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PII: S1386-1425(17)30458-4
DOI: doi: 10.1016/j.saa.2017.05.072
Reference: SAA 15214
Spectrochimica Acta Part A: Molecular and Biomolecular
To appear in:
Spectroscopy
Received date: 20 December 2016
Revised date: 25 May 2017
Accepted date: 30 May 2017
Please cite this article as: Kenia Dias Pessoa, Willian Toito Suarez, Marina Ferreira dos
Reis, Mathews de Oliveira Krambeck Franco, Renata Pereira Lopes Moreira, Vagner
Bezerra dos Santos , A digital image method of spot tests for determination of copper in
sugar cane spirits, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
(2017), doi: 10.1016/j.saa.2017.05.072
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A digital image method of spot tests for determination of copper in sugar cane
spirits
Kenia Dias Pessoaa, Willian Toito Suareza,*, Marina Ferreira dos Reisa, Mathews de
Oliveira Krambeck Francoa, Renata Pereira Lopes Moreiraa, Vagner Bezerra dos
Santosb
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a
Departamento de Química, Universidade Federal de Viçosa - UFV, Centro de
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Ciências Exatas e Tecnologia, Viçosa, MG, Brasil
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* williants@ufv.br
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ABSTRACT
determination of copper in sugarcane spirit samples is carried out. The digital image
based (DIB) method was applied along with spot test from the colorimetric reaction
employing the RGB color model. For the determination of copper concentration, it was
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used the cuprizone - a bidentate organic reagent - which forms with copper a blue
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chelate in an alkaline medium. A linear calibration curve over the concentration range
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from 0.75 to 5.00 mg L-1 (r2 = 0.9988) was obtained and limits of detection and
quantification of 0.078 mg L-1 and 0.26 mg L-1 were acquired, respectively. For the
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accuracy studies, recovery percentages ranged from 98 to 104% were obtained. The
comparison of cooper concentration results in sugar cane spirits using the DIB method
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differences between both methods, which were performed using the paired t-test in 95%
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of confidence level. Thus, the spot test method associated with DIB allows the use of
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devices as digital cameras and smartphones to evaluate colorimetric reaction with low
waste generation, practicality, quickness, accuracy, precision, high portability and low-
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cost.
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Keywords: digital image analysis, RGB model, sugar cane spirits, copper, spot test.
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1. Introduction
According to Brazilian legislation, sugar cane spirit (cachaça) is the typical and
exclusive denomination for distilled spirit made from sugar cane juice produced in
Brazil with alcoholic graduation from 38% to 48% by volume at 20°C obtained by
distillation of fermented mash of sugar cane juice with peculiar sensory features [1].
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Sugar cane spirit consists primarily of ethanol and water, but also secondary
compounds, such as higher alcohols, acids, esters, aldehydes, sugars, among others,
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which are responsible for characterization and quality of the drink [2].
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The process of sugar cane spirit production is usually conducted in distillers
made of copper, once it presents a better sensory quality in relation to sugar cane spirit
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produced in pot stills made of other materials, such as stainless steel, aluminum and
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porcelain [3]. The use of copper in distillation equipment favors the reduction of acidity
as well as the levels of aldehydes and sulfur compounds which impart unwanted flavor
and odor in the drink. However, during the distillation process in copper stills or during
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the time that the still is not in use, occurs the formation of a compound commonly
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The most known disease due to the accumulation of copper is called Wilson's
manifestations, but also by copper accumulation in the liver and in the corneas [5,6].
ethyl carbamate in sugar cane spirits, which is a potential carcinogen [7]. Thus, the
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spirit must not exceed a concentration of 5 mg L-1. In the European Union, the
Some methods have been described for the determination of copper in alcoholic
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spectrometry [16,17]. Although, the recommended method for copper determination in
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Brazilian distilled beverages is the atomic absorption spectrometry (AAS) using the
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method of standard addition [18].
the development of analytical methods with high sensitivity, robustness, quickness and
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low cost of implementation and maintenance becomes a useful alternative for the
The analytical methods based on spot test of digital images have become
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promising alternatives for the determination of several analytes, since the spot test
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procedures are simple, rapid, practical, inexpensive and employ small quantities of
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chemicals [19–21]. In addition, this method employs moderns and accessible devices,
such as cameras, webcams, scanners and mobile phones with built-in cameras, whose
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resolution and compactability have improved significantly, as well as their costs have
reduced in similar proportion [22,23]. By using the spot test coupled to digital image, it
not easy to obtain representative samples, to bring them to the laboratory, and to
perform analysis, once these are laborious and costly tasks. In addition, handling of
samples can present serious analytical errors by contamination and loss of analytes due
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problems can be avoided employing spot tests-digital image based method in situ
[22,23].
