Microchemical Journal 146 (2019) 645–649

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Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Feasibility of pyrohydrolysis as a clean method for further fluorine T

determination by ISE and IC in high purity nuclear grade alumina
Lucelia Hoehnea, Rochele S. Picolotob, Michele S.P. Endersb, Gabriel T. Druzianb,
Edson I. Mullerb, Erico M.M. Floresb,
⁎

a
Universidade do Vale do Taquari – Univates, 95914-014 Lajeado, RS, Brazil
b
Departamento de Química, Universidade Federal de Santa Maria, 97105-900 Santa Maria, RS, Brazil

ARTICLE INFO ABSTRACT

Keywords: In this work, a method based on pyrohydrolysis of high purity nuclear grade alumina and subsequent F de-
Nuclear grade alumina termination by ion chromatography (IC) and ion selective electrode (ISE) was developed. After pyrohydrolysis, F
Fluorine determination was absorbed in a suitable solution (50 mmol L−1 (NH4)2CO3, 50 mmol L−1 NH4OH, and also water were
Pyrohydrolysis evaluated). Using the selected conditions, it was possible to digest a high sample mass (500 mg) in only 10 min.
Ion chromatography
The following analytical parameters were evaluated: pyrohydrolysis temperature (550 to 1050 °C), time of re-
Ion selective electrode
action (2.5 to 20 min), air flow-rate (0.1 to 0.4 L min−1), water flow-rate (0.1 to 1.0 mL min−1), and the use of
Fluorine in alumina
V2O5 (200 mg), as an auxiliary reagent. Quantitative F recoveries were obtained using air and water flow-rates
pumped through the reactor at 0.2 L min-1 and 0.5 mL min−1, respectively. Only water was required as absorbing
solution and the use of V2O5, generally recommended for inorganic matrices, was not necessary. Detection limits
of 2.0 and 3.6 μg g−1 using IC and ISE, respectively, were obtained. Accuracy was evaluated by recovery tests
and also by comparison with the results obtained by high resolution continuum source graphite furnace mole-
cular absorption spectrometry (HR-CS GF MAS). Suitable recoveries for F were obtained (95%) and no statistical
difference (95% of confidence level) was observed for the results obtained by HR-CS GF MAS. Pyrohydrolysis
allowed the F volatilization in a relatively short time avoiding the use of concentrated reagents and making
possible further determination by both analytical techniques (IC or ISE). The pyrohydrolysis method was con-
sidered suitable for further F determination, avoiding excessive dilution of digests or matrix matching ap-
proaches, making this method a suitable option for routine F determination in nuclear grade alumina samples.

1. Introduction Fluorine determination in alumina can be performed by direct

Alumina is considered one of the most important oxide ceramics due to
its application in several fields, such as structural, electrical, optical and
nuclear technologies [1]. In view of its high resistance, outstanding che-
mical stability, excellent wear and corrosion resistance, and distinguished
mechanical properties even under radiation and high-temperature en-
vironments, alumina plays an important role for the nuclear industry [1].
The use of alumina as a nanoceramic is of great concern because it is cited
as the most promising material class for nuclear environments due to its
tolerance to radiation [2]. However, F in alumina matrices may become a
corrosive species in fission reactors due to thermolysis and radiolysis re-
actions [2]. According to the requirements of the American Society for
Testing and Materials (ASTM C method 1031-11 - Standard Specification
for Nuclear Grade Aluminum Oxide Powder) [3], the maximum F content
allowed for this material is 50 μg g−1.
analysis using prompt-gamma activation analysis (PGAA) or high-re-
solution continuum source graphite furnace molecular absorption
spectrometry (HR-CS GF MAS). Although HR-CS GF MAS can be con-
sidered a suitable alternative, it requires specific reagents for molecule
formation (such as AlF, CaF, etc) in addition to sample mass being
generally limited to < 1 mg [4–7]. Regarding the F determination by
PGAA, the most evident drawbacks include the difficulties of access to
nuclear reactors, lack of sensitivity, and relatively high detection limits
(around 18 μg g−1) [8].
