Ci a ion: Cela-Dablanca, R.;
Ba ei o, A.; Fe ei a-Coelho, G.;
Campillo-Co a, C.;
Pé ez-Rod íguez, P.;
A ias-Es é ez, M.;
Núñez-Delgado, A.;
Ál a ez-Rod íguez, E.;
Fe nández-Sanju jo, M.J. Cu and
As(V) Adso p ion and Deso p ion
on/ om Di e en Soils and
Bio-Adso ben s. Ma e ials 2022,15,
5023. h ps://doi.o g/10.3390/
ma15145023
Academic Edi o : Teo il Jesionowski
Recei ed: 2 June 2022
Accep ed: 18 July 2022
Published: 19 July 2022
Publishe ’s No e: MDPI s ays neu al
wi h ega d o ju isdic ional claims in
published maps and ins i u ional a il-
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Copy igh : © 2022 by he au ho s.
Licensee MDPI, Basel, Swi ze land.
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dis ibu ed unde he e ms and
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A ibu ion (CC BY) license (h ps://
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ma e ials
A icle
Cu and As(V) Adso p ion and Deso p ion on/ om Di e en
Soils and Bio-Adso ben s
Raquel Cela-Dablanca 1,* , Ana Ba ei o 1, Gus a o Fe ei a-Coelho 1, Claudia Campillo-Co a 2,
Paula Pé ez-Rod íguez 2, Manuel A ias-Es é ez 2, A elino Núñez-Delgado 1, Espe anza Ál a ez-Rod íguez 1
and Ma ía J. Fe nández-Sanju jo 1
1Depa men o Soil Science and Ag icul u al Chemis y, Enginee ing Poly echnic School,
Uni e si y o San iago de Compos ela, 27002 Lugo, Spain; ana.ba ei [email p o ec ed] (A.B.);
[email p o ec ed] (G.F.-C.); [email p o ec ed] (A.N.-D.); espe anza.al a [email p o ec ed] (E.Á.-R.);
[email p o ec ed] (M.J.F.-S.)
2Soil Science and Ag icul u al Chemis y, Facul y o Sciences, Uni e si y o Vigo, 32004 Ou ense, Spain;
[email p o ec ed] (C.C.-C.); [email p o ec ed] (P.P.-R.); [email p o ec ed] (M.A.-E.)
*Co espondence: [email p o ec ed]
Abs ac :
This esea ch is conce ned wi h he adso p ion and deso p ion o Cu and As(V) on/ om di -
e en soils and by-p oduc s. Bo h con aminan s may each soils by he sp eading o manu e/slu ies,
was ewa e , sewage sludge, o pes icides, and also due o pollu ion caused by mining and indus ial
ac i i ies. Di e en c op soils we e sampled in A Limia (AL) and Sa ia (S) (Galicia, NW Spain).
Th ee low-cos by-p oduc s we e selec ed o e alua e hei bio-adso ben po en ial: pine ba k, oak
ash, and mussel shell. The adso p ion/deso p ion s udies we e ca ied ou by means o ba ch- ype
expe imen s, adding inc easing and indi idual concen a ions o Cu and As(V). The i o he ad-
so p ion da a o he Langmui , F eundlich, and Temkin models was assessed, wi h good esul s in
some cases, bu wi h high es ima ion e o s in o he s. Cu e en ion was highe in soils wi h high
o ganic ma e and/o pH, eaching almos 100%, while he deso p ion was less han 15%. The As(V)
adso p ion pe cen age clea ly dec eased o highe As doses, especially in S soils, om 60–100% o
10–40%. The As(V) deso p ion was closely ela ed o soil acidi y, being highe o soils wi h highe
pH alues (S soils), in which up o 66% o he As(V) p e iously adso bed can be deso bed. The h ee
by-p oduc s showed high Cu adso p ion, especially oak ash, which adso bed all he Cu added in
a a he i e e sible manne . Oak ash also adso bed a high amoun o As(V) (>80%) in a a he
non- e e sible way, while mussel shell adso bed be ween 7 and 33% o he added As(V), and pine
ba k adso bed less han 12%, wi h bo h by-p oduc s eaching 35% deso p ion. Based on he ad-
so p ion and deso p ion da a, oak ash pe o med as an excellen adso ben o bo h Cu and As(V),
a ac a o ed by i s high pH and he p esence o non-c ys alline mine als and di e en oxides and
ca bona es. O e all, he esul s o his esea ch can be ele an when designing s a egies o p e en
Cu and As(V) pollu ion a ec ing soils, wa e bodies, and plan s, and he e o e ha e epe cussions on
public heal h and he en i onmen .
