br- :
¾ OZONE
HOCl + Br- → HOBr + Cl-
25
OClOCl- + Br- → OBrOBr- + Cl6
8
10
pH
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CHLORINATION BYBY-PRODUCTS
CHLORINATION BYBY-PRODUCTS
prec
precursors
ursors of THM + Cl2 → THMs
THMs + other byby-products
CLASSIFICATION
¾ nonvolatile halogen compounds (NVOX) - 7070-80% TOX,
TOX,
mainly:
mainly: halogenoorganic acids i and a whole variety of bybyproducts with unknown chemical structure .
¾ volatile halogen compounds (VOX) - 2020-30% TOX,
TOX, relatively
trihalometh
trihalomethanes
anes:: chloroform, bromodichlorometh
bromodichloromethane
ane, chlorodibromometh
chlorodibromomethane
ane,
bromoform,
bromoform,
haloacetonitri
haloacetonitriles
les: bromochloroacetonitri
bromochloroacetonitrile, dibromoacetonitri
dibromoacetonitrile,
dichloroacetonitri
dichloroacetonitrile, trichloroacetonitri
trichloroacetonitrile
haloacetic
aloacetic acids:
acids: chloroacetic
chloroacetic acid,
acid, dichloroacetic
dichloroacetic acid,
acid, trichloroacetic
trichloroacetic acid,
acid,
haloaldehydes
haloaldehydes:: dichloroacetic
dichloroacetic aldehyde
aldehyde, trichloroacetic
trichloroacetic aldehyde,
aldehyde,
haloketones
haloketones:: 1,11,1-dichloropropanone
dichloropropanone, 1,1,11,1,1-trichloropropanone
trichloropropanone, 1,11,1-dichlorodichloro-2butanone
butanone, 1,1,11,1,1-trichlorotrichloro-2-butanone
butanone
chloroph
enolss: 2-chloroph
enol,, 2,4enol,, 2,4,6enol
chlorophenol
chlorophenol
2,4-dichloroph
dichlorophenol
2,4,6-trichloroph
trichlorophenol
other:
other: chloropic
chloropicrine, cyanogen
cyanogen chloride,
chloride, MX.
compounds without chlorine atoms:
atoms: formaldehyd
formaldehydee and acetaldehyd
acetaldehydee
well known.
known.
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CHLORINATION BYBY-PRODUCTS
CHLORINATION BYBY-PRODUCTS
Mutagenic activity
¾ TRIHALOMETHANES
¾ HALOACETIC ACIDS
¾ MX (3-chlorochloro-4-(dichlorometh
dichloromethyl)
yl)-5-hydrox
hydroxy-2(5H)2(5H)-furanone
furanone)
¾ NDMA
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ƒ Mutagenic activity is a property of both: surface and
ground waters.
ƒ The activity is caused by a presence of mutagenic
compounds in waters.
ƒ Mutagenic activity is defined as the ability of the
compound to cause mutation in bacteria. Mutagenicity is
related to genotoxicity.
ƒ Mutagenic activity of the compound is often related to the
carcinogenicity.
ƒ Research on carcinogenicity has to be carried out on
animals, is very expensive and time consuming.
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CHLORINATION BYBY-PRODUCTS
CHLORINATION BYBY-PRODUCTS
Mutagenic activity – Ames test
Mutagenic activity
Cl
Salmonella
typhimurium
TA100, TA98
MUTATION
damaged bacteria with no ability to
synthesize histidine
Cl
H
Salmonella
typhimurium
Salmonella
typhimurium
Spontaneous
mutation
MUTAGEN
Cl
Spontaneous
and induced
mutation
O
H
O
O
H
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MX -3-chlorochloro-4-(dichlorometylo)
dichlorometylo)-5-hydroksyhydroksy-2(5H)2(5H)-furanon
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UBOCZNE PRODUKTY DEZYNFEKCJI
WODY CHLOREM
UBOCZNE PRODUKTY DEZYNFEKCJI
WODY CHLOREM
MX
MX
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CHLORINATION BYBY-PRODUCTS
CHLORINATION BYBY-PRODUCTS
Carcinogenicity according to IARC
FORMATION OF THM
1 – the agent is carcinogenic to humans
2A
– the agent is probably carcinogenic to humans
(limited evidence in humans and sufficient evidence in animals)
2B
– the agent is possibly carcinogenic to humans
(limited evidence in humans and less than sufficient evidence in animals)
3
– the agent is not classifiable as to its carcinogenicity to humans
(inadequate evidence in humans and inadequate or limited in animals)
4 – the agent is probably not carcinogenic to humans
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CHLORINATION BYBY-PRODUCTS
CHLORINATION BYBY-PRODUCTS
THM
THM – RISK
HALOACETIC ACIDS
Pokarm
10%
Skóra
20%
Skóra
30%
Pokarm
30%
HALOACETIC ACIDS – CHLORINATION BY-PRODUCTS:
65
60
55
50
45
40
-6 35
R x 10 30
25
20
15
10
5
0
ƒ monochloroacetic (MCAA), dichloroacetic (DCAA), trichloroacetic
(TCAA).
