REVISTA MEXICANA DE F´
ISICA S53 (3) 97–101 FEBRERO 2007
Radionuclides in he en i onmen in he sou h o Spain, an h opogenic
enhancemen s due o indus y
G. Manj´
on
Depa amen o de F´
ısica Aplicada 2, E.T.S. A qui ec u a, Uni e sidad de Se illa,
A . Reina Me cedes 2, 41012 – Se illa, Spain.
Recibido el 2 de ma zo de 2006; acep ado el 18 de agos o de 2006
Le els o na u al adionuclides in he en i onmen a e a ec ed by human ac i i ies in he Sou h o Spain. Indus y was es, such as phospho-
gypsum, ha e been eleased o an es ua y since six ies un il 1997. Nowadays he was es managemen is ca e ul wi h en i onmen p o ec ion,
which can be clea ly obse ed oday in he adionuclides pa e n. Di e en sou ces o adionuclides (indus y was es, idal ac ion and min-
ing) can be dis inguished in he es ua y. U anium iso opes, 226 Ra, 210Pb and 210Po we e de e mined in wa e and sedimen samples o
his s udy. An i on ecycling ac o y is wo king close o Se ille (Sou h o Spain). A 137Cs sou ce was acciden ally bu n in a u nace o
his ac o y in 2001. The en i onmen al impac o his acciden was immedia ely de e mined. Moni o ing p ocedu e and esul s a e shown
in his con ibu ion. Radionuclides measu emen in ol es di icul echniques. In his communica ion a p ocedu e o de e mine he ac i i y
concen a ion o 210Pb by liquid scin illa ion coun ing is p esen ed. Two quali y es s, using gamma- and alpha-spec ome y we e applied o
he 210Pb esul s.
Keywo ds: Radioac i i y; en i onmen ; phosphogypsum; no m.
Los ni eles na u ales de is´
o opos adioac i os en el ambien e son a ec ados po ac i idades humanas en el su de Espa˜
na. Desechos in-
dus iales, ales como phosphogypsum, han sido deposi ados en un es ua io desde los a˜
nos sesen a has a 1997. Ac ualmen e el manejo de
los desechos se ealiza de mane a a p o eje el ambien e, lo que se obse a cla amen e en la e oluci´
on de los pa ones de los is´
o opos a-
dioac i os. Las di e en es uen es de adiois´
o opos (desechos indus iales, ma eas y mine ´
ıa) pueden dis ingui se en el es ua io. Is´
o opos de
U anio, 226Ra, 210Pb y 210Po se midie on en mues as de agua y sedimen o pa a es e es udio. Una ´
ab ica de eciclado de ace o unciona
ce ca de Se illa (Su de Espa˜
na). Una uen e de 137Cs ue acciden almen e quemada en uno de sus ho nos en 2001. El impac o ambien al
de es e acciden e ue inmedia o. En es e abajo se p esen an los p ocedimien os pa a el moni o eo as´
ı como los esul ados ob enidos. La
medida de adiois´
o opos in oluc a ´
ecnicas complejas. Aqu´
ı p esen amos el p ocedimien o pa a de e mina la concen aci´
on de 210Pb po
medio de con eo en cen elleado es l´
ıquidos. Dos con oles de calidad, espec ome ´
ıa al a y gama, con i man los esul ados.
Desc ip o es: Radioac i idad; ambien al; con aminaci´
on; Espa˜
na.
PACS: 23; 29.30.k ; 29.30.Ep; 29.40.Mc; 29.40.Wk; 29.40.Cs
1. In oduc ion
The in e es on na u al adionuclides ela ed o con en ional
indus y p ocesses is clea ly obse ed in he cu en li e a u e
(Oa way e al., 2005). Al hough he s udy o na u ally occu -
ing adioac i e ma e ials (NORM) is applied o many indus-
ies (i on, zi con, coal, ...) he phospho ic acid ac o ies a e
s ill he main objec i e o hese esea ch wo ks (Beddow e
al., 2005).