Keywo ds: bio-adso ben s; hea y me als; soil pollu ion; elease; e en ion
1. In oduc ion
The inc easing sp eading o me als and me alloids included in he g oup o he so-
called “hea y me als” in o he soil h ough e ilize s, manu e/slu y, sewage sludge,
i iga ion wi h was ewa e , pes icides, o mining and indus ial ac i i ies has gi en ise o
conce ns abou hei impac on he en i onmen in gene al and human heal h in pa icu-
la [
1
–
4
]. These subs ances en e a ious en i onmen al compa men s (soil, wa e , and
ai ), and a ec di e en li ing beings (mic obial, plan , and animal communi ies) and may
ha e ad e se e ec s on indi idual biological ecep o s and popula ions [
5
]. Thei oxici y
is a ec ed by he di icul ies o o ganisms o achie e hei exc e ion, wi h a endency o
Ma e ials 2022,15, 5023. h ps://doi.o g/10.3390/ma15145023 h ps://www.mdpi.com/jou nal/ma e ials
Ma e ials 2022,15, 5023 2 o 21
bio-accumula e, and, e en in cases whe e hey do no ha e high concen a ions in speci ic
en i onmen s, hey can each ha m ul le els a e passing h ough he ood chain [6,7].
A senic is na u ally p esen in ce ain mine als, bu i s p esence as a pollu an in he
en i onmen can also be caused by ce ain human ac i i ies, such as mining, use o ossil
uels, pes icides, and he bicides. I is a semime al o me alloid ha can occu in ino ganic
o m, wi h he As(III) species being he mos equen in educing condi ions, and As(V) in
well-ae a ed media, while he o ganic o ms (wi h As included in o ganic molecules) a e
quan i a i ely less impo an [
8
]. This elemen causes special conce n due o i s high oxici y,
and i can be mobilized in he mos equen g oundwa e pH alues, hus h ea ening
d inking wa e esou ces [
9
]. I has associa ed ch onic oxic e ec s, inc easing he isks o
de eloping cance s a ec ing he skin, lung, kidney, and li e [
10
,
11
]. De ails ega ding
he e ec s o a senic on oxici y and human heal h ha e been ex ensi ely documen ed in
p e ious pape s [12–16].
As ega ds Cu, i is an essen ial mic onu ien o human beings and o plan de-
elopmen , bu i is oxic when p esen a high concen a ions [
17
,
18
]. I is less mobile
han As, bu high Cu concen a ions can al e cell di ision in some plan s, a ec mic obial
ac i i y, mic oo ganism di e si y, and soil ecosys em se ices [
19
–
22
], and cause damage
o de i i o e popula ions [
23
]. As ega ds he e ec s o Cu on human heal h, ex ensi e
e iews ha e been ca ied ou in p e ious publica ions [24–27].
Soils can ac as a sink o hese pollu an s and educe hei oxici y h ough adso p ion,
p ecipi a ion, o occlusion p ocesses, mainly a ec ed by soil o ganic ma e , low c ys allini y
mine als, and acid–base and edox condi ions [28,29].
The e en ion capaci y o he soil can be an impo an ac o in mi iga ing he oxic
e ec s o hese me als/me alloids, bu , in he long e m, soil adso ben su aces could be
sa u a ed, inc easing he isk o passage o plan s, wa e , and he ood chain. To minimize
his p oblem, di e en emedia ion s a egies ha e been de eloped, mainly aimed a ac ing
on he mobili y o he pollu an s [
30
], including he use o bio-adso ben ma e ials. In
his ega d, s udies ocusing on bio-adso ben s a e o g owing in e es , as an e icien
and low-cos al e na i e o e ain he di e en con aminan s p esen in soils and wa e .
Gene ally, ma e ials ha a e low cos and locally a ailable in la ge quan i ies a e conside ed
a good choice o be assessed ega ding hei e ec i i y [
31
]. The ood and ag o o es y
indus ies p oduce la ge amoun s o was e and by-p oduc s, such as mussel shell, biomass
combus ion ash, and pine ba k, which could be used o his pu pose. Speci ically, p e ious
s udies on pollu an e en ion on o biomass ash showed p omising esul s in in es iga ions
ocused on As [32,33] as well as on Cu [34,35].
In his iew, he objec i e o his wo k is o s udy he e en ion o Cu and As(V) in
cul i a ed soils wi h di e en cha ac e is ics, as well as he capaci y o di e en by-p oduc s
(oak ash, pine ba k, and mussel shell) o immobilize hese con aminan s. The esul s o he
esea ch could be use ul in p og am-app op ia e p ac ices o manage soils and low-cos
by-p oduc s in o de o educe he isks o en i onmen al con amina ion associa ed wi h
he sp eading o ma e ials ha con ain bo h pollu an s.
2. Ma e ials and Me hods
2.1. Soils and By-P oduc s
Fo his esea ch, six c op soils we e selec ed, which we e p e iously sampled a wo
a eas o Galicia (NW Spain) subjec ed o in ensi e a ming: S soils (sampled a Sa ia,
Lugo p o ince) and AL soils (sampled a A-Limia, Ou ense p o ince). The samples we e
aken om he su ace laye (0–20 cm), wi h each one being he esul o combining
10 sub-samples collec ed in a zig-zag manne o each soil. These soils ha e been p e iously
s udied and desc ibed [36].
