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Monitoring of the drinking Water using of alternative Analytical Techniques

Article · September 2009

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Gheorghe Valerica Cimpoca Cristiana Radulescu

Academy of Romanian Scientists, Bucharest, Romania Valahia University of Târgoviste
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Ioana Daniela Dulama Iulian Bancuta

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 Monitoring of the drinking Water using of alternative
Analytical Techniques

Gh.V.Cimpoca1, C.Radulescu1, I.V.Popescu1, I.D.Dulama1, I.Bancuta,

A.I.Gheboianu1, I.Ionita1, M.Cimpoca2, I.Cernica2

1
Valahia State University of Targoviste, 130024 Targoviste, Romania, valcimpoca@yahoo.com
2
National Institute for Research and Development in Micro technologies, 023573 Bucharest, Romania

Abstract. In this paper we study and monitoring the drinking waters with Quartz Crystal Microbalance (QCM) versus
Atomic Absorption Spectrometry (AAS) and classical analytical methods (pH, conductivity/resistivity, TDS, salinity).
Our studies present a new application of quartz crystal microbalance (QCM) for measure and identify trace quantities of
metals and volatile organic compounds (VOC) in water. QCM was adapted for many different uses by developing
electrodes that respond to different target molecules. For our experiences we use quartz crystal sensor with 1.25 cm2
sensitive area at 5 MHz resonance frequency and CrAu electrode (20 nm Cr and 200 nm Au).We monitoring in real time
the quality of water by controlling the inorganic and organic impurities. We evaluate the utility of QCM sensors to detect
a range of VOC contaminant which is complementary with AAS. Some polar VOC contaminants were tested: acetone,
isopropanol and ethylene glycol.
Keywords: Quartz Crystal Microbalance, pollution measurements,
PACS: 07.88. +y ; 47.54.Fy ; 47.85.Np

INTRODUCTION
The high sensitivity and the real-time monitoring of mass changes on the sensor crystal make Quartz
Crystal Microbalance (QCM) a very attractive technique for a large range of applications. The widespread use of the
quartz crystal microbalance (QCM) can be attributed to its excellent sensitivity to the properties of liquid and soft
solid materials with which it is brought into contact. This sensitivity arises from the coupling between the
mechanical, shear oscillation of the crystal and its electrical response at frequencies close to resonance. This
coupling depends on the details of the shear wave propagation into the material with which the QCM is in contact.
The QCM is an extremely sensitive sensor capable of measuring mass changes in the nanogram/cm2 range with a
wide dynamic range extending into the 100 μg/cm2 range. The minimum detectable mass change is typically a few
ng/cm2 and limited by the noise specifications of the crystal oscillator and the resolution of the frequency counter
used to measure frequency shifts. The sensibility depends of the detector area and the type of solid electrode in
contact with the fluids. The metal by electrode used is CrAu (20 nm Cr and 200 nm Au), deposited by spattering,
with 1.27 cm2 area. We can use other metals as electrode: TiAu or TiPt. Major advantage of the QCM technique
used for liquid systems is that it allows a label-free detection of molecules. The QCM is capable of measuring mass
changes as small as a fraction of a monolayer or single layer of atoms. The ability to provide real-time monitoring of
chemical contaminants in water samples can be used for a variety of applications: on-line monitoring of
contaminants in process, recycle, and waste water; groundwater quality monitoring; detection of contaminants in
streams, lakes and water supplies; monitoring dumping in off-shore waterways [1,2]. Other studies present a new
application of quartz crystal microbalance (QCM) for measure and identify trace quantities of volatile organic

CP1203, 7th International Conference of the Balkan Physical Union, edited by A. Angelopoulos and T. Fildisis
© 2009 American Institute of Physics 978-0-7354-0740-4/09/$25.00

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compounds (VOCs) in water [4]. QCMs are rugged, low power, easily miniaturized, and capable of direct chemical
sensing in liquids. Moreover, QCM was adapted for many different uses by developing coatings that respond to
different target molecules, adding to their versatility. Also, to evaluate the utility of QCM sensors to detect a range
of VOC contaminants, some compounds was tested [5].