Ion chromatography (IC) and ion selective electrode (ISE) techni-
ques have been routinely used for halogen determination, especially for
F [9–11]. These techniques are accessible for most of laboratories and
present relatively low cost when compared to PGAA or HR-CS GF MAS.
However, both IC and ISE require analytical solutions (or digests) with
low carbon content and suitable pH in order to avoid interferences [12].

⁎
Corresponding author.
E-mail address: ericommf@gmail.com (E.M.M. Flores).

https://doi.org/10.1016/j.microc.2019.01.053
Received 26 December 2018; Received in revised form 18 January 2019; Accepted 19 January 2019
Available online 22 January 2019
0026-265X/ © 2019 Elsevier B.V. All rights reserved.
L. Hoehne et al.
In spite of the efficiency of methods based on closed-vessels mi-
crowave-assisted acid digestion for several materials, it can be con-
sidered as not suitable for further halogen determination due to the risk
of analyte losses [8,13]. On the other hand, pyrohydrolysis has been
used as an alternative sample preparation method for the decomposi-
tion of organic and inorganic materials for further halogen determi-
nation [9,11,14–22]. Using this method, halogens are volatilized from
matrix under heating using water vapor flow causing hydrolysis reac-
tions that generate the respective volatile acids (i.e., HF, HCl, HBr and
HI) [9,11,14–22]. These species can be separated, condensed and col-
lected in diluted absorbing solution such as NH4OH [23] and
(NH4)2CO3 [24]. An important advantage is that absorbing solutions
are generally compatible with F determination by both ISE and IC.
Another advantage is that analytes are separated from the matrix then
reducing interferences that could impair the determination by ISE and
IC [9,11,14–22].
Based on the potential of pyrohydrolysis for inorganic materials, in
this work this sample preparation method was investigated for the first
time for further F determination in nuclear grade alumina by IC and ISE
with the focus on evaluating the possibility of using well diluted solu-
tion or even water for F absorption and avoiding the use of V2O5 as aid
for F volatilization. Temperature of pyrohydrolysis, air and water flow-
rates, type and concentration of absorbing solution, use of auxiliary
reagent (V2O5), and time of pyrohydrolysis reaction were investigated.
Accuracy was evaluated through recovery tests and also by comparison
with the values obtained by HR-CS GF MAS.
2. Experimental
2.1. Pyrohydrolysis system
A homemade pyrohydrolysis apparatus (Fig. 1) was used for alu-
mina samples. This system is composed of a stream generator unit, a
heater furnace, a pyrohydrolysis unit consisting of a tube and a boat,
both of quartz, a condenser, a collector for the fluoride distillate. The
steam generator is a borosilicate Erlenmeyer-type flask containing
water, which was heated and connected to a flow meter and to a water
trap via two polytetrafluoroethylene (PTFE). This water trap was used
to avoid the water droplets introduction to the pyrohydrolysis unit and
it was made of glass and adapted to the quartz tube of the pyrohy-
drolysis unit by using a silicone stopper. A pump (Minipuls, Gilson,
Middleton, USA) was used in order to pass the water steam through the
G coated graphite tubes using platforms specially designed for solid sam-
F H
C 2.3. Reagents and samples
E M I pared using distilled/deionized water that was further purified using a
D was obtained by heating of NH4VO3 solid at 550o C in a platinum
B M
L (NO3)2 and Al(NO3)3 stock solutions, respectively. For F determination
A J
Fig. 1. Pyrohydrolysis system apparatus used in this work: A) compressed air
inlet, B) flowmeter tube, C) polytetrafluoroethylene connectors, D) water vapor
generation system, E) bottle to prevent backflow of water, F) quartz reactor, G)
quartz boat, H) furnace, I) condenser, J) flask containing the absorbing solu-
tion, L) temperature control system, and M) temperature controller of oven.
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Microchemical Journal 146 (2019) 645–649
pyrohydrolysis unit and the air flow was controlled by a conventional
flow meter. The pyrohydrolysis unit is heated by an electrothermal
furnace (Sanchis, Porto Alegre, Brazil) with an automatic temperature
control (maximum temperature of 1200 °C). A glass serpentine, im-
mersed into an ice bath, was connected to the outlet of the quartz re-
actor to condense the gaseous products from pyrohydrolysis reaction,
avoiding losses of HF. The condensed solution was collected in a
polypropylene vessel containing 10 mL of a suitable absorbing solution
for the subsequent analyte determination.
