Accepted Manuscript

A new sensitive photometric procedure for the determination of

sulfate in fuel ethanol without sample preparation exploiting a
flow-batch strategy

Manoel J.A. Lima, Marcos Y. Kamogawa, Boaventura F. Reis

PII: S0026-265X(18)31520-0
DOI: https://doi.org/10.1016/j.microc.2018.12.009
Reference: MICROC 3513
To appear in: Microchemical Journal
Received date: 1 November 2018
Revised date: 7 December 2018
Accepted date: 7 December 2018

Please cite this article as: Manoel J.A. Lima, Marcos Y. Kamogawa, Boaventura F.
Reis , A new sensitive photometric procedure for the determination of sulfate in fuel
ethanol without sample preparation exploiting a flow-batch strategy. Microc (2018),
https://doi.org/10.1016/j.microc.2018.12.009

This is a PDF file of an unedited manuscript that has been accepted for publication. As
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A new sensitive photometric procedure for the determination of sulfate in

fuel ethanol without sample preparation exploiting a flow-batch strategy

Manoel J.A. Lima1, Marcos Y. Kamogawa2, Boaventura F. Reis*1

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1 Center for Nuclear Energy in Agriculture, University of São Paulo, Piracicaba,

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SP, 13400-970, Brazil
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2 University of São Paulo - College of Agriculture Luiz de Queiroz, Piracicaba,

SP, 13418-900, Brazil

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*corresponding author:

reis@cena.usp.br
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Abstract

A simple, accurate, and fast flow-batch procedure employing photometric

detection for the determination of sulfate in fuel ethanol was developed. After the

formation of soluble barium sulfate in alcoholic medium, the remaining barium

forms a product with dimethylsulfonazo III (DMS), the absorbance of which was

monitored at 655 nm directly in the reaction chamber. The proposed procedure

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does not require any sample treatment such as dilution. Under the optimized

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conditions, the technique offers the advantages of low waste generation (less

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than 5 mL), sampling throughput of 35 h-1, linear response from 0.1−1.5 mg L-1

sulfate, and a limit of detection (95%) and coefficient of variation (n = 6) of 48 µg

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L-1 and 1%, respectively. The accuracy was assessed by comparison of results

with those obtained by ion-chromatography; no significant difference was

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observed at the 95% confidence level.

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Keywords: Fuel, Bioethanol, Barium sulfate, Spectrophotometry, Green

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chemistry, Arduino due

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1. Introduction

Ethanol is the most economically and environmentally attractive biofuel.

The high octane power, low cost of production, and renewability of the resource

make ethanol a promising fuel for partial or total replacement of petroleum fuels

[1-5]. In many countries, anhydrous ethanol is mixed with gasoline (ca. 10% (v/v))

[6,7]. In Brazil, the addition of anhydrous ethanol (AE) to gasoline is mandatory

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(27% (v/v)) [8]. Furthermore, hydrous ethanol (HE) is widely used as a fuel for

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automotive vehicles [9]. Brazil is a pioneer in the use of this renewable energy

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source, thus fulfilling the guidelines for environmentally friendly fuels [10].

Despite its environmental advantages, HE must be subjected to rigorous

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quality control owing to inorganic constituents such as Cl-, SO −2 + 2+
4 , Na , Cu , and
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Fe3+ derived from the raw material and production, storage, and transport

processes. When present in high concentrations, these ions may affect the
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engine performance. These chemical species can form salts and sediments that
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can cause damage and induce corrosion [7,11,12]. In view of this, quality control
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parameters were established by the National Regulatory Agency for Oil, Natural
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Gas, and Biofuels (ANP) through the NBR10894/2012 normative [13], which

established ion chromatography as the methodology for the determination of

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sulfate and chloride. This procedure presents adequate precision and robustness

for the analysis of fuel ethanol, but the high cost of operation and the long time

for analysis are potential drawbacks when high throughput is required. In

attempts to overcome these drawbacks, alternative methods have been

proposed based on capillary electrophoresis [14,15], conductometric titration

[16], X-ray fluorescence [17], and spectrophotometry (UV-vis) [18,19].

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Generally, in these procedures, samples of the fuel are subjected to

combustion or drying, with subsequent recovery of the analytes in aqueous

solution [14,15,19]. These sample treatments are employed to eliminate matrix

effects (solvent evaporation) and for pre-concentration of the analytes. Another

recently employed strategy comprises the indirect determination of sulfate,

exploring the formation of barium sulfate, subsequent separation of the

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precipitate, and determination by X-ray fluorescence by monitoring the barium

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line [17]. Nevertheless, these alternative methods are also time consuming.