The o es by-p oduc s used in his s udy we e oak ash om a local boile a Lugo
(Spain), pine ba k ( ac ion less han 0.63 mm), a comme cial p oduc p o ided by Geolia
(Mad id, Spain), and un-calcined mussel shell (<1 mm in diame e ), supplied by Abonoma
Ma e ials 2022,15, 5023 3 o 21
S.L. (Illa de A ousa, Pon e ed a p o ince, Spain). A mo e comple e desc ip ion was
p e iously published [37].
The me hods used o he cha ac e iza ion o soils and by-p oduc s we e he ollowing:
pH in wa e and 0.1 M KCl (soil:solu ion a io 1:2.5), using a pH-me e (pH-model 2001
C ison, Spain); C and N by elemen al analysis (CHNS T uspec, Leco, S . Joseph, MI, USA);
a ailable P by he Olsen me hod [
38
]; exchangeable ca ions, ex ac ed wi h 1 M NH
4
Cl [
39
]
and quan i ied by a omic abso p ion/emission spec ome y; he e ec i e ca ion exchange
capaci y (eCEC) was calcula ed as he sum o exchangeable Ca, Mg, Na, K, and Al; non-
c ys alline Al and Fe (Al
o
, Fe
o
) we e ex ac ed wi h ammonium oxala e acidi ied a pH 3.
All de e mina ions we e pe o med in iplica e.
Tables 1and 2show he main cha ac e is ics o he soils and he h ee by-p oduc s
used, espec i ely.
Table 1.
Main cha ac e is ics o he six soils s udied. A e age alues (n= 3) wi h coe icien s o
a ia ion always lowe han 5%.
Pa ame e Uni s
Soil
3AL 19AL 50AL 6S 51S 71S
pHH2O 4.74 4.80 4.49 6.33 7.06 6.24
pHKCl 4.30 4.25 4.00 5.86 6.39 5.44
Caecmolckg−12.24 1.53 5.94 12.86 9.89 12.79
Mgecmolckg−10.64 0.41 1.48 1.13 0.97 2.88
Naecmolckg−10.35 0.25 0.42 0.36 0.28 0.41
Kecmolckg−11.00 1.27 1.14 0.61 1.40 1.20
Alecmolckg−11.68 0.61 2.66 0.00 0.01 0.11
eCEC cmolckg−15.92 4.08 11.64 14.96 12.54 17.38
Al sa u a ion % 28.43 15.00 22.83 0.00 0.05 0.06
Pmg kg−1117.90 225.43 135.90 71.42 120.03 96.77
N % 0.31 0.09 0.84 0.23 0.19 0.48
C % 3.39 1.07 10.92 1.98 1.75 6.88
OM % 5.84 1.84 18.83 3.41 3.02 11.86
C/N 10.94 11.89 13.00 8.44 9.05 14.21
Sand % 54.72 64.72 58.72 29.28 27.28 61.28
Sil % 26.00 14.00 16.00 49.28 51.28 23.28
Clay % 19.28 21.28 25.28 21.44 21.44 15.44
Alomg kg−15040.0 855.0 2995.0 18,377.5 15,755.7 50,593.5
Feomg kg−12585.0 1150.0 1430.0 56,423.8 42377.4 73,095.9
Ca
e
, Mg
e
, Na
e
, K
e
, and Al
e
= exchangeable concen a ions o he elemen s; Al
o
and Fe
o
= Al and Fe concen a ion
a e ex ac ion wi h ammonium oxala e.
Table 2.
Main cha ac e is ics o he h ee by-p oduc s used. A e age alues (n= 3) wi h coe icien s
o a ia ion always lowe han 5%.
Pa ame e Uni Oak Ash Pine Ba k Mussel Shell
C % 13.23 48.70 11.43
N % 0.22 0.08 0.21
C/N 60.13 608.75 55.65
pHH2O 11.31 3.99 9.39
pHKCl 13.48 3.42 9.04
Caecmolckg−195.00 5.38 24.75
Mgecmolckg−13.26 2.70 0.72
Naecmolckg−112.17 0.46 4.37
Kecmolckg−1250.65 4.60 0.38
Alecmolckg−10.07 1.78 0.03
Al sa u a ion % 0.02 11.91 0.11
eCEC cmolckg−1361.17 14.92 30.25
P-Olsen mg kg−1462.83 70.45 54.17
Alomg kg−18323.00 315.00 178.33
Feomg kg−14233.00 74.00 171.00
Ca
e
, Mg
e
, Na
e
, K
e
, and Al
e
= exchangeable concen a ions o he elemen s; Al
o
and Fe
o
= Al and Fe concen a ion
a e ex ac ion wi h ammonium oxala e.
Ma e ials 2022,15, 5023 4 o 21
Table S1 (Supplemen a y Ma e ials) shows da a on BET su ace a eas o he six soils
s udied, e idencing ha he alues we e highe o S soils. O no e, al hough highe su ace
a ea acili a es achie ing highe adso p ion o a a ie y o subs ances on o soils, o he
ac o s could be o e en highe ele ance, as p e iously s a ed o di e en pollu an s [
40
].