Oddech
40%
Oddech
70%
In case of bromide presence:
ƒ monobromoacetic (MBAA), dibromoacetic (DBAA), tribromoacetic
60,19
18,83
C THM
[ug/L]
17,55
10
(TBAA)
ƒ bromochloroacetic (BCAA), dibromochloroacetic (DBCAA) and
dichlorobromoacetic (DCBAA).
20
Czas [min]
H-W Kuo et.al. Sci.
Sci. Total Environ.
Environ. 218 (1998) 11-7
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CHLORINE DIOXIDE DISINFECTION
BYBY-PRODUCTS
CHLORINE DIOXIDE DISINFECTION
BYBY-PRODUCTS
Reactions with inorganic components dissolved in water
Reactions with inorganic components dissolved in water
ClO2 + Fe2+ → Fe3+ + ClO22ClO2 +
2ClO2 +
Mn2+
NO2-
+ 2H2O →
+ H2 O →
Chlorates and chlorities
2ClO2-
2ClO2-
+ MnO2 +
+
2H+
+
2ClO2 + Mn2+ + 2H2O → 2ClO2- + MnO2 + 4H+
4H+
2ClO2 + NO2- + H2 O → 2ClO2- + 2H+ + NO3-
NO3-
2ClO2 + 2 OH- → ClO2- + ClO3- + H2O
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CHLORINE DIOXIDE DISINFECTION
BYBY-PRODUCTS
OZONATION BYBY-PRODUCTS
¾ CHLORITE
¾ ALDEHYDES
ALDEHYDES
¾ CHLORATE
¾ SHORT CHAIN CARBOXYLIC ACIDS
¾ ALDEHYDES
¾ KETOACIDS
¾SHORT CHAIN CARBOXYLIC ACIDS
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METHODS OF ANALYSIS
OF CHLORINATION BYBY-PRODUCTS
METHODS OF ANALYSIS
OF CHLORINATION BYBY-PRODUCTS
ANALYSIS
ANALYSIS OF TRIHALOMETH
TRIHALOMETHANES
ANES
Isolation:
¾ extraction
traction of THMs
THMs to organic solvent:
solvent: nn-pentane
pentane, nn-hex
hexane
ane, nn-
¾ TRIHALOMETHANES
heptane
heptane, petroleum eth
ether , meth
methylcyklohex
ylcyklohexane
ane, 2,2,42,2,4-trimeth
trimethylpentane
ylpentane,
¾headhead-space analysis – both:
both: static and dynamic as well as solidsolid-phase
¾ HALOACETIC ACIDS
mic
microex
roextraction
traction (SPME),
(SPME),
¾ MX (3-chlorochloro-4-(dichlorometh
dichloromethyl)
yl)-5-hydrox
hydroxy-2(5H)2(5H)-furanone
furanone)
¾ solid phase extraction – classical
lassical and SPME,
SPME,
¾ direct aqueous injection
Analysis:
¾ GCGC-ECD
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METHODS OF ANALYSIS
OF CHLORINATION BYBY-PRODUCTS
METHODS OF ANALYSIS
OF CHLORINATION BYBY-PRODUCTS
METH
METHOD OF ANALYSIS
ANALYSIS OF HALOACETIC ACIDS
ANALYSIS OF MX
¾ acidification
DERIVATIZATION WITH:
¾ extraction to MTBE
¾ METHANOL
¾ derivatization
derivatization – meth
methylation
ylation to este
esters
¾ ISOPROPANOL
¾ Analysis by GCGC-ECD
¾ BUTANOLS
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METHODS OF ANALYSIS
OF CHLORINATION BYBY-PRODUCTS
METHODS OF ANALYSIS
OF CHLORINATION BYBY-PRODUCTS
MXMX- the most important fragmentation paths
MX – MS of methoxy derivative
Cl
H
m/z=199
m/z=83
Cl
H
Cl
Cl
H
Cl
H
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Cl
H
O
H m/z=31
O
O
H
O
H
H
M=230 D
O
O
m/z=147
H
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METHODS OF ANALYSIS
OF CHLORINATION BYBY-PRODUCTS
