Environmental Pollution 159 (2011) 474e480

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

The immobilisation and retention of soluble arsenic, cadmium

and zinc by biochar
Luke Beesley a, *, Marta Marmiroli b
a
Faculty of Science, Liverpool John Moores University, Liverpool L3 3AF, UK
b
Department of Environmental Sciences, Section of Genetics and Biotechnologies, University of Parma, 43100 Parma, Italy
Biochar retains readily soluble cadmium and zinc from a contaminated soil, significantly reducing their potential mobility, but has limited effects
on arsenic.

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

Article history: Water-soluble inorganic pollutants may constitute an environmental toxicity problem if their movement
Received 17 August 2010 through soils and potential transfer to plants or groundwater is not arrested. The capability of biochar to
Received in revised form immobilise and retain arsenic (As), cadmium (Cd) and zinc (Zn) from a multi-element contaminated
12 October 2010
sediment-derived soil was explored by a column leaching experiment and scanning electron microanalysis
Accepted 14 October 2010
(SEM/EDX). Sorption of Cd and Zn to biochar’s surfaces assisted a 300 and 45-fold reduction in their
leachate concentrations, respectively. Retention of both metals was not affected by considerable leaching
Keywords:
of water-soluble carbon from biochar, and could not be reversed following subsequent leaching of the
Biochar
Cadmium
sorbant biochar with water at pH 5.5. Weakly water-soluble As was also retained on biochar’s surface but
Zinc leachate concentrations did not duly decline. It is concluded that biochar can rapidly reduce the mobility of
Arsenic selected contaminants in this polluted soil system, with especially encouraging results for Cd.
Heavy Metals Ó 2010 Elsevier Ltd. All rights reserved.
Sorption

1. Introduction 2006; Brandli et al., 2008) and remove heavy metals and As from
waste-waters (Mohan et al., 2007) has been explored, application
Biochar is a low-density charred material produced by burning to real world contaminated soil systems has received surprisingly
biomass under conditions of low temperatures and minimal little systematic investigation to date, although initial results are
oxygen. Experimental application of this material to soils to encouraging regarding the retention of both inorganic and organic
sequester carbon (Lehmann, 2007a,b) has been encouraged by its pollutants (Beesley et al., 2010b).
very high organic carbon content (Yin Chan and Xu, 2009). In polluted soil systems, water-soluble contaminants, rather than
Furthermore, unlike fresh organic residues, biochar has been found the total concentrations in soil, determine ecological and toxicological
not to significantly increase CO2 production when it is added to soils relevance because they have the greatest immediate environmental
(Spokas et al., 2009; Novak et al., 2010) and can adsorb dissolved impact (Temminghoff et al., 1998). One factor influencing elemental
organic carbon (DOC) (Pietikainen et al., 2000). There are also wider solubility in soils is pH. Arsenic is more soluble in alkaline soils within
agro-environmental benefits of adding biochar to soils, for example, the range pH 3e8 (Fitz and Wenzel, 2002) whereas the opposite is
increasing soil pH and reducing leaching of soluble macronutrients true of some metals, such as Zn (Kiekens, 1990). Given that some
(Novak et al., 2009; Laird et al., 2010). The microscopic physical biochars have been reported to have a pH greater than 8 (Yin Chan and
structure of biochar is one of the key determinants in its soil Xu, 2009), there could be opposing impacts on the mobility of specific
conditioning properties because, during the charring process, the trace elements if such alkaline materials are added to contaminated
surface area of the pre-charred source material can be increased soils. Furthermore, co-mobilisation of soluble carbon and some trace
several thousand fold, greatly enhancing its water holding capacity metals has previously been found in soil pore water collected in field
(Thies and Rillig, 2009). Although the capability of carbonaceous experiments in both contaminated (Clemente et al., 2008) and non-
materials, such as biochar, to adsorb organic compounds (Oen et al., contaminated soils (Beesley and Dickinson, 2010), which raises further
concerns regarding the addition of carbon-rich materials to soils.
* Corresponding author at: The Macaulay Land Use Research Institute, Craigie-
The present study evaluates the efficacy and permanence of
buckler, Aberdeen AB15 8QH, UK. element retention by biochar, examining concentrations of As, Cd
E-mail address: [email protected] (L. Beesley). and Zn in successive leachate samples from a column leaching test

