=Paper= {{Paper |id=Vol-2030/HAICTA_2017_paper61 |storemode=property |title=Quality Monitoring of Natural Water from Southwest District of Moscow Using Total Reflection X-ray Fluorescence Analysis |pdfUrl=https://ceur-ws.org/Vol-2030/HAICTA_2017_paper61.pdf |volume=Vol-2030 |authors=Nikolai Alov,Pavel Sharanov,Olga Abramova |dblpUrl=https://dblp.org/rec/conf/haicta/AlovSA17 }} ==Quality Monitoring of Natural Water from Southwest District of Moscow Using Total Reflection X-ray Fluorescence Analysis== https://ceur-ws.org/Vol-2030/HAICTA_2017_paper61.pdf

Quality Monitoring of Natural Water from Southwest
District of Moscow Using Total Reflection X-ray
Fluorescence Analysis

Nikolai Alov, Pavel Sharanov, Olga Abramova

Department of Chemistry, Lomonosov Moscow State University, Moscow, Russia
e-mail: n_alov@mail.ru

Abstract. Pollution of drinking and natural waters is the fundamental
environmental problem. Due to the rapid development of human economic and
industrial activity, monitoring of the environmental situation is necessary.
Total Reflection X-ray Fluorescence Analysis makes it possible to determine
the elemental composition of water quickly and accurately for a large number
of elements simultaneously. The work is devoted to the study of water sources
in the southwest district of Moscow: Ramenka and Rogachevka rivers and the
drinking water source in the park of the 50th anniversary of the October.
During the work, suitable conditions were found that make it possible to
perform the analysis quickly (the analysis time does not exceed 10 min. for one
sample) and to determine a number of elements at the macro-, micro- and trace
levels. The obtained results are compared with the current Russian sanitary
standards.

Keywords: water, quality monitoring, elemental composition, Total Reflection
X-ray Fluorescence

1 Introduction

The human impact on the environment leads to a change in the chemical composition
of water used in everyday life, compared with its natural composition. Water is used
by humankind everywhere, including cooking and drinking, so attention should be
paid to water analysis. One of the most effective modern methods for determining the
elemental composition of water is Total Reflection X-ray Fluorescence Analysis
(TXRF). The method allows to determine small amounts of substance (less pg in
absolute values) with low detection limits (down to ng/l for liquid samples) (Alov,
2011). This method allows investigating a wide variety of objects: water, soils,
geological, mineralogical, technological, archaeological and food samples, it is
suitable in medical industry, art and forensic. TXRF method has a number of
advantages: a small amount of analyzed sample, a simplified procedure for
quantitative analysis due to the use of the internal standard and the elimination of
matrix effects. The TXRF method is characterized by a small amount of reagents and
hence a low cost of analysis (Klockenkämper, von Bohlen, 2013). The method is

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widely used for the analysis of liquid objects, which is facilitated by a very simple
and fast sample preparation procedure. In most papers the sample preparation
procedure consists of the following steps: 1) getting an aliquot, 2) introduction of an
internal standard into aliquot, 3) transfer of a sample drop onto a reflector substrate,
4) drying the droplet in a vacuum desiccator or on a hot plate, 5) measuring the
TXRF spectrum and calculation of concentrations by the internal standard technique
(De La Calle et al., 2013). Similar approach was used for determination of heavy
metals in Mexican Lerma river (Zarazua et al., 2006) and monitoring of water quality
of Toledo river in Brazil (Espinoza-Quinones et al., 2010) by TXRF with
synchrotron radiation excitation.
The purpose of this work is to determine the elemental composition of the natural
waters of the southwest district of Moscow: Ramenka and Rogachevka rivers and the
drinking water source in the park of the 50th anniversary of the October using the
TXRF method, as well as comparing the data obtained with the Russian sanitary
standards.

2 Samples

Several samples from water system of Moscow southwest district were taken for the
analysis. The pond in the flow of Ramenka river (sample 1), Ramenka river itself
(sample 2), Rogachevka river (sample 3), which is a confluent of Ramenka,
Ramenka river after the confluence of both rivers (sample 4), the artesian source of
drinking water (sample 5) and also sample of the snow from a slope of Ramenka
river. The sampling scheme is shown on Fig. 1.