Li et al. [24] developed an integral optical density (IOD) method combined with
the model of response difference of crystallite change (MRDCC) in order to analyze the
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al. [25] employed an iPhone-based digital image colorimeter (DIC), fabricated as a
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portable tool for monitoring tetracycline (TC) in bovine milk, to carry out an analysis
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after pre concentration on C18 SPE (solid phase extraction) sorbent.
The presence of sensors in the image capture devices such as CCD (Charge
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Coupled Device) and CMOS (Complementary Metal Oxide Semiconductor) has
quickness and low cost of implementation. These sensors are able to convert the
intensity of the incident radiation into an analog electrical signal, which is converted to
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a digital value stored in the form of bits and pixels arranged in a matrix, similar to the
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In the RGB system, three matrices are used to store the information. These
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matrices are related to the present colors, red (R), green (G) and blue (B).
This model is used to establish a relationship between the color components and the
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[12,28]. However, as the reflected radiation is part of incident radiation that was not
absorbed, this radiation could be used for analytical purposes [29,30]. The values
relating to responses RGB colorimetric reaction (I) are compared with the values
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acquired from the R, G, or B obtained from the blank. The equation y = -log(I/I0)
cane spirit. This methodology was based on digital image analysis of spot test involving
the reaction between copper ions and the cuprizone that forms a blue chelate, and the
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images captured by a camera containing a CCD type sensor. The method developed can
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be applied to in situ determination of copper concentration in sugar cane spirit, which
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can be important for the quality control, especially for small producers with limited
financial resources. Furthermore, the method allows a fast, simple, low cost and low
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waste generation analysis.
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2. Experimental
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The colorimetric reaction for determination of copper(II) in sugar cane spirit was
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automatic pipettes were used to transfer volumes of reagents and/or samples to the
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porcelain plaque and spot tests were photographed employing a camera Sony Cyber-
For the image capture, it was built a portable simple device with internal lighting
system illustrated in Fig. 1(a). This apparatus consists of a black plastic box of
Emitting Diodes) white light BLUEX 20-100 mA with variable resistors to intensity
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the reproducibility of the acquisition of digital images and minimize the reflection or
shadow effects caused by external light, the device was built using four punctual LEDs
evenly distributed on top of the equipment. Inside the box it was applied a matte black
ink layer to ensure more homogeneous environment. To evaluate the effect of light
intensity on the analytical response, it was employed a luximeter Minipa MLM 1011.
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For the comparative method, the sugar cane spirit samples were analyzed using an
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Agilent Technologies spectrometer Model 240 FS AA.
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2.2. Chemicals and samples
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The solutions were prepared with ultrapure water (resistivity >18.0 MΩ cm)
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obtained from a Millipore Milli-Q system (USA) and all chemical reagents were of
analytical grade. The stock solution of Cu(II) 500 mg L-1 (0.0078 mol L-1) was prepared
mg L-1 (0.0018 mol L-1) was prepared in a solution of ethanol-distilled water 60% (v/v)
and stored at 4° C. The other solutions were obtained by diluting the stock solution in
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The 0.250 mol L-1 phosphate buffer at pH 8.0 was prepared by dissolving
Na2HPO4 and NaH2PO4 in distilled water and stored at room temperature. Stock
solutions of concentration 1.0 × 10-4 mol L-1 of the following dyes: Blue Coomassie
Brilliant, Tartrazine and Direct Red 80 were prepared by dissolving the respective dye
with distilled water, and the other solutions were obtained from dilutions of stock
solutions.
