ISSN 10619348, Journal of Analytical Chemistry, 2015, Vol. 70, No. 1, pp. 98–105. © Pleiades Publishing, Ltd., 2015.

Original Russian Text © V.V. Sursyakova, G.V. Burmakina, A.I. Rubaylo, 2015, published in Zhurnal Analiticheskoi Khimii, 2015, Vol. 70, No. 1, pp. 83–91.

ARTICLES

Optimization of the Conditions of Phenol Determination in Natural

and Potable Waters by HPLC with Sorption Preconcentration
V. V. Sursyakovaa, *, G. V. Burmakinaa, b, and A. I. Rubayloa, b
a
Institute of Chemistry and Chemical Technology, Siberian Branch, Russian Academy of Sciences,
Akademgorodok 50 str. 24, Krasnoyarsk, 660036 Russia
b Department of Chemistry and Metallurgy, Siberian Federal University, Svobodnyi pr. 79, Krasnoyarsk, 660041 Russia

*email: viktoria_vs@list.ru.
Received January 21, 2013; in final form, December 27, 2013

Abstract—The conditions of the sorption preconcentration of phenols from samples of natural and potable
waters in Diapak P concentrator cartridges filled with supercrosslinked polystyrene are optimized. Coun
tercurrent desorption with acetonitrile or methanol ensures the elimination the step of organic solvent evap
oration. The observed reduction of the sorption of humic and fulvic acids (HFA) on the addition of sodium
sulfite to the samples of natural and potable waters prior to their processing probably relates to the change of
pH. The preconcentration of phenols from natural and potable waters at pH 6–8 substantially reduces the
sorption of HFA. The method is used to determine phenols in samples of tap water and water from the Yenisei
river by the added–found method.

Keywords: phenols, natural water, potable water, highperformance liquid chromatography, sorption precon
centration, solidphase extraction, backflush desorption
DOI: 10.1134/S1061934814110124

According to the data of the Federal Agency for
Hydrometeorology and Environmental Monitoring,
phenols are the most abundant organic river pollutants
in Russia. For the majority of phenols the maximum
permissible concentrations (MPCs) are set at a level of
n µg/L [1], so for their determination one should use
preconcentration procedures, the most widespread of
which are liquid–liquid extraction and sorption pre
concentration (solidphase extraction, SPE) [2–6].
The SPE method is experimentally less complicated,
takes less time, and reduces the loss of samples and the
expenditure of costly and highly toxic solvents. As
adsorbents here analysts use modified silicas, poly
mers, graphitized soot, ionexchange resins, etc. [7, 8].
In the sorption preconcentration of phenols from
aqueous solutions, adsorbents based on supercross
linked polystyrene are used most widely. Their advan
tages are the absence of swelling in organic solvents,
high mechanical resistance, higher distribution ratios,
and the simplicity and completeness of desorption by
small portions of organic solvents [9–17]. SPE car
tridges filled with adsorbents based on supercross
linked polystyrene are manufactured under the brands
Diapak P, Diapak P3 (BioChemMak, Russia), Puro
sep (Purolite), StrataX (Phenomenex), LiChrolut
(Merck), Isolute ENC+ (IST), etc. [8, 16].
Sorption preconcentration can be accomplished
both independently of the following instrumental
quantification [9–12, 14, 16, 17] and as a part of on
line sorption/liquid chromatography determination
[11, 13, 15]. Normally, the autonomous sorption pre
concentration of phenol from water samples on super
crosslinked polystyrenes is accomplished in acidic
media, pH 2–3 and is followed by desorption with an
organic solvent, which is then subjected to evaporation
in a flow of nitrogen for additional preconcentration
by 5–10 times. To prevent possible losses of phenols,
solvent evaporation in a nitrogen flow should be car
ried out at a rate of not more than 1–2 mL per hour
[18, 19], which extends the time and deteriorates the
total precision of the analysis. The remained organic
solvent, if it differs from the one used in HPLC as an
eluent, normally acetonitrile or methanol, may be
responsible for the drift of the baseline and result in the
loss of sensitivity for a number of phenols [20].
In a number of papers on the determination of phe
nols with preliminary SPE concentration acetonitrile
was used for desorption [9, 12, 14, 17]. Adsorbents
based on supercrosslinked polystyrene differed from
each other and from Diapak P cartridges by some of
their properties, i.e., specific surface, pore size, bead
size, and presence or absence of attached groups mod
ifying polystyrene surface. The geometrical sizes of the
column and the sorbent mass were also different, so
the data reported cannot be extrapolated to other
adsorbents based on supercrosslinked polystyrene. A
limited number of phenols was considered in [9, 12];
in particular, hydrophobic 2,4,6trichlorophenol and

