1. Valencia, September, 2016
Evaluation of solid-phase chromatography as a method for natural organic matter characterization
Dr Aleksandra Tubić, Dr Jasmina Agbaba,
Dr Jelena Molnar Jazić, Dr Božo Dalmacija
Department of Chemistry, Biochemistry and Environmental Protection
Faculty of Science, University of Novi Sad, R. Serbia

2. Overview Relevance of NOM in drinking water resource and treatment
Valencia, September, 2016
Overview
Relevance of NOM in drinking water resource and treatment
Methods for NOM characterisation
Solid phase extraction as a tool for NOM characterisation
Conclusion

3. What is NOM? Complex mixture of organic compouns Acid Base Neutral
Valencia, September, 2016
What is NOM?
Complex mixture of organic compouns H Y D R O F I L C
Acid
Base
Neutral
Aliphatic structures
Carbohydrates
Proteins
Sugars
Aminoacids B IC
Aromatic structures
Phenol structures
Structures whit conugated doble bonds

4. Hypothetical structures
Natural organic matter (NOM) found has extreme mixture and molecular structural complexity
Valencia, September, 2016
Attempts to determine molecular structural
components of NOM into pure compounds required for structural analyses have not yet been successful.
Hypothetical structures
(Schulten, 1999, J.Analytical Applyed Pyrolysis 49, )

5. NOM Local issue in Serbia As NOM NOM-As interactions
Valencia, September, 2016
NOM
Microbial growth in distribution system
DBP formation
Influence on other constituents behaviour
Increase in chemical demand during treatment
Influence on organoleptic characteristics of water
Local issue in Serbia
NOM-As interactions
NOM As

6. Characterisation of NOM?
Valencia, September, 2016
Leenhee, 1981; Marhaba et al., 2003
Matilainen, 2010; Amy, 2011
Fractionation
NOM alteration
Filtration
XAD-8 resin
Hydrophobic bases and neutrals
Week hydrophobic acids
Cation exchange resin
Hydrophylic bases
Anion exchange resin
Hydrophylic acids
Hydrophylic neutrals left in water
Protocol for characterisation without NOM alteration
HPSEC
FTIR
NMR
LC-OCD-OND
F-EEM
TEP
Get knowledge and separate on MW
Humic/fulvic like structures
Protein like structures
hydrophilic surface active acid polysaharides
Comparison of efforts nowdays and 30 years ago- how we see them?

7. Solubility based fractionation
Valencia, September, 2016
Raw water
cc HCL, pH 2
0.1 N NaOH
cc HCl pH 1
Precipitate
Dissolution in
0.1N NaOH
0.45 µm membrane filter
Molnar, 2011

8. XAD-8 – hydrofobic fractions fulvic acid fraction - FAF
Valencia, September, 2016
Developed in (Leenheer, 1981, Environmental Science and Technology, 15(5), )
Standard method for isolation of humic and fulvic acids – International Humic Substance Society
XAD-8 – hydrofobic fractions
fulvic acid fraction - FAF
humic acid fraction - HAF
XAD-4 – hydrophilic fractions
week hydrophilic acid fraction - HPIA
hydrophilic non-acid fraction – HPI-NA
Hydrophilic fraction further fractionation (Marhaba i sar., 2003, J.Hazard. Mater. B101,43-54)
AG-MP-50 – cation resin
WA-10 – week anion resin

9. Disadvantages of the method?
Valencia, September, 2016
Disadvantages of the method?
Possible:
change of chemical/physical structure of NOM due to extreme pH
irreversible adsorption of NOM molecules on resins
contamination by leaking from the resin
exclusion effect

10. DOC Recovery Bulk water After fractionation 10.2 mg C/L 10.1 mg C/L
Valencia, September, 2016
DOC Recovery
Bulk water
10.2 mg C/L
After fractionation
10.1 mg C/L
Higher than 98%
Fraction
Fraction ratio
% of total DOC
Average SD
RSD x1 x2 x3
HAF
14.0
15.5
13.0
14.2
1.26
8.9
FAF
68.0
66.5
67.8
67.4
0.81
1.2
HPINA
12.0 13 1
7.7
HPIA
6.0
5.0
5.2
5.4
0.53
9.9

11. Recovery after resin regeneration
I cycle – 99%
Valencia, September, 2016
Recovery after resin regeneration
II cycle – 97%
III cycle – 88%

12. Groundwater of Vojvodina region, Republic of Serbia
Valencia, September, 2016
Example from my collegues related to our groundwater characterisation
Molnar et al. (2012) Environmental Science and Pollution Research, 19,
Tubić et al. (2013) Journal of Environmental Management, 118,
Agbaba et al. (2015) Water Science & Technology: Water Supply, 15(1),

13. Thank you for your attention
Valencia, September, 2016
Authors
Thank you for your attention
Aleksandra Tubić
Assistant professor
Jasmina Agbaba
Full professor
Jelena Molnar
Božo Dalmacija