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wavelengths combination in the electromagnetic spectrum in the visible light region that
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arrangement of color such as RGB (Red, Green, Blue) and the channels are correlated
with the absorbed selectively certain wavelengths of light [34,35]. The radiation emitted
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by the white LEDs is composed by a combination of several monochromatic beams that
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can be represented by RGB tridimensional arrangement.
As shown in Figure 1(b), radiation beams arrive at the solution contained in the
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porcelain plaque and part of this radiation is absorbed, and further reflected by the
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color. In fact, if the color blue is displayed by the solution, the channel that has the
highest absorption is red [36]. After the absorption of radiation by the solution of the
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remaining radiation is reflected and reaches at the Bayer filter mosaic, which is a color
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filter array (CFA) for arranging RGB color filters on a square grid of photosensors.
Color is identified by the use of a color filter which allows only one color of light from
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the visible spectrum into each pixel. In CCD cameras, the level of photons recorded is
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converted to a proportional electrical signal. This sensor converts the light intensity
incident on matrices digital used to store the information. The intensities of the
generated color is stored in 256 levels in a scale from 0 to 255 for each primary color
(R, G or B) where 0 is pure black (0 for each one of the 3 primary colors) and 255 is
So, for analytical propose, the images acquired from colorimetric reaction are
decomposed employing a free software Image J in a system of arrays based on the RGB
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model. From this, it is possible to obtain analytical responses related to three channels
for each spot in the porcelain plaque. For the analytical response -log (I/I0) was used,
solution and I0 is the average value acquired from the analytical blank. Thus, the
analytical curve is presented as –log (I/I0) vs. the copper concentration. For this, a
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performed such as the R, G, or B values directly, or its combination as R x G x B
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generating exponential, polynomial or linear behavior versus concentration. However, -
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log (I/I0) is commonly used once it is linearly correlated with the concentration being
very employed for colorimetry and spectrophotometry [30, 37, 38]. By using this
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calculation, it is possible to use a reference value (Blank) and to avoid performing the
subtraction from the analytical signal, being similar to the Lambert-Beer law for
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colorimetry. The signal captured from a digital camera is due to reflective, however, this
signal is correlated with the absorbed signal, and so, the logarithm signal can be used
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employed a luximeter and the light intensity incident varied at five levels: 20, 35, 90,
240 and 980 LUX. To evaluate the effect of sample volume on the analytical response,
it was varied the volume of the solution of the dye Brilliant Blue 1.0 × 10-5 mol L-1 of
100 to 800 µL with 100 µL of increment on the spot. To verify the RGB channels linear
response due to the analyte concentration, analytical curves were constructed employing
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the dyes Brilliant Blue, Tartrazine and Direct Red 80, whose concentration ranges were
tested from 1.00 × 10-6 mol L-1 to 1.00 × 10-4 mol L-1, using the light intensity and the
image for each curve was captured and the coefficient of determination was evaluated.
comparison of two standard curves constructed using Brilliant Blue dye, and the images
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were captured by a camera Sony Cyber-shot DSC-W610 with resolution 14.1
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Megapixels (MP) and also through camera Sony Cyber-shot DSC-S730 with 7.2 MP.
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Assays were performed in replicate (n = 7) with only one image being captured for each
test. The results were compared using the paired t-test with 95% confidence.
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2.5.Copper(II) Determination in Sugar Cane Spirit
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For the copper determination in sugar cane spirit, it was employed the cuprizone,
a bidentate organic reagent, which forms with copper a blue chelate in a slightly
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Insert Figure 2
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would generate a range of suitable colors for screening analysis type. The concentration
of cuprizone was evaluated in four levels using a fixed concentration of Cu(II) (1.25 mg
L-1; 0.0019 x 10-3 mol L-1): 44 (0.16 x 10-3 mol L-1), 88 (0.32 x 10-3 mol L-1), 132 (0.48
x 10-3 mol L-1) and 176 mg L-1 (0.64 x 10-3 mol L-1) all of them with a fixed volume of
100 µL. Furthermore, to verify the effect of the kinetic of reaction on the analytical
response, the reaction was monitored at 1 min intervals for 10 min employing a solution
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of Cu(II) 1.25 mg L-1 (0.0019 x 10-3 mol L-1) at a volume of 400 µL. The analytical
blank was obtained by replacing the Cu(II) solution for distilled water. After reaction
optimization, the volumes were fixed in: 100 µL phosphate buffer pH 9, 400 µL
solution of Cu(II) 1.25 mg L-1 or sample and 100 µL of cuprizone. The tests were
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different proportions of analyte/interferent. The study of the matrix effect was done by
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comparing the parameters of the analytical curve obtained for standard aqueous
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solutions of Cu(II) with the parameters of analytical curve using a sugar cane spirit free
of copper(II). The mean responses were compared using statistical test F (Snedecor) of
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homogeneity of variances and through the paired t test with 95% confidence.