CHLORINATION BYBY-PRODUCTS
MX
MX – MS of isopropoxy derivative
Cl
Cl
H
Cl
H *
O
O
O
H
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MX -3-chlorochloro-4-(dichlorometylo)
dichlorometylo)-5-hydroksyhydroksy-2(5H)2(5H)-furanon
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METHODS OF ANALYSIS
OF CHLORINATION BYBY-PRODUCTS
METHODS OF ANALYSIS
OF CHLORINATION BYBY-PRODUCTS
MX – diastereoisomers of secsec-butanol derivatives
MX – widmo MS pochodnej derywatyzowanej enancjomerem secsec-butanolu
CHCl2
CH3
* O
H
H
*
O
CHCl2
* O
CH3
H
H
O
R,S
C 2 H5
CHCl2
Cl
*
C2H5
O
R,R
CHCl2
Cl
H
H
O
S,S
Cl
O
O
CH3
O *
H
O
C2H5
Cl
O *
*
*
O
C 2 H5
H
CH3
S,R
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METHODS OF ANALYSIS OF CHLORINATION
BYBY-PRODUCTS
MX - Intensywność
Intensywność jonó
jonów izotopowych o m/z= 199, 201 i 203 w zależ
zależnoś
ności od rodzaju derywatyzacji.
derywatyzacji. (Me - MX + metanol, iP - MX
+izopropanol,
izopropanol, iB - MX +izobutanol
+izobutanol,, sB1 - pierwszy pik MX +sec+sec-butanolu, sB2 - drugi pik MX+secMX+sec-butanolu, nB - MX +n+n-butanol)
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
203
Me
iP
iB
sB1
sB2
Wz g lę dna inte nsyw no ść
100%
201
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METHODS OF ANALYSIS
OF CHLORINATION BYBY-PRODUCTS
199
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203
201
199
nB
alkohol
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MX – Determination of MX with vacuum preconcentration and derivatization
derivatization with
isopropanol or enantiomer
enantiomer of secsec-butanol.
butanol.
1- 2 l water sample
↓
Acidification with HCl to pH 2
↓
Vacuum preconcentration of water sample
↓
Extraction
traction with etyl acetate (3 x 4 ml)
↓
Evaporation of solvent (to dryness)
dryness)
↓
Derivatization
Derivatization with:
with:
·
2-propanol (85 oC 1h) or
·
S(S(-) or R(R(-) 22-butanol (90 oC 1h)
↓
Extraction with hex
hexane (3 x 0.3 ml)
↓
GCGC-LRMS SIM m/z= 199, 201, 203
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METHODS OF ANALYSIS OF CHLORINE
DIOXIDE BYBY-PRODUCTS
METHODS OF ANALYSIS OF CHLORINE
DIOXIDE BYBY-PRODUCTS
CHLORITES I CHLORATES
CHLORITES I CHLORATES
METH
METHOD OF A SIMULTANEOUS DETERMINATION OF ALL FORMS OF
¾ COLORIMETRIC TITRATION
AVAILABLE CHLORINE,
CHLORINE, Cl
ClO2 AND ClO2- WITH N,NN,N-DIETH
DIETHYLYL-pPHENYLEN
EDIAMINE
PHENYLENE
DIAMINE (DPD).
¾ AMPEROMETRIC DETERMINATION OF
FREE
Cl2, ClO2, ClO2-,
¾ Determination of ClO2 and ClO2- with N,NN,N-dieth
diethylyl-p-phenylen
phenyleneediamine
diamine an
application of DPD method for determination of free chlorine and chloramines
chloramines in
water
ClO3-
¾ it is based on reactions of different forms of chlorine with DPD at pH 6,5 ,
leading to the formation of Wurster red.
red.