Two ac o ies manu ac u e phospho ic acid, e ilize s
and de e gen s using phospha e ock om No h A ica as
aw ma e ial. Phospha e ock is he aw ma e ial o he phos-
pho ic acid indus y. Sedimen a y ocks, such as mine al
om Ma oc used in he ac o ies o Huel a (Sou h o Spain),
p esen high ac i i y concen a ions o na u al adionuclides
(U-iso opes, 226Ra, 210Pb and 210Po), which a e in secula
equilib ium in he mine al (Bol´
ı a e al., 1996). The high
amoun s o ea ed mine al, abou 2 ×109kg pe yea in
he case o he Huel a ac o ies, become he acid phospho ic
indus y as he i s objec i e o he NORM egula o y imple-
men a ions.
Al e na i ely, an igneous ock, such as mine al om Kola
Peninsula (Ru ge s an de Loe e al., 2003), gene ally
p esen lowe le els o na u al adioac i i y, bu ela i ely
high amoun s o Th-iso opes. The use o his aw ma e ial
could dec ease he le els o adionuclides in he p oduc s and
was es o phospho ic acid indus ies.
In he we ea men o phospha e ock o p oduce phos-
pho ic acid he secula equilib ium o he adionuclides, be-
longing he U-se ies, is b oken. Thus, a high ac ion o
226Ra, 210Pb and 210Po is associa ed o phosphogypsum, a
by-p oduc ha is eleased in o he en i onmen , whe eas a
high ac ion o U-iso opes is associa ed o phospho ic acid,
e ilize s and de e gen .
Since 1960’s un il 1998 he 20% o phosphogypsum
was es was di ec ly discha ged in o he Odiel Ri e , jus a -
e high idal e en s, and he es (80%) was s o ed in ai -
opened piles. Fo ha , phosphogypsum was pumped wi h
seawa e un il he piles, hen phosphogypsum was deposi ed
and he supe na an d i ed by d ainage un il he Tin o Ri e .
Acco ding o phospho ic acid ac o ies da a, he amoun o
phosphogypsum eleased was 3 ×109kg pe yea .
In 1998 he was e managemen o indus ies loca ed in
he es ua y o he Odiel and Tin o i e s was deeply changed.
The di ec eleases o he Odiel Ri e we e s opped and he
ai opened piles we e well-p o ec ed agains any impac on
he Tin o Ri e en i onmen .
98 G. MANJ ´
ON
The objec i e o his wo k was o compa e he adioac-
i e impac o he phospha e e ilize indus y in he es ua y
o he Odiel and Tin o i e s since 1998 un il 1998, and he
sel -cleaning si ua ion caused by he change o was es man-
agemen in he es ua y.
2. Expe imen al
Di e en adiome ic and adiochemical echniques we e ap-
plied o en i onmen al samples in o de o ob ain he ac i -
i y concen a ions o adionuclides (226Ra, U-iso opes and
210Po. These echniques we e well-es ablished by p e i-
ous wo ks (Ma ´
ınez-Agui e e al., 1996; Pe i´
a˜
nez, 2002;
Mo eno e al., 2000; Ma ´
ınez-Agui e and Ga c´
ıa-Le´
on,
1994). Howe e he expe imen al echniques co esponding
o he de e mina ion o 210Pb we e de eloped by ou g oup
o he analysis o i e sedimen s collec ed a e 1998 in he
es ua y o Odiel and Tin o i e s. Fo ha we only p esen
he main cha ac e is ics o hese expe imen al echniques in
his pape .
2.1. Radiochemical p ocedu e
Sedimen samples we e i s ly d ied. Once d ied, 5 g o sedi-
men s we e selec ed o e e y analysis. Nex , 25 mg o Ba2+
and 30 mg o Pb2+ we e added o e e y sedimen aliquo .
Samples we e bu n a 550oC o 24 h. Ashes whe e dilu e
wi h aqua egia o 4 h and hen oxidized (wi h HNO3and
H2O2)o e nigh . The supe na an is sepa a ed by il a ion.
The dissolu ion is neu alized. Then, Ba-Pb SO4is p ecipi-
a ed wi h H2SO410M. The p ecipi a ed is sepa a ed by il-
a ion (Milipo e 45 µm po e size) and dissol ed again wi h
EDTA a pH= 9. A second p ecipi a ion a pH= 4.5 is made o
sepa a e 226Ra. Finally, PbSO4 is p ecipi a ed wi h H2SO4
a pH= 3 (Al-Mas i e al., 1997).