In addi ion, Table S2 (Supplemen a y Ma e ials) shows da a on BET su ace a eas
o he h ee by-p oduc s, e idencing ha he highes alue co esponded o oak ash
(1.3336 m
2
g
−1
), ollowed by mussel shell (1.1318 m
2
g
−1
), and being much lowe o pine
ba k (0.3320 m2g−1).
2.2. Adso p ion and Deso p ion Expe imen s
To pe o m adso p ion s udies, ba ch- ype expe imen s we e ca ied ou , s i ing
1 g o each soil o by-p oduc o 24 h wi h 40 mL o 0.005 M CaCl
2
and wi h di e en
concen a ions o Cu o As(V) (100, 200, 400, 800, and 1000
µ
mol L
−1
), wi h each pollu an
added indi idually. The solu ions we e p epa ed om analy ical g ade Cu(NO
3
)
2
.3H
2
O
and Na
2
HAsO
4
(Pan eac, Ba celona, Spain). A e 24 h o agi a ion, he samples we e
cen i uged (a 4000 pm) and il e ed. In he equilib ium solu ion, he dissol ed o ganic
ca bon (DOC) was de e mined by means o UV-1201 spec oscopy (Shimadzu, Kyo o,
Japan), he pH using a glass elec ode (C ison, Mad id, Spain), and he concen a ions o
Cu o As using an ICP-MS equipmen (Va ian 820-NS, Palo Al o, CA, USA). The amoun o
Cu o As adso bed was calcula ed by he di e ence be ween he added concen a ion and
ha emaining in he equilib ium solu ion.
Rega ding deso p ion expe imen s, 40 mL o 0.005 M CaCl
2
was added o each o he
samples used in he p e ious adso p ion es s, hen s i ing o 24 h, cen i uging, il e ing
and quan i ying Cu o As(V) in he equilib ium solu ion, ollowing he same me hodology
indica ed abo e.
2.3. Da a Analysis and S a is ical T ea men
The expe imen al adso p ion da a we e checked as ega ds hei i ing o he F e-
undlich (Equa ion (1)), Langmui (Equa ion (2)), and Temkin (Equa ion (3)) models:
qa=KFCn
eq (1)
qa=KFCn
eq (2)
qa=βln KT+βln Ceq (3)
whe e q
a
is he amoun o Cu o As(V) adso bed in equilib ium (
µ
mol kg
−1
); C
eq
is he
concen a ion o Cu o As(V) p esen in he solu ion in he equilib ium (
µ
mol L
−1
); K
F
is he
F eundlich a ini y pa ame e (L
nµ
mol
1−n
kg
−1
); nis he F eundlich linea i y pa ame e
(dimensionless); K
L
is a Langmui pa ame e ela ed o he adso p ion ene gy (L
µ
mol
−1
),
and q
m
is he Langmui ’s maximum adso p ion capaci y (
µ
mol kg
−1
). In addi ion,
β
is calcula ed as RT/b ;b is he Temkin iso he m cons an ; Tis Tempe a u e (K = 298
◦
)
(25
◦
C); Ris he uni e sal gas cons an (8314 Pa m
3
/mol K); and K
T
is he Temkin iso he m
equilib ium binding cons an (L g−1).
Deso p ion was exp essed as he amoun o Cu o As(V) deso bed (in
µ
mol kg
−1
, and
also as pe cen age) wi h espec o he amoun p e iously adso bed.
The s a is ical so wa e R e sion 3.1.3 and he nls ools package o R [
41
] we e used o
check he i ings o he adso p ion models. The SPSS 15.0 so wa e was used o ca y ou
bi a ia e Pea son co ela ions be ween adso p ion and deso p ion da a and cha ac e is ics
o he so ben ma e ials, and mul iple linea eg ession analyses.
3. Resul s
3.1. Cu and As(V) Adso p ion on o Soils
The adso p ion cu es o he soils and bio-adso ben s s udied a e shown in
Figu es 1and 2, espec i ely.
Ma e ials 2022,15, 5023 5 o 21
Figu e 1.
Cu and As(V) adso p ion cu es and selec ed g aphical i ings o he a ious adso p ion
models o he six soils s udied. E o ba s ep esen wice he s anda d de ia ion o he mean (n= 3).
When ba s a e no isible, hey a e smalle han he symbols.
Ma e ials 2022,15, 5023 6 o 21
Figu e 2.
Cu and As adso p ion cu es and selec ed g aphical i ings o he a ious adso p ion
models o he h ee bio-adso ben s s udied. E o ba s ep esen wice he s anda d de ia ion o he
mean (n= 3). When ba s a e no isible, hey a e smalle han he symbols.
Figu e 1shows a a ie y o shapes in he adso p ion cu es, wi h di e ences be ween
he AL and S soils. In ac , hese cu es show ha o e all Cu adso p ion was highe o
S soils (which ha e highe su ace a ea) han o AL soils, while As(V) adso p ion was
simila o bo h kinds o soils.
Figu e 2shows ha Cu and As(V) adso p ion esul s we e clea ly highe o oak ash
as compa ed o pine ba k and mussel shell.