¾ absorbance at 515 nm. is measured.
hod is described in details in
measured. The met
meth
¾ DETERMINATION OF ClO2- AND ClO3- BY
IONION-CHROMATOGRAPHY
„Standards Methods for Water and Wastewater Examination”
Examination”
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METHODS OF ANALYSIS OF CHLORINE
DIOXIDE BYBY-PRODUCTS
METHODS OF ANALYSIS OF CHLORINE
DIOXIDE BYBY-PRODUCTS
CHLORITES I CHLORATES
CHLORITES I CHLORATES
DETERMINATION OF FREE CHLORINE,
CHLORINE, CHLORINE DIOXIDE,
ANALYTICAL PROCEDURE HAS TO CONSIDER THE FOLLOWING
CONCLUSIONS:
¾At pH 7 Cl2 and 1/5 of ClO2 is determined (reactions
reactions 1+2)
¾ pH is lowered to pH 2 and 4/5 of ClO2 and all chlorites are determined
(reactions
reactions 3 +4).
¾ second water sample is purged with N2 to remove ClO2, and left Cl2 is
determined at pH 7.
¾pH of third water sample is lowered to pH 0.1 (ok.5M HCl)
HCl) and all forms of
chlorine are determined (reactions
reactions 1+3+4+5).
¾Relatively high LOD of chlorates (0.25 mg/l)
mg/l) is a disadvantage of this method.
method.
Real chlorate
hod is described
chlorate concentrations may be lower than the LOD . The met
meth
in details in „Standards Methods for Water and Wastewater Examination”
Examination”
CHLORITES AND CHLORATES
CHLORATES IS POSSIBLE WITH AMPEROMETRIC
TITRATION FOR A SERIES OF REACTIONS AT DIFFERENT pHs
pHs:
¾ at pH 7 the following reaction proceeds:
proceeds:
¾2 ClO2 + 2 I- → I2 + 2 ClO2¾ at pH 7; 2; <0.1 reaction
reaction proceeds:
proceeds:
¾Cl2 + 2 I- → I2 + 2 Cl¾ at pH 2; <0.1 the reactions proceed:
proceed:
¾2 ClO2 + 10 I- + 8 H+ → 5 I2 + 2 Cl- + 4 H2O
¾ClO2- + 4 I- + 8 H+ → 2 I2 + Cl- + 2 H2O
¾ at pH <0.1 zachodzi:
¾ClO3- + 6 I- + 6 H+ → 3 I2 + Cl- + 3 H2O
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METHODS OF ANALYSIS OF CHLORINE
DIOXIDE BYBY-PRODUCTS
METHODS OF ANALYSIS OF CHLORINE
DIOXIDE BYBY-PRODUCTS
CHLORITES I CHLORATES
CHLORITES I CHLORATES
IonIon-chromatography is the only fully selective and reliable
method for determination of chlorites and chlorates in
drinking water
InoIno-chromatography method is recommended by EPA –
meth
method 300.0 for determination of chlorites
chlorites and chlorates
chlorates in
drinking waters.
waters.
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METHODS OF ANALYSIS OF CHLORINE
DIOXIDE BYBY-PRODUCTS
METHODS OF ANALYSIS OF
OZONATION BYBY-PRODUCTS
CHLORITES I CHLORATES
ALDEHYDES AND CARBOXYLIC ACIDS
Ion
concentration
[µg/l]
Standard
deviation
[µg/l]
Relative
standard
deviation
[%]
Chlorites(III)
Chlorates(V)
10
10
0,76
0,34
7.99
4,38
Chromatographic
methods
(specific)
specific)
ALDEHYDES
CARBOXYLIC ACIDS
Spectrophotometric
methods
(unspecific)
unspecific)
Chromatographic
methods
(Ion and ionion-exclusion)
exclusion)
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METHODS OF ANALYSIS OF
OZONATION BYBY-PRODUCTS
DETERMINATION OF ALDEHYDES
DETERMINATION OF FORMALDEHYDE