Recovery studies were tested in unaged and aged sugar cane spirit samples
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employing standard addition method using three concentration levels: 0.75; 2.88 and
5.00 mg L-1. The accuracy of the method was evaluated by comparing the results
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obtained by digital analysis method with the reference method (Flame Atomic
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The DIB method was applied for determination of Cu(II) in samples of aged and
unaged sugar cane spirit collected in supermarkets in the cities of Viçosa and Bom Jesus
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do Amparo - Minas Gerais/ Brazil. No treatment of samples was need before the
analysis.
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After preliminary tests, the light intensity was set at 20 LUX due to the greater
the analyte. To verify the effect on the analytical response, volumes of solutions from
400 to 800 µL were used on the spot, and the intensity of the analytical signal remained
nearly constant, with a slight increase until 600 µL. Using 600 µL, an excess of light
“brightness regions” appeared only on the edges of the spot, and thus in the center more
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homogeneous regions were obtained. According to Benedetti et al. [29], the analytical
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response can be affected by sample volume similar to optical path in spectrophotometry.
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In fact, the depth of the vessel is correlated with the absorbance and consequently the
reflected RGB values. Few microliters of the colorimetric reaction generate poor
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sensitivity. However, high volumes generate a great amount of residue. Thus, 600 µL
some solution based on dyes. The linear ranges obtained for the concentration of
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Brilliant Blue, Direct Red 80 and Tartrazine were: 1.75 × 10-5 to 1.00 × 10-4 mol L-1,
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1.00 × 10-6 to 8.35 × 10-5 mol L-1 and 1.00 × 10-6 to 1.00 × 10-4 mol L-1, respectively.
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The coefficients of determination (R2) were obtained exceeding 0.99, what indicated
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that the channels R, G and B linearly respond to these studied concentration range.
range 580-700 nm, 500-580 nm and 400-500 nm, respectively. Therefore, the spectrums
obtained for the dyes were compared with the response obtained by the RGB model
showing agreement results and that the Blue Coomassie Brilliant presents response in
The effect of the camera resolution was evaluated by comparing standard curves
constructed using Brilliant blue dye. The test was done by comparing all analytical
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responses for each concentration level. The 0.50 value t calculated was lower than the
critical t (3.18), indicating that the camera resolution did not influence the analytical
methodology. Thus, low cost photographic cameras and smartphones can be used, being
very attractive and encouraging for small producers to use them for quality control
purposes.
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3.2. Copper(II) determination in sugar cane spirit
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The colorimetric reaction between Cu(II) and cuprizone is a mixture of colors
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and therefore, more than one channel can present a satisfactory response to variations in
the concentrations of the chelate. Thus, R, G and B channels were monitored in order to
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determine which of them has greater sensitivity as a function of the copper(II)
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concentration. The channel R showed a better response, so it was employed for the
determination of copper in the carried out studies. In fact, the red color is exactly the
complementary color from the reaction blue color. Green and blue channel presented
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lower sensitivity than red, but the blue channel presented lower sensitivity than
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of spot tests, it is essential to find the most stable and color gradient - changing in color
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levels. In this regard, different concentrations of cuprizone were tested from 44 to 176
mg L-1. The evaluated cuprizone concentrations were always higher than the range of
For all evaluated levels, a fixed volume of 100 µL of cuprizone solution was
used. For lower concentrations of cuprizone such as 44 and 88 mg L-1, the color
remained almost the same in all spots. In fact, low concentrations of chelant reduce the
formation of the product, and so, lower sensitivity. Therefore, the experiments were
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continued employing the cuprizone solution of 132 mg L-1. For more concentrated
It was evaluated the reaction kinetic of cuprizone and copper ions. The
analytical signal increased up to 7 min of reaction as shown in Fig. 3. After this time,
there was a decrease of the analytical signal, probably due to the low stability of the
generated chelate.