3 Experimental

Water samples were acquired in plastic bottles. The measurements were carried out
on the TXRF spectrometer S2 PICOFOX (Bruker Nano GmbH, Germany) using
quartz reflectors. The excitation was performed by Mo Kα (17.5 keV) radiation. The
time of the spectrum acquisition is 250 s. Gallium solution with the concentration
1000 mg/l is used as an internal standard. This element is easily detected by TXRF. It
does not present in sample and does not cause spectral interference with elements in
sample. The volume of the aliquots was chosen to be 0.5 ml, the volume of the
internal standard solution was 5 µl. The volume of the analyzed solution deposited on
the reflector is 1-2 µl.

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Fig. 1. Scheme of water sampling from the park of the 50th anniversary of the October located
in southwest district of Moscow.

4 Results and discussion

In water samples S, Cl, K, Ca macroelements, Fe, Cu, Zn, Br, Sr microelements and
trace elements Ti, Mn, Ba, Pb were detected. Analysis results are listed in Table 1.
Analysis of water reservoirs (samples 1-4) shows that water from Ramenka river
(sample 2) has the highest mineralization of all investigated water samples (fig. 2).
The highest concentration of such elements as S, Cl, K, Ca, Cu, Zn, Br was found in
this sample. At the same time the content of same elements is much lower in the
pond from which the river flows (sample 1). It is presumably due to the
sedimentation of water followed by transition of elements to muddy sediment at the
bottom of the reservoir.
In the confluent of the Ramenka river – Rogachevka river, the content of elements
of S, Cl, K, Ca, Cu, Zn, Br is also lower than in Ramenka (sample 3). The
mineralization of water after confluence of Rogachevka to Ramenka decreases due to
dilution.
Waters investigated meet the standards set for a household water (see Table 2),
with the exception of the Ramenka river (sample 2), in which chlorine content is
exceeds the maximum allowed concentration (488 mg/l).
Sample 5 – drinking water sample was also compared with standards for drinking
water. As can be seen from Tables 1, 2, content of (S, Cl, Ca, Fe, Cu, Zn, Ba) is
within the permissible concentrations. In addition to these elements, traces of
titanium and lead were found in drinking water in an amount several times lower
than maximum allowed concentrations.

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Fig. 2. TXRF spectrum of water from Ramenka river (sample 2).

The results of the analysis of the snow (sample 6) showed that it contains the
minimum amounts of all the elements. This can be explained by the fact that the
snow condenses in the atmosphere and absorbs only volatile and aerosol
contamination. Also a sample of snow was selected in a place that is located quite far
from the roadways. Consequently, the snow did not have time to become
contaminated with additional substances. The melt water, formed during the melting
of snow, also meets the requirements for the purity of water by the parameters
studied.

Table 1. TXRF results of water elemental composition determination for rivers located in
southwest district of Moscow.

Concentraion, mg/l
1 2 3 4 5 6
S 9.2±1.5 15.7±5.6 15.3±4.6 21.5±4.8 16.8±3.3 0.22±0.13
Cl 42.7±3.7 488±132 56±11 154±15 20.3±3.0 1.25±0.19
K 8.8±0.6 7.5±1.2 10.7±2.3 12±1 1.2±0.3 0.34±0.03
Ca 56.8±3.9 146±54 42±10 81±40 44.1±15.1 0.66±0.05
Fe 0.14±0.07 < 0.03 < 0.03 < 0.03 < 0.03 0.04±0.02
Cu 0.012±0.003 < 0.002 not det. not det. < 0.002 0.0021±0.0003
Zn 0.02±0.01 0.047±0.01 0.013±0.005 0.04±0.02 0.015±0.006 0.024±0.004
Br 0.036±0.02 0.10±0.03 0.05±0.01 0.05±0.01 0.17±0.02 0.0019±0.0002
Sr 0.33±0.02 0.54±0.21 6.2±1.0 5.95±0.70 0.19±0.03 0.0011±0.0003
Mn 0.12±0.01 < 0.005 not det. not det. not det. 0.005±0.002
Ti < 0.02 < 0.02 not det. < 0.02 < 0.02 0.004±0.002
Pb < 0.002 not det. < 0.002 not det. 0.005±0.002 < 0.002
Ba < 0.05 < 0.06 < 0.05 not det. < 0.05 not det.

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Table 2. Element concentration allowed by the Russian sanitary standards for household and
drinking water.

Element Cl- Fe Cu Zn Br- Sr Mn Ti Pb Ba
Concentraion, mg/l 350 0.3 1 1 0.2 7 0.1 0.1 0.01 0.1

Acknowledgment. This work was financially supported by the Russian Science
Foundation (project no. 14-23-00012).

References

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