2.2. Instrumentation
Fluorine determination in absorbing solutions obtained after pyr-
ohydrolysis method was carried out using an ion chromatography
system (819 model, IC detector, Switzerland). The IC system consists of
a pump (model 833 IC liquid handling unit, Metrohm) and a con-
ductivity detector. A column (model Metrosep A Supp 5, 150 × 4 mm
i.d., Metrohm) with packing material composed by polyvinyl alcohol
with quaternary ammonium groups and a particle size of 5 μm and a
guard column (model Metrosep A Supp 4/5 Guard), packed with the
same material and particle size of the analytical column, were used. An
anion self-regeneration suppressor (model 833 suppressor unit,
Metrohm) was used to reduce the conductivity of mobile phase. A so-
lution containing 3.2 mmol L−1 Na2CO3 and 1 mmol L−1 NaHCO3 was
used as mobile phase and 0.7 mL min−1 and 100 μL, were used as flow-
rate and sample loop, respectively, according to the manufacturer re-
commendation [25]. Fluorine was also determined using a potenti-
ometer (781 model, Metrohm, Switzerland) equipped with a fluoride
ISE electrode (Part number: 80502.150, Metrohm) in solutions obtained
after pyrohydrolysis.
For comparison of results obtained using the proposed pyrohydrolysis
method, a high-resolution continuum source graphite furnace molecular
absorption spectrometer, model ContrAA 700 (Analytik Jena, Germany)
equipped with a manual solid sampling system model SSA 600 (Analytik
Jena) for direct analysis of nuclear grade alumina was used. The optical
system comprises a xenon short-arc lamp (XBO 301, GLE, Germany)
operating in “hot-spot” mode as the radiation source, which emits a high-
intensity continuum spectrum within the wavelength range from 180 to
900 nm. The spectrometer is equipped with a prism as a pre mono-
chromator and an echelle grade as monochromator to provide the high
resolution required for HR-CS GF MAS analysis. Measurements were
carried out at the 274.461 nm rotational molecular absorption line of AlF
with 3 pixels (central pixel ± 1). Transversely heated pyrolytically
pling (Analytik Jena) were used throughout. An ultra-micro balance
(Sartorius, Moldel M2P, Germany) with a resolution of 1 μg was used for
sample weighing before F determination by HR-CS GF MAS.
All chemicals used were of analytical grade. Solutions were pre-
Milli-Q (18.2 MΩ cm, Millipore, Billerica, MA). Vanadium pentoxide
free of F, generally used as accelerator auxiliary during pyrohydrolysis,
crucible during 4 h [21]. For F determination by HR-CS GF MAS, Ba2+
and Al3+ solutions were prepared by serial dilutions of 1000 mg L−1 Ba
by IC, Na2CO3 and NaHCO3 salts were used to prepare the mobile
phase. Glass materials or quartz apparatus used in this work were
soaked in 10% (m/v) HNO3 solution for 24 h and washed with water
before of the used. Absorbing solutions, used for collecting the analyte,
were prepared from NH4OH (25%) and (NH4)2CO3 salt and the con-
centration used for both solutions was 50 mmol L−1.
Stock standard solution of F (1000 mg L−1) was prepared by dis-
solving NaF salt in water. Fluorine calibration curve in the range of 10
L. Hoehne et al.
to 1000 μg L−1 for IC and 250 to 2500 μg L−1 for ISE were prepared by
sequential dilution of stock solution (1000 mg L−1) in water. Fluorine
determination by ISE was performed in presence of buffer TISAB so-
lution. For the preparation of TISAB solution, sodium chloride (58 g),
1,2-cyclohexilenediaminetetraacetic acid (4 g), and acetic acid (57 mL)
were dissolved in water (500 mL) [11]. After, the pH was adjusted
between 5.2 and 5.5 using a NaOH solution (20% m/v). Finally, the
final volume was completed to 1000 mL with water [11]. Three nuclear
grade alumina powder samples (purity higher than 99.5%) were do-
nated by a supplier of nuclear grade materials (samples A, B, and C).
