Radiation Measurements 72 (2015) 66e69

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Radiation Measurements
journal homepage: www.elsevier.com/locate/radmeas

High- and very-high-dose dosimetry using silicate minerals

Shigueo Watanabe a, Nilo F. Cano b, *, Lucas S. Carmo a, Renata F. Barbosa b,
Jose F.D. Chubaci a
a ~o Paulo, Rua do Mata
Instituto de Física, Universidade de Sa ~o 187, CEP 05508-090 Sa ~o Paulo, SP, Brazil
b
Departamento de Ci^ ~o Paulo, Av. Alm. Saldanha da Gama 89, CEP 11030-400 Santos, SP, Brazil
encias do Mar, Universidade Federal de Sa

h i g h l i g h t s

 The TL dose responses of eight different natural silicate minerals have been investigated.
 All minerals show a more or less linear thermoluminescence signal with gamma ray dose.
 The saturation dose varies from 5 kGy up to 1000 kGy.

a r t i c l e i n f o a b s t r a c t

Article history: In the present study, certain natural silicate minerals such as aquamarine (AB), morganite (PB), goshenite
Received 27 May 2014 (WB), white jadeite (JW), green jadeite (JG), pink tourmaline (PT) and two varieties of jadeite-like quartz,
Received in revised form denoted here by JQ1 and JQ2, were investigated using the thermoluminescence technique to evaluate
6 November 2014
their potential for use as very-high- and high-dose dosimeters. These minerals respond to high doses of
Accepted 13 November 2014
Available online 15 November 2014
g-rays of up to 1000 kGy and often to very high doses of up to 3000 kGy. The TL response of these
minerals may be considered to be satisfactory for applications in high-dose dosimetry. Investigations of
electron paramagnetic resonance and optically stimulated luminescence dosimetry are in progress.
Keywords:
High dose
© 2014 Elsevier Ltd. All rights reserved.
Dosimetry
TL
Silicates

1. Introduction doses on LiF doped with Mg and Ti (called MTS) and with Mg, Cu
and P (called MCP) since the beginning of this century; the low-
A number of materials have been investigated not only for low- dose regime has been under investigation at the IFJ since the
dose dosimetry, which is useful in medical applications, but also for 1960s in the case of MTS and the 1980s in the case of MCP materials.
high-dose dosimetry, which is important in retrospective or in- This group has tested these materials under irradiation with g-rays,
dustrial dosimetry (Mesterha zy et al., 2012; Inrig et al., 2008; electrons, protons, alpha particles and also neutrons. Their most
Wieser et al., 1994; Rocha et al., 2003; Teixeira et al., 2011; Vila important result is that these materials, particularly the MCP ma-
and Caldas, 2011). There are various scenarios in which very high terials, exhibit interesting and unexpected behavior when irradi-
doses are involved, such as very-high-energy particle accelerators, ated with high doses of up to 500 kGy. A high-temperature TL peak
nuclear power plants and very-high-dose irradiation facilities for is observed at above 300  C, and this peak shifts to higher tem-
food preservation or the modification of the properties of solid peratures of up to 460e470  C as the dose reaches approximately
materials. One such type of detector is based on LiF, doped either 500 kGy. These authors refer to this peak as peak B (Obryk et al.,
with Mg and Ti or with Mg, Cu and P (Bilski et al., 2007; Obryk et al., 2009). High neutron fluences on the order of 1015 per cm2 also
2008, 2011). produce similar results. In the article published by Obryk et al.
A group of physicists at the Institute of Nuclear Physics (IFJ), (2014), references prior to that date can be found.
Krakow, Poland, has been investigating the effects of high radiation Camargo and Isotani (1988) have measured the optical bands in
natural pink tourmaline and have identified bands at 8500, 14,800,
19,500 and 25,500 cm 1, with intensity of all of them growing up to
* Corresponding author. 13,000 kGy. These authors irradiated tourmaline at this very high
E-mail addresses: nfcano@gmail.com, nilo.cano@unifesp.br (N.F. Cano). dose value, and their results indicated that with further irradiation,

http://dx.doi.org/10.1016/j.radmeas.2014.11.004
1350-4487/© 2014 Elsevier Ltd. All rights reserved.
 S. Watanabe et al. / Radiation Measurements 72 (2015) 66e69 67