FORMALDEHYDE IN WATER ACCORDING TO (PN(PN71/C71/C-04593)
ALDEHYDES AND CARBOXYLIC ACIDS
ALDEHYDES
¾ according to PNPN-71/C71/C-04593
¾ colorimetric by Hach
¾Based on the reaction of formaldehyde with chromothropic
acid
¾ analytical range for water and wasterwater:
wasterwater: 50 do 1000 µg/L
¾ with DNPH (2,4(2,4-dinitrophenylhydrazyne)
dinitrophenylhydrazyne)
¾ with PFBOA (O(O-(2,3,4,5,6(2,3,4,5,6-pentafluorobenzyl)
pentafluorobenzyl) hydroxyloamine)
hydroxyloamine)
¾ with TCPH (2,4,6(2,4,6-trichlorophenylohydrazyne)
trichlorophenylohydrazyne)
¾ interferring substances:
substances:
¾ acetaldehyde,
acetaldehyde,
¾ with DNSH (danyslhydrazyne
(danyslhydrazyne))
¾ with fluoral (4(4-aminoamino-3-pentenopenteno-2-on) (only
(only for formaldehyde)
formaldehyde)
¾ phenols,
phenols,
¾ metal ions,
ions,
¾ oxidants
¾ with CHD (1,3(1,3-cykloheksandione)
cykloheksandione)
CARBOXYLIC ACIDS
¾ IONION-CHROMATOGRAPHY
¾ IONION-EXCLUSION CHROMATOGRAPHY
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DETERMINATION OF ALDEHYDES
DETERMINATION OF ALDEHYDES
COLORIMETRIC DETERMINATION OF FORMALDEHYDE
FORMALDEHYDE IN WATER
ACCORDING TO HACH PROCEDURE
DETERMINATION OF ALDEHYDES
ENYLHYDRAZINE
INE
ALDEHYDES WITH 2,42,4-DINITROPH
DINITROPHENYLHYDRAZ
(DNPH)
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Adam Mickiewicz University,
University, Poznań
DETERMINATION OF ALDEHYDES
DETERMINATION OF ALDEHYDES
PENTAFLUOROBENZYL) HYDROX
HYDROXYLAMINE
YLAMINE (PFBOA)
F
R2
F
100
R1
F
F
metyloglioksal
dekanal
200
R2
CH2 O N C
oktanal
F
F
nonanal
trans-2-nonenal
CH2 O N C
benzaldehyd
F
R1
F
heksanal
F
300
heptanal
R2
F
400
pentanal
O
butanal
F
C
NH2
acetaldehyd
F
O
propanal
R1
CH2
aceton
F
formaldehyd
F
F
glioksal
DETERMINATION OF ALDEHYDES
ALDEHYDES WITH O-(2,3,4,5,6(2,3,4,5,6-
PENTAFLUOROBENZYL) HYDROX
HYDROXYLAMINE
YLAMINE (PFBOA)
Voltage [mV]
DETERMINATION OF ALDEHYDES
ALDEHYDES WITH O-(2,3,4,5,6(2,3,4,5,6-
0
10
15
20
25
30
Time [min.]
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Adam Mickiewicz University,
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DETERMINATION OF ALDEHYDES
DETERMINATION OF ALDEHYDES
PENTAFLUOROBENZYL) HYDROX
HYDROXYLAMINE
YLAMINE (PFBOA)
The total aldehyde formation vs. the ozone dose and the contact time.
PENTAFLUOROBENZYL) HYDROX
HYDROXYLAMINE
YLAMINE (PFBOA)
DETERMINATION OF ALDEHYDES
ALDEHYDES WITH O-(2,3,4,5,6(2,3,4,5,6-
DETERMINATION OF ALDEHYDES
ALDEHYDES WITH O-(2,3,4,5,6(2,3,4,5,6-
20
Forma lde hyde
Ac e ta lde hyde
15
Ac e tone
10
5
30oC/s unlight
Initia l
4oC/da rk
Ac e ta lde hyde
Forma lde hyde
0
Ac e tone
Amo unt o f ca rbo nyl
co mpo unds [µg /l]
25
S a mple s
Aldehydes in bottled waters vs. conditions of storage
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Adam Mickiewicz University,
University, Poznań
DETERMINATION OF ALDEHYDES
DETERMINATION OF ALDEHYDES
PENTAFLUOROBENZYL) HYDROX
HYDROXYLAMINE
YLAMINE (PFBOA)