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There is a consensus that steps such as combustion, solubilization, and filtration

are sources of errors and also reduce the analytical throughput.

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In this report, we describe a new procedure for the determination of sulfate

in fuel ethanol without sample pre-treatment. The spectrophotometric procedure

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is based on the reaction between sulfate and barium with the formation of soluble

barium sulfate (in alcoholic medium) and subsequent reaction of the remaining
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barium with dimethylsulfonazo III, forming a compound that is

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spectrophotometrically monitored at 655 nm [18]. The procedure is automated

using a flow-batch approach [20,21] controlled by an Arduino due board [22,23].

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2. Experimental

2.1. Reagents and solutions

All solutions were prepared in ultrapure water (resistivity >18.2 M cm).

Analytical grade chemicals were acquired from Merck (Germany), except for
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dimethylsulfonazo III (DMS), which was acquired from Tokyo Chemical Industry,

Japan.

Stock solutions (20.0 mmol L-1) of barium chloride dihydrate (BaCl₂.2H₂O),

2.0 mol L-1 nitric acid (HNO3), 50 mmol L-1 potassium nitrate (KNO3) and 15 mmol

L-1 dimethylsulfonazo III (DMS; C24H20N4O14S4) were prepared in water. Reagent

solution (R1) comprising 1.0 mmol L-1 BaCl2 was prepared in 50 mmol L-1 HNO3

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solution. Reagent solution (R2) comprising 1.0 mmol L-1 DMS and 1.0 mmol KNO3

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was prepared by dilution of the stock solutions in absolute ethanol. A 500 mg L-1

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stock solution of sulfate was prepared using potassium sulfate that was

previously dried in an oven (110 °C) for 2 h. Working solutions (0.0−2.0 mg L-1)
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were prepared by dilution in absolute ethanol.
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Evaluation of the potential interfering species was performed using

solutions of Ca(NO3)2, Mg(NO3)2, Na2SO4, Cu(NO3)2, Fe(NO3)3, and acetic acid;

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using a 0.5 mg L-1 sulfate solution in absolute ethanol as a reference.

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Samples of ethanol fuel were supplied by several ethanol fuel producers

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in São Paulo State (Brazil). The samples were analyzed without any previous
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treatment. Samples with a concentration greater than the working range were

diluted with absolute ethanol.

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2.2. Equipment and accessories

The fluid handling setup consisted of three compact peristaltic pumps

(Welco Co., Ltd., Tokyo, Japan), two solenoid pumps (25 µL per pulse; Bio-Chem

Valves Inc., Boonton, NJ, USA), and a tree-way solenoid valve (NResearch, USA,

100 psi). The detection system was assembled using a flow batch chamber
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(made of borosilicate glass, 50 mm height and 10 mm in diameter), a magnetic

stirring bar, a radiation source (tungsten lamp), and a UV–vis USB-4000

spectrometer (Ocean Optics, Dunedin, FL, USA). The flow-lines comprised

Teflon tubes (0.8 mm i.d.).

Control of the fluid handling setup was performed using an Arduino Due

board furnished with peripheral interfaces, which was assembled as described in

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the Supplementary Material Fig. 1s. (Supporting Information), including the

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software algorithm.

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2.3. Flow-batch diagram and procedure
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The analytical module depicted in Fig. 1 was designed based on the flow-

batch strategy [21], and was controlled with an Arduino Due microcontroller.
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The procedure comprises four steps carried out under continuous stirring:
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(i) filling the channels with the reagent solutions (P1, P2, and PB1) and
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subsequently cleaning the chamber by powering pumps PB2 and PB3 both with
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flow rate of 200 µL s-1; (ii) a sampling stage where pumps P1 (25 µL per stroke)

and PB1 (flow rate 208 µL s-1) are used to inject the reagent (R1) and sample or
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standard into the chamber (GC), respectively, with a delay time of 20 s prior to

the next step; (iii) injection of reagent R2 solution into the reaction chamber by

switching on mini-pump P2, followed a delay time of 10 s for monitoring the

compound formed; (iv) a cleaning step carried out by sequentially switching on

pumps PB3 to empty the GC, PB2 to wash with water, and PB3 again to empty.

Afterwards, the system repeats the actions from the second step in order perform

the number of replicates programmed. When the standard solution or sample is

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replaced, the valve (V1) is switched on to wash the flow-line, diverting the stream

towards the waste.

