Applied Geochemistry 25 (2010) 1688–1698

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Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem

Effects of desferrioxamine-B on the release of arsenic from volcanic rocks

Barbara Casentini ⇑, Maurizio Pettine
Istituto di Ricerca sulle Acque, Water Research Institute CNR, Via Salaria km 29300, 00015 Monterotondo (RM), Italy

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

Article history: Microorganisms play an important role in As mobilization into groundwater by directly influencing As
Received 14 April 2010 speciation or indirectly inducing solubilisation from As-bearing phases, such as Fe, Mn and Al oxides. Iron
Accepted 27 August 2010 oxide dissolution could also be induced by siderophores, small-molecule compounds produced by micro-
Available online 25 September 2010
organisms to favour Fe uptake. Well waters exceeding the potable water limit of 10 lg As L1 (0.133 lM)
Editorial handling by B.T. Ngwenya
have been widely reported in geothermal areas. Mechanisms responsible for these high As concentrations
have not yet been thoroughly elucidated and the complexity of As mobilization in volcanic aquifers is still
open to multiple interpretations. The present study was based on batch release experiments aimed at
verifying and quantifying the effect of siderophores on As mobilization from volcanic rocks (lava, tuff,
peperino and fallout deposit) at different pH and ligand concentration. In the experiments the sidero-
phore trihydroxamate desferroxamine B (Dfob) was used and its effect on As release from volcanic rocks
was manifest after the first days. The most favourable pH for As release was pH 6 while concentrations
above 250 lM Dfob considerably enhanced As and Fe concentrations in solution. The As release from
rocks was between 2.0–10% at pH 6 and 2.4–8.8% at pH 8. The As/Fe ratio in solution changed with time
suggesting different release mechanisms and higher mobility of As compared to Fe during the first phase
of the experiment. The presence of siderophore increased Fe dissolution rates up to 10 orders of magni-
tude. The As release correlated with Al, Mn, Fe, Si, V, Ga and Sb and the release of all these elements
increased with increasing Dfob concentration. In alkaline environments also Cu, Zn and Pb were mobi-
lized. The presence of siderophores represents a possible trigger for As mobilization from iron binding
minerals to the water phase, with interesting implications for groundwater quality, plant uptake and bac-
terial communities.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction Arsenic associated with geothermal waters has been reported in

Arsenic is considered an ubiquitous element, occurring as a ma-
jor constituent in more than 200 minerals. In the Earth’s crust its
average concentration is 2–5 mg kg1 although much higher con-
tents may be found in Fe deposits, sedimentary Fe ores, Mn nodules
and arsenian pyrite (Mandal and Suzuki, 2002; Smedley and Kinni-
burgh, 2002). Anthropogenic sources of As are represented by As-
containing pesticides, dust from burning fossil fuels, disposal of
industrial and animal wastes, drug preparations, feed additives,
desiccant and wood preservatives, leachates from mining activities,
and highly soluble As2O3 stockpiles (Ferguson and Gavis, 1972;
Smedley and Kinniburgh, 2002). Geogenic materials are also signif-
icant contributors to high As concentrations in water: organic-rich
or black shales, Holocene alluvial sediments with slow flushing
rates, mineralized and mined areas (most often Au deposits), volca-
nogenic sources and thermal springs (Nordstrom, 2002). Volcanic
rocks, especially ashes, are often implicated in the generation of
high-As waters although they do not have high As concentrations.
⇑ Corresponding author. Tel.: +39 06 90672769; fax: +39 06 90672787.
E-mail address: casentini@irsa.cnr.it (B. Casentini).
Argentina, Japan, New Zealand, Chile, Kamchatka, Iceland, France,
Dominica, USA, Italy, China and Greece (Nicolli et al., 1989; Mandal
and Suzuki, 2002; Smedley and Kinniburgh, 2002; Smedley et al.,
2002; Bundschuh et al., 2004; Aiuppa et al., 2006; Kouras et al.,
2007).
Groundwater aging processes and changes in the pH conditions
of the aquifer are involved in As mobilization (Pedersen et al.,
2006). Well known As release mechanisms are also the oxidation
of As-sulfide minerals, reduction of Fe(III) oxy-hydroxide (HFO),
complexation in the presence of organic matter, anion exchange
with competitive ions such as phosphate, carbonate, fluoride and
silicate (Buglyó et al., 1995; Cornell and Schwertmann, 1996;
Appelo et al., 2002; Bose and Sharma, 2002; Sracek et al., 2004;
Casentini et al., 2010). The long-term fate of As in aqueous environ-
ments is strongly controlled by sorption/mobilization mechanisms
onto/from Fe oxyhydroxides (Goldberg and Johnston, 2001;
Sherman and Randall, 2003; Wang and Mulligan, 2008). The struc-
ture and the role of oxides, especially those of Fe, Mn and Al have
been widely studied (Stumm and Morgan, 1996; Fendorf et al.,
1997; Hiemstra and Van Riemsdijk, 1999; Appelo and Postma,
2005). In particular, detailed studies have been conducted on redox