TEORY AND OPERATION

When the QCM comes in contact with a solution, there is a decrease in frequency that is dependent upon
the viscosity and the density of the solution. This problem was first treated by Glassford, and later by Kanazawa and
Gordon [6]. Kanazawa’s treatment of the influence of the solution properties on the crystal (equation 1) permits the
prediction of the change in resonance frequency which accompanies immersion of the crystal into a viscous
medium:
1/ 2
⎛ ρη ⎞
Δf = − fU 1/ 2 ⎜ L L ⎟⎟ (1)
⎜ πρ μ
⎝ q q ⎠

Where fU = frequency of oscillation of unloaded crystal, ρq = density of quartz = 2.648 g cm-3, μq = shear modulus of
quartz = 2.947 x 1011 g cm-1 s-2, ρL = density of the liquid in contact with the electrode, ηL = viscosity of the liquid in
contact with the electrode. Viscous coupling of the liquid medium to the oscillating crystal surface results not only in
a decrease in the series resonant frequency but also in damping of the resonant oscillation - the viscous loss is
manifested as an increase in series resonance resistance, R, of the QCM resonator. Thus, R serves as an excellent
independent measure of viscous loading by the medium (liquid or soft-film) at the crystal’s surface. Frequency shift
Δf and resistivity ΔR measurements are both routinely used as independent indicators of mass loading and viscosity
at the crystal-liquid interface of the QCM resonator during chemical depositions in solution. In a separate study, a
Butterworth-Van Dyke equivalent circuit model was applied to derive a linear relationship between the change in
series resonance resistance, ΔR, of the quartz oscillator and (ρLηL) 1/2 under liquid loading:

1/ 2
⎛ nω L ⎞ ⎛ 2ωs ρ Lη L ⎞
ΔR = ⎜ s u ⎟ ⎜⎜ ⎟⎟ (2)
⎝ π ⎠ ⎝ ρ qη q ⎠
Where:
ΔR = change in series resonance resistance in Ω, n = number of sides in contact with liquid, ωs = angular frequency
at series resonance (2πfs), Lu = inductance for the unperturbed (dry) resonator, usually in mH.

EXPERIMENTAL EQUIPMENTS
The head experimental apparatus are: Quartz Crystal Microbalance (QCM) and Spectrometer with Atomic
Absorption (AAS). Other apparatus are conductivity/resistivity-meter and pH-meter. Because, the Spectrometer with
Atomic Absorption, conductivity/resistivity-meter and pH-meter are usual equipments and known as apparatus for
analytical methods, we insist to describe the new system for monitoring the drinking water in real-time. Our studies
present a new application of quartz crystal microbalance (QCM) for measure and identify trace quantities of metals
and volatile organic compounds (VOC) in water. This system gives as more information about water features. The
developed detection system provides rapid determinations with little sample preparation or instrument supervision.
The high sensitivity and the real-time monitoring of mass changes on the sensor crystal make Quartz Crystal
Microbalance (QCM) a very attractive technique for many applications, including water monitoring.
The QCM System (from Stanford Research Systems-SRS) is a stand-alone instrument with a built-in
frequency counter, resistance meter, flow pump, special flow cell and accessories, personal computer and printer
(figure 1). It includes controller, crystal oscillator electronics, crystal holder, and quartz crystals. Series resonance
frequency and resistance are measured and displayed directly on the front panel. In addition, the QCM has an RS-
232 interface and comes with both Windows and LabVIEW software providing real-time display, analysis and
storage of our QCM data. Supplementary, we have Ultra-stable Rubidium Frequency Standard with 2ppb stability
and 0.0001 Hz sensibilities and the ultra precise temperature meter measure “in situ” temperature, between 4 K and
700 K with 0.1 K.

