Nuclea Ins umen s and Me hods in Physics Resea ch B75 (1993) 334-337
No h-Holland NOM B
Beam In e ac ions
wi h Ma e ials&A oms
En i onmen al con ol o Tin o and Odiel i e basins by PIXE *
M.A. Respaldiza a, A. J. Lbpez-Ta ida b and J. G6mez-Camacho a
a Dp o. Fisica A hica, Molecula y Nuclea , Facul ad de Fisica, Uni e sidad de Se illa, Apdo. 1065, 41080 Se illa, Spain
b Dp o. Fisica Aplicada, E.U. A qui ec u a Tknica, Uni e sidad de Se illa, Se illa, Spain
A s udy o he elemen al concen a ions o sedimen s o he i e s Tin o and Odiel, in Huel a, Spain, has been pe o med using
PIXE. Thi een samples ha e been collec ed, se en in he Tin o and six in he Odiel. Concen a ions o 19 elemen s ha e been
de e mined in each o hem. The analysis o he da a illus a es he en i onmen al impac o he mining and e ilize plan s in he
a ea.
1. In oduc ion
Sedimen s om i e basins cons i u e a na u al
a chi e om which many use ul da a can be ob ained.
In pa icula , om he de e mina ion o elemen al
concen a ions, specially o hea y elemen s, he en i-
onmen al impac o human ac i i y on he lu ial
ecosys em can be in e ed.
A echnique e y sui ed o de e mine elemen al
concen a ions is TTPIXE [l]. Some o i s ad an ages
a e he sho collec ion ime (a ew minu es pe sam-
ple), he sensi i i y (ppm) and he mul ielemen al cha -
ac e , ha allows he de e mina ion o all elemen s a
he same ime.
Ou s udy is abou he i e s Tin o and Odiel, in he
p o ince o Huel a, in he sou h-wes o Spain. Tha
a ea was hea ily indus ialized om 1950 o 1960, and
has mining indus ies and phospha e e ilize indus-
ies placed mos ly along he Odiel. As a esidue o he
e ilize plan s, gypsum piles we e o med be ween he
i e s (see ig. 1). We ha e analyzed 13 samples o
sedimen s, aken in 11 poin s du ing he summe o
1989, 5 along he Tin o and 6 along he Odiel. The
loca ion o hese poin s is shown on ig. 1.
2. Expe imen al me hods
Each o he samples was homogeneized. The wa e
con en was de e mined by desicca ion a 100°C. The
o ganic ma e ac ion was ob ained by calcina ion a
550°C ( able 1). I should be poin ed ou ha sample
05 has a e y small con en in wa e and o ganic
ma e . We shall see la e ha his sample is composed
* Wo k pa ially suppo ed by he p ojec DGICyT PB89-
0621.
Else ie Science Publishe s B.V.
mos ly o i on and hea y me als coming om he
UERT (Uni6n Explosi os Rio-Tin 0 SA), a mine al
p ocessing plan . On he o he hand, samples Tl and
06 ha e he la ges con en in o ganic ma e . This
may be due o he ac ha hey a e he leas a ec ed
by indus ial pollu ion.
La e , 333 mg o sedimen and 133.5 mg o wax
Hoechs -C we e mixed, homogeneized and p essed in o
pelle s o 11 mm diame e . The pelle s we e analyzed
by TTPIXE using 1.7 MeV p o ons om he Van de
G aa accele a o o he LNETI (Saca Cm, Po ugal)
[2]. Cha ac e is ic X- ays we e measu ed wi h a Si(Li)
de ec o , wi h 0.2 keV esolu ion a 5.9 keV, connec ed
o a mul ichannel analyze h ough a con en ional
elec onic chain. Two uns we e made on each pelle ,
one wi h 7 nA in ensi y, o accumula e 1 JLC cha ge,
and he o he wi h 25 nA in ensi y, o accumula e 20
p,C cha ge, bu pu ing a C il e 10 km wide in on
Table 1
Wa e and o ganic ma e con en s (in %) ob ained in Tin o
and Odiel i e sedimen s. Numbe s wi hin pa en heses e e
o he e o o he las igu e.