0883-2927/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apgeochem.2010.08.016
 B. Casentini, M. Pettine / Applied Geochemistry 25 (2010) 1688–1698
changes involving those oxides and the effect of re-crystallization
processes responsible for both As(V) and As(III) release (Cornell
and Schwertmann, 1996; Bose and Sharma, 2002; Dixit and Hering,
2003; Radloff et al., 2007). Natural organic matter can affect the
fate and mobility of As species in the environment by competing
for available adsorption sites, acting as an electron donor for
microbes respiring on As-bearing Fe(III) or Mn(IV) mineral phases
or As(V) itself, forming aqueous complexes and/or changing the re-
dox potential of site surfaces (Grafe et al., 2002; Nicholas et al.,
2003; Islam et al., 2004; Lin et al., 2004; McArthur et al., 2004; Bus-
chmann et al., 2006; Wang and Mulligan, 2006; Rowland et al.,
2007). Molecular-scale microbial activities are often able to influ-
ence large-scale environmental processes (Newman and Banfield,
2002) and over time microorganisms probably play an essential
role in both the direct reduction or oxidation of As species and
indirect solubilisation from As-bearing minerals (Langner and Ins-
keep, 2000; Oremland and Stolz, 2003, 2005; Weldon and MacRae,
2006).
Iron in aerobic soils is sequestered into minerals and scarcely
available to microorganisms. Calculated free Fe concentrations in
pore solutions is in the range of 109–1018 M (Miethke and Mar-
ahiel, 2007). Many organisms have developed a strategy to produce
small-molecule compounds called siderophores (generally <1 kDa)
that strongly bind Fe, inducing mineral dissolution, (Neilands,
1995; Macrellis et al., 2001; Boukhalfa and Crumbliss, 2002; Kra-
emer, 2004) and shuttle this element to cell surfaces. Siderophores
are produced and released into the soil by some bacteria, fungi and
plants in terrestrial and marine environments (Granger and Price,
1999; Butler, 2005; Winkelmann, 2007). In natural systems sider-
ophore concentrations are generally low, previous studies mea-
sured 0.3–7 nM in marine environments (Kraemer, 2004), 0.01–
0.1 lM hydroxamate in soil (Powell et al., 1980), 2–12 nM sidero-
phore, identified as ferrichrome and ferricrocin in podzolic forest
soils (Essén et al., 2006), and Hersman et al. (1995) estimated
0.01–2 mM aqueous siderophores in soil environments.
Plants are able to exude phytosiderophore at high rates into the
rhizosphere, up to 1 mM in the soil solution (Römheld, 1991).
Complexation studies involving the affinity of siderophores for
metals have been conducted by several authors (Batinic-Haberle
et al., 1991; Farkas et al., 1999; Hernlem et al., 1999; Dubbin and
Ander, 2003; Duckworth and Sposito, 2007; Codd, 2008; Pettine
et al., 2008; Duckworth et al., 2009). Siderophores influence the
mineral weathering and biogeochemical cycle of Fe-bearing phases
(Hersman et al., 1995; Kraemer, 2004). Mineral dissolution studies
have been conducted on hematite (Hersman et al., 1995), goethite
(Holmén and Casey, 1996; Cervini-Silva and Sposito, 2002; Cocozza
et al., 2002; Neubauer et al., 2002; Cheah et al., 2003; Kraemer,
2004; Reichard et al., 2007a), horneblende (Kalinowski et al.,
2000; Liermann et al., 2000; Buss et al., 2007), arsenopyrite and ga-
lena (Cornejo-Garrido et al., 2008), clay minerals (Neubauer et al.,
2000; Borer et al., 2005) and Mn oxides (Duckworth and Sposito,
2007). It has been reported that the presence of Pseudomonas gen-
era bacteria can lead to siderophore secretion favouring Fe oxide
dissolution and consequent mobilization of adsorbed As (Garcı́a-
Sánchez et al., 2005). Drewniak et al. (2008) proved the existence
in an ancient Au mine of bacterial isolates, hyper tolerant to As,
and found that high local As concentrations correlated with the
presence of produced siderophores, probably responsible for the
mobilization of Fe3+ from insoluble minerals and the consequent
mobilization of As. Cornejo-Garrido et al. (2008) conducted a study
on the influence of Dfob on As release from the most common As-
