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Universidad de la Frontera

Doctorado en Ciencias de Recursos Naturales

Colorimetric Method for the Determination of Arsenic (III) in Potable Water.

Rodrigo Castro & Wence Herrera

1. Technique Fundamentals

Arsenic is a highly environmentally distributed element. It tends to be detectable in almost every


compartment and usually appears in the lithosphere in concentrations between 1.5 to 2 ppm,
occupying the 52 in abundancy (12). Arsenic is present in soil, water, air and food, therefore the
human being is continuously exposed to this contaminant [10]. The arsenic interval in soil varies from
0.2 to 40 g/kg in the air of the urban zones and the concentration is approximately of 0.02 µg/m3 in
the air. Exposition via water consumption is usual worldwide. In continental waters the concentration
tends to be below 1 µg/m3, while in sea water the mean concentration of Arsenic is around 1.5 µg/m3
[13]. The highest amount of exposure to Arsenic is due to superficial water contaminated due to
anthropogenic or geologic origin. It is estimated that thirty million people are exposed to water
contaminated with Arsenic.

Two forms of arsenic exist in the human environment, pentavalent and trivalent (Sandhu, 1976).
The biological activities of arsenic in these valence states differ markedly. Several methods used for
the determination of arsenic at low concentrations in water are total elemental analysis procedures.
The colorimetric method proposed by Sandhu (1976) offers a number of advantages over other
standard methods, such as using silver diethyldithiocarbamate. The colorimetric procedure is
sensitive and simple, and the results are accurately reproducible at microgram per litre (ppb)
concentration levels, and also allows differencing between III and V states of arsenic, which gives us
and idea of the toxicity that the drinkable water might have.
Universidad de la Frontera
Doctorado en Ciencias de Recursos Naturales

The analyte of interest in this case is the Arsenic (III), which is a redactor agent and reacts
quantitatively with iodate, releasing an equivalent amount of iodine in presence of sulphuric acid:

5AsO33− + 2IO3− + 2H + → I2 + 5 AsO43− + H2 O

This could be decomposed on its two corresponding semi-reactions:

Reduction semi-reaction

IO3− + 3e− → I2

Oxidation semi-reaction

AsO33− → AsO43− + 2e−

2. Materials and Methods

a. Equipment and materials

i. Equipment

 Spectronic 20 spectrophotometer capable of reading a signal of 520 nm


 Set of 1.27 cm cuvettes, Bausch and Lomb, Cat Nº 33-29-27
 Rotavapor Model 4358-S50
 Whatman Nº42 filter-paper
 125 mL separating funnels

b. Necessary Reactors
 Sodium arsenate (Na3 AsO4 )
 Sodium arsenite (NaAsO2)
 18 N sulphuric acid (H2 SO4 )
 Potassium Iodate (KiO3 )
 Carbon Tetrachloride (CCl4 )

Standard precautions for trace analysis were taken throughout the measurements. Analytical-
reagent grade chemicals were used, except for carbon tetrachloride, which was of Nanograde quality.
Universidad de la Frontera
Doctorado en Ciencias de Recursos Naturales

3. Solutions and protocol


A series of solutions containing 0.002 – 100.0 mg/l of As (III) have to be prepared from sodium
arsenate Na_3 AsO_4. As (V) Standards have to be prepared from sodium arsenate. A number of
standard solutions containing 0.10 – 10.0 mg/l of As (III) as well as 0.50 – 20.0 mg/l of As (V) have
to be prepared also. The sampling must be done on drinkable water sources, such as drinking
fountains, lakes and rivers, and preferably analyzed within a few hour of collection.

𝑚𝑔
Standard solutions (50 ml) of As(III) containing 1, 2, 5, 10 𝑎𝑛𝑑 20 𝑙
of metal cations have

to be transferred in triplicate into 125 mL separating funnels. A pre-determined volume of 18 N


sulphuric acid have to be added to each to adjust the hydrogen-ion concentration to 3 N. The contents
of each separating funnel have to be treated with an excess of potassium iodate (about 200 mg) and
10 mL of carbon tetrachloride. The amount of potassium iodate used in this method could be varied
in accordance with the concentration of As (III) expected in the various aliquots.

𝑚𝑔 𝑚𝑔 𝑚𝑔
50 mL of the 100 𝑙
, 100 mL of the 0.5 𝑙
and 150 mL of the 0.1 𝑙
As(III) standard
solutions have to be treated in a similar manner except that 50, 5 and 3 mL of carbon tetrachloride,
respectively, have to be used for extraction of the liberated iodine.

