Talanta 219 (2020) 121297

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Talanta
journal homepage: www.elsevier.com/locate/talanta

Classification and determination of total hardness of water using silver T

nanoparticles
Masoud Shariati-Rada,b,∗, Saeideh Heidaria
a
Department of Analytical Chemistry, Faculty of Chemistry, Razi University, Kermanshah, Iran
b
Research Group of Design and Fabrication of Kit, Razi University, Kermanshah, Iran

ARTICLE INFO ABSTRACT

Keywords: Herein a semi-quantitative and quantitative method for rapid determination of water hardness was introduced.
Total hardness The method was based on color change of silver nanoparticles (AgNPs) in the presence of real water samples.
Silver nanoparticles Carbon dots were prepared from mulberry in a hydrothermal procedure and used as reductant of silver ion for
Water synthesis of AgNPs. A classification method based on the color change of AgNPs in the presence of different
Image analysis
water samples was also founded. The analysis based of the proposed method was cheap and rapid. On site semi-
Colorimetric classification
quantitative determination of total hardness of water can be performed by the proposed method. A linear ca-
libration model based on the color analysis of the images of AgNPs in the presence of water samples was con-
structed. The model was applicable for determination of total hardness of water in the range of 116-248 mg L−1
of calcium carbonate. A variety of real water samples were included in the calibration model. The calibration
method can be used to predict total hardness of water in a critical range above the soft water and below the very
hard water. The results were compared by the standard titrimetric method based on ethylenediaminetetraacetic
acid. Prediction of total hardness of real water samples based on the color model was in most cases below 20%.

✓ Silver nanoparticle were generated using carbon dots that had been
synthesized using mulberry.
✓ The change in color of the AgNPs in the presence of water samples of
differing total hardness was examined.
✓ Image of the mixture of AgNPs with different water samples was
converted to R, G and B indices.
✓ Color index of R was used to model and predict total hardness of
water samples.
1. Introduction
Water hardness results in the precipitation of soap. It is produced by
various dissolved polyvalent metallic cations. Predominately, it is
caused by Ca2+ and Mg2+ ions. However, other cations like Ba2+,
Sr2+, Fe3+ and Zn2+ also contribute to the hardness of water [1].
Traditionally, total hardness is defined as the sum of the concentrations
of Ca2+ and Mg2+ expressed as mg L−1 of CaCO3.
In order of abundance in natural waters, calcium and magnesium
are the fifth and eight species, respectively. Concentrations of these
species cover a range of a few to hundreds of mg L−1 depending on the
treatment to which the water has been subjected and its source. Water
containing calcium carbonate at different concentrations can be clas-
sified as Table 1 [2].
The threshold of taste for Ca2+, depending on the associated anion
corresponds to the range of 100–300 mg L−1. Although higher con-
centrations are yet acceptable by consumers [1]. Taste of drinking
water is affected by dissolved minerals in different degrees.
Apart from the above mentioned taste effects of water hardness,
hard water can increase consumption of soap and deposition of scale in
the system of distribution of water and in the heated water applications
in suitable pH and alkalinity. In these conditions, insoluble metal car-
bonates are formed which coat surfaces and reduce the efficiency of
heat exchangers. On the other hand, soft water that has not been sta-
bilized may corrode metal pipes and surfaces. This can result in the
release of heavy metals like copper, cadmium, zinc and lead to drinking
water and reduced lifetime of distribution system and appliances [3].
Therefore, monitoring and rapid determination of some relevant
parameters of water quality such as total hardness is very important in
industrial and environmental fields such as the water quality control of
water in drinking water plants.
The standard method for determination of hardness in water sam-
ples is based on ethylenediaminetetraacetic acid (EDTA) titrimetric

∗
Corresponding author. Department of Analytical Chemistry, Faculty of Chemistry, Razi University, Kermanshah, Iran. .
E-mail address: mshariati_rad@yahoo.com (M. Shariati-Rad).