bearing mineral FeAsS (arsenopyrite) at pH 5.
Groundwaters exceeding the limit of 10 lg L1 (0.133 lM) for
As have often been recorded during the last 20 a in the volcanic
area situated in central Italy, Rome province (Dall’Aglio et al.,
2001; Vivona et al., 2007). Mechanisms involved in producing such
1689
high As concentration have not yet thoroughly been elucidated and
the complexity of processes driving As release in volcanic areas is
capable of multiple interpretations. The high affinity of As for Fe
hydroxide and siderophore capacity to favour Fe-bearing mineral
dissolution stimulated interest in studying the possible role of
siderophores in promoting As mobilization from volcanic rocks
in batch leaching experiments at different pH and ligand
concentration.
2. Materials and methods
2.1. Rock samples
Surface volcanic rock samples, including lava, peperino, red tuff
with black scoria (known also as ‘‘Ignimbrite C” and simply named
tuff in the following) and an unspecified fallout deposit (U.F.D.),
were collected from geological outcrops of the Vico Lake in North-
ern Latium, Central Italy. In this volcanic region widespread hydro-
thermal circulation has been reported as underlined by the
occurrence of geothermal fields (Dall’Aglio et al., 2001). Collected
samples were weathered on the surface therefore they were
brushed and polished before use to minimize the effect of external
deposits on batch experiments. Rocks were then powdered using a
steel mill and sieved at 0.5 mm. The chemical composition of pow-
dered samples was determined following the procedure described
in Section 2.3. The abundance of the individual crystalline phases
was determined by X-ray diffraction (XRD) techniques using a Bru-
ker D8 Advance powder diffractometer. Polished thin sections from
the various samples were further analyzed using a Cameca SX-50
WDS electron microprobe at Istituto di Geologia Ambientale e Geo-
ingegneria (IGAG), University of Rome La Sapienza. The electron
microprobe analyses were performed on oxide spots that were
identified in the prepared sections, using an accelerating voltage
of 15 kV and a regulated beam current of 15 nA with 5 lm beam
diameter. Eight to ten measurements were performed on each
sample and analytical reproducibility was within 2%. Elemental
concentrations in the analyzed spot were converted to oxide con-
centrations as Fe2O3, MnO2, Al2O3 and TiO2.
2.2. Experimental setup
Experiments in the presence of the siderophore trihydroxamate
desferroxamine B (Dfob) were run by using solid suspensions
(4 g L1) of 0.4 g powdered and sieved rocks (lava, tuff, peperino
and U.F.D.) in 100 mL 0.01 M NaClO4 solutions. Dfob was added
to the batch solutions at levels of 0, 100, 250, 500 and 1000 lM.
Dfob has been a widely studied siderophore (Neubauer and Furrer,
1999; Cervini-Silva and Sposito, 2002; Cheah et al., 2003; Borer
et al., 2005; Duckworth and Sposito, 2007; Carrasco et al., 2008).
Its molecule consists of a C/N backbone with four acidic function-
alities, three of which are due to the hydroxamate moieties and the
other to the amino group. pKa values are 8.38, 8.90, 9.35, 10.46 and
the Fe-complex formation constant (pKf) is 31.9 (Kraemer et al.,
1999; Martell et al., 2004). At pH values (<8) commonly found in
groundwater, Dfob is a cationic species due to protonation of the
terminal amine group. The suspensions were prepared in glass bot-
tles that were capped and placed on a rotatory shaker table at 250
rpm continuous speed at 20 °C in a thermostatically controlled
room. The solution were buffered at pH 6 and 7 with 3-(N-morpho-
lino)propanesulfonic acid (MOPS, 10 mM) and at pH 8 with 10 mM
Tri(hydroxymethyl)aminomethane (TRIS) and TRIS/HCl. Subsam-
ples of 10 mL were collected from the suspensions at intervals over
a period of 1–2 months and then filtered through 0.45 lm cellulose
nitrate membrane Whatman filters. The use of magnetic stirrers
was avoided since it was noticed that they tend to accumulate Fe
1690 B. Casentini, M. Pettine / Applied Geochemistry 25 (2010) 1688–1698