Tl
T2A
T2B
T3
T4A
T4B
T5
01
02
03
04
05
06
Wa e O ganic ma e
4.079 (2) 12.026 (2)
3.380 (2) 8.505 (2)
3.308 (2) 8.601 (2)
3.234 (2) 6.724 (2)
3.188 (2) 7.024 (2)
3.112 (2) 8.006 (2)
3.032 (2) 6.119 (2)
2.140 (2) 6.985 (2)
2.827 (2) 8.938 (2)
1.962 (2) 8.677 (2)
1.648 (2) 6.047 (2)
0.490 (2) 0.326 (2)
3.810 (2) 13.749 (2)
MA. Respaldiza e al. / En i onmen al con ol o i e basins 335
Fig. 1. Map
B gypsum piles
co esponding o he sampling s a ions o Tin o and Odiel i e s a ound he own o Huel a (by cou esy o G.
and A. Ma inez).
Manj6n
o he Si(Li) de ec o o supp ess he so X- ays.
Cha ge build-up e ec s we e supp essed by using an
elec on gun placed inside he sca e ing chambe .
The X- ay spec a we e i ed using he code AXIL
[3]. The elemen al concen a ions we e ob ained om
TI’PIXE o malism, using ou own code [4]. Ligh
elemen s (13 I Z I 26) and Sn concen a ions we e
ob ained om he da a wi hou il e . Hea y elemen s
we e ob ained om he da a wi h he C il e . The
con en in oxygen was de e mined assuming a ypical
s oichiome y o he me allic oxides [4]. The con en in
C, H, 0 and N o he wax was gi en by he manu ac-
u e . The Na an Mg con en s we e de e mined by
a omic abso p ion spec ome y.
3. Resul s and discussions
Concen a ions o 19 elemen s we e ob ained o
each sample. Tables 2 and 3 show he concen a ion o
he majo elemen s (w .%) in he i e s Tin o and
Odiel espec i ely, and ables 4 and 5 show he concen-
a ion o he mino elemen s (ppm).
Table 2
Mass concen a ion (in %) o he majo elemen s in Tin o i e sedimen s. Numbe s wi hin pa en heses e e o he e o o he
las igu e (ND : no de ec ed).
Tl T2A T2B T3 T4A T4B T5
Al 1.1 (2) 8.0 (5) 7.6 (4) 9.1 (5) 8.0 (5) 7.6 (4) 7.1 (4)
Si 6.8 (4) 16.5 (8) 18.0 (9) 24 (1) 20 (1) 21 (1) 22 (1)
P ND 1.0 (1) 0.8 (1) 1.7 (1) 3.6 (3) 3.7 (2) 5.8 (4)
s 12.7 (6) 15.7 (8) 14.5 (7) 4.6 (2) 6.4 (3) 5.8 (3) 5.5 (3)
K 0.55 (3) 2.0 (1) 2.2 (1) 2.1 (1) 1.8 (1) 1.8 (1) 1.6 (1)
Ca 0.34 (2) 11.9 (6) 10.5 (5) 2.9 (2) 1.3 (1) 1.3 (1) 2.7 (1)
Fe 47 (2) 7.7 (4) 8.5 (4) 10.2 (5) 14.1 (7) 14.0 (7) 8.9 (4)
IV. ENVIRONMENTAL SAMPLES
336 M.A. Respaldiza e al. / En i onmen al con ol o i e basins
Table 3
Mass concen a ion (in %) o he majo elemen s in Odiel
i e sedimen s. Numbe s wi hin pa en heses e e o he
e o o he las igu e.
01 02 03 04 05 06
Al 9.4 (5) 9.4 (5) 1.2 (2) 5.3 (3) 2.3 (2) 8.8 (5)
Si 18.4(9) 18.1 (9) 5.7 (3) 20 (1) 3.1 (2) 15.1 (8)
P 4.9 (3) 4.6 (3) 3.4 (2) 5.4 (3) 0.6 (1) 7.9 (4)
S 6.9(4) 6.8 (4) 22 (1) 3.2(2) 1.6 (1) 5.4(3)
K 1.8(l) 2.1 (1) 0.57 (4) 1.0(l) 0.19 (1) 1.5 (1)
Ca 2.1 (1) 3.0 (2) 32 (2) 15.1 (8) 0.19 (1) 5.2(3)
Fe 12.3 (6) 11.6 (6) 1.1 (1) 4.5 (2) 56 (3) 11.0(6)
T2A and T2B a e wo independen samples co e-
sponding o he same sampling poin T2. The same is
ue o T4A and T4B, co esponding o T4. The ac
ha esul s a e compa ible suppo s he ep oducibili y
o ou analysis.