0269-7491/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2010.10.016
 L. Beesley, M. Marmiroli / Environmental Pollution 159 (2011) 474e480 475

and determining relative abundance of these elements on soil and analysed for pseudo-total As, Cd and Zn by ICP-MS (XSERIES 2 ICP-MS; Thermo
and biochar surfaces before and after the leaching test, by scanning Scientific, MA, USA). Certified reference material (CMI 7004) was used to verify
accuracy, with recoveries of >80% for all elements.
electron microscope X-ray emission (SEM/EDX). Additional influ- Biochar was produced by pyrolysis of hardwoods including Oak (Quercus spp.),
ences of pH and soluble carbon are also considered in the context of Common Ash (Fraxinus excelsior), Sycamore (Acer spp.), Birch (Betula spp.) and
their effects on element mobility. Cherry (Prunus spp.) at 400
C in steel ring furnaces (Bodfari Charcoal, Denbigh,
North Wales, UK). Biochar’s pH and TOC were determined as above.

2. Materials and methods

2.2. Leaching column test
2.1. Study site and soil analysis
The leaching column test used six identical glass columns (XK50, Pharmacia
Soil was sourced from a canal embankment in Kidsgrove, Staffordshire, UK Biotech, UK), 20 cm in length and 5 cm in internal diameter, of which two were
(53
050 23.000 N, 02
150 05.700 W) which has been previously studied in relation to packed with 400 g of air-dried soil and the remaining four were packed to 3/4 of their
transfer of Cd and Zn to vegetation (Lepp and Madejon, 2007), mobility of As, Cd and length with biochar. Biochar had a low density (0.3 g ml1) compared to soil
Zn in the soil profile (Beesley et al., 2010a), and the effects of greenwaste compost (1.8 g ml1; Beesley et al., 2010b) so biochar was packed into the columns not
and biochar on the mobility of As, Cd, Cu, Pb and Zn (Beesley et al., 2010b). The origin by weight, but to the equivalent length of 400 g of air-dried soil in the columns.
of the excess levels of pollutants in this soil are believed to be due to the discharge or Columns were leached upwards from their base continuously with de-ionised water
spillage of contaminated effluent from neighbouring manufacturing industries into (pH 5.5) at 0.1 ml min1 flow rate, maintained by a peristaltic pump following
the canal during the early decades of the last century. Some years hence the canal Beesley et al. (2010a). Two of the columns containing biochar were linked in parallel
is thought to have been dredged and the sediments piled onto the banks without to the preceding two columns containing soil (shown in Fig. 1a) to allow biochar to
further treatment. Over subsequent decades the area has become spontaneously intercept contaminated eluate directly leached from the soil columns. Eluate
vegetated and presently supports a variety of shrubs (mainly Salix caprea and samples (10 ml) from soil were collected prior to passing through the biochar
S. viminalis) and perennial herbs (Lepp and Madejon, 2007). columns, by means of a small outlet at the joint between columns which remained
For the present study, bulk soil samples were taken from three faces of a shallow, closed at all times except during sample collection (see Fig. 1a). The remaining
30 cm deep soil trench excavated by hand in a secluded area of the study site which had two biochar filled columns were leached by the same method, but independently of
not been sampled by previous studies. Triplicate 500 g soil samples collected in the the soil columns, to provide a biochar control. Columns were leached for 8 weeks
field were bulked and mixed in the laboratory to create a single, representative sample in total. For the first 5 weeks (fractions 1e5) eluate was collected from all of the
of the soil for use in the column leaching test. Large debris and biological remnants columns. In fractions 6, 7 and 8 (weeks 6, 7 and 8) leaching of soil columns was
were removed and soil was crushed and sieved to <2 mm prior to the following terminated, but both the intercepting biochar and biochar control columns
analysis. Particle size distribution was determined using a Beckman Coulter LS 13 laser continued to be leached as previously described (see Fig. 1b). This method was
diffraction particle size analyser, with samples having been carefully pre-treated with designed to test the reversibility of any element retention by the intercepted biochar
hydrogen peroxide (H2O2, 30%) to remove organic matter. Soil pH was determined in after the source of contaminated eluate had been removed. The pH of the eluate
a 1:10 suspension of soil in de-ionised water, shaken for 3 h and allowed to settle for samples from each fraction was determined using the same equipment described
45 min at room temperature (22
C), measured by a digital pH meter (Jenway, Staf- earlier, whilst water-soluble total (WSTC) and water-soluble organic carbon (WSOC)
fordshire, UK). Total organic carbon (TOC) in solid samples was determined using an were analysed by a TOC-VE water analyser (Shimadzu, Tokyo, Japan). Arsenic, Cd,
SSM-5000A/TOC-VE analyser (Shimadzu, Tokyo, Japan). Aliquots of soil (0.2 g) were and Zn concentrations in the eluate samples were determined by ICP-MS following
microwave digested in concentrated 14 M, general purpose reagent (GPR) grade HNO3 Beesley et al. (2010a).