mineral deposits over long stirring periods and this might affect Table 1
the results. Two different leaching experiments were carried out. Bulk concentration (mean ± standard deviation) of major cations and potentially
harmful elements (mg kg1) in the studied rocks.
In the first one, the effect of a constant ligand concentration
(500 lM) on As release at different pH (6, 7 and 8) over a two Lava Peperino Tuff U.F.D.a
month period was investigated in comparison to a blank. In the B 321 ± 86 272 ± 51 226 ± 43 198 ± 89
second experiment the effect of Dfob concentration in the range Na 10,947 ± 135 11,016 ± 41 21,107 ± 101 5224 ± 103
0–1000 lM on the mobilization of As and Fe at pH 6 and 8 over Mg 11,614 ± 110 6499 ± 74 7177 ± 55 10,341 ± 140
Al 59,797 ± 106 47,252 ± 2457 56,634 ± 42 42,239 ± 725
30 days was studied. Variations of pH during the runs were within K 65,173 ± 53 34,546 ± 61 10,790 ± 28 6815 ± 21
±0.2 pH units. The bulk soil digestion analyses and pH influence Ca 52,655 ± 152 33,581 ± 138 46,524 ± 51 42,943 ± 68
leaching experiment were conducted in duplicate. V 151 ± 1 106 ± 2 124 ± 3 116 ± 1
Cr 168 ± 4 87 ± 4 34 ± 1 35 ± 2
Mn 785 ± 1 573 ± 3 585 ± 5 418 ± 7
2.3. Analytical methods Fe 43,613 ± 2283 33,123 ± 1694 31,502 ± 472 29,290 ± 762
Cu 103 ± 3.8 76 ± 0.1 86 ± 0.1 22 ± 1.0
Rock samples were digested using a microwave assisted proce- Zn 640 ± 1.2 190 ± 0.7 966 ± 1.5 1516 ± 1.5
As 13 ± 0.3 14 ± 0.1 10 ± 0.1 17 ± 0.1
dure with an Ethos-Milestone Microwave advanced Labstation.
Cd 88 ± 0.0 89 ± 0.0 94 ± 0.0 101 ± 0.1
Five mL 15.3 M HNO3 (Romil, superpure) and 1 mL 11.5 M HCl Pb 53 ± 1.9 26 ± 0.9 30 ± 0.1 14 ± 0.3
(Romil, superpure) were added to 0.2 g of dried sample. The use
a
U.F.D. = unconsolidated fallout deposit.
of HF digestion was avoided even though the silicate fraction in
volcanic rocks could represent a sink of As as reported by Pascua
et al. (2005). Nevertheless the undigested fraction was calculated oxides are known to act as important sorbents for dissolved species
to be less than 10% initial weight. Digested samples for total ele- and in particular for As (Appelo et al., 2002; Wang and Mulligan,
ment analysis and those collected in the leaching tests were ana- 2008; Zhu et al., 2009), analysis of oxide subsamples identified
lyzed with an Octopole Reaction System Inductively Coupled by WDS Cameca SX-50 electron microprobe was also performed
Plasma Mass Spectrometer (ORS-ICP-MS) and by Hydride Genera- on spots in polished thin sections. The average results expressed
tion Atomic Absorption Spectrometry (HG-AAS). The method in terms of principal oxide components Fe2O3, Al2O3, TiO2 and
detection limit (LOD) for As was 0.2 lg L1 using HG-AAS and MnO2 (Table 2) indicate a dominance of Al, Fe and Ti oxides. From
0.1 lg L1 using ORS-ICP-MS under the experimental conditions. total digestion data, expressing Al, Fe and Mn as percentage abun-
Iron was determined by AAS in the flame absorption mode with dances in the bulk rock powder, the following values were ob-
a detection limit of 0.02 mg L1 and by ORS-ICP-MS with a detec- tained: 6.0%, 4.4% and 0.08% in lava; 4.7%, 3.3% and 0.06% in
tion limit of 0.2 lg L1. peperino; 4.2%, 2.9% and 0.04% in U.F.D. and 5.7%, 3.2% and 0.06%
in tuff. The occurrence of those elements based on total content
2.4. Reagents and standards is quite low but Scanning Electrode microprobe results for the
identified oxide subsamples suggest Fe oxide to be the dominant
The reagents used for HG-AAS or ICP-MS analyses have been de- phase (about 80% as Fe2O3) in all the different rocks.
scribed elsewhere (Pettine et al., 2007). All reagents were of analyt-
ical grade, unless otherwise stated. Desferrioxamine B stock 3.2. Siderophore effect on As release
solution (10 mM) was prepared by mesylate salt [C25H46N5O8NHþ 3
(CH3SO3)] registered as Desferal (Novartis, Switzerland). Sodium 3.2.1. Effect of pH
perchlorate was added from a 1 M stock solution prepared from Arsenic mobilization experiments were conducted in batches
anhydrous NaClO4 (Sigma). Iron calibration solutions (0.1–5.0 varying pH and siderophore concentration under aerobic condi-
mg L1) for AAS analysis were prepared from Aristar ICP stock solu- tions. The release of As and Fe over 60 day periods from four differ-
tion (1 g L1, BDH). Arsenic (V) calibration solutions (0.1–50 ent volcanic rock types at pH 6, 7 and 8 in the presence (500 lM)
lg L1) for HG-AAS analyses were prepared from di-sodium hydro- and in the absence of Dfob is reported in Table 3. After one week of
gen arsenate heptahydrate Na2HAsO47H2O (Fluka). The 1 M buffer the experiment, the As concentrations in siderophore treated sam-
stock solution for pH 6 and 7 was prepared with 3-(N-morpho- ples and blanks were already significantly different, confirming the
lino)propanesulfonic acid (MOPS) (Carlo Erba) and 1 M buffer stock hypothesis that siderophores may affect As mobilization from vol-
solution for pH 8 was prepared with Tri(hydroxymethyl)amino- canic rocks. At pH 8 some release was observed also in the blanks,
methane (TRIS) and TRIS/HCl salts (Fluka). The final buffer solution most probably due to binding site competition of OH with arse-
concentration in the samples was in both the cases (MOPS and nate. Different authors have reported that alkaline dissolution
TRIS) 10 mM. can be denoted as a special case of ligand dissolution with reaction
rate dominated by the surface concentration of deprotonated hy-
3. Results and discussion droxyl groups that act as ligands (Furrer and Stumm, 1986; Kra-
emer, 2004).
3.1. Rock characterization
Table 2
Samples of lava, tuff, peperino and U.F.D. were characterized in Results of analyses performed by WDS microprobe Camera SX-50 electron micro-
terms of major and trace element content by microwave assisted probe on oxide particles individuated in polished thin sections as sub-set of the four
rock samples. Mean (%) ± standard deviation reported.
acid digestion (Table 1). Arsenic concentrations (mg kg1) in the
sampled rocks were 13, 14, 10 and 17 in lava, peperino, tuff and Oxide Lava U.F.D. Peperino Tuff
U.F.D., respectively. This amount is comparable to natural back- TiO2 6.7 ± 3.0 4.7 ± 0.5 4.7 ± 3.0 7.0 ± 1.8
ground (1–20 mg kg1) for ordinary sediments (Nordstrom, Al2O3 10.8 ± 6.4 3.2 ± 0.5 12.0 ± 4.3 15.1 ± 2.2
2002). The major minerals in the rock samples identified by XRD MnO2a 0.9 ± 0.3 1.1 ± 0.2 0.5 ± 0.2 0.6 ± 0.1
Fe2O3 80.6 ± 4.2 91.4 ± 1.7 72.9 ± 8.5 78.2 ± 3.7
analysis were muscovite and quartz in U.F.D.; leucite, augite and
a
muscovite in lava; leucite, augite, muscovite and analcime in pepe- Mn content in identified oxides is quite low as average, but in tuff and peperino
rino and analcime, augite and leucite in tuff. Since Al, Mn and Fe randomly occurring black spots containing up to 80% MnO2 were identified by SEM.
 B. Casentini, M. Pettine / Applied Geochemistry 25 (2010) 1688–1698 1691