Figu e 3shows he esul s co esponding o Cu and As(V) adso p ion on o he di -
e en soils (bo h in absolu e alue and pe cen age) as a unc ion o he concen a ion
added. Conside ing he absolu e alues, i is clea ha he highe he Cu o As(V) concen-
a ions added, he highe he adso p ion o all soils, while he adso bed pe cen age shows
a dec easing end. Adso p ion was gene ally highe o Cu han o As, especially in
S soils.
When he highes Cu o As(V) concen a ions (1600
µ
mol L
−1
) we e added, Cu
maximum adso p ion alues we e eached in soils 51S and 71S (37,687
µ
mol kg
−1
and
44,019
µ
mol kg
−1
, espec i ely), while o As(V), he highes sco es co esponded o soils
50AL and 71S (17,076
µ
mol kg
−1
and 22,980
µ
mol kg
−1
, espec i ely) (Figu e 3). In con as ,
he minimum Cu adso p ion co esponded o soils 19AL and 3AL (5963
µ
mol kg
−1
and
12,523
µ
mol kg
−1
, espec i ely), while o As(V), he minima we e o soils 19AL and 6S
(6290 µmol kg−1and 5868 µmol kg−1, espec i ely).
Rega ding pe cen age adso p ion, wi hin AL soils, he one wi h he highes o ganic
ma e con en (soil 50AL, Table 1) adso bed abou 90% o Cu o he h ee lowes doses
added, while his pe cen age d opped o 57% o he highes dose; howe e , o soil 19AL
Ma e ials 2022,15, 5023 7 o 21
( he one wi h he lowes o ganic ma e con en ), Cu adso p ion ne e exceeded 56%,
being less han 12% o he highes dose. The p og essi e dec ease in he adso p ion a e
a ec ing hese h ee AL soils could be ela ed o a sa u a ion o he adso p ion si es, many
o which would be unc ional g oups in o ganic compounds, and ha dec ease would
be mo e p onounced o hose soils wi h a lowe o ganic ma e con en . In S soils, he
adso p ion was close o 100% o he h ee lowes doses o Cu added, dec easing o 82%
in he soil wi h he highes o ganic ma e con en (soil 71S) and o 56% in soil 6S when
he maximum Cu dose was added, again due o he sa u a ion o he unc ional g oups
in ol ed in adso p ion, many o which lie in o ganic ma e .
Figu e 3.
Cu and As (V) adso p ion, exp essed in
µ
mol kg
−1
and as pe cen age, o he soils s udied,
as a unc ion o he pollu an concen a ions added. E o ba s ep esen wice he s anda d de ia ion
o he mean (n= 3). When ba s a e no isible, hey a e smalle han he symbols.
Table 3shows da a co esponding o Cu and As(V) adso p ion o he a ious ini ial
concen a ions added o bo h pollu an s o he soils s udied, in pa allel o da a co espond-
ing o pH and DOC alues in he equilib ium solu ion.
3.2. Cu and As(V) Deso p ion om Soils
Figu e 4shows he amoun s o Cu and As(V) deso bed om he soils as a unc ion o
he concen a ions added. As he added dose o each elemen inc eased, bo h he amoun
Ma e ials 2022,15, 5023 8 o 21
and he pe cen age deso bed we e highe . All AL soils had a simila deso p ion o bo h
elemen s, while S-zone soils (wi h highe pH) deso bed much mo e As han Cu (Figu e 4).
Table 3.
Values o Cu and As(V) adso p ion (Q) as well o pH and DOC in he equilib ium solu ion
o he a ious Cu and As(V) ini ial concen a ions (C0) added o he soils.
Cu As(V)
Soil C0µmol L−1Qµmol kg−1pH DOC mg L−1Qµmol kg−1pH DOC mg L−1
3AL
0.00 0.00 4.75 0.08 0.00 4.76 0.19
100 2127.04 4.64 0.20 2394.39 4.78 0.19
200 3225.97 4.46 0.13 3764.03 4.97 0.23
400 6951.04 4.43 0.13 6037.21 5.17 0.16
800 10,467.99 4.25 0.12 9344.48 5.37 0.17
1600 12,523.80 4.10 0.10 16,882.19 5.92 0.16
19AL
0.00 0.00 4.71 0.20 0.00 5.00 0.08
100 1433.70 4.57 0.13 888.39 5.19 0.14
200 2088.81 4.45 0.19 1153.99 5.33 0.21
400 3969.43 4.34 0.29 5778.18 5.74 0.09
800 6659.33 4.27 0.17 4126.55 6.11 0.12
1600 5963.30 4.07 0.28 6290.39 6.60 0.09
50AL
0.00 0.00 4.27 0.26 0.00 4.50 0.13
100 2524.26 4.24 0.19 2272.59 4.37 0.18
200 5106.61 4.13 0.26 3939.78 4.38 0.20
400 11,086.25 4.03 0.28 6058.32 4.45 0.28
800 20,244.49 3.79 0.34 10,856.87 4.66 0.23
1600 28,481.45 3.69 0.23 17,075.78 4.89 0.22
6S
0.00 0.00 5.61 0.20 0.00 5.88 0.19
100 2558.33 5.66 0.19 3048.25 5.87 0.12
200 5253.62 6.26 0.13 3015.26 6.33 0.08