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Insert Figure 3
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After checking the optimal reagent concentrations, volumes used for each
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solution were set as follows: 400 µL Cu(II), 100 µL of phosphate buffer pH 9 and 100
Insert Figure 4
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range from 0.75 to 5.00 mg L-1 using the R channel as shown in Fig. 4. The linearity of
the developed method was verified by calibration curve analysis using the method
named least squares methods (LSM) following the regression equation: −log (I/I0) = -
limits of detection (LOD) and quantification (LOQ) were calculated using the relations
3 × σ/m and 10 × σ/m, respectively, where σ is the standard deviation of ten times blank
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analytical and m the slope of the analytical curve. Thus, the LOD and LOQ were 0.078
Some metallic ions that could be present in sugar cane spirit were tested, as
described by [41] which consequently may form chelates with cuprizone. Previously,
Spectrometry (FAAS) in all sugar cane spirit samples used in this study. The aluminum
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and zinc were found in some samples, however in concentrations below the
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quantification limit. The iron ions were found in only one sample at a concentration
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below the quantification limit. Other metals were not detected in sugar cane spirit
samples. Therefore, the metals analyzed were not considered important in determining
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interfering Cu(II) employing cuprizone as a complexing agent.
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Insert Table 1
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Recovery studies were established in aged and unaged sugar cane spirits in three
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concentration levels: 0.75; 2.88 and 5.00 mg L-1. Recovery percentages ranged from
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98.3 to 104% were obtained. The results were compared with the values described by
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0.1 mg L-1 to mg L-1. Therefore, all the values obtained from the recovery study were
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satisfactory. The analytical curves obtained from aqueous solutions and sugar cane
spirit in the absence of Cu(II) were compared using F test (Snedecor), and it was found
that there are no differences among the variances for the obtained curves.
For comparison of means pairs in each concentration level it was used the paired
t-test with 95% confidence with n = 3. The 1.19 t value was lower than the t critical
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curves. It can be concluded that there were no significant effects of matrices in samples
of sugar cane spirit. In addition to the recovery tests, the accuracy was evaluated by
comparing the results obtained using the method developed by the results provided by
Some samples of sugar cane spirit were analyzed using the proposed method and
the reference method. The results are shown in Table 2. The 1.29 t value calculated was
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lower than the critical t (2.30) for n = 3, therefore, no statistically significant differences
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in the results were generated by both methods at a confidence level of 95%. It can be
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concluded that the six samples of sugar cane spirit analyzed presented copper(II)
concentrations within the limits required by the Ministry of Agriculture, Livestock and
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Supply, except AE11 sample, whose concentration of Cu(II) was approximately eight
Insert Table 2
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In Table 3 some analytical features acquired from DIB were compared to those
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obtained by other methods reported in the literature for determination of Cu(II) in sugar
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Insert Table 3
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4. Conclusions
The method developed for the determination of copper(II) in sugar cane spirit
consumption and waste generation. The device employed for image capture is easy to
build and it uses low cost components such as LEDs, battery and accessible apparatus as
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smartphones or digital camera. In addition, it is versatile, robust and portable, very
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interesting for in situ analysis.
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The digital image method presented good repeatability and robustness to
photography is enough to complete the analytical analysis- analytical curve and sample-
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generating only 600 µL/spot (miniaturization) at 7 min of analysis. Thus, each analysis
could be performed at 35 s. The DIB method presented a good linear range, precision
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performance as the reported voltammetric method. Thus, the spot test with digital
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analytical tool for laboratory with limited financial resource and for quality control in
coupled plasma atomic emission spectroscopy (ICP OES), it showed that all metals
tested were found in concentrations lower than the copper concentration in sugar cane
spirit samples ratifying the obtained results. Finally, the method can be used for
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Acknowledgment
(CNPq).