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 FIGURE 1. QCM System: a) Display with data graphics ; b) Electronic System: 1) QCM oscillator; 2) fluidic pump; 3)
Rubidium Frequency Standard with 2ppb stability; flow cell; 5) PC; and c) Schematic Diagram of flux by system

REZULTS AND DISCUSSIONS

Static measurements
In this case the fluids are static (the flow is zero) and the sample apply direct on quartz sensor of cell from
QCM system. The quantity of solution is 1mL for each sample. For our experience we use three types of water:
deionised water; drinking water from town Targoviste (sample 1) and groundwater from countryside (sample 2). The
results from QCM static are shown in figure 2.

a) b)
FIGURE 2. Date from QCM static: frequency shift (a) and resistance (b) versus time for deionized water, drinking water
(sample 1) and groundwater (sample 2)

Figure 2 show that in the pure water (deionized water) adsorption of molecule practically missing when in
the sample 1 and sample 2 the adsorptions are present. For deionized water, which has 18.2 MΩ resistivity and
which is obtained by reverse osmosis and exposed at UV light, the frequency shift and resistivity are near constant.
Small variations occur because traces after purification, especially from calcium and its compounds. For sample 1
witch has water from town Targoviste, prepared by standard methods for drinking water we obtain in the first 3
minutes an desorption followed by adsorption about 10 minutes and after this remain constant. An explanation of
this behavior is that traces of metals in drinking water, not removed by purification, end up being adsorbed on metal
electrode surface. For sample 3, which has a groundwater from countryside, from a depth of 10 meters, without
purification, we obtain in the first 4 minutes an strong desorption followed by adsorption about 10 minutes and after
this remain constant. An explanation of this behavior is that traces of metals in groundwater water, also, end up
being adsorbed on metal electrode surface. This groundwater has several metals in larger quantities. The results are
in concordance with the other analytic methods: Atomic Absorption Spectroscopy (AAS): conductivity/resistivity;
Total Dissolved Solid (TDA), pH and salinity. In the Table 1 and the Table 2 we present the results after these
methods. In table 1 is observed as drinking water is better than groundwater, because it contains two times less lead.

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Also, is observed as some metals: Cr, Pb, Se and Zn were adsorbed on metal electrode of quartz sensor (Au),
remained attached there and not included in our solution. In table 2 is observed as salinity of groundwater is twice
higher than drinking water, which explains value of resistivity and Total Dissolved Solid (TDS), which are, also,
twice higher.
Table 1
The results after AAS of waters analyses for determination the metal contaminants

Cd Cr Cu Fe Ni Pb Se Zn
(mg/L) (mg/L) (mg/mL) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)
Sample 1 (drinking water) 0.001 0.513 < 0.001 < 0.001 < 0.001 0.022 1.256 0.006
Sample 2 (groundwater) 0.001 0.433 < 0.001 < 0.001 < 0.001 0.054 1.155 0.004
Sample 1 after QCM < 0.001 0.313 < 0.001 < 0.001 < 0.001 0.011 0.214 < 0.001
Sample 2 after QCM 0.001 0.279 < 0.001 < 0.001 < 0.001 0.033 0.322 0.003

Table 2
The results after pH; Conductivity; Salinity; and TDS for water analyses at 250C

Conductivity Salinity Total Dissolved Solid Temperature

pH
μS/m ‰ mg/l °C
Sample 1 (drinking water) 7.02 629 0.3 301 25
Sample 2 (groundwater) 7.35 1237 0.6 601 25

Dynamic measurements
We can measure the parameters of water both static and dynamic using a pump with adjustable flow from
0.01 mL/minute to 10 mL/minute. The maximum flow is for to clean cell and to remove previous fluid. After this
step the flow is kept constant for measurement of parameters. The flows used were between 0.3 mL/minute and 1
mL/minute. If the flow is null after cleaning we can measure in the static condition. Use the Axial Flow Cell Adapter
for adsorption/desorption studies when: (1) well defined flow conditions are needed, (2) high sensitivity is required,
(3) small rinse volume is desirable and (4) flow-induced surface shear forces need to be minimized.