Particle size distribution of samples ranged from 53 to 210 μm.
2.4. Pyrohydrolysis method
For the proposed method, 500 mg of alumina, previously mixed
with 200 mg accelerator auxiliary (V2O5, when it was used), were
weighted in a quartz boat. It was introduced into a quartz reactor,
which was placed inside a furnace with a maximum temperature of
1050 °C. Experiments were performed using 10 min as reaction time,
temperature set at 950 °C, air flow-rate of 0.2 L min−1, and water flow-
rate pumped through the reactor set at 0.5 mL min−1. Volatilized F
after the pyrohydrolysis reaction was condensed and collected in a
vessel containing 5 mL of an absorption solution (water, 50 mmol L−1
NH4OH, and 50 mmol L−1 (NH4)2CO3 were evaluated). After pyrohy-
drolysis reaction, solutions were transferred to volumetric vessels, di-
luted with water to 25 mL and the determination of F was performed by
IC and also by ISE.
2.5. Fluorine determination in alumina by HR-CS GF MAS
The formation of AlF molecule in the presence of Ba allowed the F
determination by HR-CS GF MAS. Previously to the determination of F
by HR-CS GF MAS, graphite platforms were covered with 2.5 μg of Al
and 10 μg of Ba by the addition of aliquots of the respective solutions of
Al3+ and Ba2+. Platform heating inside of graphite furnace and cooling
down before analysis of alumina samples were performed according to
a method described in literature [26]. After, alumina samples were
weighed (masses up to 0.3 mg) directly on the graphite platform. Sub-
sequently, platform was inserted into the graphite furnace and the
heating program was applied as previously described [26]. Calibration
curve (1 to 25 μg L−1) was obtained by direct pipetting aliquots of F
standard solution on the graphite platform and subsequent applying the
same conditions and heating program used for powder alumina sam-
ples.
3. Results and discussion
Initially, F determination in alumina sample “A” was performed by
HR-CS GF MAS [26] providing a concentration for F of 109 ± 2 μg g−1
(n = 5). This value was used as reference for further evaluations.
3.1. Pyrohydrolysis method
It is well known that the choice of absorbing solution is a key
parameter for developing pyrohydrolysis methods, since it has a strong
influence in the analyte recovery [12]. Particularly in case of halogen
determination the absorbing solution should be carefully optimized due
to the risk of analyte losses. Moreover, it must be compatible with the
determination technique and also to be non-toxic and environmental
friendly as for as possible. In this sense, 50 mmol L−1 (NH4)2CO3,
50 mmol L−1 NH4OH, and also water were evaluated as absorbing so-
lutions and F determination was determined by ISE. The evaluation of
parameters was performed using alumina sample A. The follow ex-
perimental conditions were used: volume of absorbing solution of
10 mL, sample mass of 500 mg, temperature of 1000 °C during 10 min,
and air flow-rate of 0.2 L min−1. Obtained results using all evaluated
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Microchemical Journal 146 (2019) 645–649
solutions presented no statistical difference (ANOVA, 95% of con-
fidence level) with reference value (obtained by HR-CS GF MAS). The
use of both water and alkaline absorbing solutions allowed relative
standard deviations (RSDs) lower than 7%. Therefore, water was se-
lected as absorbing solution for subsequent experiments. This result was
in agreement with a previous work showing that, depending on the
adjusted conditions, only water could be suitable for the quantitative
absorption of F [9]. It is important to mention that blank values ob-
tained after pyrohydrolysis were always negligible.
In general, some auxiliary reagents have been used in pyrohy-
drolysis to help halogen release mainly from inorganic matrices. One of
the most used reagents for this purpose is V2O5 [14,15]. This reagent
has been used due to the relatively low melting point, about 750 °C, and
suitability for several matrices [21,22,27]. Moreover, this reagent can
be produced in high purity from ammonium metavanadate, resulting in
lower blank values, which is an important aspect to achieve low de-
tection limits. Then, the use of V2O5 (100 to 500 mg) as aid for the
volatilization of F during the hydrolysis reaction at high temperature
was evaluated. The experimental conditions used for this evaluation
were: 10 mL of water (used as absorbing solution), sample mass of
500 mg, temperature of 1000 °C during 10 min, and air flow-rate of
0.2 L min−1 (F determination was performed by ISE). As no differences
were observed when pyrohydrolysis was carried out using or not V2O5
(results not shown), subsequent experiments were performed without
using V2O5.