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References
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[1] Ministry of Agriculture, Livestock and Supply (2005a) Instrução Normativa
n°13, de 30 de junho de 2005. Aprova o Regulamento Técnico para Fixação dos
NU
Padrões de Identidade e Qualidade para Aguardente de Cana e para Cachaça.
Diário Oficial da União, Brasília.
MA
[2] L. Odello, G.P. Braceschi, F.R.F. Seixas, A.A. da Silva, C.A. Galinaro, D.W.
Franco, Avaliação sensorial de cachaça, Quim. Nova. 32 (2009) 1839–1844.
doi:10.1590/S0100-40422009000700029.
D
carvão ativado para remoção de cobre em cachaça, Quim. Nova. 29 (2006) 247–
250. doi:10.1590/S0101-20612008000500014.
AC
[5] P.J. Gow, R. A. Smallwood, P.W. Angus, A L. Smith, A. J. Wall, R.B. Sewell,
Diagnosis of Wilson’s disease: an experience over three decades., Gut. 46 (2000)
415–9. doi:10.1136/gut.46.3.415.
[6] G. Loudianos, J.D. Gitlin, Wilson’s Disease, Semin. Liver Dis. 20 (2000) 353–
364. doi:10.1055/s-2000-9389.
[7] A.J.B. Lima, M.G. Cardoso, L.G. L. Guimarães, J.M. Lima, D.L. Nelson, Efeito
de substâncias empregadas para remoção de cobre sobre o teor de compostos
secundários da cachaça, Quim. Nova. 32 (2009) 845–848. doi:10.1590/S0100-
40422009000400004.
18
ACCEPTED MANUSCRIPT
[8] J Mehlig. Colorimetric Determination of Copper with Ammonia, Ind. Eng. Chem.
Anal. 13 (1941) 533–535. doi: 10.1021/i560096a006
[9] J.C. Souza, A.T.; Toci, M.A.; Beluomini, S.P. Eiras, J. Carlos De Souza, A.T.
Toci, M.A. Beluomini, S. De, P. Eiras, Spectrophotometric Determination of
Copper(II) in Sugarcane Spirit Using 1-(2-pyridylazo)-2-naphthol and a
Homogeneous Ternary Mixture of the Solvents Water, Ethanol and Methyl
Isobutyl Ketone, Rev . Virtual Quim. 8 (2016) 687–701. doi:10.5935/1984-
6835.20160052.
PT
[10] Ministry of Agriculture, Livestock and Supply (2005b) Instrução normativa no
24, de 08 de setembro de 2005. Manual operacional de bebidas e vinagres. Diário
RI
Oficial da União, Brasília.
[11] L.F.S. Caldas, B.B.A. Francisco, A.D.P. Netto, R.J. Cassella, Multivariate
SC
optimization of a spectrophotometric method for copper determination in
Brazilian sugar-cane spirits using the Doehlert design, Microchem. J. 99 (2011)
NU
118–124. doi:10.1016/j.microc.2011.04.008.
[12] J.C. Souza, H.R. Pezza, L. Pezza, A simple and green analytical method for
MA
zinc, lead and copper in sugar cane spirits by anodic stripping voltammetry,
E
[14] P.R. Oliveira, A.C. Lamy-Mendes, E.I.P. Rezende, A.S. Mangrich, L.H.
Marcolino Junior, M.F. Bergamini, Electrochemical determination of copper ions
CE
in spirit drinks using carbon paste electrode modified with biochar, Food Chem.
171 (2015) 426–431. doi:10.1016/j.foodchem.2014.09.023.
AC
[15] M. Bıngöl, G. Yentür, B. Er, A.B. Öktem, Determination of some heavy metal
levels in soft drinks from Turkey using ICP-OES method., Czech J. Food Sci. 28
(2010) 213–216.
[16] T. Capote, L.. Marcó, J. Alvarado, E.. Greaves, Determination of copper, iron
and zinc in spirituous beverages by total reflection X-ray fluorescence
spectrometry, Spectrochim. Acta Part B At. Spectrosc. 54 (1999) 1463–1468.
doi:10.1016/S0584-8547(99)00082-8.