The sample Tl was aken in Niebla, 40 km up-s eam
he Tin o Ri e . I was aken o iginally o p o ide da a
ee om indus ial pollu ion. Howe e , i has a high
con en in i on (47%) and o he me als, ha is cha ac-
e is ic o he zone. In ac , he name “Tin o” e e s o
he ed colo o he wa e s ( in o is he Spanish o ed
wine), coming om i on oxides. I should be no iced
ha up-s eam i he Rio in o mine is placed, om
which Fe and Cu a e ob ained om he py i e mine al.
So he abundance o py i e in he a ea can also explain
he high con en in S (12.7%).
The es o he samples o i e Tin o ha e much
lowe alues o i on. Sulphu le els also dec ease,
excep in he si e T2, whe e he high le els in sulphu
(15.1%) a e co ela ed wi h high le els in calcium
(11.2%). This is due o he p oximi y o a gypsum pile.
In ac , om he sampling poin T2 a pipe could be
seen d aining he pile o he i e .
Samples T3 o T5 show an impo an inc ease in he
concen a ion o P, as one goes downs eam (0.9% o
T2, 1.7% o T3, 3.6% o T4 and 5.8% o T5). This
con amina ion comes p obably om he ac o ies along
he Odiel i e and i is in oduced in he Tin o i e
due o he e ec s o he ides. Simila e ec s we e
seen in adiac i i y measu emen s [5].
In he Odiel i e , he samples 01 and 02 do no
show e idence o an h opogenic con amina ion, excep
o he high con en s o P and Fe. Samples 03 and 04
we e aken close o Fo e S.A. and Fos o ico Espaiiol
S.A. espec i ely, wo plan s ha p oduce e ilize s
ich in phospho us. They accumula e solid esidues in
gypsum piles (Bl and B2 in he map). The con amina-
ion in 03 is cha ac e ized by he high le els o Zn
(1.6%) and Cl (4.7%). This may be ela ed o he
p esence o sal -wo ks nea 03, in he bank opposi e o
he ac o y. High le els o S and Ca in 03 and 04
come om gypsum (phosphogypsum) eleased di ec ly
by he ac o ies. I should be no iced ha he P-le els
ligh ly inc ease owa ds he sea (excep o 05, whe e
hea y me als con amina ion masks his e ec ), and also
a ec he Tin o Ri e as we men ioned be o e.
Sample 05 was aken close o UERT. The con en
in Fe (56%) is abou i e imes la ge han he o he
samples in he Odiel i e and in he Tin o i e , wi h
he excep ion o Tl. Simila inc eases a e ound in
o he hea y me als like Zn (2.1%), Pb (4.7 X lo3 ppm)
and Cu (6.6 x lo3 ppm), and consequen ly he e is a
educ ion in “na u al” elemen s as Al (2.3%) and Si
(3.1%). Thus, UERT seems o be he main sou ce o
con amina ion o hea y me als in he i e Odiel.
Rega ding he mino elemen s, i should be poin ed
ou ha he y ium, no de ec ed in he Tin o i e ,
can be seen in he Odiel i e , wi h concen a ions o
abou 100-400 ppm. One should expec ha he ele-
men s coming om he na u al composi ion o he
Table 4
Mass concen a ion (in lo3 ppm) o he mino elemen s in Tin o i e sedimen s. Numbe s wi hin pa en heses e e o he e o o
he las igu e (ND : no de ec ed).