Fig. 1. a) Three of the six leaching columns, showing a soil column (left) connected to an intercepting biochar column (middle). The small outlet at the joint of the columns
(indicated by a white arrow) was used for collecting eluate samples from the soil column before it passed through biochar. Note that this photograph was taken at the beginning of
the experiment and the passage of water into the soil upwards from the base of the column can clearly be seen by the darker colouration of the soil. b) Schematic explanation of the
column leaching test fractions where ‘EC’ denotes eluate collection points. Note that biochar columns intercepted contaminated soil eluate in fractions 1e5, but were leached
independently of the soil columns, in accordance with the biochar control (marked *), for fractions 6, 7 and 8 of the test.
476 L. Beesley, M. Marmiroli / Environmental Pollution 159 (2011) 474e480

Table 1 cadmium and red for zinc. In the dot maps, lighter shades of colour correspond to
Characteristics of soil and biochar before the column leaching test commenced the higher intensity of the signal, which is directly proportional to the element
(mean n ¼ 3; s.e.m.). concentration. Therefore these dot maps are a relative indicator of concentrations of
elements before and after the leaching test, but do not indicate actual concentrations.
Soil Biochar Dot maps were acquired at 180 magnification and 600 frames each to optimized
pH 6.2 (0.1) 9.9 (0.0) electron detection from the surface of the soil and biochar samples.
TOC (%) 11 (0.2) 53 (2.4)
Sand (2 mme63 mm) % 43 (2.6) e 2.4. Statistical analysis
Silt (62.9e2 mm) % 48 (2.3) e
Clay (<2 mm) % 8.4 (0.3) e ANOVA analysis of trace metals, arsenic, pH and water-soluble total and organic
Pseudo-total (mg kg1) carbon in eluate was used to determine the effects of both leaching time and biochar
As 96 (6.6) nd on these parameters, whilst Pearson correlations were used to check for relation-
Cd 119 (1.8) nd ships between parameters. All analyses were carried out using SPSS v.14 for
Zn 249 (41) nd Windows.
Fe (%) 9.7 (0.4) nd
Al (%) 12.9 (0.9) nd
3. Results and discussion
nd ¼ Not determined.