FIGURE.3. The Axial Flow Cell Adapter and schematic representation of the liquid flow pattern in this
(From Stanford Research Systems)

A cross sectional view of the Axial Flow Cell, including a schematic representation of the stagnation point
flow, is shown in Figure 3. In the axial flow cell the sample flows radially outward from the input port at the center
of the cell to the exit channel at the edge of the cell, in a volume of about 150 μl. The sample solution is
perpendicularly injected towards the flat surface of the QCM crystal. The stagnation point is located at the center of
the crystal electrode, overlapping the area of highest sensitivity of the flat QCM oscillator. The hydrodynamics
associated with stagnation point flow are well understood. At the stagnation point there is zero hydrodynamic flow -
i.e. without surface shear forces. While the injected solution flows about the stagnation point, any exchange with the
Surface of the crystal is diffusion limited. Thus the rate of adsorption of the sample molecules (or particles) to the
crystal surface is diffusion limited as well. The hydrodynamics and deposition of molecules in stagnation point flow

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conditions have been investigated by Dabros and Van de Ven [7]. In the figure 4 we are presented the date from
QCM dynamic for frequency shift (fig.4a) and resistance (fig.4b) versus time for pure water, drinking water from
tower Targoviste and groundwater from countryside with flow 0.5 ml/minute. The results show that for pure water
the frequency shift is about zero for all time. Small variation from zero is due small variation of temperature [fig.4a].
Also, for pure water, value of resistance is big, about 240 Ω and is constantly [fig.4b]. For drinking water (sample 1)
we obtain for all time a negative frequency shift or an adsorption of metals on metallic electrode [fig.4b] and a 160
Ω for resistance. For groundwater (sample 2) we obtain in first 10 minutes a positive frequency shift or desorption
followed by negative frequency shift or absorption. The value of resistance is the smallest, about 130 Ω. The results
are in concordance with the other methods: AAS, resistivity/conductivity and TDS.

FIGURE.4. Date from QCM dynamic: frequency shift (a) and resistance (b) versus time for deionized water, drinking
water (sample 1) and groundwater (sample 2)

One thing for sure is that, in these waters which were measure, we did not detect traces of volatile organic
compounds (VOC). As we shall see in the figure 5, the characteristics of frequency shift and resistance for any trace
of volatile organic compounds are specifics.

FIGURE.5. Date from QCM: frequency shift and resistance for volatile organic compounds (VOC) in water:
a) Acetone in pure water (1mg/L or 1ppm); b) Isopropanol in pure water (1mg/L or 1ppm) and c) Ethylene glycol in
pure water (1mg/L or 1ppm)

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 For our experiences we prepared pure water with 1 part per million (ppm) of VOC: acetone, isopropanol
and ethylene glycol. In the figure 5a it can seen that the variations of frequency shift and resistance of acetone are
cyclical processes of adsorption/desorption. The variation of frequency shift are very high, 120 Hz or about 2088 ng
in mass. Also, and for isopropanol and ethylene glycol, the variations for frequency shift are very high, over 100 Hz,
or 1740 ng in mass desorption/adsorption. Characteristic for each substance and concentration for traces VOC in
water are the diagrams: frequency shift and resistance versus time, which are unique, as fingerprints.

CONCLUSIONS
In this paper we develop a modern analytical method for monitoring the drinking waters with Quartz
Crystal Microbalance (QCM). The ability to provide real-time monitoring of chemical contaminants in water
samples can be used for a variety of applications: on-line monitoring of contaminants in process, recycle, and waste
water; groundwater quality monitoring; detection of contaminants in streams, lakes and water supplies; monitoring
dumping in off-shore waterways. The test system was assembled using a piezoelectric quartz crystal, a standard
clock oscillator, a frequency counter and a data acquisition hardware and software package. Adsorption of standard
volatile components water: acetone, isopropanol and ethylene glycol and uncoated quartz crystal surfaces was
measured as a function of time. Results indicated that nature of the coating greatly influences total adsorbed masses,
which was attributed to the binding specificity between coatings and volatile compounds.

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