[Insert Fig 1 here]

3. Results and discussion

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3.1. Preliminary studies

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Preliminary studies were performed to obtain spectral information

concerning the reagent solutions. The results followed trends similar to those
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found in the literature [18,19]. The procedure is based on the formation of barium

sulfate that is soluble in alcoholic medium (solubility: 2 x 10-9 M). The remaining
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barium ions form a complex with dimethylsulfonazo III (DMS) (Fig. 2), and owing

to the absorbance decreased while sulfate concentration increased. In this first

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study, the reagent solutions were prepared in 50% (v/v) ethanol and the results
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are shown in Fig. 2. Additional assays showed that the blank absorbance

increased with increasing ethanol concentration. This effect was exploited to

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develop the current procedure for the determination of sulfate in ethanolic

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medium (>90%) [24,25]. The absorbance of the product (DMS-Ba) was monitored

at 655 nm and the optimizations were done by univariate assays. As the

development of gas bubbles is common in the reaction of ethanol in a water

medium, a setup module based on the flow-batch strategy was used to prevent

this drawback.

[Insert Fig 2 here]

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3.2. Effect of ethanol concentration

The ethanol concentration was evaluated from the analytical response by using

solutions of 1.0 mg L-1 sulfate and the corresponding analytical blank. The ethanol

concentration was varied from 30.0 to 99.9% (v/v), yielding the results shown Fig.

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3. As demonstrated, the signal of the blank increased with the ethanol

concentration, presenting a linear trend (r = 0.978). However, for the standard

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solutions, there was a slight increase in the signal magnitude up to 50% (v/v),

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after which the signal remained practically constant up to 70% (v/v), followed by

a decrease in the absorbance from 60% to 80% (v/v), and the signal remained
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practically constant for higher concentrations. This result is quite different from
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that presented at the Ref. 18, where it was pointed out that a dilution with water

at least 50% was required to generate a mensurable signal. Comparing the signal
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obtained with 50% and 99.9% (v/v) ethanol, the difference between the blank and
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the standard signal was about 41%, indicating a significant increase in the
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sensitivity of the procedure. Based on these results, for further assays, the

standards of sulfate were prepared in ethanol 99.9%.

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Besides the effect on the molar absorptivity in DMS, the high concentration

of ethanol (ca. 99% (v/v)) promoted high solubility of barium sulfate (solubility: 2

x 10-9 M) [26], making it unnecessary to use cleaning solutions. Only water was

used during the cleaning steps.

[Insert Fig 3 here]

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3.3. Effect of reagent volume

In order to render the procedure more practical and easily, reagents R1

(1.0 mmol L-1 BaCl2 in HNO3) and R2 (1.0 mmol L-1 DMS and KNO3) were added

by the different devices. In this study, the time for barium sulfate formation and

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DMS-Ba were 30 and 15 s, respectively. PB1, which controls addition of the

sample, was switched on for 15 s (flow rate = 208 µL s-1). The experiments were

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conducted under continuous stirring (600 rpm).

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The reaction exploited herein is dependent on the barium concentration
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because it is an indirect determination; thus, the first experiment was carried out

to verify the barium response range in relation to DMS. The number of pulses of
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reagent R1 was varied from 0 to 5 (0 at 125 µL), while the injection of reagent R2

(150 µL, ca. 48 µmol L-1) was kept constant at six pulses. Fig. 4 shows the
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analytical response of the blank and sulfate standard with 0.7 mg L-1 sulfate.
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A linear response was observed (Fig. 4) for up to 75 µL of barium (ca. 24

µmol L-1), and the blank absorbance was about 1.7 under this condition.
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Therefore, the ensuing studies were conducted using three pulses of reagent R1

and six pulses of reagent R2. Under these conditions, there was a good
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compromise condition, meeting both the limits of detection and the linear

response range of the DMS-Ba complex.

[Insert Fig 4 here]

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3.4. Acidity effect

The effect of the acidity was monitored by varying the concentration of

nitric acid solution (R1) in the range of 5 to 100 mmol L-1. The figures of merit are

summarized in Table 1. The results demonstrate that nitric acid concentrations

higher than 10 mmol L-1 provide a suitable medium for formation of barium sulfate

in ethanol. For further studies, the solution R1 was prepared in 50 mmol L-1 HNO3.

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Higher acidity did not provide any further improvement in the figures of merit, but

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it is convenient to work under more acidic conditions to avoid interference from

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carbonates and phosphates. Hydrochloric acid (50 mmol L-1) was also evaluated,

providing similar results; however, the sensitivity was about 5% lower.