Table 3
pH influence on As (white cells) and Fe (grey cells) release (lM) in the presence of 500 lM Dfob (bold) and in the absence of Dfob (blank). Mean and standard deviation (SD, italic)
values reported.

The findings clearly suggested that Dfob at 500 lM affects As
release more at pH 6 than pH 8, for all the rocks except tuff (where
the differences were comparable to LOD). The concentrations of As
and Fe decreased with increasing pH from 6 to 8. After two months,
values for As and Fe were lowered, respectively, from 0.1 to
0.045 lM and from 42.1 to 21.7 lM in lava, from 0.032 to 0.021
and 41.2 to 29.5 lM in tuff, from 0.086 to 0.058 and 22.6 to
18.6 lM in peperino. In contrast, in U.F.D. the highest As release
(0.097 lM) was observed at pH 8 and the lowest (0.023 lM) at
pH 7 while Fe release decreased from 90.6 to 52.3 when increasing
pH from 6 to 8.
In all the rock samples Fe re-precipitation occurred in the
batches after 30 days, thus the second leaching experiment was
shortened to one month duration. The inferred Fe re-precipitation
was probably due to oversaturation of the solution caused by Fe
mobilized over time during the leaching experiments.
The dissolution kinetics of most slightly soluble oxides are con-
trolled by chemical surface processes. Such reactions consist of (1)
1692 B. Casentini, M. Pettine / Applied Geochemistry 25 (2010) 1688–1698

the attachment of the reactants at the surface sites, where they does not substantially differ from that at 1000 lM. The complete
polarize and weaken the critical metal O bonds, (2) the rate-limit- dataset for both experiments is presented as Supplementary mate-
ing detachment of the reacting surface metal species, and (3) the rial for comparison.
transport of the detached metal complex into the bulk solution The reproducibility of the experiment at 500 lM and at the
and the regeneration of the initial active site by fast protonation same pH is quite good, bearing in mind that natural non homoge-
reactions. If the system is far from equilibrium, the back reaction neous solid materials were used and there was no sterile control in
can be neglected (Furrer and Stumm, 1986). the batches. Considering the low release in the blank solutions, it
The presence of siderophores generates unsteady state condi- can be excluded that bacteria alone are able to mobilize As from
tions that promote Fe oxide dissolution by a direct surface-con- the rocks in such a short time, but it is not possible to exclude that
trolled mechanism and also by facilitating proton-promoted or there is a synergic effect with the presence of Dfob, even if the
ligand-promoted dissolution mechanisms (Kalinowski et al., experiment duration and proportionality of As release and ligand
2000; Kraemer, 2004; Reichard et al., 2007b). A hexacoordinate presence does not indicate microbial activity as the major driving
complex with 1:1 stoichiometry is formed between Dfob and force in the observed As mobilization. The presence of Dfob mark-
Fe(III), positively charged at a pH below 8 due to the protonation edly affects As release from all the rock samples at both pH 6 and 8
of its terminating alkylammonium group (Hersman et al., 1995; with respect to the corresponding blank values in the absence of
Kalinowski et al., 2000; Cheah et al., 2003; Borer et al., 2005;
Reichard et al., 2007a). Usually at more acidic pH lower Dfob
deprotonation should limit ligand adsorption onto mineral
surfaces, the first step in ligand-promoted dissolution, hence
reducing Fe oxide dissolution and complexation, but the opposite
behaviour was observed when lowering the pH. This may suggest
that the role of the proton promoted dissolution mechanism
should be considered together with ligand-promoted dissolution.
Proton-promoted dissolution is the precursor in the Fe detach-
ment mechanism, allowing the formation of hexadentate com-
plexes. Synergic effects of ligand and proton on the dissolution
may enhance the As and Fe release at pH 6. This process should
be further investigated.

3.3. Effect of ligand concentration on the temporal release of metals

The effect of Dfob concentrations ranging from 0 to 1000 lM

with time was investigated in a second experiment at both pH 6
and 8. Fig. 1a–d shows the release (lM) of As and Fe versus time
for the various rocks. Data corresponding to 500 lM Dfob are omit- Fig. 2. As/Fe molar ratio change in solution as a function of the leaching time at pH
ted for clarity since the behaviour observed at this concentration 6 (black) and 8 (white) in lava (O, .) and tuff (h, j) in the presence of 500 lM Dfob.

Fig. 1. As and Fe release from lava (a), tuff (b), peperino (c) and U.F.D. (d) as a function of the leaching time in the absence (, ) and in the presence of 100 lM (O, .), 250 lM
(h, j) and 1000 lM Dfob (}, ) at pH 6 (black) and 8 (white).
 B. Casentini, M. Pettine / Applied Geochemistry 25 (2010) 1688–1698 1693

the siderophore. In the blanks Fe release was negligible at any pH,
while As release was negligible at pH 6 and significant at pH 8,
especially for U.F.D. The effects of increasing Dfob concentrations
on As and Fe release are more evident over leaching time at higher
pH, where the activity of siderophores is favoured. At pH 6.0 the
differences in the releases after short leaching period in the pres-
ence of different Dfob concentrations are small. Some re-precipita-
tion/re-adsorption phenomena were still observed after 15–20
days in all the solutions at the lowest Dfob level (100 lM). Concen-
tration of 100 lM Dfob are insufficient to keep the amount of As
and Fe mobilized at pH 6 over the duration of the experiment in
solution. Solubility limitations for Fe and re-adsorption of As on
freshly formed (hydr)oxides may occur during the leaching period,
following adjustments in the speciation of the various released
elements.
The released Fe at pH 8 was about 50% lower if compared to the
levels measured at pH 6, while in the case of As the release at pH 6
and 8 was not so diverse especially at 1000 lM Dfob. Generally, the
release of Fe and As is quite fast in the initial phase and then slower
after the first 5 days. Similar behaviour has been reported by other
authors (Reichard et al., 2007a), observing fast non-steady state
dissolution of kinetically labile Fe from Fe oxide surfaces in the