3.1. Influences on trace element concentrations in

2.3. Scanning electron microanalysis (SEM/EDX) leaching column eluate

The purpose of using the following assay was to evaluate, by visual comparative
Given that biochar had a higher pH than soil (Table 1) and effec-
means, the relative abundance of As, Cd and Zn on soil and biochar surfaces before
and after the leaching test to establish the extent to which sorption and de-sorption tively buffered the mildly acidic pH of eluate from the soil (Fig. 2a) at
had occurred. Following the collection of the last fraction of eluate from the leaching mildly alkaline levels (wpH 8) throughout the column test (Fig. 2b), it
columns (for soils this was fraction 5 and for biochar this was fraction 8; Fig. 1b), 25 g might have been expected that any soluble As from soil would not be
of soil and biochar were immediately removed from their respective columns and retained by biochar; an increase in arsenic solubility with more
air-dried as previously described. Small sub-samples of the leached soil and biochar,
along with soil and biochar that had not been leached were treated for scanning
alkaline pH at soil pH > 7 has previously been reported (O’Neill, 1990;
electron microscope analysis as follows. Each sample was ground to fine powder Fitz and Wenzel, 2002). However, arsenic concentrations were by
and deposited into a 1.8  1.8 cm2 polyethylene mould with a depth of 3 cm and far the lowest of all elements measured in the eluate from the soil
oven-dried at 35
C for 24 h. The samples were impregnated with epossidic resin, (Fig. 3a; <10 mg l1), but did increase slightly when soil eluate was
which is a thermosetting polymer of epoxide and polyamine, to eliminate air within
passed through biochar (Fig. 3b), merely suggesting a cumulative
the powder micro-holes, then kept under vacuum at 50 cm Hg for 12 h after which
they were vulcanised. Each sample was taken out of its mould, horizontally cut with effect given that concentrations were also very low from the biochar
a diamond blade and polished on a cast-iron plate with SiC powder (12 mm) for 12 h. alone (Fig. 3c). Indeed no significant correlation was found between
The samples were sonicated to eliminate residual SiC powder from their surface, pH of the eluate and As concentrations in the eluate (data not shown).
dried for 12 h, then polished with a Texmet pad (Buehler, Illinois, USA) before being Soluble organic substances can also enhance trace element leaching
impregnated with ethylene glycol and Al2O3 powder (0.05 mm) for 48 h. The samples
were sonicated for 10 min to eliminate residues of Al2O3 powder and dried at room
in soils through complexation (Bernal et al., 2009) and hence co-
temperature for 24 h. Each replicate sample had a surface area of 1.8  1.8 cm2 and mobilisation. In the present study however, no positive correlation
a thickness of 0.5 cm. Samples were placed onto slides, each of which had been between metals or As concentrations and soluble carbon in eluate was
coated, under vacuum, with colloidal graphite to ensure conductivity. Samples were found, with the exception of Cd with WSOC (R2 ¼ 0.93; p < 0.001),
analysed with a Jeol 6400 Scanning Electron Microscope (SEM; Osaka, Japan)
a relationship that was only found in the biochar control, where
equipped with an Oxford X-ray detector (EDX; Oxford Instruments, Oxford, UK).
Images and element dot maps were visualised by LINK-ISIS 4.0 software (Oxford concentrations of this metal were consistently very low (Fig. 3c, f and
Instruments, Oxford, UK). Soil and biochar’s microscopic surfaces were compacted i). Indeed, concentration of water-soluble total and organic carbon in
and smoothed by the process described above to allow a full and even coverage by eluate from the soil were stable throughout the test (15e20 mg l1 for
the electron beam across the whole sample. Without smoothing and polishing, WSTC and 7e15 mg l1 for WSOC; Fig. 2a) whereas, in the biochar
highly anisotropic electron beam scatter can occur and hence lead to erroneous
results. For each analysis the voltage was set at 20 keV (Marmiroli et al., 2004), whilst
columns, both water-soluble total and organic carbon were signifi-
the working distance was 9 mm and the dead time for X-ray acquisition between 20% cantly reduced by successive leaching from initially far higher
and 25%. A colour code was assigned for the elements; blue for arsenic, green for concentrations (Fig. 2b and c; Table 2). Given the configuration of this

250 10
Soil Soil & Biochar
Biochar WSTC
WSOC
200 pH 9
-1
Concentration in eluate mg l

150
8
Eluate pH

100
7

50
6

0
a b c 5
1 2 3 4 5 1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8

------------------------------------------------------------- Fraction -----------------------------------------------------------

Fig. 2. Water-soluble total carbon concentration (WSTC), water-soluble organic carbon concentration (WSOC) and pH of eluate from soil (a.), soil leached through intercepting
biochar (b.) and biochar control (c.). Dotted, vertical line indicates where the leaching of soil was terminated and the leaching of the intercepting biochar and biochar control
continued (mean n ¼ 3 and error bars represent  s.e.m.).
 L. Beesley, M. Marmiroli / Environmental Pollution 159 (2011) 474e480 477

14 14

−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−
As Soil Soil & Biochar
12 12 Biochar

10 10

8 8

6 6

4 4

2 2

0
a 0
b c
600 6
Cd
500 5
Concentration in eluate µg l-1

400 4

300 3

200 2

100 1
−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−

0
d 0
e f
350 60
Zn
300
50

250
40
200
30
150

20
100

50 10

0
g 0
h i
1 2 3 4 5 1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8

------------------------------------------------------------- Fraction -----------------------------------------------------------

Fig. 3. Concentration of arsenic (a, b and c), cadmium (d, e and f) and zinc (g, h and i) in eluate from soil, soil leached through intercepting biochar and biochar control. Note the
differing scales between soil and biochar for Cd and Zn. Dotted, vertical line indicates where the leaching of soil was terminated and the leaching of the intercepting biochar and
biochar control continued (mean n ¼ 3 and error bars represent  s.e.m.).