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[Insert Table 1 here]

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3.5. Time interval for formation of barium sulfate

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The formation of barium sulfate in aqueous medium is slow and depends

on factors such as the presence of excess barium and the acidity of the medium.
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Considering its high solubility in ethanol medium, the time required for formation
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of barium sulfate was determined by using sulfate standard solutions with

concentrations of 0.0, 0.3, 0.5, and 1.0 mg L-1. The results shown in Fig. 5 indicate

that after 10 s, there was no significant difference in the absorbance, and

extending the time up to 50 s produced no variation in the signal magnitude, thus

indicating the high stability of the products formed by the remaining barium ions

with DMS, characterized by an excellent linear relationship (R2 = 0.999). These

assays were carried out by setting the time for the reaction of DMS with barium
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ions to 15 s. Based on these results, the time for barium-sulfate formation, and

as well as for the DMS reaction, was maintained at 15 s for the further assays.

[Insert Fig 5 here]

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3.6. Effect of surfactants and KNO3

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The influence of surfactants was evaluated using 1% (m/v) Tween 80,

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Tergitol-NP9, polyethylene glycol (PEG), polyvinyl alcohol (PVA), and

cetyltrimethylammonium bromide (CTAB) solutions. The PEG, CTAB, and Tween

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surfactants presented a good linear correlation (r > 0.999, n = 5), and angular

coefficients of 0.568, 0.550, and 0.542, respectively. The PVA and Tergitol
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surfactants did not present a linear correlation. The analytical curve achieved

without surfactants presented a linear response (r > 0.999, n = 5) and an angular

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coefficient of 0.620. Therefore, the remaining studies were performed without

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surfactants, thus simplifying preparation of the reagent solutions, thereby

minimizing the generation of effluents and improving the environmental

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sustainability of the proposed procedure.

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The use of potassium nitrate is recommended in order to maintain the ionic

strength [25]; therefore, the possible influence of this compound was evaluated

by performing assays with sulfate standard solutions (0 to 1.5 mg L-1) with and

without 10 and 30 mmol L-1 KNO3. All curves presented a good linear correlation

(r > 0.992) and reproducibility. However, the curves obtained with 10 and 30 mmol

L-1 KNO3 presented angular coefficients of 7 and 10%, respectively, which are
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higher than that achieved without KNO3. Therefore, for the further studies, the

DMS solution was prepared with 10 mmol L-1 KNO3.

3.7. Effect of potential interferents

The selectivity of the procedure in the presence of potentially interfering

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chemical species (Na+, Ca2+, Mg2+, Cu2+, and Fe3+) was evaluated (using

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concentrations higher than that established by the regulatory agency [27]) in the

presence of 1.0 mg L-1 of sulfate. A signal difference of ± 5% was taken as the

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criterion for identifying interference. For Na+ and Fe3+ ions, the tolerance was 10
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times the sulfate concentration, whereas for Mg2+ and Ca2+, the tolerance was 4

times the concentration, and for Cu2+ it was two times higher. In fuel ethanol, the
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concentrations of Mg2+, Ca2+, and Cu2+ are ca. 50-fold lower than the assayed

concentrations.
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3.8. Comparison of analytical performance

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Table 2 presents a summary of the analytical features of the methods

available in the literature for sulfate determination in fuel ethanol. Three of these
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procedures are based on the reaction with barium, [17-19] and compared with

the present procedure, the linear response range and the limit of detection are

similar, but the sensitivity of the current procedure is higher. Moreover, the low

volume of effluent generated and the non-requirement for sample treatment are

additional advantages of the current technique. In the cited procedures, prior to

analysis, the samples were subjected to combustion [19], gravimetric

precipitation [17], or dilution [18]. In the last case, some samples presented
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turbidity when diluted with water at a ratio higher than 30% (v/v), probably due to

the presence of markers, additives, and/or excess hydrocarbons.

The procedures employing capillary electrophoresis (Table 2) [14,15]

presented good analytical characteristics (e.g., low detection limit and effluent

generation); nevertheless, these procedures use a sample combustion step to

eliminate the sample matrix; making them time consuming and more prone to

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contamination.