[17] A.C. Noble, B.H. Orr, W.B. Cook, J.L. Campbell, Trace elements analysis of
wine by proton-induced x-ray fluorescence spectrometry, J. Agric. Food Chem.
19
ACCEPTED MANUSCRIPT
PT
doi:10.1016/j.foodcont.2009.08.006.
[21] S. Paciornik, A. V. Yallouz, R.C. Campos, D. Gannerman, Scanner image
RI
analysis in the quantification of mercury using spot-tests, J. Braz. Chem. Soc. 17
SC
(2006) 156–161. doi:10.1590/S0103-50532006000100022.
[22] J.M. Prats-Montalbán, A. Juan, A. Ferrer, Multivariate image analysis: A review
NU
with applications, Chemom. Intell. Lab. Syst. 107 (2011) 1–23.
doi:10.1016/j.chemolab.2011.03.002.
[23] B.G. Botelho, L.P. Assis, M.M. Sena, Development and analytical validation of a
MA
simple multivariate calibration method using digital scanner images for sunset
yellow determination in soft beverages, Food Chem. 159 (2014) 175–180.
D
doi:10.1016/j.foodchem.2014.03.048.
[24] Q. Li, H. Li, Q. Gao, The influence of different sugars on corn starch
E
colorimeter for detecting tetracycline in milk, Food Chem. 184 (2015) 23–29.
doi:10.1016/j.foodchem.2015.03.089.
AC
[26] R.C. Sena, M. Soares, M.L.O. Pereira, R.C.D. da Silva, F.F. do Rosário, J.F.C. da
Silva, A simple method based on the application of a CCD camera as a sensor to
detect low concentrations of barium sulfate in suspension, Sensors. 11 (2011)
864–875. doi:10.3390/s110100864.
[27] P. M. Santos, E.R. Pereira-Filho, Digital image analysis – an alternative tool for
monitoring milk authenticity, Anal. Methods. 5 (2013) 3669.
doi:10.1039/c3ay40561c.
[28] V.H.M. Luiz, L.M. Saraiva, Â.P. Martins, L. Pezza, H.R. Pezza, V.H.M. Luiz,
L.M. Saraiva, Â.P. Martins, L. Pezza, H.R. Pezza, Rapid Determination of Lead
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PT
Digital Color Image Analysis and Colored Solutions, J. Chem. Educ. 83 (2006)
644. doi:10.1021/ed083p644.
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[31] M.B. Lima, S.I.E. Andrade, I.S. Barreto, L.F. Almeida, M.C.U. Araújo, A digital
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image-based micro-flow-batch analyzer, Microchem. J. 106 (2013) 238–243.
doi:10.1016/j.microc.2012.07.010.
NU
[32] L.P.S. Benedetti, V.B. Santos, T.A. Silva, E.B. Filho, V.L. Martins, O. Fatibello-
Filho, A digital image analysis method for quantification of sulfite in beverages,
Anal. Methods. 7 (2015) 7568–7573. doi:10.1039/C5AY01372K.
MA
[33] D. Damasceno, T.G. Toledo, M.S. Godinho, C.P. Da Silva, S.B. De Oliveira,
A.E. De Oliveira, Análise multivariada de imagens na química: um experimento
D
[37] K. Cantrell, M.M. Erenas, I. de Orbe-Payá, L.F. Capitán-Vallvey, Use of the Hue
Parameter of the Hue, Saturation, Value Color Space As a Quantitative
Analytical Parameter for Bitonal Optical Sensors, Anal. Chem. 82 (2010) 531–
542.
[38] L. Byrne, J. Barker, G. Pennarun-Thomas, D. Diamond, S. Edwards, Digital
21
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Determinação de Cobre e Zinco em cachaça por espectrometria de absorção
atômica com chama usando calibração por ajuste de matriz, Rev. Anal. 17 (2005)
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48–50.