Fig. 3. As versus Fe release relative to the 4 rock samples at pH 6 and 8 in the presence of 100 (), 250 (M), 500 (j) and 1000 lM (}) Dfob.
1694 B. Casentini, M. Pettine / Applied Geochemistry 25 (2010) 1688–1698

presence of siderophores. Previous workers concluded that the ef- when the ligand dissolution process becomes predominant. These
fect of Dfob on ligand controlled dissolution is twofold: it absorbs findings are consistent with the observation that the sidero-
to the surface and serves as a reactant in a ligand controlled disso- phore-assisted Fe solubilisation process is slow and depends on
lution mechanism and also complexes dissolved Fe by shifting the the structure of the Fe-containing mineral and the siderophore
solution saturation state far from equilibrium conditions (Cheah (Boukhalfa and Crumbliss, 2002).
et al., 2003). Since the adsorption of a ligand should be followed
by the slow step of detachment to generate Fe and As in solution, 3.4. Dissolution rate constant
it is possible that during the first days of leaching, when the more
labile Fe fraction is readily mobilized, the role of the siderophore in There are three principal reactions by which solid Fe(III) oxides
shifting the saturation equilibrium conditions is more important may release Fe into an aqueous solution: protonation, reduction
than its direct complexation. The ligand controlled dissolution and complexation producing Fe(III) cations, Fe(II) cations and Fe(II)
seems to take place after 10 days as proved by increasing Fe and or Fe(III) complexes, respectively (Schwertmann, 1991):
As release proportionally to Dfob present in solution. A surface
FeOOH þ Hþ $ FeðOHÞþ2 ð1Þ
spectroscopic characterization for both As and Fe would have
helped to better understand their association in the rock sample, FeOOH þ e þ 3Hþ $ Fe2þ þ 2H2 0 ð2Þ
but it was not possible to perform such analyses. FeOOH þ nL þ 3Hþ $ ½FeLn 3n þ 2H2 O ðL ¼ ligandÞ ð3Þ
Differences in the above properties have major implications for
As mobilization in aquifers. While adsorbed As may be mobilized Often dissolution processes can be described by mass transfer the-
by competitive anion exchange this is not the case for structurally ories (Nerst, 1904), which predict that the instantaneous dissolu-
incorporated As (Pedersen et al., 2006). The As/Fe ratio can be used tion rate varies in proportion to a driving force, usually the
as a rough approximation of the As/surface site ratio. The reported concentration gradient between dissolved species at the solid sur-
As content of naturally occurring Fe oxides shows great variation face and in the bulk solution. Kabai (1973) proposed the following
ranging from an As/Fe molar ratio of 2.4  106–0.09 (Pedersen modified first-order Nerst equation to better describe processes
et al., 2006). The initial As/Fe molar ratio in the rocks used here, involving metals and metal oxides (Franke et al., 1987):
calculated using the bulk data reported in Table 1, is 2.6  104 a
C=C 0 ¼ 1  eðktÞ ð4Þ
in lava, 3.8  104 in U.F.D. , 3.3  104 in peperino and 2.3 
104 in tuff. After 4 days and 500 lM Dfob, these ratios in solution that can be expressed as the following linear form:
at pH 6 became 5.5  103, 3.8  103, 1.1  103 and 6.1  104
ln½ln C0 =C0  C ¼ a ln k þ a ln t ð5Þ
in lava, U.F.D., peperino and tuff, respectively. At the beginning of
the experiment, the As/Fe ratios in solution are one order of mag-
nitude higher than the corresponding ratios calculated from the C0 Fe initial rock content expressed in lM.
bulk content in the rocks, suggesting a faster initial mobilization C Fe (lM) in solution at time t.
of As than Fe. Arsenic was probably adsorbed by aquifer materials a constant characteristic of the solid phase.
during upflow of geothermal As-rich fluids and more occurs on the k dissolution rate constant (min1).
mineral surface than is incorporated into crystalline phases. Fig. 2
shows that in tuff (a similar trend was observed for peperino) the The Kabai Eq. (5) expresses the rate of dissolution as a function
As/Fe ratio is low at both pH 6 and 8 and quite constant during the of changing particle size, morphology and dissolution site density
leaching period; this suggests a significant amount of Fe is released (Cornell and Schwertmann, 2003). This equation was successfully
compared to As. In contrast, in lava (same trend for U.F.D.) the ini- applied to calculate the dissolution rate in Mn goethites and
tial As/Fe ratio is much higher in the first 10 days and can be ex-
plained by a higher initial mobilization of As from the rocks Table 4
compared to Fe. The ratio decreases with time at both pH 6 and Fe dissolution constant rate in volcanic rocks at Dfob 100 and 1000 lM calculated
8 and tends to approach the low value observed for tuff at the according to Kabai equation.
end of the experiment. These findings show that the initial As or Rock pH Dfob (lM) k (min1) R2
Fe content of a rock does not give sufficient information in order
Lava 6 0 2.22E-21 0.79
to predict As mobilization from As-bearing minerals, while sequen- 100 1.68E09 0.96
tial extraction and surface spectroscopic information on As-specia- 1000 2.24E07 1.00
tion and Fe oxide binding phases would help in explaining the 8 0 2.22E21 0.79
observed phenomena. 100 2.93E08 0.91
1000 2.13E07 1.00
The release of As versus Fe at pH 6 and 8 and in the presence of
different Dfob concentration (100, 250, 500 and 1000 lM) is repre- Peperino 6 0 4.04E14 0.79
100 2.61E08 0.99
sented in Fig. 3 for all the rock samples. There is a good correlation
1000 6.25E07 0.95
between the levels of As and Fe in solution at Dfob concentration 8 0 8.38E12 0.79
higher than 100 lM. The relationship between the presence of As 100 1.49E09 0.97
and the presence of Fe at 100 lM Dfob is not linear and this is 1000 9.71E08 0.99
probably due to the above mentioned re-adsorption/re-precipita- Tuff 6 0 8.87E21 0.79
tion processes. The mechanisms of release at Dfob >250 lM seem 100 2.86E09 1.00
to be similar and related releasing trends overlap at both pH 6 1000 1.24E07 0.99
8 0 9.22E12 0.79
and 8. In many cases the release of As as a function of Fe is not de- 100 1.64E09 0.97
scribed by a single linear function, as indicated by variable slope 1000 1.04E07 0.99
during the leaching period, while a two-phase process would bet- U.F.D. 6 0 1.31E15 0.80
ter explain the observed behaviours. The As vs Fe slope is higher at 100 1.44E08 0.96
lower Fe concentration and tends to decrease with increasing Fe 1000 9.54E08 1.00
release. This would support that the major part of the readily mo- 8 0 1.83E13 0.75
100 5.43E09 0.92
bile As is released at lower Fe concentration (beginning of the
1000 6.72E08 0.99
experiment) and further As release occurs together with Fe release
 B. Casentini, M. Pettine / Applied Geochemistry 25 (2010) 1688–1698 1695