400 12,030.50 5.57 0.15 4393.79 6.44 0.09
800 22,000.77 5.07 0.13 5849.58 6.73 0.09
1600 29,540.60 4.75 0.17 5866.52 6.88 0.06
51S
0.00 0.00 6.04 0.16 0.00 6.61 0.15
100 2615.99 6.09 0.18 2016.28 6.80 0.14
200 5202.90 6.06 0.19 3091.30 6.83 0.12
400 12,205.87 5.93 0.14 4485.69 6.85 0.09
800 24,061.91 5.55 0.13 6775.33 6.96 0.12
1600 37,687.91 5.09 0.11 10,962.17 7.18 0.08
71S
0.00 0.00 5.49 0.29 0.00 6.00 0.11
100 2618.82 5.53 0.20 2516.39 5.85 0.09
200 5282.88 5.49 0.19 4786.28 5.84 0.13
400 11,962.35 5.36 0.16 8174.64 5.84 0.14
800 25,655.79 5.13 0.18 14,047.81 5.92 0.13
1600 44,019.57 4.69 0.15 22,979.85 6.07 0.13
In ela ion o Cu, deso p ion was much highe om AL soils han om S soils ( he
la e ha ing a highe su ace a ea). The maximum pe cen age alues o AL soils we e
be ween 39% o he soil wi h less o ganic ma e (19AL) and 12% o he one con aining
mos o ganic ma e (soil 50AL), while he ange o he S zone was na owe : be ween
15% (soil 6S) and 5% (soils 51S and 71S). In gene al, soils wi h low deso p ion alues ma ch
hose wi h high adso p ion sco es.
3.3. Cu and As(V) Adso p ion on o he Th ee By-P oduc s
Figu e 5shows Cu and As(V) adso p ion on o he h ee by-p oduc s as a unc ion
o he concen a ion added. Adso p ion was always much highe o Cu han o As(V),
especially o pine ba k and mussel shell, while o oak ash, he di e ences we e clea ly
smalle , al hough becoming mo e e iden as he added dose inc eased.
Ma e ials 2022,15, 5023 9 o 21
Figu e 4.
Cu and As (V) deso p ion, exp essed in
µ
mol kg
−1
and as pe cen age, o he soils s udied,
as a unc ion o he pollu an concen a ions added. E o ba s ep esen wice he s anda d de ia ion
o he mean (n= 3). When ba s a e no isible, hey a e smalle han he symbols.
Figu e 5.
Cu and As (V) adso p ion, exp essed in
µ
mol kg
−1
and as pe cen age, o he h ee bio-
adso ben s s udied, as a unc ion o he pollu an concen a ions added. E o ba s ep esen wice he
s anda d de ia ion o he mean (n= 3). When ba s a e no isible, hey a e smalle han he symbols.
Ma e ials 2022,15, 5023 16 o 21
ha he ex en is me al(loid)-speci ic when amended o soils. Pa k e al. [
74
] s udied ly and
bo om ash om wood pelle he mal powe plan s, inding ha hese by-p oduc s ha e
a high po en ial o hea y me al emo al, al hough he au ho s ocused speci ically on Cd.
In addi ion, he quali y o he bio-adso ben s is ele an , as shown by Lucchini e al. [
75
]
wo king wi h ash de i ed om Cu-based p ese a i e- ea ed wood, whe e he au ho s
epo ed ha hese by-p oduc s can lead o ex emely high Cu concen a ions in soil and
nega i ely a ec plan g ow h.
In iew o he layou o some o he iso he m g aphs, i could be conside ed ha he
concen a ions o some o he so ben s and/o he concen a ion ange o he so ba es we e
no op imal, in luencing he accu acy o he i ing o a ious models. In his ega d, we
ha e published p e ious pape s dealing wi h hese and o he aspec s ela ed o Cu and As
adso p ion/deso p ion s udies, using simila alues o hose o he cu en wo k o mola
concen a ions o hese pollu an s, which acili a es he easie compa ison o e en ion
e icacy, al hough o he concen a ions and anges would be clea y in e es ing o u u e
in es iga ion, o shed u he and mo e speci ic ligh on he o e all p ocesses. As examples,
he e e ences [76–78] co espond o some o hese pape s.
4.4. Cu and As(V) Deso p ion om he Th ee By-P oduc s
Acco ding o [
79
], Cu binds o OC occupying high-a ini y si es when Cu ac i i y is
low, bu i ha ac i i y inc eases, Cu would also occupy low-a ini y si es, which would
acili a e deso p ion, and his could explain he ob ious inc ease in deso p ion aking place
only in pine ba k as he concen a ion o Cu added ises. In ela ion o he pe cen age
deso bed (Figu e 6), a g adual inc ease is obse ed o pine ba k as he dose o Cu added
ises, eaching a maximum alue o 15%. Fo oak ash and mussel shell, deso p ion a es
we e e y low, no exceeding 2% in any case.