SC
[42] N.M. Brito, O.D.P.A. Junior, L. Polese, M.L. Ribeiro, Validação De Métodos
Analíticos: Estratégia E Discussão, Pestic. R.Ecotoxicol. E Meio Ambient. 13
NU
(2003) 129–146. doi:http://dx.doi.org/10.5380/pes.v13i0.3173.
[43] S.A. do N. Rocha, A.F. Dantas, H.V. Jaeger, A.C.S. Rocha, E. dos S. Leão, M.R.
Gonçalves, Spectrofotometric determination of copper in sugar cane spirit using
MA
biquinoline in the presence of ethanol and Triton X-100, Spectrochim. Acta Part
A. 71 (2008) 1414–1418. doi:10.1016/j.saa.2008.04.013.
[44] D.A. Costa, R.M. Takeuchi, A.L. Santos, Direct Quantification of Cu2+ in Cachaça
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Using a Solid Paraffin- Based Carbon Paste Electrode Chemically Modified with
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doi:10.1016/j.microc.2010.02.011.
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FIGURE CAPTIONS
Fig. 1. (a) System built for the image capture (b) It indicates the interaction
phenomenon of electromagnetic radiation with a solution at porcelain plaque and how
the reflected light reaches the digital camera detector.
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Fig. 2. Scheme of chelate forming reaction between copper (II) ions and cuprizone.
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Fig. 3. Intensity values in function of reaction time. Concentration of copper equivalent
to 1.5 mg L-1 (n = 3).
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Fig. 4. Digital image (a) obtained for porcelain plaque containing spot test reactions at
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different copper(II) concentration levels: (1) 0.0, (2) 0.75, (3) 1.25, (4) 2.50, (5) 3.75,
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FIGURES
Figure 1
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Figure 2
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Figure 3
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Figure 4
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TABLES
Table 1. Selectivity study for determination Cu(II) in sugar cane spirits (n=3).
Ratio
Interferent Relative Error (%)
Cu(II):Interferent
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a
1:0.1 - 9.94
Lead (II)
1:0.5 - 6.46
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1:1 + 6.02
1:1 + 5.52
Iron (II)
1:5 - 6.73
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1:10 - 12.4
1:1 - 7.13
Iron (III)
1:5 - 9.85
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1:10 - 10.8
a
1:0.01 - 5.53
Nickel (II)
1:0.1 - 12.1
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1:0.5 - 10.1
1:1 - 8.5
Manganese (II)
1:5 - 9.3
1:10 - 15.2
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1:1 + 8.2
Aluminum (III)
1:5 + 7.4
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1:10 - 4.5
1:1 + 0.13
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Zinc (II)
1:5 - 1.79
1:10 - 1.52
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Ratio 1:1 showed an intense interference
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a
ANE4 1.03 ± 0.11 1.02 ± 0.03 +1.01
a
ANE5 <LQ <LQ -
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ANE6 1.78 ± 0.15 1.93 ± 0.01 -7.61
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ANE7 <LD <LD -
b
AE8 2.99 ± 0.18 2.79 ± 0.01 +7.16
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b
AE9 1.86 ± 0.34 1.97 ± 0.02 -5.41
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AE10 3.14 ± 0.21 3.41 ± 0.03 -8.03
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AE11 40.60 ± 0.40 43.30 ± 0.04 - 6.26
a b
ANE = unaged sample. AE = aged sample.
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Gin
Voltametry Sugar cane spirit 0.3 to 5.0 0.11 0.33 1.9 [44]
Flame atomic absorption Sugar cane spirit 0.10 to 4.0 0.015 0.050 6.9 [45]
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spectrometry (FAAS)
Digital Imaging Sugar cane spirit 0.25 to 5.0 0.078 0.26 5.9 Presente
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method
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Values expressed in mg L-1
LR= Linear range; LOD= Limit of detection; LOQ= Limit of quantification; RSD= Relative Standard
Deviation (medium).
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Graphical Abstract
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Highlights
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- A portable system with cheap materials to obtain images from a digital camera was
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developed
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- The system was employed in the determination of copper(II) in sugar cane spirits
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(cachaça)
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- The developed method has some economic and environmental benefits, since it has
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- The fast response with ca 35 s/spot, low-cost and handle-easy devices are very
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