experiment, in which the acidic soil eluate, with low water-soluble the leaching test (Fig. 3d and g; Table 2) suggesting strong initial
carbon concentrations flowed into the biochar columns, soil itself was de-sorption from soil which reduced as the water-soluble pool was
not subject to an increase in alkalinity or flushing with soluble organic depleted. In this particular soil significant concentrations of soluble
substances (soluble carbon) whereas the effects could be different if Cd and Zn have been associated with a relatively high water-soluble/
the two media were mixed together. Similarly time did not influence readily exchangeable fraction whereas a very rapid depletion of the
arsenic concentration in eluate in the respect that concentrations small water-soluble pool of As was observed because the labile
were not significantly reduced or increased during the leaching test
(Table 2), probably because As was so weakly water-soluble in this soil
despite high pseudo-total concentrations (Table 1). Table 2
Unlike arsenic, whose solubility was low and whose concentra- Changes in heavy metal and arsenic concentrations, pH and water-soluble total/
tions in eluate were negligible, cadmium and zinc concentrations in organic carbon concentrations in eluate during the first 5 fractions of the column
leaching test. ‘[’ denotes a significant increase, ‘Y’ denotes a significant decrease at
eluate from soil were high, especially in the first 2 leaching fractions
*p < 0.05, **p < 0.01, ***p < 0.001. n.s. ¼ not statistically significant (ANOVA).
(200e500 mg l1 in each fraction; Fig. 3d and g) which resulted in
cumulative removals of w4 mg Cd per kg1 and w2.5 mg Zn per kg1 As Cd Zn pH WSTC/WSOC
of soil over the first 5 fractions of the column test. Both metals had Soil n.s. Y** Y* n.s. n.s.
a similar trend to decrease successively and significantly (p ¼ 0.009 Soil þ Biochar n.s. n.s. n.s. [** Y***
Biochar control n.s. Y** n.s. n.s. Y***
and 0.017 for Cd and Zn respectively) after the second fraction of
478 L. Beesley, M. Marmiroli / Environmental Pollution 159 (2011) 474e480

Fig. 4. Scanning Electron Microscope (SEM) image of the surface of biochar at 190 magnification showing variously sized pores (A.) and longitudinal, vertically cut cross-section of
those pores at 550 magnification (B.). Note both the vast surface area and interior pore structure.

fractions of this metalloid form only a small proportion of its total pH and Cd (p < 0.01) in eluate from soil when it had passed through
concentration (Beesley et al., 2010a). biochar, indicating that raising the pH could be one mechanism by
which Cd mobility was reduced by biochar, considering the high
3.2. Reductions in soluble cadmium and zinc by biochar soluble Cd concentrations in this soil. The rapid increase in alkalinity
of eluate from soil after it had passed through biochar (p < 0.05;
Biochar rapidly and significantly (p < 0.05) reduced concentra- Fig. 2b) would therefore have assisted Cd retention. Other workers
tions of both Cd and Zn as it intercepted contaminated eluate from have previously noted that increases in soil pH increased the reten-
the soil columns (Fig. 3e and h). There was an especially stark effect tion of Cd in solution by adsorption (Azeez et al., 2010).
on Cd, with consistent reductions in eluate concentrations of this The reversibility of the retention of Cd and Zn was tested by
metal in every fraction of the column test (Fig. 3e) indicating a strong disconnecting the intercepting biochar from the contaminated soil
tendency of biochar to retain this metal. A similar, albeit columns and continuing to leach this material independently of
less pronounced effect was also found in a field study measuring soil (Fig. 1b). In these final 3 fractions of the column test (leaching
pore water concentrations of Cd and Zn after mixing biochar with fractions 6, 7 and 8, collected, 1, 2 and 3 weeks after leaching of soil
soil (Beesley et al., 2010b). In that study it was speculated that was terminated) there was a small, but none significant increase in
the mechanisms of individual element mobility were different. For Cd in eluate from the intercepting biochar (Fig. 3e), indicating that
example Cu was influenced primarily by dissolved organic carbon the removal of the high concentrations of this metal by this material
(DOC), arsenic by an increase in pH but the mechanisms controlling were not readily reversible. The permanence of the immobilisation
the large decrease in Cd and Zn were more difficult to elucidate. effect at least in the immediacy suggested strong sorption of the
The present study found a significant negative correlation between soluble metals to the surface of biochar. Given biochar’s pore

Fig. 5. Scanning Electron Microscope (SEM) image and colour coded SEM/EDX dot maps (acquired at 600 frames, for 3 h and 30 min at 180 magnification; blue for arsenic, green
for cadmium and red for zinc) of soil before (A.) and after a 5 week column leaching test (B.). Note the reduction in relative concentrations of elements, especially Cd, after leaching,
shown by darker colour shades.
 L. Beesley, M. Marmiroli / Environmental Pollution 159 (2011) 474e480 479