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[Insert Table 2 here]
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3.9. Analytical characteristics and application
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Using the optimized conditions, the system presented a linear response

0.1 to 1.5 mg L-1 (eq: Abs = -0.621 × C (mg L-1) + 1.841); n = 6; R2 = 0.999, a
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coefficient of variation <1.0%, and a limit of detection (3*σ) of 48.0 µg L-1. In

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addition, the system is environmentally friendly, consuming about 10 µg of

barium, 107 µg DMS, and 3.12 mL sample per determination. Including the
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washing steps, the total effluent generated was less than 5.0 mL. Fig. 6 shows
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the record profile of the photometer readout, where we can deduce a sampling

throughput of thirty-five determinations per h-1 with good repeatability of the

measurements.

[Insert Fig 6 here]

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Under these conditions, a set of fuel ethanol samples was analyzed by

applying the proposed procedure and the results were compared with those

obtained by ion chromatography (ANP 10894) [13]; the results are shown in Table

4. Applying the student t-test to the results, an agreement at the 95% confidence

level was observed. In addition, a linear correlation of 0.985 between the results

of the proposed method and those of the official methodology was also obtained.

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[Insert Table 3 here]

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4. Conclusions
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In this study, a robust, practical, fast, and sensitive system for the

determination of sulfate in fuel ethanol was proposed. Stages of sample

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preparation, such as combustion/drying, precipitation, and/or even simple

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filtration, are not necessary in the present approach. No drawbacks concerning

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the sample matrix were observed. The flow-batch strategy proved to be highly

versatile, allowing the development of a highly robust analytical procedure,

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implemented using a cost-effective setup. Automation of the process was

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performed using free code, as described in the Supplementary Material. The

analytical module assembled with compact mini-pumps afforded versatility as

well as portability, allowing its use for in situ measurements. Finally, the current

procedure presents higher sensitivity compared with the existing analytical

procedures, negligible generation of hazardous effluent, and a suitable working

range for fuel ethanol samples.

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Supporting Information

Control of the fluid handling setup using an Arduino Due board furnished

with peripheral interfaces and software algorithm.

Acknowledgments

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The authors are grateful for the financial support provided by the Brazilian

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funding agencies CNPq (Conselho Nacional de Desenvolvimento Científico e

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Tecnológico) (proc: 165478/2015-2; 309036/2016-0), CAPES (Coordenação de

Aperfeiçoamento de Pessoal de Nível Superior), FAPESP (Fundação de Amparo

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à Pesquisa do Estado de São Paulo) (proc. 2011/23498-9), and INCTAA

(Instituto Nacional de Ciências e Tecnologias Analíticas) (proc. CNPq

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573894/2008-6).
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[26] E. Suito, K. Takiyama, Formation and Aging of Precipitates. III. Electron

Microscopic Studies on Barium Sulfate Precipitates in Aqueous Alcohol, B.

Chem. Soc. Jpn. 28 (1955) 305−307.

[27] Agência Nacional do Petróleo, Gás Natural e Biocombustíveis, Resolution

Nº 19, of April 15, 2015.

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Table 1. Comparison of the figures of merit as a function of the acidity of the

medium

HNO3 (mmol L-1) Slope Detection limit r

5 0.563 0.124 0.9680

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10 0.595 0.089 0.9995

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30 0.601 0.088 0.9949

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50 0.605 NU 0.087 0.9961

100 0.597 0.088 0.9952

Analytical curve of sulfate for 0.2 to 1.5 mg L-1 (n = 5) in ethanol.

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Table 2. Analytical features of procedures for the determination of sulfate in ethanol fuel samples

Procedure Limit of Coefficient Linear Barium DMS Consumption Reference

detection of response consumption (µg)
(mg L−1) variation (mg L−1) (µg)

Evaporation of ethanol with subsequent 0.08

(%)
0.8 – –
P T – [14]
recovery of the analyte with water.
Detection: CE-CCD
R I
Evaporation of ethanol with subsequent
recovery of the analyte with water. (mg kg )
Detection: CE-UV detectionii
0.027
-1
<0.5 0.2–4.0
-1
(mg kg )
S C – – [15]

DBS-Ba colorimetric reaction

presence of surfactant and buffer with
in 0.14 2.0 0.45–6.50

N U 0.09 800 [18]

50% sample dilution. Detection: UV-vis

Precipitation of the analytes as barium
sulfate, followed by filtration through a
0.03 5.9

M A
0.05–2 12.4 – [17]

paper filter and direct measurement on

the filters using barium lines. Detection:
EDXRF spectrometry
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Pre-treatment by combustion and
subsequent recovery of the analyte with
P T
0.27 <2.5 0–10 0.0015 0.0093 [19]

water. DMS-Ba colorimetric reaction was

monitored by a flow-based system.
Detection: UV-Vis
C E
A C
Analysis of the fuel without pre-treatment
in a flow-batch system exploring the
reaction of the remaining barium with
0.048 1.0 0.1–1.5 0.01 0.107 This work