PENTAFLUOROBENZYL) HYDROX
HYDROXYLAMINE
YLAMINE (PFBOA)
DETERMINATION OF ALDEHYDES
ALDEHYDES WITH O-(2,3,4,5,6(2,3,4,5,6-
DETERMINATION OF ALDEHYDES
ALDEHYDES WITH O-(2,3,4,5,6(2,3,4,5,6-
Aldehydes as chlorination by-products
to tal alde hydes [µg /L]
140
DERIVATIZATION AND ANALYSIS:
¾ derivatization
derivatization in water sample,
sample, liquidliquid-liquid extraction
and GCGC-ECD analysis,
analysis,
120
100
1h
80
4h1
60
24h
¾ derivatization
derivatization in SPE bed,
bed, elution with organic solvent
and GCGC-ECD analysis
¾ application of SPME ,
48h
40
20
0
0,2
0,4
0,8
1,2
mg Cl 2 /mg TOC
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Adam Mickiewicz University,
University, Poznań
DETERMINATION OF ALDEHYDES
DETERMINATION OF ALDEHYDES
PENTAFLUOROBENZYL) HYDROX
HYDROXYLAMINE
YLAMINE (PFBOA)
PENTAFLUOROBENZYL) HYDROX
HYDROXYLAMINE
YLAMINE (PFBOA)
DETERMINATION OF ALDEHYDES
ALDEHYDES WITH O-(2,3,4,5,6(2,3,4,5,6-
DETERMINATION OF ALDEHYDES
ALDEHYDES WITH O-(2,3,4,5,6(2,3,4,5,6-
SPME
20 ml sample
APPLICATION OF SPME:
¾ derivatization
derivatization in water sample,
sample, sorption of oximes by
immersion,
immersion, GCGC-ECD
PFBOA derivatization
H2SO4
extraction with hexane
¾ derivatization
derivatization in water sample,
sample, sorption of oximes from
headspace,
headspace, GCGC-ECD
¾sorption
sorption of aldehydes
aldehydes from headspace,
headspace, derivatization on
separation of organic layer
Acid treatment
fiber of SPME,
SPME, GCGC-ECD
GC/ECD analysis
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Adam Mickiewicz University,
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Adam Mickiewicz University,
University, Poznań
DETERMINATION OF ALDEHYDES
DETERMINATION OF ALDEHYDES
PENTAFLUOROBENZYL) HYDROX
HYDROXYLAMINE
YLAMINE (PFBOA)
PENTAFLUOROBENZYL) HYDROX
HYDROXYLAMINE
YLAMINE (PFBOA)
DETERMINATION OF ALDEHYDES
ALDEHYDES WITH O-(2,3,4,5,6(2,3,4,5,6-
Voltage [mV]
DETERMINATION OF ALDEHYDES
ALDEHYDES WITH O-(2,3,4,5,6(2,3,4,5,6-
Variants of SPME applications
700
600
1
500
2
400
Direct sorption
of PFBOA on
the fiber
5
3
6
7
4
9
10
11
8
13
300
Headspace sorption
of PFBOA
12
14
15
200
100
0
5
10
15
20
25
30
Chromatogram of oximes (GC-ECD) after derivatization in water sample and sorption of oximes from the headspace
PFBOA
1mg/ml
Voltage [mV]
PFBOA
1mg/ml
35
[min.]
700
600
500
headspace aldehyde
extraction
to SPME fiber
7
1
6
400
Desorption of oximes
and GC-ECD analysis
fibre with
PFBOA
9
10
11
8
13
5
300
12
3
200
2
4
14
15
100
GC/ECD
0
5
10
15
20
25
30
Chromatogram of oximes (GC-ECD) after sorption from the headspace and derivatization on fiber.
Aldehydes
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14 PFBOA 1 formaldehyd, 2 acetaldehyd, 3 aceton, 4 propanal, 5 butanal, 6 pentanal, 7 heksanal, 8 heptanal, 9 oktanal, 10 benzaldehyd, 11 nonanal, 12 trans-2-nonenal, 13 dekanal, 14 glioksal, 15 metyloglioksal
35
[min.]
