COLORIMETRIC KIT FOR MERCURY DETERMINATION

(copyright CETEM, 1989)

Principles

It is an usual practice in colorimetric mercury analysis the use of ditizone as a colorimetric
and extraction reagent (Koch & Koch, 1974). In an acid environment, mercury ions react
with ditizone, forming ditizonates, Hg(HDz), with a orange-red color, dissolvable in
solvents such as chloroform and carbon tetrachlorid. The color complex presents maximum
absorption at 485 nm and molar extinction of 7,1 x 10
4.
Mercury ditizonate presents great stability and forms rapidly, even in a strongly acid
(5 M
H
2
SO
4
)
or alcaline
(2 M NaOH)
medium, which allows washing out the ditizone excess
remaining in the extract using an alcaline sollution.

Ditizone, despite its excellente reactivity with mercury ions Hg(I) and Hg(II), isn`t a
selective reagent and, according to conditions, may react with a great quantity of other
cathions. Fletcher (1981) remarked that colorimetric analysis of total mercury with ditizone
in a highly acid medium (pH < 1) eliminated all interferants, excepting silver. Some anions
also interfere in the mercury extractions procedures using ditizone (Litman et alii, 1977).

To geochemical samples, Kosoy et all (1967) analysed critical parameters in vaporization
methods. One of the salient aspects in the study is the need to grind the samples to
guarantee the results ability to be reprodeced. The grain size is of fundamental importance
to the mercury liberation. The author suggests that geochemical samples must be classified
in granular sizes inferior to 200 mesh (0,074 mm).

The method developed by Silva, A.P. (1996), besides taking the previous aspects in
consideration, also optimizes the following parameters: drag gas; pyrolisis time; inert
matrix; mass and grain size, and digestion sollution composition.

Analytical procedure

After the sample is dried on the shadow, divided in four parts and weighted, it is then
submitted to pyrolisis. The pyrolisis is to be made under heating by a Bunsen burner (450-
500
o
C) in a borosylicate, pyrex type, glass tube (120 mm high by 30 mm diameter) with
emeryzed female joint (19 x 24 mm). Hg vapors are then conducted to the digestion
sollution through the glass tube, connected to the pyrolisis tube by a emeryzed malejoint
(19 x 24), that funnels on the immersion part in the digestion sollutions becker. Vapor
containing mercury are sparkled in the digestion sollution (KMnO
4
in sulfuric sollution)
under magnetic agitation.

Following the reduction of the oxidants excess with 4 M hydroxilammonium chlorid
solution, the dissolved mercury must be extracted to the organic phase (ditizone solution
0,01% in chloroform). After agitation (for 1 minute), the organic phase is washed with a
3M acetic acid solution, allowing the cromatic stabilization of the formed mercury
ditizonate. The organic extract is then measured through pattern comparison (visual
colorimetry) or spectrophotometry (e.g. photometer UV- VIS Beckman, model Spectronic
20).

The sintetic pattern is developed with mixtures of potassium dicromate and cobalt chloride
solutions, through the simulation of the colors of ditizonate formed when mixed with
mercury solutions of 0,1; 0,3 ; 0,5 ; 1,0 e 2,0 ppm. Due to optic density, for visual
comparison it is not possible to use patterns of higher concentrations.

Taking into account all the procedures needed to the realization of the analysis, and the
necessary time to its execution, it is estimated in up to 15 samples/day tha analytical
capacity of each colorimetric kit.

The following picture describes the steps of the proposed analytical procedure. Mercury
determination in sediments consists in its extraction by volatilization through heating.





Quality Control

Total mercury determination in sediments using this colorimetric, semi-quantitative
methodology developed was applied in samples with low and high concentrations taken in
various spots along the Tanque dos Padres (Pocon-MT) riverbed, near the places pointed
by the miners as locations where the resumo was processed.

To evaluate the quality of the results acquired with the proposed methodology, some
samples were analysed at the same time by atomic absorption spectrophotometry using the
cold vapor technic (AAS-CV). The results can be seen on table 1.

Table 1: Results of total Hg determination in sediment samples by instrumental
analysis (AAS-CV) and the proposed colorimetric kit (data in ppm)
Sample AAS-CV Colorimetry
STP-01 0,085 +/- 0,005 Interval: 0,1
STP-02 0,076 +/- 0,009 Interval: 0,1
STP-03 1,027 +/- 0,018 Interval: 0,5-2,0
STP-04 0,074 +/- 0,006 Interval: 0,1
STP-05 0,178 +/- 0,012 Interval: 0,1-0,3
STP-06 0,112 +/- 0,008 Interval: 0,1-0,3
STP-07 0,580 +/- 0,013 Interval: 0,5-1,0
STP-08 0,069 +/- 0,006 Interval: 0,1
STP-09 1,230 +/- 0,015 Interval:1,0-2,0
STP-10 0,095 +/- 0,006 Interval: 0,1
STP-11 3,835 +/- 0,243 Interval: 2,0
STP-12 0,803 +/- 0,011 Interval: 0,5-1,0