ISSN 1070-4272. Russian Journal of Applied Chemistry, 2006, Vol. 79, No. 3, pp. 390 !396. + Pleiades Publishing, Inc., 2006.
Original Russian Text + V.F. Vakulenko, M.V. Milyukin, V.V. Goncharuk, 2006, published in Zhurnal Prikladnoi Khimii, 2006, Vol. 79, No. 3,
pp. 397! 403.
OF CHEMISTRY AND TECHNOLOGY
Influence of the Conditions of Photooxidation of Natural Water
on the Yield of Carbonyl Compounds
V. F. Vakulenko, M. V. Milyukin, and V. V. Goncharuk
Dumanskii Institute of Colloid Chemistry and Water Chemistry, National Academy of Sciences of Ukraine,
Received August 3, 2005; in final form, January 2006
Abstract-The yield of carbonyl compounds in treatment of river water and model solutions of humic acid as
a function of the ozone uptake and conditions of UV irradiation was analyzed.
Formation and stability of the oxidation by-prod-
ucts is one of insufficiently studied aspects of applica-
tion of ozone to potable water treatment. The primary
products of the ozonolysis of organic impurities con-
tained in natural water are aldehydes, ketones, and
carboxylic acids [1, 2]. Ozonation of humic acid (HA)
and fulvic acid (FA) solutions  and of natural
water [1, 2, 437] leads to the formation of aliphatic
, aliphatic carboxylic acids C
unsaturated aldehydes, dialdehydes, ketones, keto
acids, dibasic aliphatic acids, hydroxy- and dihydroxy-
benzoic acids, esters, and other products.
Aldehydes, if present in a concentration of 0.23
, impart to the ozonized water a specific
smell (fruit, flower, or less pleasant), which then
rapidly disappears . Certain aldehydes and ketones
are mutagenes and carcinogenes . In addition, car-
bonyl compounds and chlorine react with the forma-
tion of trihalomethanes and other potentially hazar-
dous organochlorine products. The concentration of
some aldehydes and ketones in potable water is regu-
lated on the basis of the Governmental Sanitation
Rules and Regulations . The presence of other
compounds in water reservoirs is regulated by the
maximum permissible concentration (MPC) .
The MPCs for aldehydes and ketones in potable water
are as follows (mg dm
): formaldehyde 0.05, acetal-
dehyde 0.2, benzaldehyde 0.003, propenal 0.02,
2-butenal 0.3, 3-pentanone 0.1, and acetone 2.2.
Aliphatic aldehydes C
, glyoxal, methylglyoxal,
and benzaldehyde are included into the list of by-prod-
ucts that are subject to monitoring in potable water in
the United States .
The presence of 1380 mgdm
pounds in natural reservoirs results from the bio-
chemical processes of oxidation of organic impurities
[2, 4]. In ozonized water their total concentration
exceeds many times the natural background [2, 4, 6,
7]. The formation of aldehydes in ozonation of natural
water depends on a number of factors such as the
structure of natural organic impurities, concentration
of total organic carbon (TOC), ozone uptake, tempera-
ture, the pH of water, etc. . The primary carbonyl
compounds formed in ozonation of natural water are
formaldehyde, acetaldehyde, glyoxal, and methyl-
glyoxal. Aliphatic aldehydes C
and other substances are less common and are present
in lower concentrations [4, 6].
Presently, the new combined oxidation processes,
so-called Advanced Oxidation Processes (AOP), are
being actively introduced into practical water treat-
ment. Examples are combined application of ozone
and hydrogen peroxide (O
) or of ozone and
UV irradiation (O
/UV). The composition of the by-
products products formed by the AOP in preparation
of potable water is studied insufficiently and the
results obtained are controversial [12, 13].
This study is concerned with the composition of
carbonyl compounds formed in ozonation, UV irradia-
tion, and in the case of the O
/UV treatment of river
waters. We also studied how the yields of the above
compounds are affected by the ozone uptake, condi-
tions of UV irradiation, and by the quality of water.
We studied the action of ozone alone and the com-
bined action of ozone and UV radiation under the dif-
ferent irradiation conditions on the water from the