Rega ding As(V), he deso p ion sequence was: mussel shell
≥
pine ba k> oak ash. Fo
mussel shell, As(V) deso p ion inc eases as he added concen a ion ises (Figu e 6), anging
om 186.25 o 1556.26
µ
mol kg
−1
, which co esponds o a alue o 34% as maximum
deso p ion. Fo pine ba k, deso p ion eaches 35%, while o oak ash As(V) deso p ion was
p ac ically ze o, p obably due o he s ong adso p ion aking place a i s high pH alues,
especially adso p ion on he Fe and Al oxy-hyd oxides e y abundan in his by-p oduc
(Table 2), as indica ed abo e. This shows he excellen adso p ion capaci y o oak ash o
bo h Cu and As(V).
4.5. Fi ing o Cu and As(V) Expe imen al Da a o Di e en Adso p ion Models
Table 4shows ha he Langmui q
m
pa ame e , ela ed o adso p ion capaci y, is
gene ally highe o Cu han o As(V), and o soils and by-p oduc s ha ing highe pH
alues. In addi ion, among he mos acidic soils and so ben s, q
m
is highe o hose wi h
highe o ganic ma e con en , which will be he ones equi ing highe concen a ions o
hese elemen s o become sa u a ed [
80
]. The q
m
alues ob ained o Cu a e signi ican ly
co ela ed wi h he N con en ( = 0.838, p< 0.01), N being ela ed o o ganic ma e ,
which co obo a es he ole o o ganic subs ances in Cu adso p ion. Rega ding As(V),
q
m
alues a e signi ican ly and posi i ely co ela ed wi h he ca ion exchange capaci y
( = 0.905), Ca ( = 0.864), K ( = 0.913), and pH
KCl
( = 0.71), which could sugges ha he
As adso bed is in anionic o m, wi h adso p ion aking place h ough a ca ionic b idge
on he nega i ely cha ged componen s o a iable cha ge (mainly o ganic ma e and
non-c ys alline mine als).
As ega ds he Langmui K
L
pa ame e , i s alue was highe o Cu han o As(V),
which sugges s a highe adso p ion ene gy o Cu [
81
]. K
L
is signi ican ly and posi i ely
co ela ed wi h pH in wa e ( = 0.95, p< 0.01, o Cu, and = 0.74, p< 0.05, o As),
indica ing an inc ease in he e en ion ene gy wi h inc easing nega i e soil cha ge.
The alues o he F eundlich pa ame e K
F
pa ame e , ela ed o he mul ilaye
adso p ion capaci y o a gi en adso ben [
82
], we e also much highe o Cu han o
As(V) (Table 5). In gene al, he highes K
F
alues we e ound in hose soils and by-
Ma e ials 2022,15, 5023 17 o 21
p oduc s ha ing highe pH, wi h a signi ican co ela ion (p< 0.01) be ween K
F
and pH
H2O
( = 0.941 and 0.85 o Cu and As, espec i ely) and also be ween K
F
and a pa ame e
closely ela ed o soil pH, especially in soils wi h a iable cha ge, which is eCEC ( = 0.89
and 0.88 o Cu and As, espec i ely). The nF eundlich pa ame e indica es he eac i i y
and he e ogenei y o he ac i e si es o he adso ben , wi h Table 5showing ha he n
alue is always lowe han 1 (speci ically, i a ies be ween 0.219 and 0.649), excep o Cu
adso p ion on oak ash. This indica es he exis ence o non-linea and conca e adso p ion
cu es, wi h he e ogeneous adso p ion su aces, which leads o a dec ease in adso p ion
si es as he added me al/me alloid concen a ion inc eases [
83
], which coincides wi h he
dec ease in he adso bed pe cen age as he dose o Cu and As added inc eases.
Temkin’s model is ela ed o he adso p ion ene gy and is cha ac e ized by a uni o m
dis ibu ion o binding ene gies up o a maximum le el [
84
]. I is also assumed ha his
ene gy dec eases linea ly wi h su ace co e age due o adso ben –adso ba e in e ac ions.
The Temkin pa ame e s in he cu en s udy show R
2
alues gene ally >0.80. Acco ding
o [
85
], alues o he Temkin cons an (b ) lowe han 20 KJ mol
−1
would indica e he
exis ence o physical adso p ion p ocesses. Table 4shows ha , in gene al, b alues a e
always highe , which would jus i y he p esence o chemiso p ion eac ions [
84
]. Acco ding
o [
86
], hese high b alues would indica e a high deg ee o in e ac ion be ween bo h
pollu an s (As and Cu) and he adso ben s used in he p esen s udy.