The PbSO4p ecipi a e is dissol ed wi h 2 ml o EDTA
0.2 M and 8 ml o NH4OH 0.2 M, hen is e apo a ed un il 9
ml and mixed wi h a liquid scin illa ion cock ail (Op iphase
Hisa e 3) in a liquid scin illa ion ial (low-po assium glass
ial). The ial o adioac i e sou ce is immedia ely measu ed
be o e 210Bi will be p esen .
2.2. Ac i i y concen a ion measu emen
The measu emen o 210Pb was made wi h a liquid scin il-
la ion spec ome e Quan ulus 1220. Two pho omul iplie
ubes we e used o he be a coun ing, whe eas o he wo pho-
omul iplie s (gua d) we e connec ed in an icoincidence o
ob ain an ul a-low backg ound. Alpha- and be a- coun s
we e analyzed in wo di e en spec a using a pulse shape
analyze p e iously calib a ed o 210Pb measu emen s (Villa
e al., 2003).
Ac i i y concen a ion o 210Pb was calcula ed acco ding
o nex equa ion:
A=Rs−Rb
·ε·m·Rq·60
whe e, Rsis he be a-coun ing a e de e mined in a 210Pb
sou ce (wi hou 210Bi), Rbis he be a-coun ing a e in a blank
sou ce, εis he coun ing e iciency co esponding o a 210Pb-
210Bi calib a ion sou ce, m is he mass o he en i onmen al
sample, and Rqis he adiochemical yield o e e y analysis.
Finally, is a co ec ion ac o , which mus be used o aking
in o accoun he con ibu ion o 210Bi o he be a-coun ing
a e o he calib a ion sou ce.
2.3. Coun ing e iciency
The de e mina ion o he coun ing e iciency was made using
sou ces o 210Pb-210Bi, bo h adionuclides in secula equilib-
ium. The con ibu ion o 210Po (decay daugh e o 210Pb) is
a oided by he pulse shape analyze because his is an alpha-
emi e .
A so-called 210Pb-window (low-ene gy chanels) is se-
lec ed o coun ing in he be a-spec um. Howe e he low-
ene gy ail o 210Bi is also coun ed in hese condi ions. Fo
ha he 210Bi con ibu ion mus be co ec ed o he e alua-
ion o he 210Pb ac i i y concen a ion o he sedimen sam-
ples. Anyway, he alue o he coun ing e iciency was 0.749
±0.005, in ou wo king condi ions.
Fo de e mining he co ec ion ac o , , a se ies o sed-
imen samples we e aced wi h known amoun s o 210Pb.
Once he adiochemical p ocedu es p esen ed abo e was ap-
plied, he co ec ion ac o was e alua ed as he slope o a
i ed line (Fig. 1), whe e x- alues whe e mass (ms)o Pb in
e e y p ecipi a e and y- alues whe e he esul o he equa-
ion
y=Rs−Rb
60 ε A mi
being mi he mass o Pb o ca ie , A he ac i i y o ace and
he es o pa ame e s he same as de ined abo e. Acco ding
o ou expe imen he alue o co ec ion ac o , , was 0.622.
2.4. Radiochemical yield
The adiochemical yield o analyses we e e alua ed by a
g a ime ically p ocedu e. Fo ha he mass o Pb ob ained
in he p ecipi a e is compa ed o he mass o Pb o ca ie
FIGURE 1. Resul s ob ained using sedimen samples aced wi h
210Pb. Fi ed line was used o he de e mina ion o co ec ion ac-
o , , o he 210Bi con ibu ion. See ex o a be e comp ehension.
Re . Mex. F´
ıs. S 53 (3) (2007) 97–101
RADIONUCLIDES IN THE ENVIRONMENT IN THE SOUTH OF SPAIN, ANTHROPOGENIC ENHANCEMENTS DUE TO INDUSTRY 99
added o he sedimen aliquo a he s a ing s ep o he p o-
cedu e. Then, an unce ain y due o a possible ac ion o
p ecipi a e, which was no dissol ed, mus be assumed.