hematites (Alvarez et al., 2006), nickeliferous goethite (Landers
et al., 2009) and synthetic goethite (Schwertmann, 1991). When
the Kabai equation was applied to describe the dissolution of Fe-
bearing phases in the volcanic rocks, a good fit of the data was ob-
tained with R2 0.70–0.80 in the absence of Dfob, 0.91–1.00 at Dfob
100 lM and 0.95–1 at Dfob 1000 lM (Table 4). The high calculated
R2 proved that the dissolution process of Fe minerals in volcanic
rocks in the presence of siderophores can be explained by the
Kabai equation. Dissolution rate in the absence of siderophore
were in the range of 2.22  1021–9.22  1012 while the addition
of low Dfob concentration (100 lM) enhanced the rate to 1.49 
109–2.93  108. Further increase of the ligand concentration
from 100 to 1000 lM augmented the rates by 1–2 orders of mag-
nitude. At Dfob 1000 lM and pH 6 the highest rate was observed
in peperino (6.25  107) and the lowest in U.F.D. (9.54  108),
while at pH 8 the highest rate was in lava (2.13  107) and the
lowest in U.F.D. (6.72  108).
Previous workers have investigated the dissolution rates of goe-
thite in the presence of Dfob using ligand-promoted dissolution
rate equations (Kraemer et al., 1999; Cocozza et al., 2002; Cheah
et al., 2003). A linear relationship was found between the surface
excess of siderophores and dissolution rates by Cheah et al.

Table 5
Literature data on mineral dissolution constant rate in the presence of H+ (proton promoted) or siderophore (ligand promoted).

Rock Conditions Method k (min1) Reference

Al-goethite lower HCl proton-promoted dissolution Kabai model 1.84E03 Cervini-Silva and
substitution Sposito (2002)
Al-goethite higher HCl proton-promoted dissolution Kabai model 2.03E04 Cervini-Silva and
substitution Sposito (2002)
Goethite Dfob (240 lM) ligand-promoted Pseudo first order coefficient (mass normalized dissolution 8.33E04 Cocozza et al. (2002)
dissolution rate to surface excess)
Goethite Dfob (20–80 lM) ligand-promoted Pseudo first order coefficient (mass normalized dissolution 2.50E04 Cheah et al. (2003)
dissolution rate to surface excess)
Goethite Dfob (40 lM) ligand-promoted Pseudo first order coefficient (mass normalized dissolution 8.00E05 Reichard et al. (2007a)
dissolution rate to surface excess)

Fig. 4. Metal and As release (%) at pH 6 and 8 and different Dfob concentrations (0; 100; 250; 500; 1000 lM h j) for the four rocks samples. The percentage release of
metals is expressed as the ratio between the concentration in solution and the total amount present in the solid rocks as given by microwave acid assisted digestion (Table 1).
1696 B. Casentini, M. Pettine / Applied Geochemistry 25 (2010) 1688–1698