https://doi.org/10.1016/j.talanta.2020.121297
Received 12 March 2020; Received in revised form 10 June 2020; Accepted 11 June 2020
Available online 20 June 2020
0039-9140/ © 2020 Elsevier B.V. All rights reserved.
M. Shariati-Rad and S. Heidari
Table 1
Classification of water based on total hardness.
Type of water Total hardness as mg L−1 of CaCO3
Soft 0–50
Moderately soft 50–100
Slightly hard 100–150
Moderately hard 150–250
Hard 250–350
Very hard 350 <
method [4] but the method is labored and needs a lot of time. Analy-
tical techniques like atomic absorption spectrometry are suitable for
analysis of water for total hardness in the laboratory. However, they are
not useful for in situ and continuous measurements. Moreover, these
techniques are time consuming. In contrast, potentiometry by ion-se-
lective electrodes (ISEs) is a useful technique for continuous and au-
tomatic analysis [5–10]. Despite their names, ISEs are not selective
devices since they work based on ionophores designed for interacting,
holding or complexing the analytes in a cavity.
A synthetic oligonucleotide has been used as a fluorescent beacon
for the reagent-less determination of total hardness in bottled and tap
waters [11]. Though it has been claimed that the sensor uses a reagent-
less mechanism, in its construction an aptamer beacon with fluores-
cence labels has been used. Moreover, the preparation of the sensor is
expensive and the recording of the fluorescence requires using a spec-
trofluorimeter.
Transparent test strips have been introduced for spectrophotometric
determination of Ca2+ in water based on chlorophosphonazo III and
4,13-bis[(N-adamantylcarbamoyl)propionyl]-1,7,10,16-tetraoxa-4,13-
diazacyclooctadecane as reagent in plasticized PVC membrane [12,13].
Alternatively, using 18-crown-6-ether as ionophore in test strip im-
proved the range of Ca2+ determination [14]. However, in spite of their
good sensitivity, fast response and low expense, they suffer from low
reproducibility, stability and selectivity.
The quantitative or semi-quantitative determination of total hard-
ness using rapid methods has also attracted a great interest in this field.
Among different types of rapid test methods, test strips are of great
importance. By these methods, it can be possible to detect or determine
the desired analyte without any expert user and sample pretreatment.
Therefore, the cost of the analysis is reduced and rapid decisions can be
made without any laboratory.
In the analysis of water, the most common test strips can determine
sum of Ca2+ and Mg2+ ions (total hardness). This is the case with EM
Quant® (Merck), Aquadur® (Macherey-Nagel) or Serim™ (Serim
Research Co.) test strips. These strips work based on a reaction between
a chromogenic reagent immobilized on it and Ca2+ and/or Mg2+ in
water. Then, the produced change in color is compared with a color
scale to estimate the total hardness semi-quantitatively.
In the present work, silver nanoparticles (AgNPs) were synthesized
and used in a simple procedure to determine total hardness of water
semi-quantitatively and quantitatively. Image analysis of the solutions
of AgNPs in the presence of different water samples was used to extract
signal relating to the total hardness.
AgNPs have been employed in determination of different cations in
water [15–29]. However, application of AgNPs for determination of
Ca2+ and Mg2+ and especially determination of total hardness has not
yet been reported.
Image analysis has been used in determination of total hardness. For
example, Damasceno et al. [30] and Lopez-Molinero et al. [31] by using
EDTA and glyoxal bis(2-hydroxyanil) have determined total hardness
and Ca2+ content in water, respectively. These methods require mul-
tiple reagents and steps which prolongs the analysis. Moreover, the
calibration model in ref 31 contains low Ca2+ concentrations which
requires high dilution of the water samples. Based on EDTA titrimetric
method, Karita and Kaneta introduced a paper based device for
2
Talanta 219 (2020) 121297
determination of total hardness [32]. However, the method is based on
titration and in application to the real samples, it needs cyanide ion to
prevent interferents.
2. Experimental
2.1. Chemicals, solutions and apparatus
Ammonia 25% concentrated solution, ethanol (99.5%) and silver
nitrate (99.0%) were purchased from Merck (Darmstadt, Germany). For
preparation of buffer solution based on NH4+/NH3, 0.1 M solutions of
sodium hydroxide and hydrochloric acid prepared by reagent grade
sodium hydroxide (≥98%, Merck) and hydrochloric acid (37%, Merck)
were used. Ethylenediaminetetraacetic acid (EDTA) disodium salt
(≥99.0%) was prepared from BDH chemicals (Ltd Poole England) and
eriochrome black T sodium salt (ECBT) for complexometric titration as
ACS indicator grade was prepared from Sigma-Aldrich. Ethanol was
used in preparation of carbon dots. All of the solutions were prepared in
deionized water.
For pH measurements, a Jenway 4330 combined pH and con-
ductivity meter was used. Transmission electron microscopy (TEM) was
performed using a Zeiss EM900 transmission electron microscope.
Water samples include bottled drinking waters purchased from local
markets and some spring and tap waters taken in different locations of
Kermanshah city and Kermanshah province, Iran. Random sampling
was followed for taking the samples of spring water in different times in
the summer. After sampling, waters were placed in polyethylene ter-
ephthalate (PET) bottles and stored in room temperature until analysis.
2.2. Synthesis of AgNPs
AgNPs were synthesized following the procedure reported by Jin
et al. [33]. CDs were synthesized by simply heating mulberry in hy-
drothermal method [34]. The mulberries were picked off from trees in
Razi University and washed carefully by deionized water. After adding
20 mL of ethanol to 10 g of pulverized mulberry, the mixture was he-
ated at constant temperature of 150 °C for 4 h in an autoclave. After
that, the dark brown reaction mixture was cooled to room temperature
and after addition of 20 mL ethanol was filtered. Next, the solution was
freeze dried and solid CD was obtained. In the next step, CD was em-
ployed as reductant of AgNO3 to produce the AgNPs.
Briefly, to 100 mL boiling deionized water, 100 μL of the synthe-
sized CD solution (50 mg mL−1) was added and boiled for 15 min.
Then, after addition of 1 mL ammonia solution (10%, w/w), fresh
AgNO3 solution (5 mL, 20 mM) was added while stirring for 2 min. This
reaction was continued for 50 min at 90 °C. Finally, the yellow solution
of AgNPs was obtained.
2.3. Determination of water hardness by standard method and by using
AgNPs
In order to analysis water samples for total hardness, 50.0 mL ali-
quot of the test water was placed in the titration vessel. After addition
of 10.0 mL of NH4+/NH3 buffer with pH of 10.0 and two drops of ECBT
prepared in methanol (1% w/v), the mixture was titrated with EDTA
0.01 M standard solution until the red color of the mixture changed to
blue. For each water sample, the titration was repeated three times and
the mean total hardness was reported.
For employing AgNPs for determination of total hardness of water
samples, 1000 μL of the synthesized AgNPs was placed in the sample
tube and after addition of 500 μL of the test water, the total volume was
reached to 2000 μL by addition of deionized water. Immediately, the
color of the mixture changed based on the amount of total hardness of
the examined water in room temperature. The color of the mixture was
stable for about 1 h. It must be mentioned that all determinations were
carried out in room temperature.
M. Shariati-Rad and S. Heidari Talanta 219 (2020) 121297