3.2. Effect of experimental conditions
3.2.1. Influence of temperature and reaction time of pyrohydrolysis
In order to assure the complete F volatilization from matrix, ex-
periments were performed to evaluate the effect of temperature on the
proposed pyrohydrolysis method. In this way, temperatures from 550 to
1050 °C were evaluated and the following experimental conditions were
set: 10 mL of water as absorbing solution, sample mass of 500 mg, re-
action time of 10 min, and air flow-rate of 0.2 L min−1. According to
literature, pyrohydrolysis reaction is thermodynamically favorable at
temperatures higher than 500 °C [14]. However, it has already been
observed that F could be quantitatively released from inorganic com-
pounds only at temperatures higher than 700 °C. These results are
shown in Table 1.
As can be seen in Table 1, when temperatures up to 850 °C were
evaluated, the F concentration was lower than 45 μg g−1 (agreement
around of 43% with the reference value). This result could be attributed
to the non-quantitative release of analyte from alumina due to the in-
sufficient temperature. On the other hand, when temperatures of 950
and 1050 °C were evaluated, the F concentration was 108 and
107 μg g−1, respectively (agreement close to 100% with the reference
value). A relative standard deviation of 6% was obtained for tempera-
tures of 950 °C, but using 1050 °C the RSD was of 8%. In this way, a
Table 1
Influence of temperature and reaction time on F volatilization from alumina
(n = 3).
Parameter F, μg g−1
Temperature, °C 550 5.22 ± 1.51
650 7.34 ± 2.81
750 20.2 ± 4.2
850 40.3 ± 10.1
950 108 ± 6
1050 107 ± 8
Time, min 2.5 20.2 ± 8.0
5.0 72.1 ± 21.6
10 109 ± 5
15 109 ± 5
20 107 ± 5
Reference value for F obtained by HR-CS GF MAS was 109 ± 2 μg g−1.
L. Hoehne et al.
Table 2
Influence of air flow-rate on F determination by ISE after
pyrohydrolysis (n = 3, mean ± standard deviation).
Air flow-rate, L min−1 F, μg g−1
0.1 58.0 ± 3.4
0.2 109 ± 4
0.3 108 ± 4
0.4 110 ± 5
Reference value for F obtained by HR-CS GF MAS was
109 ± 2 μg g−1
Table 3
Concentration of F (μg g−1) in nuclear grade alumina determined by IC and ISE
after decomposition using pyrohydrolysis method (n = 3, mean ± standard
deviation).
Sample Pyrohydrolysis method HR-CS GF MAS
IC ISE
A 107 ± 4 108 ± 5 109 ± 2
B 101 ± 5 95 ± 4 96 ± 6
C < 0.5 < 5.0 < 1.5
temperature of 950 °C was selected as suitable temperature for F vola-
tilization from the matrix.
The time of reaction is another important parameter that also
should be evaluated. In general, the time of pyrohydrolysis reaction
must be sufficient for complete F release and transport of the volatile
analyte species to the absorbing solution. In this sense, the time of re-
action in the proposed method was evaluated in the range of 2.5 to
20 min and the following experimental conditions were set: 10 mL of
water as absorbing solution, sample mass of 500 mg, pyrohydrolysis
temperature of 950 °C, and air flow-rate of 0.2 L min−1. The results are
shown in the Table 1.
As can be seen in Table 1, up to 5 min of pyrohydrolysis reaction
were not enough for the complete F volatilization (agreement about
67%). However, quantitative recoveries of F were reached after 10 min
of heating, at 950 °C. No significant difference (ANOVA, 95% of con-
fidence level) was observed by using 10 to 20 min of pyrohydrolysis
time. The RSD values were lower than 5% (n = 3) if the time given for
pyrohydrolysis was at least 10 min. Therefore, this time was established
for further experiments.