Fig. 1. TL intensity versus g dose for the TL peaks of (a) JQ1 and (b) JQ2; the dashed line indicates linearity. In the insets are presented the glow curves of JQ1 and JQ2 samples
irradiated with 2 kGy of g-rays.

these bands could continue to intensify. This is an extraordinary 30 min and subsequently irradiated with g rays at doses in the
result; no other researchers have performed similar ultra-super- range of hundreds of kGy up to 2000 kGy.
high-dose irradiation experiments. The TL measurements were performed in a nitrogen atmo-
In the study reported here, we investigated certain natural sil- sphere using a model 4500 Harshaw TL reader equipped with two
icate minerals and found that some of them responded to high to photomultiplier tubes, which could record luminescence signals
very high radiation doses. Here, ‘high dose’ refers to a dose of up to independently. The reader was controlled by WinREMS Software,
1000 kGy, whereas ‘very high dose’ refers to doses above this value; which was supplied with the spectrometer and was run on a
such doses are typically of up to 2000 or 3000 kGy, but in one case a Windows computer. The heating rate used in the TL measurements
much higher dose has been applied. In this work, we report high- was 4  C/s. Each point in the glow curve represents an average of
dose dosimetry conducted using several silicate minerals; these five readings.
materials were irradiated with g-ray doses from a few tens of kGy
up to 3000 kGy.
3. Results

2. Materials and experiments Samples JG, JW, JQ1 and JQ2 we acquired as samples of jadeite.
X-ray fluorescence analysis indicated that JG and JW were in fact
The following natural silicate minerals were acquired from jadeite, but JQ1 and JQ2 were much more similar, although not
stone dealers in Teofilo Ottoni, State of Minas Gerais, Brazil, for the identical, to quartz. The JQ1 glow curve exhibited TL peaks at 110,
present study: morganite (PB), goshenite (WB), aquamarine (AB), 260 and 340  C, whereas JQ2 presented peaks at 190, 260 and
white jadeite (JW), green jadeite (JG), pink tourmaline (PT) and two 340  C. Both these materials were initially irradiated with g rays up
varieties of jadeite-like quartz (JQ1) and (JQ2). to 70 kGy. Subsequently, however, JQ2 was irradiated to a higher
Here, we studied the TL of these crystals to determine their dose of 3000 kGy. Fig. 1 presents the TL response of the 260 and
dosimetric behavior. For this purpose, we first crushed the samples 340  C peaks as functions of the dose for JQ1 and JQ2. The
and then sieved them, retaining grains of between 0.080 and maximum peak height was used to quantify the TL response. The TL
0.180 mm in size. These powders were then annealed at 500  C for glow curves of JQ1 and JQ2 samples that were pre-heated at 500  C

Fig. 2. TL intensity behavior of the TL peaks as a function of g radiation dose for the JW and JG samples, respectively; the dashed line indicates linearity. In the insets are presented
the TL glow curves of JW and JG samples pre-annealed at 500  C in air and then irradiated with a g dose of 2 kGy.
68 S. Watanabe et al. / Radiation Measurements 72 (2015) 66e69

Fig. 3. (a) TL glow curves of morganite, goshenite and aquamarine and TL response curves as functions of radiation dose of (b) goshenite, (c) morganite and (d) aquamarine.