Fig. 1. TEM image of the synthesized AgNPs before addition of real water sample (a and c) and after addition of real water sample (b and d).

2.4. Data acquisition and data analysis

Digital images of the solutions of AgNPs in the presence of different

water samples were recorded by camera (13 megapixel) of a SUMSUNG
Galaxy Smartphone. Then a maximum possible area of the images with
100 × 100 pixels were selected and analyzed by MeeSoft Image
Analyzer version 1.33 to extract red (R), green (G) and blue (B) color
indices as signals for analysis of waters for total hardness.

3. Results and discussion

3.1. Characterization of the synthesized AgNPs

Transmission electron micrograph of the synthesized AgNPs can be

seen in Fig. 1a. As can be seen, the size of the synthesized AgNPs is
relatively uniform with a small size distribution. In the presence of real
water sample, the color of the synthesized AgNPs turns to orange-red-
Fig. 2. Size distribution of the synthesized AgNPs.
brown. TEM of AgNPs in these conditions (Fig. 1b) shows that the na-
noparticles adhere to each other and agglomerate. In Fig. 1c and d the
agglomeration can be observed more clearly. intensity and location of the absorption spectrum of AgNPs is observed.
Size distribution of the synthesized AgNPs has been shown in Fig. 2. Solution of the synthesized AgNPs is yellow in color and stable.
A normal distribution can be inferred and average diameter of AgNPs
was 17.9 nm. Absorption spectrum of the synthesized AgNPs has been 3.2. Analysis of water for total hardness using AgNPs and image analysis
shown in Fig. 3. The synthesized AgNPs possess a single main absorbance
maximum located at 406 nm. In the presence of real water samples, In Table 2, the names and corresponding total hardness of the ex-
depending on the total hardness of the analyzed water, variation in amined real water samples have been collected. Total hardness of

3
M. Shariati-Rad and S. Heidari Talanta 219 (2020) 121297

Fig. 3. UV–Vis spectrum of the synthesized AgNPs.