5. Conclusions
In he soils and by-p oduc s used in his s udy, adso p ion was highe o Cu han
o As(V). In he soils, pH and o ganic ma e con en we e he mos in luen ial ac o s as
ega ds Cu adso p ion, which inc eased wi h bo h pa ame e s. In addi ion, Cu in ca ionic
o m would be adso bed by binding o he nega i ely cha ged si es gene a ed by aising
he pH in he a iable cha ge componen s (mainly o ganic ma e and low-c ys allini y
mine als). Rega ding As(V) adso p ion, he in luence o pH and o ganic ma e was no so
clea , since, a a low pH, As in anionic o m binds o he posi i ely cha ged colloids, while a
highe pHs, o he mechanisms in e ene, such as ca ionic b idges o ligand exchange. Fo
As(V) and, o a lesse ex en , o Cu, he pe cen age o adso p ion dec eases wi h inc easing
dose o he added pollu an , indica ing he sa u a ion o he adso p ion si es. Rega ding
deso p ion, in soils wi h mo e acidic pH (AL soils), Cu and As deso p ion we e simila ,
while in soils wi h highe pH (S soils), mo e As is deso bed. O e all, oak ash pe o med as
an excellen Cu and As(V) adso ben and could be used in soil and wa e decon amina ion
p ocesses, possibly due o i s high pH and con en o ca bona es, oxides, and non-c ys alline
mine als. Mussel shell and pine ba k could also be used o e ain Cu, bu i s capaci y o
adso b As was low and i s deso p ion was high. The adso p ion da a o bo h elemen s
can be pa ially i ed o he Langmui , F eundlich, and Temkin models. The alues o
he di e en pa ame e s o he equa ions indica e a highe adso p ion ene gy o Cu on o
he so ben su aces, compa ed o As(V), and he exis ence o he e ogeneous adso ben
su aces wi h he g adual sa u a ion o he adso p ion si es, as well as he p edominance o
chemiso p ion eac ions. In addi ion, he high co ela ions ob ained among he di e en
pa ame e s o he equa ions and pa ame e s o he so ben s suppo he in luence o pH,
exchange ca ions, as well as o ganic ma e and non-c ys alline Fe and Al oxy-hyd oxides in
Cu and As(V) adso p ion. These esul s can be conside ed ele an o p og am an app op ia e
managemen o soils a ec ed by Cu and As(V) pollu ion, as well as he use o low-cos
bio-adso ben s, such as hose es ed in his s udy. In u u e esea ch, soils wi h di e en
cha ac e is ics could be e alua ed, as well as o he bio-adso ben s and/o s udy condi ions,
and on he o he hand, complemen a y s udies could be designed in o de o ad ance
he elucida ion o he mechanisms ha in e ene in he adso p ion p ocesses o bo h
con aminan s in he so ben ma e ials unde conside a ion.
Ma e ials 2022,15, 5023 18 o 21
Supplemen a y Ma e ials:
The ollowing suppo ing in o ma ion can be downloaded a :
h ps://www.mdpi.com/a icle/10.3390/ma15145023/s1, Table S1: Da a co esponding o he BET
su ace a ea esul s o he six soils s udied. Mean alues (n= 3) wi h coe icien s o a ia ion
always <5%; Table S2. Da a co esponding o he BET su ace a ea esul s o he h ee bio-adso ben
ma e ials s udied. Mean alues (n= 3) wi h coe icien s o a ia ion always <5%.
Au ho Con ibu ions:
Concep ualiza ion, M.J.F.-S., E.Á.-R., A.N.-D., M.A.-E. and P.P.-R.; me hod-
ology, M.J.F.-S., E.Á.-R., A.N.-D., M.A.-E. and P.P.-R.; so wa e, R.C.-D., A.B., G.F.-C. and C.C.-C.;
alida ion, M.A.-E., A.N.-D., E.Á.-R., A.N.-D. and M.J.F.-S.; o mal analysis, R.C.-D.; in es iga ion,
R.C.-D., A.B., G.F.-C. and C.C.-C.; esou ces, E.Á.-R., M.J.F.-S. and M.A.-E.; da a cu a ion, R.C.-D.,
A.B., M.J.F.-S. and E.Á.-R.; w i ing—o iginal d a p epa a ion, R.C.-D., A.B., M.J.F.-S. and E.Á.-R.;
w i ing— e iew and edi ing, A.N.-D.; isualiza ion, R.C.-D., A.B., G.F.-C., C.C.-C., P.P.-R., M.A.-E.,
A.N.-D., E.Á.-R. and M.J.F.-S.; supe ision, M.J.F.-S.; p ojec adminis a ion, E.Á.-R., M.J.F.-S. and
M.A.-E.; unding acquisi ion, E.Á.-R., M.J.F.-S. and M.A.-E. All au ho s ha e ead and ag eed o he
published e sion o he manusc ip .
Funding:
This wo k was suppo ed by he Spanish Minis y o Economy and Compe i i eness (g an
numbe s RTI2018-099574-B-C21 and RTI2018-099574-B-C22), wi h Eu opean Regional De elopmen
Funds (FEDER in Spain).
Ins i u ional Re iew Boa d S a emen : No applicable.
In o med Consen S a emen : No applicable.
Da a A ailabili y S a emen : No applicable.
Con lic s o In e es :
The au ho s decla e no con lic o in e es . The unde s had no ole in he design
o he s udy; in he collec ion, analyses, o in e p e a ion o da a; in he w i ing o he manusc ip , o
in he decision o publish he esul s.
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