DMS. Detection: UV-Vis

CE-CCD: Capillary electrophoresis with contactless conductivity detection; EDXRF: Energy dispersive X-ray fluorescence; UV-vis:
Ultraviolet-visible spectrophotometry; DBS-Ba: dibromosulfonazo III–barium; ii: 10-fold pre-concentration.
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Table 3. Comparison of results for determination of sulfate in ethanol fuel

Sample Proposed procedure Reference procedure[13]

(mg kg-1)

1 0.878 ± 0.002 0.846 ± 0.03

2 0.104 ± 0.002 0.095 ± 0.03

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3 0.076 ± 0.037 0.080 ± 0.05

4 1.147 ± 0.006 0.956 ± 0.04

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5 0.194 ± 0.031 0.164 ± 0.03

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6 0.149 ± 0.016 0.138 ± 0.03

7 0.396 ± 0.011 0.308 ± 0.01

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8 0.242 ± 0.019 0.275 ± 0.01

9 0.342 ± 0.013 0.395 ± 0.03

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10 1.068 ± 0.018 1.118 ± 0.04

11 0.131 ± 0.005 0.145 ± 0.05

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12 0.383 ± 0.063 0.367 ± 0.03

PT

13 0.588 ± 0.084 0.631 ± 0.03

Results are average of three consecutive measurements.

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Figure captions

Fig. 1. Flow batch analysis module for the determination of sulfate in fuel ethanol.

P1 and P2 are the solenoid pumps; PB1, PB2, and PB3 are the compact peristaltic

pumps; V1 is the solenoid valve (three-way); GC is the glass chamber. OFR and

OFD are optical fiber cables coupled to the tungsten light source and miniature

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spectrometer (Ocean Optics, USB4000-UV-VIS), respectively; b is the magnetic

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bar; MS is the magnetic stirrer. Bottles R1 and R2 contain the reagent solutions,

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as previously described. S is the standard/sample of sulfate. W are the waste

bottles.
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Fig. 2. Absorption spectra of DMS-Ba in (a) absence and (b) presence of sulfate

in ethanol; (c) only DMS in ethanol.

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Fig. 3. Effect of ethanol concentration on the analytical response of DMS-Ba

reagent in the (a) absence and (b) presence of 1.0 mg L -1 sulfate.

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Fig. 4. Effect of volume of barium on the analytical response. (a) Blank and (b)

0.7 mg L-1 sulfate.

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Fig. 5. Temporal response for reaction; a, b, c, and d correspond to sulfate

concentrations of 0.0, 0.3, 0.5, and 1.0 mg L-1 in ethanol. The inset shows the

linear response after 10 s of reaction.

Fig. 6. Typical records of the measurements. From right, increasing sulfate

PT
concentrations in ethanol.

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Fig. 1
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1.5
a

b
Absorbance 1.0

0.5 c

PT
0.0
550 600 650 700

RI
 (nm)
Fig. 2

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1.8

a
Absorbance 1.5

1.2 b

PT
0.9

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0.6

SC
0.3
20 30 40 50 60 70 80 90 100

Ethanol concentration % (v/v)

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Fig. 3
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2.0

1.8

1.6

a
Absorbance 1.4

1.2

1.0 b

PT
0.8

0.6

RI
0 30 60 90 120

Volume of BaCl2 (L)

Fig. 4

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1.8

1.6 a
b
1.4
c
1.2
d
Absorbance

1.0

0.8
1.5

Absorbance
0.6

PT
0.4 1.2

0.2
0.0 0.2 0.4 0.6 0.8 1.0

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-1
Sulfate concentration (mg L )
0.0
0 10 20 30 40 50

Time for reaction (s)

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Fig. 5
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2.0
0
0.2
1.6
0.6
0.9
D

1.2
Absorbance

1.2 1.5
PT

0.8
CE

0.4
AC

0.0
0 500 1000 1500

Time / s

Fig. 6
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Graphical abstract
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Highlights

- Novel procedure for sulfate determination in fuel ethanol without sample treatment

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- Miniaturized and cost-effective system for point-of-care determination of sulfate

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- Highly sensitive and robust procedure implemented with a flow-batch setup
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- Exploitation of DMS-Ba color bleaching by soluble BaSO4 formation in ethanol
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- It meets green chemistry guidelines concerning to reagent use and waste generation
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