Fig. 6. Scanning Electron Microscope (SEM) image and colour coded SEM/EDX dot maps (acquired at 600 frames, for 3 h and 30 min at 180 magnification; blue for arsenic, green
for cadmium and red for zinc) of biochar not leached (A.) and after leaching with contaminated soil eluate in a 5 week column leaching test (B.). Note the increase in relative
concentrations of elements after leaching, shown by lighter colour shades.

structure, large surface area (Fig. 4) and thus high water retention surfaces as the leaching test progressed associated with re-
capability (Thies and Rillig, 2009) it was also important to establish distribution from the iron-rich soil to the iron-retentive biochar.
that biochar alone was free from significant amounts of As, Cd and Biochar’s structure might also explain some of the effects
Zn in water-soluble form and would be safe to use as a soil treatment observed. It is thought that oxidation of biochars occurs most rapidly
without itself contributing to any environmental toxicity effects. on their outer surfaces, followed by interior pores (Nguyen et al.,
Very low concentrations of all elements were measured in the eluate 2008), which might result in differential element retention
of the biochar control columns (Fig. 3c, f and i). between surface and interior sites as a result of shifting CEC for
example (Cheng et al., 2008). In the present study, arsenic sorption
3.3. Retention of trace elements by biochar might only have occurred on the outer surfaces of the biochar, where
the SEM/EDX detected relatively high amounts after the leaching
Cadmium and, to a lesser proportion, Zn and As were de-sorbed test. Cadmium and Zn, which were far more abundantly water-
from the soil surface during the column leaching test, indicated by soluble and present in far higher concentrations may have been
the SEM/EDX element dot maps (Fig. 5A and B), explaining the retained both to outer surfaces and, when those retention sites were
elevated concentrations of Cd and Zn in eluate from soil during the effectively saturated, further adsorbed to the network of pores and
column test (Fig. 3d and g). In turn both of these metals were sorbed fissures that form biochar’s complex inner micro-structure (Fig. 4B).
to the intercepting biochar, indicated by relative increases in their Such differential nutrient retention and leaching effects related to
surface concentrations after the leaching test (Fig. 6B) compared to pore sizes, outer and inner surfaces of biochar are discussed further
before (Fig. 6A). In the case of arsenic, pseudo-total concentration by Major et al. (2009) but in the present study it is only possible to
was high in the soil (Table 1) but solubility was low (Fig. 3a) because speculate on such effects relating to As, Cd and Zn until further work
the majority of As is considered to be in a more stable form (residual is carried out. For the purposes of this study the SEM/EDX method
>60%), compared to Cd and Zn (residual <5% and <25% respectively provided a useful mechanistic illustration of the transfer of soluble
Beesley et al., 2010a). Despite its lack of retention by the biochar and readily exchangeable elements from soil to biochar, confirming
observed from the leaching test, arsenic was also shown to be surface retention.
retained by biochar (Fig. 6A and B). There could be several possible
explanations for this. Laird et al. (2010) examined macro-nutrient 4. Conclusions
immobilisation by biochar in a column experiment, finding that
hardwood derived biochar could act as a sink for dissolved P added Biochar has proven to be effective at reducing high concentra-
to soil by supplementary manure amendment. Phosphorous and tions of soluble Cd and Zn originating from a contaminated soil and
arsenic are chemically analogous, with the possibility that As we can now more affirmatively say that sorption is one of the
could be sorbed to biochar’s surfaces given low concentrations of mechanism by which those metals are retained. It is even further
competing soluble P. Previous increases in As mobility in biochar encouraging that the retention of these pollutants was not imme-
treated soils have been explained by out-competition of P with As diately reversible. For arsenic more investigation is required on soils
for binding sites in alkaline pH conditions, and the subsequent with high water-soluble concentrations of this metalloid. However,
release of As (Hartley et al., 2009). Furthermore the soil used in this in wider environmental terms the results of this study allow us to
experiment was relatively Fe rich, to which a high proportion of As is visualise biochar assisting the interception and arresting the
bound in this soil (>30%), compared to Cd and Zn (<10%; Beesley migration of toxic elements to groundwater or its deployment in
et al., 2010a). Nguyen et al. (2008) found that ageing black carbon, shallow, immature polluted soils to reduce soil-plant transfer of
often synonymously referred to with biochar, retained Fe on particle metals in the rhizosphere. There are also implications of our results
surfaces after exposure to soils. It is possible that, in the present beyond soils, to the treatment of contaminated waters. The focus of
study that there was a cumulative retention of As onto biochar’s future work should now determine the repeatability of our results
480 L. Beesley, M. Marmiroli / Environmental Pollution 159 (2011) 474e480

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