Table 2
The examined water samples and corresponding total hardness as mg L−1 of
CaCO3.
Number Water Sample Total hardnessa
Fig. 4. Image of the solution of AgNPs (1.00 mL) in the presence of different
1 Blank 0 water samples (0.50 mL) with the total volume of 2.00 mL (a) and corre-
2 Vatta 56 ± 7 sponding UV–Vis spectrum (b).
3 Aquafina 84 ± 7
4 Dasany 116 ± 17
5 Veen 140 ± 3 rightmost location in Fig. 4b. On the other hand, for water samples
6 Souver 144 ± 20 Vatta, Dasany and Auafina with low total hardness, it is not observed a
7 Oxab 160 ± 11
8 Alise 168 ± 3
detectable change in the absorption spectrum of AgNPs (blank).
9 Vagol 184 ± 8 Color dependence of the AgNPs to the total hardness was in-
10 Taghbostan 224 ± 2 vestigated by image analysis of the solutions shown in Fig. 4b. Each
11 Azmar 228 ± 9 image was converted to the corresponding R (red), G (green) and B
12 Kimia 232 ± 2
(blue) indices based on the procedure explained in section 2.4 and their
13 University 240 ± 20
14 Sanjabi 240 ± 6 hardness dependence were explored. The results showed that the most
15 Farhangian 248 ± 10 sensitive index to variation in total hardness is R index. The ranges of
16 Kahar 264 ± 18 variation in R, G and B indices for the same range of total hardness were
17 Taavon 264 ± 5 170.05-32.98, 47.44-15.40 and 19.54-21.24, respectively. Therefore,
18 Cheshmeh 280 ± 2
19 Elahieh 280 ± 3
for color analysis, R index was used. Plot of the relation of R index with
20 O 400 ± 15 total hardness for all of the studied real water samples has been shown
in Fig. 5a.
a
Values in the parentheses are confidence interval in the prediction at 95% Sensitivity of the method was defined as the slope of the linear re-
confidence level with three replicates. lation between R index and total hardness. Based on Fig. 5a, the sen-
sitivity of the method was estimated as 1.22. On the other hand, in-
waters has been determined by standard titrimetric method by EDTA in spection of Fig. 4a and b shows that the lowest amount of total hardness
the presence of ECBT as indicator as explained in section 2.3. of water which can be detected by the method is about 100. A cali-
In Fig. 4a, color changes of the real water samples have been shown. bration curve was extracted from the relation between R and total
A relatively ordered changes in colors with increasing total hardness is hardness (Fig. 5b). Statistical parameters of the linear regression have
observed (left to right). In very low total hardness (below 100), the been collected in Table 3.
color of the AgNPs was not highly changed in the presence of the real For three replicates, images were analyzed and error bars were
water samples (water samples 2 and 3). After that, an orange color is calculated and shown in Fig. 5b. Statistically, the linear relation
appeared (water samples 4 and 5) which corresponds to total hardness (Fig. 5b) is reliable with F-statistics equal to 289.3 and p value
of 100–140. In higher values of total hardness, the color changes to pale of < 0.0001. This means that variation in the response (R index) is
red and subsequently varies to intense red (140–224), and finally to significantly due to the variation in the total hardness. The linear re-
brown (higher than 224). These color changes are regular and in fact, a lation is applicable in the range of 116–248 of total hardness. Con-
color spectrum corresponding to different values of total hardness is sidering the slope of the calibration curve, using image analysis results
observed. The classification scheme obtained here well corresponds to in a sensitive relation between signal and total hardness. The linear
the classification table (Table 1) reported by Gray [2]. Therefore, a range is relatively broad and based on it, an important range of total
simple tool for classification of real water samples based on total hardness can be evaluated.
hardness and color of AgNPs in the presence of water samples is in- For examination of the constructed calibration curve (Fig. 5b), new
troduced. It is the first time that a color scale is introduced to classify real water samples were analyzed. The image of the solutions was also
waters to soft, moderately hard, hard and very hard. analyzed by the calibration based on the R color index (Fig. 5b). The
In Fig. 4b, UV–Vis spectrum of the mixtures shown in Fig. 4a have results have been collected in Table 4.
been shown. A new peak at wavelengths higher than 470 nm appears Images analysis of the real water samples were also performed three
with total hardness. As can be seen from Fig. 4b, a relatively gradual times. The results showed that the variation due to replication is low as
change in the maxima of this new peak toward higher wavelengths can be inferred from relatively narrow confidence intervals (Table 4).
occurs with total hardness. For example, spectra of water samples like This verifies the usefulness of the image analysis for determination of
O, Cheshmeh and Taavon with high total hardness can be seen in the

4
M. Shariati-Rad and S. Heidari Talanta 219 (2020) 121297

Table 4
Results of the analysis of different real water samples by constructed calibration
curve based on the images analysis.
Water sample Predicted total hardnessa Percent relative error