for 30 min and then g irradiated at a dose of 2 kGy are presented in Fig. 4 reveals an interesting result. For a sample of pink tour-
the insets of Fig. 1(a) and (b), respectively. maline irradiated at high doses, the TL reading reached a high value
The JW sample exhibited peaks at 110, 190 and 240  C, whereas of close to 9  108 a.u. for a dose close to 100 kGy, but when this
JG exhibited peaks at 140, 210, 250 and 330  C. The intensity of the sample was irradiated at a very high dose, from hundreds of kGy up
peak at 190  C in JW increased by two orders of magnitude as the to 3000 kGy, the TL response exhibited a well-behaved decrease in
dose increased from 50 Gy to approximately 10 kGy and then
saturated (see Fig. 2(a)). Fig. 2(b) presents the behavior of the TL
intensity (based on the peak height) as a function of dose; it is
observed that the 140  C peak grew slowly with increasing dose,
whereas the 210  C peak grew more rapidly and 330  C peak grew
very rapidly with increasing dose. The response of this last peak
increased by nearly three decades as the dose was increased to
approximately 20 kGy. With the exception of the 330  C TL peak, all
other TL peaks grew linearly for doses of up to 200 Gy and then
supralinearly for g doses of up to approximately 20 kGy, saturating
thereafter. The linearesupralinear behavior and the stability at
room temperature of the TL peaks at 210, 240 and 330  C allow the
use of natural jadeite as a dosimetric material.
The TL glow curves of beryl samples that were pre-annealed at
500  C for 30 min and then irradiated to a g dose of 10 kGy are
presented in Fig. 3(a). Fig. 3(b,c,d) presents the TL response curves
as functions of dose for all three studied types of beryl: PB, WB and
AB. In PB, the TL response saturated at approximately 5 kGy; in WB,
the TL response described a parabola-like with a maximum at
approximately 1250 kGy and then decreased beyond this dose
value, although the TL intensity at 2000 kGy remained high. In AB,
the TL response increased for doses of up to approximately 250 kGy,
Fig. 4. TL response curves as functions of radiation dose for pink tourmaline. In the
rapidly decreased for doses of up to approximately 1300 kGy and inset are presented the TL glow curves of pink tourmaline irradiated with 10, 25, 50,
then decreased slowly beyond that point. 75, 100, 250, 500, 750 and 1000 Gy of g-rays. (For interpretation of the references to
color in this figure legend, the reader is referred to the web version of this article.)
 S. Watanabe et al. / Radiation Measurements 72 (2015) 66e69 69