This me hod was applied o h ee aliquo s o a same sam-
ple and he s anda d de ia ion o esul s was 1 % (1σ). Fi-
nally, ac i i y concen a ion ob ained in 12 sedimen samples
by liquid scin illa ion coun ing was compa ed wi h he esul s
ob ained by gamma-spec ome y (Hu ado e al., 2004) and
alpha-spec ome y, measu ing 210Po (Absi, 2005), in o de
o make su e de goodness o me hod.
3. Resul s and discussion
Samples o sedimen s we e collec ed in he es ua y o he
Odiel and Tin o i e s (Sou h o Spain). Sampling campaigns
s a ed in 1988 and hey will be con inued un il 2001. The
sampling s a ions we e he same o e e y sampling cam-
paign and can be loca ed in he map o Fig. 2. The ac i i y
concen a ion o 220Pb ob ained in he sampling made in
FIGURE 2. Map o he es ua y o he Odiel and Tin o i e s (Sou h
o Spain).
FIGURE 3. Ac i i y concen a ion o 210 Pb in sedimen s collec ed
in he Odiel Ri e .
FIGURE 4. Ac i i y concen a ion o 210 Pb in sedimen s collec ed
in he Tin o Ri e .
1999 and 2001 in e e y poin a e p esen ed in Fig. 3 ( he
Odiel Ri e ) and Fig. 4 ( he Tin o Ri e ).
The esul s ob ained in he Odiel Ri e in 1999 and 2001
show highe ac i i y concen a ions in he icini y o he
was es discha ges poin (O4), which is consequen wi h he
ole o his o ic iles o sedimen s (Ridgway and Shimmield,
2002). Howe e a dec easing endency can be in e ed om
he mean le els obse ed in 1999 and 2001, which is con-
i med by he 226Ra mean alues obse ed in he same sam-
ples. An easy calcula ion can be used o e alua e a hal -li e o
his dec easing o ac i i y concen a ion o sel -cleaning. Fo
ha we ha e i ed he mean alues (Fig. 5) o an exponen ial
cu e. Then he hal -li e will be 630 days, which is simila o
he hal -li e calcula ed by nume ical models (Pe i´
a˜
nez e al.,
2005).
The esul s o 210Pb in he Tin o Ri e (Fig. 4) show a
homogeniza ion in he ange 50 – 200 Bq/kg. An anomalous
high le el obse ed in 1999 in T3 could be ela ed o an acci-
den o he phosphogypsum pile happened in 1998. Finally,
he high ac i i y concen a ion obse ed in T5 could be con-
side ed as a consequence o he ole o sedimen a ion ocus
o he con luence o bo h i e s (Odiel and Tin o), which can
Re . Mex. F´
ıs. S 53 (3) (2007) 97–101
100 G. MANJ ´
ON
FIGURE 5. A e age ac i i y concen a ion o 210Pb and 226Ra cal-
cula ed in he es ua y o he Odiel and Tin o i e s i ed o he
sampling ime (mon h) coun ed since Janua y 1998. Resul s we e
i ed o an exponen ial unc ion in o de o es ima e a hal -li e co -
esponding o sel -cleaning p ocess.
FIGURE 6. Ac i i y concen a ion o a) 226Ra; b) 210Po; c) 238U;
in sedimen s collec ed in he Odiel Ri e .
FIGURE 7. Ac i i y concen a ion o a) 226Ra; b) 210Po; c) 238U;
in sedimen s collec ed in he Tin o Ri e .
be con i med by he ac i i y concen a ion obse ed in O7 (in
he Odiel Ri e ).
Al hough he dec ease o he ac i i y concen a ion in he
sampling s a ion di ec ly a ec ed by phosphogypsum dis-
cha ges (O4 and T4) was easily obse ed since 1998 (Villa
e al., 2005); a mo e de ailed discussion abou he ime e o-
lu ion o he na u al adionuclides le els in he es ua y could
be made i he es o he es ua y is also conside ed. Fo ha ,
we p esen he ac i i y concen a ion o 226Ra, 210Po-210Pb
and 238U in he samples collec ed in he es ua y since 1988
un il 2002.