98
 OPTIMIZATION OF THE CONDITIONS OF PHENOL DETERMINATION
pentachlorophenol were not studied, whereas their
presence strongly influences the volume of organic
solvent required for the complete desorption of all
phenols from a Diapak P cartridge. As the step of extra
preconcentration by solvent evaporation was not used,
the sensitivity of procedures was insufficient for the
quantification of phenol and 2,4dichlorophenol at
the MPC level.
The use of an additional step of phenol preconcen
tration before their determination by instrumental
methods results in the deterioration of the precision of
analysis. To some extent the problem can be solved
using an internal standard, added to the sample prior
to sorption preconcentration. Moreover, the internal
standard allows the control of the recovery of phenols
in the analysis of samples with increased concentra
tions of interferents. In the method of phenol precon
centration on Diapak P cartridges, components that
can be used as such internal standards for the subse
quent HPLC analysis of phenols were not proposed [5,
16]. In the EPA 528 method with preliminary sorption
preconcentration, 1,2dimethyl3nitrobenzene and
2,3,4,5tetrachlorophenol were proposed, but phenols
were determined by gas chromatography [10]. The use
of internal standards of 2bromophenol [21], 2,4,6
tribromophenol [22, 23] in a SPE–GC method, 4flu
orophenol in SPE–HPLC with UVdetection [24],
and 3bromophenol in a SPE–HPLC method with
electrochemical detection [25] was described. Note
worthy, because of a difference in the principles of sep
aration, an internal standard applicable to an SPE–
GC method may not be used in an SPE–HPLC
method.
In sorption preconcentration from natural and
potable waters at pH 2–3, a substantial extraction of
humic acids occurs, which was revealed in chromato
grams as a drift of the baseline [26–29] and sometimes
results in the impossibility of the quantification of
phenol [30]. The published data on the reduction of
HFA adsorption on polymeric adsorbents by adding a
sodium sulfite solution to samples are contradictory
[26–29].
The aim of this work was the optimization of the
conditions of the sorption preconcentration of phe
nols from natural and potable waters on Diapak car
tridges followed by HPLC determination in order to
eliminate the above disadvantages.
EXPERIMENTAL
Reagents. All reagents were of analytical or better
grade. Standard samples of phenols were purchased
from Ekros (St. Petersburg) or SigmaAldrich (Mos
cow); Diapak P cartridges based on supercross
linked polystyrene with a specific surface of 1000–
1200 m2/g, bimodal distribution of pore sizes (meso
pores 10–50 nm, micropores 1–2 nm), and adsorbent
particle size 45–70 µm, in BioChemMak (Moscow,
Russia). We used acetonitrile for gradient HPLC
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 70
99
(Panreac, Spain), acetone of highpurity grade (Kri
okhrom, Russia), and methanol of highpurity grade
(Khimreaktivsnab, Russia). Twicedistilled water was
used.
Instruments. Instruments of the Krasnoyarsk
Regional Center of Research Equipment of the Sibe
rian Branch of the Russian Academy of Sciences were
used: an Agilent HPLC 1200 chromatograph and an
Agilent 3DCE G 1600A capillary electrophoresis system
(Agilent Technologies, United States). The collection
and processing of the data was accomplished using the
HP Chemstation B.03.02 and Rev.A.10.02 software.
A Zorbax eclipse XDBC18 chromatography column,
5 µm, was used. The method of capillary electrophore
sis was utilized to check the purity of sodium sulfite
using a Forensic Anion Solution Kit (Agilent Technol
ogies, United States), comprised of a pH 12.1 buffer
solution for anion analysis and a capillary of the length
112.5/104 cm and inner diameter 50 µm.
Standard scheme of phenol preconcentration from
aqueous media on Diapak P cartridges [5, 16]. For
preconcentration 5 mL of acetone were passed
through a cartridge followed by 20 mL of water. A
500.0mL sample of water was filtered through a
membrane filter with a pore size of 0.45 µm, acidified
with 0.5 M HCl to pH 2–2.5, and passed through the
cartridge with a vacuum pump at a rate of 3–
5 mL/min, preventing the drying of the cartridge and
the penetration of air bubbles into it. Then the car
tridge was washed with 20 mL of distilled water and the
phenols retained were eluted with 5 mL of acetone
into a 10mL evaporation flask using a Luer lock
syringe. The eluent was added in portions of 0.5 mL
with intervals of 1–2 min to equilibrate the system and
more completely extract the components. The eluate
was evaporated in a water bath at a temperature not
higher than 25°С in a weak flow of nitrogen. The vol
ume of the residue was measured by a micropipette;
the residue was diluted to 500 µL with a wateraceto
nitrile mixture (9 : 1) and subjected to HPLC analysis.
Conditions of sample preparation and analysis. In
investigating the degree of phenol desorption from
Diapak P cartridges by different organic solvents, ace
tone, acetonitrile and methanol, in dependence on the
eluate volume, the step of solvent evaporation after
desorption was excluded to eliminate addition errors
possible. In the backflush desorption of phenols from
cartridges, the eluent was introduced in portions of
0.25 mL at 2 min time intervals. As adapters for the
attachment of a Luer syringe with a plug to the exit
from the cartridge we used polyethylene or Teflon
tubes of the length 2 cm and inner diameter 4 mm;
these were preliminarily rinsed with acetone, acetoni
trile, or methanol.
The chromatography column was thermostated at
30°С. The mobile phases were a mixture of aqueous
acetic acid, pH 3.3–3.4, with acetonitrile: 35 vol % of
ACN for 0–6.6 min, then 60 vol % of ACN, from
6.6 min on. The volume of samples was 20 µL. The
No. 1 2015