Table 1 In the case of a TL versus dose curve with one increasing branch
TL peaks and dose response of investigated materials. (A) and one decreasing (B) branch, if the measured TL value could
Material TL peak ( C) Saturation dose be representative of either (A) or (B), we offer the following sug-
JQ1 260 70 kGy
gested method of distinguishing the correct dose in the ambiguous
340 70 kGy region of the calibration: use at least two aliquots to measure TL,
JQ2 260 70 kGy one for the actual TL value measurement and the second subse-
340 500 kGy quently irradiated with an additional dose. If an increase in the TL
JW 110 10 kGy
response is measured, the original measurement lies on the (A)
190 10 kGy
JG 140 20 kGy branch; otherwise, it lies on the (B) branch. In this manner, the
210 20 kGy entire TL vs. dose curve can be used for high-dose dosimetry.
250 20 kGy
330 200 kGy
AB 380 250 kGy Acknowledgments
PB 330 5 kGy
WB 330 1000 kGy The authors wish to thank Ms. E. Somessari and Mr. C. Gaia,
PT 190 10 kGy
Instituto de Pesquisas Energeticas e Nucleares (IPEN), Brazil, for
330 100 kGy
kindly carrying out the irradiation of the samples, Mr. F. Reichmann
from CBE e EMBRARAD, Tecnologia em esterilizaça ~o, for kindly
carrying out irradiation of the samples and Dr. R.A.S. Guttler from
departamento de Mineralogia do Instituto de Geocie ^ncias da USP,
value (curve). The inset of Fig. 4 presents the TL glow curves of pink for kindly given the samples. This work was performed with the
tourmaline irradiated at doses varying from 10 to 1000 Gy. The TL financial support of the FAPESP and CNPq.
versus dose curve is already shown in Fig. 4. It is observed that the
TL intensity is still increasing for doses of >1000 Gy, indicating that
the TL growth curve extends into the region corresponding to References
hundreds of kGy. Bilski, P., Olko, P., Puchalska, M., Obryk, B., Waligo  rski, M.P.R., Kim, J.L., 2007. High-
dose characterization of different LiF phosphors. Radiat. Meas. 42, 582e585.
Camargo, M.B., Isotani, S., 1988. Optical absorption spectroscopy of natural and
irradiated pink tourmaline. Am. Mineral. 73, 172e180.
4. Comments and conclusion
Inrig, E.L., Godfrey-Smith, D.I., Khanna, S., 2008. Optically stimulated luminescence
of electronic components for forensic, retrospective, and accident dosimetry.
Although JW and JG were both jadeite crystals and morganite, Radiat. Meas. 43, 726e730.
Mesterha zy, D., Osvay, M., Kov acs, A., Kelemen, A., 2012. Accidental and retro-
goshenite and aquamarine were all beryl crystals, they presented
spective dosimetry using TL method. Radiat. Phys. Chem. 81, 1525e1527.
distinct TL behaviors under heavy irradiation. They differed in the Obryk, B., Bilski, P., Budzanowski, M., Fuerstner, M., Glaser, M., Ilgner, C.J., Olko, P.,
impurities they contained, but it is difficult to attribute the various Pajor, A., Stuglik, Z., 2009. Development of a method for passive measurement
behaviors described above solely to impurities. The differences of radiation doses at ultra-high dose range. IEEE TNS 56, 3759e3763.
Obryk, B., Bilski, P., Budzanowski, M., Fuerstner, M., Ilgner, C., Jaquenod, F., Olko, P.,
among the responses of these materials require further study. Puchalska, M., Vincke, H., 2008. The response of different types of TL lithium
A summary of the saturation doses of the investigated ther- fluoride detectors to high-energy mixed radiation fields. Radiat. Meas. 43,
moluminescence dosimeters, as determined in the present study, is 1144e1148.
Obryk, B., Bilski, P., Olko, P., 2011. Method of thermoluminescent measurement of
provided in Table 1. All silicate minerals that were investigated here radiation doses from micrograys up to a megagray with a single LiF: Mg,Cu, P
exhibited dose-dependent TL responses upon high- or very-high- detector. Radiat. Prot. Dosim. 144, 543e547.
dose (g) irradiation at doses up to the order of 2000 kGy, but in Obryk, B., Khoury, H.J., Barros, V.S., Guzzo, P.L., Bilski, P., 2014. On LiF: Mg,Cu, P and
LiF: Mg, Ti phosphors high & ultra-high dose features. Radiat. Meas. 71, 25e30.
the case of JG and pink tourmaline, this behavior extended to http://dx.doi.org/10.1016/j.radmeas.2014.02.002.
3000 kGy; in other words, these materials can be used for very- Rocha, F.D.G., Oliveira, M.L., Cecatti, S.G.P., Caldas, L.V.E., 2003. Properties of sintered
high-dose dosimetry. amethyst pellets as thermoluminescent dosimeters. Appl. Radiat. Isot. 58,
In the case of tourmaline, both the 190 and 330  C peaks 85e88.
Teixeira, M.I., Souza, D.N., Caldas, L.V.E., 2011. Onyx as radiation detector for high
increased in intensity with increasing dose for doses of up to doses. Radiat. Meas. 46, 1894e1896.
approximately 10 and 100 kGy, respectively, and then began to Vila, G.B., Caldas, L.V.E., 2011. Brazilian biominerals for high-dose dosimetry. Radiat.
decrease, describing a parabola-like similar to those observed in the Meas. 46, 1900e1902.
Wieser, A., Go € ksu, H.Y., Regulla, D.F., Vogenauer, A., 1994. Limits of retrospective
JQ samples, JW and JG. In all these cases, the TL response was accident dosimetry by EPR and TL with natural materials. Radiat. Meas. 23,
observed for high (1000 kGy) to very high doses (2000e3000 kGy). 509e514.