Yavari 97.8 ( ± 8.6) 17.7

Miandarband 103.3 ( ± 10.3) 18.8
Pure life 145.5 ( ± 6.1) −16.0
Sarab Sahneh 148.9 ( ± 11.1) 12.6
Sarab Gian 151.1 ( ± 8.5) 11.0
Sarab Ghanbar 164.4 ( ± 7.7) 2.2
Bisetoun 177.8 ( ± 10.5) 17.9
Emamzadeh 180.0 ( ± 9.8) 18.7
Rijab 187.8 ( ± 8.6) 13.3
Damavand 203.3 ( ± 9.4) −2.1

a
Values in the parentheses are confidence interval in the prediction at 95%
confidence level with three replicates.

was shown in the previous sections. This is similar to the mechanism of

the detecting end point in the classical method of determination of total
hardness using EDTA.
It should be mentioned that the color change is attributed to the
interaction of the polyvalent cation species in the water samples with
AgNPs not CD. This was investigated by addition of 500 μL of Kimia
water sample (with total hardness of 232) to 100 μL of the synthesized
CD solution (5 mg mL−1) with total volume of 2000 μL. The image of
CD with and without Kimia water sample can be seen in Fig. 7. It is
clear that no observable color change is seen. Total concentration of CD
Fig. 5. (a) Relation between R (red) index of the solutions shown in Fig. 1 and in this mixture is 5 times higher than concentration of CD in the re-
total hardness and (b) calibration curve obtained by relation between R and action mixture for synthesize of AgNPs.
total hardness. (For interpretation of the references to color in this figure le- For comparison, the results obtained by Damasceno et al. [30] and
gend, the reader is referred to the Web version of this article.)
Lopez-Molinero et al. [31] can be considered. Damasceno et al. have
performed the same classic EDTA titrimetric method except that they
Table 3 have employed image analysis for determination of total hardness.
Statistical parameters of the calibration based on the image ana- Glyoxal bis(2-hydroxyanil) has been selected as reagent by Lopez-Mo-
lysis. linero et al. for water analysis. By their method, only analysis of water
Statistical parameter Value sample for Ca2+ is possible and the range of the constructed calibration
is such that its application to the real water samples requires high di-
Linear range 116–248 lution of the sample.
Slope −1.22 ( ± 0.07)a
Intercept 325.97 ( ± 14.23)a
The points which differentiate the proposed method over the pub-
Correlation coefficient 0.9832 lished works are: (a) using AgNPs for the first time in determination of
F statistics 289.3 total hardness of water, (b) applicability to determine total hardness of
P < 0.0001 real water samples without interference, (c) rapid elucidation of the
a class of the examined water based on total hardness.
The values in the parentheses are standard deviation of the
corresponding parameter.

total hardness of water. Percent relative errors were calculated using
total hardness predicted by images analysis and total hardness esti-
mated by EDTA titrimetric method. By image analysis, water samples
have been analyzed with satisfactory errors. The errors in prediction are
acceptable considering the simplicity and speed of the analysis.
In order to investigate about the causes of the color change of AgNPs
in the presence of different water samples, different common ion spe-
cies in water were examined (Fig. 6). As can be seen in Fig. 6, ag-
gregation of AgNPs is induced by nonspecific interactions of different
polyvalent cation species contained in real water samples. This ag-
gregation is accompanied by color variations. Color changes can be
seen with most polyvalent cations. However, for species like Zn2+,
Cd2+, Cu2+ and Fe3+, color changes different from those for Fe2+,
Ca2+, Mg2+, Sr2+ and Ba2+ is observed. Species in the first group
specially Zn2+, Cd2+ and Cu2+ can be detected in natural and drinking
water samples at lower concentrations. On the other hand, Ca2+ and
Mg2+ are considered as responsible for total hardness of water.
Therefore, it can be concluded that color changes of AgNPs in the
presence of different water samples is related to the total hardness as
4. Conclusions
Total hardness of water is produced by a variety of di- and trivalent
metal ions. Due to the non-specific but selective behavior of prepared
AgNPs to these ions, it was successfully employed for determination of
total hardness of water. This is the same event that occurs in standard
titrimetric method by EDTA for determination of total hardness of
water. AgNPs prepared in a safe and green method can be used for
determination of total hardness of water.
Color changes of AgNPs in the presence of different water samples
was confirmed to be a good indicator of the total hardness of water
samples. This was quantitatively and semi-quantitatively used to simply
determine total hardness of water samples.
Credit author statement
Masoud Shariati-Rad: Conceptualization, Methodology, Software,
Analysis, Reviewing, Editing Saeideh Heidari: Experimental, Data col-
lection.

5
M. Shariati-Rad and S. Heidari
Fig. 6. Study of the color changes of the synthesized AgNPs in the presence of common ions in water samples. Concentration of all ions is 10 mg L−1. (For
interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)
Fig. 7. (a) Solution of CD and (b) CD in the presence of Kimia real water
sample.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
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