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DETERMINATION OF ALDEHYDES
DETERMINATION OF ALDEHYDES
DETERMINATION OF ALDEHYDES
ALDEHYDES WITH 2,4,62,4,6TRICHLOROPH
ENYLOHYDRAZINE
INE (TCPH)
TRICHLOROPHENYLOHYDRAZ
DETERMINATION OF ALDEHYDES
ALDEHYDES WITH DANSYLHYDRAZINE
DANSYLHYDRAZINE (DNSH)
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Adam Mickiewicz University,
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DETERMINATION OF ALDEHYDES
DETERMINATION OF CARBOXYLIC
ACIDS
DETERMINATION OF FORMALDEHYDE
FORMALDEHYDE WITH FLUORAL P (4(4-AMINOAMINO-3PENTENOPENTENO-2-ON)
¾ ionion-chromatography
¾ ionion-exclusion chromatography
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DETERMINATION OF CARBOXYLIC ACIDS
DETERMINATION OF
CARBOXYLIC ACIDS
Removal of formic acids along biologicaly active carbon filter
350
300
fo rmic ac id
[10-3mg /l]
250
200
150
100
50
0
0
50
100
150
200
250
c arbo n filte r de pth [c m ]
FORMIC + OXALIC ACIDS
vs. OZONATION CONDITIONS
27.07
13.08
17.08
30.08
18.09
20.09
8.10
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H2O
IONION-EXCLUSION
CHROMATOGRAPHY
CHROMATOGRAPHY .
StyrenStyrendiwinylobenzen
Hipotetyczna membrana
Donnana
H+
SO3-
Faza stacjonarna
H+
H2O
NO3-
SO3H2O
H+
H2O
SO3-
H+
SO3-
SO3-
AOC
Eluent
H+
SO4-
BDOC –Biodegradable
iodegradable
disolved organic carbon
BOM
BDOC
BOC
CH3COO-
H2O
H+
IMPORTANCE AND DETERMINATION METH
METHODS
ODS
SO4-
-assimilable organic carbon
H2O
SO3-
H2O
H+
Adam Mickiewicz University,
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BIODEGRADABLE
BIODEGRADABLE ORGANIC MAT
MATTER
H2O
Faza ruchoma
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ORGANIC MAT
MATTER
Próbka
CH3COOH
H2O
Refractive
efractive organic matter
H+
– does not biodegrade in a reasonable time
J. Siepak (pod redakcją) Zastosowanie chromatografii jonowej... Poznań 1999
1999
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Adam Mickiewicz University,
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INCREASE OF BDOC UPON OZONATION
OZONATION OR
DISINFECTION WITH CHLORINE DIOXIDE
BDOC DETERMINATION METHODS
¾ van der Kooij method of AOC determination – observation of the
(FOR WATER FROM MOSINA INTAKE AFTER AERATION AND SAND FILTRATION).
FILTRATION).
development of P17 strain of Pseudomonas fluorescens or NOX
6
Spirillum
BDOC
¾ determination of AOC by Werner method – the rate of bacteria
DOC-BDOC
5
development in aqueous environment;
environment;
4
DOC - BDOC [mg/L]
¾ determination of BOM
BOM by Servais method – is based on the
determination of biomas increase;
increase;
¾ determination of BOM
BOM by Joret method – detremination of a
3
4,41
4,9
5,08
4,79
2
decrease of DOCin examined water inoculed with bacterias
1
characteristic for the water under question.
question.
0,96
0
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0,41
0,52
0,4 mg ClO2/L
0,8 mg ClO2/L
0,26
MWI
1,96 mg O3/L
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BDOC vs OZONE DOSE
CORRELATION BETWEEN SUM OF CARBOXYLIC ACIDS
(OZONATION BYBY-PRODUCTS)
PRODUCTS) AND
AND BDOC
Zależność BDOC od dawki ozonu
1,4
1,4
1,2
1,2
y = 0,0011x + 0,5428
R2 = 0,9737
1
BDOC [mg/L]
B DOC mg /L
1
0,8
0,6
0,4
0,8
0,6
0,4
OWO - 5,9 mg/L
0,2
0,2
0
0
0
1
2
3
4
5
6
0
100
200
Dawka ozonu mg/L
300
400
500
600
700
Total carboxylic acids [ug/L]
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CONTRIBUTION OF CARBOXYLIC ACIDS AND
ALDEHYDES TO BDOC
(after ozonation of MOSINA water with 2,8 mgO
mgO3/L)
/L)
DEPARTMENT of WATER
TREATMENT TECHNOLOGY TEAM
¾ Prof. dr hab. Jacek Nawrocki
¾ dr Przemysław Andrzejewski
BDOC - 0,88mg/L
TOC - 5,50mg/L
¾ dr inż. Agata Dąbrowska
acids
25%
¾ dr Joanna Świetlik
aldehydes
¾ mgr Karolina Gromadzka
3%
others
¾ mgr Barbara KasprzykKasprzyk-Hordern
acetone
2%
¾ mgr Urszula Stanisławiak
70%
¾ tech.
tech. Roman Skolarus
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