3.2.2. Influence of water and air flow-rates on pyrohydrolysis
The evaluation of the water flow-rate pumped through the reactor is
important in order to provide enough water for the pyrohydrolysis re-
action. In this work, this parameter was evaluated from 0.10 to
1.0 mL min−1 by using water flow-rate below or higher than
0.5 mL min−1 the RSDs were higher (up to 10%). However, using a
water flow-rate of 0.5 mL min−1 the RSD was 5% and this flow-rate was
selected for further experiments allowing minimum decrease on reac-
tion temperature and providing a suitable F recovery (higher than
95%).
The air flow-rate is another important parameter that must be
evaluated to ensure a complete transport of volatile pyrohydrolysis
products from the quartz tube reactor to the absorbing solution flask. In
the present work, experiments were carried out to evaluate the effect
air flow-rate on F release. In this sense, alumina sample (500 mg) was
heated at 950 °C and experiments were performed using air flow-rates
ranging from 0.1 to 0.4 L min−1. The results are shown in Table 2.
It is possible to observe (Table 2) that an air flow-rate of 0.1 L min−1
was not enough to obtain quantitative results to F (F = 58 μg g−1,
agreement around 74% with reference value). On the other hand, when
air flow-rates of 0.2, 0.3, and 0.4 L min−1 were evaluated, the con-
centration of F was 109 ± 5, 108 ± 4, and 110 ± 5 μg g−1,
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Microchemical Journal 146 (2019) 645–649
respectively (agreement close to 100% to reference value). In this way,
air flow-rate was set at 0.2 L min−1 that was considered as enough for
the quantitative volatilization and transport of F using the proposed
pyrohydrolysis method and determination by ISE.
3.3. Fluorine determination in alumina by IC and ISE after pyrohydrolysis
Three nuclear grade alumina samples were analyzed using the op-
timized pyrohydrolysis conditions and F determination was carried out
by IC and also ISE (Table 3). Experiments were performed using 500 mg
of alumina samples, 10 mL of water (used as absorbing solution),
10 min of pyrohydrolysis reaction at 950 °C, water flow-rate of
0.5 mL min−1, and air flow-rate of 0.2 L min−1.
According to the results showed in Table 3, the concentration of F in
two of the nuclear grade alumina samples (samples A and B) was higher
than the maximum value allowed (50 μg g−1) for this kind of material
(provided by ASTM C1031-11). On the other hand, only sample C was
considered as suitable for nuclear applications (F concentration lower
than 0.5 μg g−1 by IC and 5.1 μg g−1 by ISE). However, it is important
to highlight that F concentration obtained by ISE and IC after pyrohy-
drolysis for samples A and B were in agreement with reference values
(obtained by HR-CS GF MAS). In this sense, the proposed method can be
considered as accurate (significant difference was not observed by
comparison of pyrohydrolysis and HR-CS GF MAS results). Moreover,
the LODs achieved by pyrohydrolysis method combined to IC
(2.0 μg g−1) or ISE (3.6 μg g−1) were suitable for the quality control of
alumina even better than those provided by HR-CS GF MAS, probably
due the higher sample mass used in pyrohydrolysis system. It is im-
portant to mention that there is no certified reference material for
alumina with F information.
4. Conclusion
The pyrohydrolysis method was successfully applied to nuclear
grade alumina for subsequent F determination by IC and ISE. The
proposed method provided a suitable analytical tool for quality control
in compliance with ASTM C1031-11. As an important advantage of the
proposed method, only water was considered a suitable absorbing so-
lution and the analyte separation from the matrix prevented inter-
ferences in IC and ISE determination. Moreover, final solution was
suitable to be analyzed directly by IC and ISE without further dilution.
Statistical difference was not observed between results obtained by
pyrohydrolysis (F determination by IC and ISE) and HR-CS GF MAS.
Finally, due to the simplicity, low sample preparation time and as the
possibility of the use water as absorbing solutions, the pyrohydrolysis
method, it can be suggested for the quality control of alumina used for
nuclear applications.
Acknowledgements
The authors are grateful to CNPq and FAPERGS for supporting this
study. E.I. Muller and E. M. M. Flores have research scholarship from
CNPq, grant numbers: 304336/2015-7 and 309297-2016/8, respec-
tively. Moreover, this study was financed in part by the Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior - Brazil (CAPES) -
Finance Code 001.
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