𝑚𝑔
Standard solutions containing less than 0.1 of As(III) and natural water samples have to be
𝑙

placed in a rotary flash evaporator (for the case of study a Rotavapor Model 4358-S50) to reduce the
volume from 700 to 20 mL. When found necessary, concentrated natural waters have to be filtered
(in the case of study using a Whatman Nº42 filter-paper) to remove the insoluble constituents. The
reduced volume in each instance has to be transferred quantitatively into a 125 mL separating funnel
and treated as described above for the reaction of As(III) with potassium iodate. The liberated iodine
have to be extracted with 3 ml of carbon tetrachloride. The contents of each separating funnel have
to be mixed by shaking manually for about 2 minutes and allowed to stand for 15 minutes for a
complete separation of organic and aqueous phases. The iodine – carbon tetrachloride extracts should
be directly drained into a matched set of cuvettes (1.27 cm, Bausch and Lomb, Cat Nº 33-29-27 for
this case) and the absorbance must be read on a spectrophotometer (in this case a Spectronic 20
spectrophotometer) at 520 nm.
Universidad de la Frontera
Doctorado en Ciencias de Recursos Naturales

a. Calibration curve

Standards have to be prepared from sodium arsenate. A number of standard solutions


𝑚𝑔 𝑚𝑔
containing 0.10 – 10.0 of As(III)(0.1, 0.5, 1, 2, 5, 10 ). Standard solutions (50 ml) of As(III)
𝑙 𝑙
𝑚𝑔
containing 1, 2, 5, 10 𝑎𝑛𝑑 20 of metal cations have to be transferred in triplicate into 125 mL
𝑙
𝑚𝑔 𝑚𝑔 𝑚𝑔
separating funnels. 50 mL of the 100 𝑙
, 100 mL of the 0.5 𝑙
, and 150 mL of the 0.1 𝑙
As(III)

standard solutions have to be treated in a similar manner. The total curve was created from all these
solutions. Three means were taken for the determined concentrations*.

Table 1 Recovery of As (III) by the colorimetric method compared with theoretical values and
atomic absorption spectrophotometric results

Concentration of As(III) mg/l


Recovery by AAS
Theoretical Determined* Recovery % SD %
%
0.005 0.0053 106 5.3 -
0.01 0.0096 96 2.4 -
0.05 0.052 104.0 4.3 -
0.1 0.09 90.0 8.4 -
0.5 0.52 104.0 4.5 103.0
1.0 0.98 98.0 1.2 104.0
2.0 2.11 105.0 3.8 101.0
5.0 5.22 104.0 3.2 101.0
10.0 10.09 100.9 1.4 99.0
20.0 21.75 108.7 4.8 101.0
100.0 103.0 103.0 3.4 -

4. Discussion

The main analytic challenge for the analysis of arsenic species at trace level is related to the low
concentrations in which they are presents and the requirements for the identification of chemical
forms in which the metalloid is. Both requirements are far from being reached satisfactorily by most
of the commercial instrumental available for organic and inorganic analysis [11].
Universidad de la Frontera
Doctorado en Ciencias de Recursos Naturales

Generally, measurements precise a low quantity detection (trace), this measurements should
provide information about the forms or chemical structures in which it is present. From this point of
view, we could immediately appreciate the technical difficulties related to elemental speciation. Due
to its low sensibility, a lot of popular techniques (UV, IR) that has been extensively and successfully
used for the identification of forms and structures in an organic analysis, are not usually adequate for
elemental speciation. However, the technique proposed by Sandhu (1976) shows low detection limits
(near 0.001 ppm) and also has shown that it has a high recollection efficacy (near 100%), therefore it
is highly recommendable for arsenic (III) measurements in water, nevertheless, if the aim of the
objective is based on determining total As, another methodology should be found since there is no
reaction to this arsenic form (Sandhu, 1976). Comparing the sensibility presented by this technique
in front of other similar used for the measurement of total arsenic such as the one proposed by Sidhu
et al. (2016) we found that it presents similar sensibility since its detection limits are near 0.01 ppm
with the particularity that the method that Sidhu includes the addition of a chelating agent (EDTA
0.01%) to hinder the reaction of another heavy metal with iodate.

In the same way, Sadhu (1976) reports that the values determined by this colorimetric method
are similar to the ones obtained by other more pricey and robust analysis such as Inductively Coupled
Plasma (ICP) (van de Wiel, 2003) and atomic absorption spectrometry (AAS).

5. Advantages and disadvantages.

Table 3. Advantages and disadvantages of the method proposed by Sandhu (1976).

Advantages Disadvantages
Could react with other contaminants present in
Quick determination
water
High sensibility Other methods give more information
High specificity High specificity
Low sample volume
Low sample preparation time
Low detection limits
Low Cost
Universidad de la Frontera
Doctorado en Ciencias de Recursos Naturales

6. Conclusions

The presented method has shown being efficient in the determination of As (III) in drinkable
water samples, as such, it is a quick, cheap reaction, with low detection limits, even lower than the
maximum values allowed by international standards of arsenic in water. Also, this technique has
shown having a recollection of the metalloid near 100% and with similar determinations to the ones
obtained through more robust models such as ICP and ASS.