Tl T2A T2B
Ti 1.7 (1) 3.5 (2) 3.9 (3)
Sn ND ND ND
Zn 7.6 (4) 3.3 (2) 1.31 (7)
Pb 1.1 (2) 1.9 (1) 1.9 (1)
Cl ND ND ND
cu 0.77 (5) 0.61 (3) 0.72 (4)
As 2.4 (1) 0.68 (4) 0.86 (4)
Mn 0.09 (1) 0.15 (1) 0.20 (2)
C ND 0.15 (8) 0.08 (8)
Rb ND 0.027 (3) 0.052 (5)
S ND 0.16 (1) 0.22 (1)
Y ND ND ND
T3 T4A T4B T5
4.1 (2) 4.0 (2) 4.4 (3) 3.8 (2)
ND ND ND ND
5.5 (3) 2.2 (1) 2.6 (1) 4.9 (2)
1.22 (6) 2.8 (1) 3.4 (2) 1.18 (6)
5.0 (4) 0.8 (2) 0.9 (2) 4.2 (3)
1.16 (6) 2.2 (1) 2.2 (1) 1.87 (9)
1.02 (5) 1.83 (9) 1.73 (9) 1.15 (6)
0.24 (2) 0.26 (2) 0.26 (2) 0.20 (1)
0.12 (6) 0.15 (7) 0.16 (8) 0.25 (8)
0.035 (3) 0.033 (5) ND ND
0.139 (9) 0.27 (2) 0.25 (2) 0.34 (2)
ND ND ND ND
MA. Respaldiza e al. / E:lL~~ o~ nen~al con ol o ice basins 337
Table 5
Mass concen a ion (in 10” ppm) o he mino elemen s in Odiel i e sedimen s. Numbe s wi hin pa en heses e e o he e o o
he las igu e (ND: no de ec ed).
Ti
Sn
Zn
Pb
Cl
cu
As
Mn
C
Rb
S
Y
01 02 03 04 05 06
4.6 (3) 5.0 (3) 1.6 (2) 2.8 (2) ND 4.2 13)
ND ND 10(l) 5.7 (7) ND ND
2.7 (1) 2.6 (1) 15.8 (8) 2.4 (1) 21(l) 4.0 (2)
2.1(l) 2.1(l) 0.31 (2) 0.77 (4) 4.7 (31 1.50 (8)
0.8 (2) 7.7 (5) 47 (2) 4.8 (3) 0.8 (1) 3.1(3)
1.82 (9) 2.2 (1) 0.31 (2) 2.2 (1) 6.6 (3) 2.6 (i
1.83 (9) 1.15 (5) 0.070 (5) 0.32 (2) 2.0 (1) 1.60 (8)
0.35 (3) 0.34 (2) 0.036 (4) 0.14 (2) ND 0.25 (2)
0.13 (8) ND 0.4 (1) 0.5 (1) ND ND
ND 0.030 (3) ND ND 0.04 (1) ND
0.39 (2) 0.45 (3) 0.20 (1) 0.40 (2) ND 0.59 (3)
0.126 (9) 0.26 (2) 0.145 (9) 0.37 (21 ND 0.31 (2)
sedimen s should dec ease sha ply in si es 03, 04 and
05, due o he con ibu ion o an h opogenic ma e ial.
Tha is he case o Ti and Mn. Tin and ch omium can
mos ly be seen in 03 and 04, so hey a e p obably
p oduced in he e ilize plan s. A senic can be seen
in 05 bu no in 03 and 04, showing ha is p obably
eleased by UERT.
To summa ize, we ha e shown ha PIXE analysis
o sedimen s p o ides e y use ul in o ma ion o de e -
mine he en i onmen al impac o indus ies in he
i e s Tin o and Odiel. This analysis, howe e , is p e-
limina y and should be con i med wi h mo e da a,
complemen ed wi h chemical and geological in o ma-
ion and co ela ed wi h measu emen s o adiac i e
iso opes.
The au ho s acknowledge he use o he PIXE
acili ies o he Depa men o Physics o he LNETI
and he kind hospi ali y and mul iple help ecei ed
om i s s a . D s. R. Ga cia-Tenci io and M. Ga cia-
Leon also ecei e ou g a i ude o hei help ui com-
men s and sugges ions.
Re e ences
M.A. Respaldiza, R. Ga cia-Teno io and F. El-Daoushy,
Nucl. Ins . and Me h. B64 (1992) 538.
M.A. Respaldiza, G. Madu ga and J.C. Soa es, Nucl.
Ins . and Me h. B28 (1987) 67.
H. Nullens and P. Van Espen, P o-Axil Use ’s Manual
(Canbe a Elek onik, Vienna, 1984).
M.A. Respaldiza, M. Ga cia-Leon and G. Madu ga, J.
T ace Mic op obe Techn. 6 (1988) 87.
C. Manjon, A. Ma inez-Agui e and M. Ga cia-Leon,
Nucl. Ins . and Me h. A312 (1992) 231.
IV. ENVIRONMENTAL SAMPLES