Figu e 6 show he ac i i y concen a ion in he Odiel
Ri e sedimen s o 226Ra, 210Po-210Pb and 238U, espec-
i ely. A simila pa e n o ac i i y concen a ion o 226Ra
and 210Po-210Pb is obse ed in hese igu es. These esul s
a e a consequence o he p esence o hese adionuclides in
he phosphogypsum was es. Thus, le els obse ed be o e
1998 a e deeply a ec ed by phosphogypsum was es. How-
e e , le els obse ed a e 1998 show a dec ease un il en i-
onmen al le els obse ed in an una ec ed es ua y.
On he o he hand, he ac i i y concen a ion o 238U in
sedimen s (Fig. 6c) a e simila in ei he he pe iod be o e
Re . Mex. F´
ıs. S 53 (3) (2007) 97–101
RADIONUCLIDES IN THE ENVIRONMENT IN THE SOUTH OF SPAIN, ANTHROPOGENIC ENHANCEMENTS DUE TO INDUSTRY 101
1998 (s op o discha ges) and a e 1998. In his case we
mus no ed he p esence o h ee sou ces o adionuclide in
he es ua y: he phosphogypsum was es, he idal ac ion and
he u anium dissol ed and d i en om he i e head o he
es ua y (G ande e al., 2003; Sainz e al., 2003). This las
sou ce could be he mos impo an in bo h pe iods.
A simila p esen a ion could be made o he esul s ob-
se ed in he Tin o Ri e . Ac i i y concen a ion o na u-
al adionuclides (226Ra, 210Po-210Pb and 238U) in sedimen
samples a e p esen ed in Fig. 7. Na u al adionuclides p esen
in he phosphogypsum piles could a ec ed he Tin o Ri e
sedimen s in he icini y o he piles (T4). Tha is clea ly
obse ed in Figs. 7a and 7b, whe e ac i i y concen a ion o
226Ra and 210Po-210Pb a e p esen ed. Howe e , ac i i y con-
cen a ion o 238U was simila in he samples collec ed be o e
1998 (close o no p o ec ed piles) and a e 1998 (s a o dis-
cha ges in he well-p o ec ed pile). 238U pa e n is a ypical
o a no a ec ed es ua y, inc easing he ac i i y concen a ion
as high as close o he sea.
4. Conclussions
The measu emen o 210Pb ac i i y concen a ion in sedimen
samples collec ed in he es ua y o Odiel and Tin o i e s
ha e con i med he en i onmen al impac o phospho ic acid
in he en i onmen and he sel -cleaning p ocess s a ed in
1998, when di ec was es discha ges we e s opped and a new
well-p o ec ed ai opened pile was used o phosphogypsum
s o age.
Na u al adionuclides, such as 226Ra, 210Po and 210Pb,
ha e p esen ed a di e en dis ibu ion in he es ua y. Be o e
1998 he dis ibu ion shows a deep con amina ion e en , how-
e e na u al le els become ypical o a no a ec ed es ua y
a e 1998.
The case o 238U was clea ly di e en . Al hough a ac-
ion o he amoun o u anium p esen in he aw ma e ial is
p ocessed wi h phosphogypsum, he impac on he i e sed-
imen s could be negligible due o he p esence o u anium
leached om he i e heads and deposi ed in he es ua y.
Acknowledgemen s
This wo k was pa ially suppo ed by ENRESA (Spanish Nu-
clea Was e Managemen En e p ise) and Consejo de Segu i-
dad Nuclea (Spanish Nuclea Sa e y Regula o y Adminis-
a ion). Logis ic help o sampling campaigns was done
by Jun a de Andaluc´
ıa (Regional Go e nmen o Andalusia,
Sou h o Spain). Physicis s, om Uni e sidad de Huel a,
ha e pa ially con ibu ed o ob ain expe imen al da a.
Collabo a ion and assis ance o R. Ga c´
ıa-Teno io, J. M.
Ab il, J. D´
ıaz, M. Villa, S. Hu ado, A. Absi, H. P. Mo eno
and R. Pe i´
a˜
nez a e deeply acknowledged. This p og am
is ali e oday and wo new young esea che s, J. Man e o
and A. Calleja, ha e al eady ob ained impo an esul s. The
wen y-yea old esea ch p og am, de o ed o he adioac i e
con ol o es ua y, has been de eloped unde he supe ision
o P o esso M. Ga c´
ıa-Le´
on.
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