(2003), therefore, they concluded that siderophore-controlled dis- favourable pH for As release was pH 6. At this pH the ligand pro-
solution is surface-controlled and can be described by the pseudo moted process is synergic with the proton promoted dissolution.
first order rate law. The calculated rates in Table 4 are significantly The effect is only partially observed at lower siderophore levels
smaller than rates reported in the literature for Fe mineral dissolu- due to solubility limitations of Fe and the consequent possible As
tion experiments in the presence of Dfob (Table 5). The difference re-adsorption on freshly formed (hydr)oxides. These phenomena
can be explained by the purity of Fe minerals used by other may complicate data interpretation in laboratory experiments,
authors, since their work refers to synthetic goethite while the while in the field it may be expected that low siderophore concen-
present study dealt with natural volcanic rocks containing random trations could exert a role over longer leaching periods.
Fe minerals. The release of As from the different rocks was from 2.0% to 10%
at pH 6 and from 2.4% to 8.8% at pH 8. Arsenic and Fe were mobi-
lized faster during the first week. The As/Fe trend shape evidenced
3.5. Effect of Dfob on the contemporary solubilisation of other
different release mechanisms in the studied volcanic rocks, most
elements
probably related to the peculiarity of As distribution on the surface
and the strength of Fe bonds present in the rocks. A more detailed
The ability of Dfob to form hexadentate complexes with several
characterization of the mineral properties (surface area, As-bearing
cations has been proved to enhance the solubility of various ele-
phase identification) together with spectroscopy investigation of
ments and Pt group metals (Neubauer et al., 2000; Cervini-Silva
the Fe oxides present in the solid phase could contribute to better
and Sposito, 2002; Dahlheimer et al., 2007; Duckworth and Sposi-
elucidate the mechanism of As release induced by Dfob in volcanic
to, 2007). Fig. 4 illustrates the release (%) of elements after 30 days
rocks.
as a function of Dfob concentration. The siderophore concentration
The presence of siderophores can increase Fe mineral dissolu-
affects the release of As, Al, Fe, V and Mn at any pH. The effect of
tion rates, calculated according to the Kabai equation, by up to
Dfob on the release of Al and Fe is very important although the
10 orders of magnitude. Arsenic mobilization significantly corre-
mobilized amounts expressed as a percentage of their bulk con-
lated with Al, Mn, Fe, Si, V, Ga and Sb. The presence of Dfob also sig-
tents appear quite small (<3%) in all rocks under any condition
nificantly affected Mn release at any pH and Cu, Zn and Pb
(Dfob concentration and pH). At pH 6 and 1000 lM, the released
mobilization at alkaline pH. Based on the study results it may be
As fractions were 10.3%, 2.8%, 5.6% and 7.8% in lava, tuff, U.F.D.
concluded that the presence of siderophores, which is not only re-
and peperino, respectively, while the corresponding releases at
stricted to low Fe environments, represents a possible trigger in As
pH 8 were 4.7%, 3.4%, 7.0% and 6.7%. The released Mn was more
release from Fe-binding minerals to water phases, with interesting
than 25% in tuff and peperino at high Dfob concentrations, while
implications for groundwater quality, plant uptake and bacterial
it was in the range 5–8% for U.F.D. and 2–4% for lava. Total Dfob-
communities. Although the role of siderophores has been well
promoted dissolution rates of Mn(III,IV) are typically higher than
studied in soil environments, near-surface layer and rhizosphere,
that of Fe (hydr)oxides, suggesting that the presence of Mn(III,IV)
their effects on As mobilization in topsoil or direct mobilization
oxides may be a kinetically competitive process, and this may af-
in aquifers should also be considered.
fect siderophore induced solubilisation of Fe (Duckworth and Spos-
Natural systems contain a complex assemblage of mineral
ito, 2007).
phases, microbial species and natural organic matter. Synergic ef-
Under alkaline conditions the release of Cu, Zn and, to a minor
fects on mineral dissolution due to the co-presence of siderophores
extent, of Pb is considerable in tuff and lava and proportional to
and other organic ligands (such as oxalate, malonate or citrate) or
Dfob concentrations. The complexing strength of Dfob on metal
natural organic matter have also been highlighted by several
cations is increased by the deprotonation of binding groups (amine
authors (Grafe et al., 2002; Redman et al., 2002; Cheah et al.,
excluded) at higher pH. In the experiment reported by Cornejo-
2003; Kraemer, 2004; Borer et al., 2005; Reichard et al., 2005,
Garrido et al. (2008), the effectiveness of Dfob in releasing Pb
2007a; Tao et al., 2006). This aspect is of great interest for environ-
was almost 10 times higher than for Fe release. In soil solutions
mental processes as oxalate and other low molecular weight or-
where concentrations of dissolved Fe+3 are generally small,<1018
ganic ligands are ubiquitous in soil systems. Many soil bacteria
M at pH 7, other metal ions may be more available for chelation
are known to release biosurfactants (Alam et al., 2001; Mulligan
if they are dissolved or adsorbed on soil minerals instead of being
and Wang, 2006) and their role in biological Fe acquisition mech-
incorporated in the lattice of the mineral (Neubauer et al., 2002). In
anisms involving siderophores have been also studied (Carrasco
all the rock types investigated, at pH 6 and 8, the mobilized
et al., 2007, 2008). Therefore the co-presence of siderophores with
amount of As significantly correlates with released Al, Si, Mn and
other commonly found ligands suggests further studies on their
Fe as major rock constituents and V, Ga, Sb as minor elements.
role in mineral dissolution and induced As release.
These latter elements are common in geothermal fluid and a corre-
lation between As and V has been widely reported (Nicolli et al.,
1989; Smedley et al., 2002; Bundschuh et al., 2004; Vivona et al., Acknowledgments
2007). The release of As showed a significant correlation with Fe
and Al in solution (the most abundant oxides in the matrices) in The authors wish to thank Dr. Daniel Moraetis from the Techni-
the presence of the different Dfob concentrations investigated. cal University of Crete (Chania, Greece) for XRD analysis and Mar-
The determination coefficients (R2) are highest for lava (0.83 and cello Serracino from IGAG-CNR (Rome, Italy) for WDS electron
0.97 for Fe and 0.78 and 0.93 for Al at pH 6 and 8, respectively) microprobe analysis.
and lowest for the U.F.D. sample (0.75 and 0.75 for Fe and 0.56
and 0.75 for Al at pH 6 and 8, respectively). Appendix A. Supplementary material

Supplementary data associated with this article can be found, in

4. Conclusions
the online version, at doi:10.1016/j.apgeochem.2010.08.016.

Batch leaching experiments evidenced the possible significant

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