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Environmental Pollution 157 (2009) 2654–2662

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

Arsenic mobility in brownfield soils amended with green waste compost


or biochar and planted with Miscanthus
William Hartley a, *, Nicholas M. Dickinson a, Philip Riby b, Nicholas W. Lepp a
a
Faculty of Science, Liverpool John Moores University, Byrom Street, Liverpool L3 3AF, UK
b
School of Pharmacy and Biomolecular Sciences, Liverpool John Moores University, Byrom Street, Liverpool L3 3AF, UK
Green waste compost enhances water-soluble iron, phosphorus and carbon, increasing arsenic mobility in soil pore water.

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

Article history: Degraded land that is historically contaminated from different sources of industrial waste provides an
Received 21 February 2009 opportunity for conversion to bioenergy fuel production and also to increase sequestration of carbon in
Received in revised form soil through organic amendments. In pot experiments, As mobility was investigated in three different
23 April 2009
brownfield soils amended with green waste compost (GWC, 30% v/v) or biochar (BC, 20% v/v), planted
Accepted 3 May 2009
with Miscanthus. Using GWC improved crop yield but had little effect on foliar As uptake, although the
proportion of As transferred from roots to foliage differed considerably between the three soils. It also
Keywords:
increased dissolved carbon concentrations in soil pore water that influenced Fe and As mobility. Effects of
Green waste compost
Biochar BC were less pronounced, but the impacts of both amendments on SOC, Fe, P and pH are likely to be
Bioenergy crop critical in the context of As leaching to ground water. Growing Miscanthus had no measurable effect on As
Water-soluble organic carbon mobility.
Iron Ó 2009 Elsevier Ltd. All rights reserved.
Arsenic transfer

1. Introduction linked with residual pollutants from atmospheric deposition and


former usage (Dickinson, 2003). Improving soil properties by
Bioenergy crops offer a source of renewable energy and it has amendment with compost may initially immobilise metals
been forecast that around 12% of the UK’s energy could be supplied (Gadepalle et al., 2007; van Herwijnen et al., 2007b), but these may
from biomass-derived materials by 2050 although there is limited be later released as the compost decomposes (van Herwijnen et al.,
scope to achieve this target due to restricted land availability and 2007a). The current European Union requirement to divert biode-
competition with food crops. The use of 7% of agricultural land gradable wastes from landfill has led to the increased use of green
would be necessary to meet carbon emissions targets of 2010 waste compost (GWC) as both a mulch and soil-forming material on
(Anon, 2004). However, in England there are an estimated brownfield land (Saebo and Ferrini, 2006; Gadepalle et al., 2007;
66,000 ha of brownfield land (land that has been previously Sere et al., 2008). Biochar (BC), a wood charcoal, is a less common
developed) that are either vacant or derelict awaiting redevelop- more recalcitrant amendment that has been shown to increase
ment (National Land Use Database, 2001). This could provide fertility, whilst improving soil structure and biological activity
a significant opportunity to cultivate bioenergy crops without (Glaser et al., 2002; Lehmann et al., 2003; Lehmann and Rhodon,
impacting on agricultural land use. Attention is now being focused 2006).
on brownfield and urban soils as a currently neglected resource There is a lack of agreement over the influence of organic matter
(Lehmann and Stahr, 2007). (OM) on arsenic (As) mobility. For example, both Mench et al.
Urban and brownfield soils are often degraded, with a lack of (2003) and Hartley et al. (2009) observed large increases in
significant topsoil that rely on the import of soil or soil-forming leachable As from soils amended with compost probably due to
materials such as recycled green wastes to improve their properties dissolved organic carbon (DOC) competing with As for sorption
(Fasham, 2000; Dickinson et al., 2005; Lorenz and Kandeler, 2005; sites such as those on iron-oxide surfaces, causing increased As
Scharenbroch et al., 2005; Kaye et al., 2006; Bell et al., 2007). There mobility and subsequent plant uptake (Redman et al., 2002). In
are problems associated with the redevelopment of such land contrast, Cao and Ma (2004) used compost to remediate CCA-
contaminated soils and recorded an effect of As adsorption, as
found by others after compost application (Xu et al., 1991; Perez-
* Corresponding author. Tel.: þ44 0151 231 2224. de-Mora et al., 2007). The objectives of the present work were (i) to
E-mail address: w.hartley@ljmu.ac.uk (W. Hartley). evaluate the effects of two organic treatments (GWC and BC) on

0269-7491/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2009.05.011
W. Hartley et al. / Environmental Pollution 157 (2009) 2654–2662 2655

growth and As uptake in Miscanthus x giganteus grown in three Biochar was obtained from Bodfari Charcoal, Denbigh, UK (www.bodfari-charcoal.
diverse As-polluted soils and (ii) to determine if water-soluble co.uk); it is manufactured from hardwoods including Common Ash (Fraxinus
excelsior), Oak (Quercus spp.) and Cherry (Prunus spp.). The wood is heated to 400  C
organic carbon (WSOC) derived from these amendments affected in the absence of oxygen in ring kilns and upon reaching this temperature, volatile
As mobility, assessed by changing concentrations in soil pore water. gases from the wood continue the charring process. Green waste compost (PAS 100
quality) was sourced from Whitemoss Horticultural Supplies, Kirby, UK. Untreated
2. Materials and methods soils were used as controls. A proprietary peat-based potting compost from
Whitemoss Horticultural Supplies was used as a positive control.
2.1. Study sites and sources of arsenic
2.3. Pore water sampling
Three soils, with different sources of As contamination were collected for
a glasshouse-based pot investigation. Site 1, Rixton clay pits (hereafter referred to as
Once filled with soil, a hole was drilled in the side of each pot 10 cm below the lip
Rixton) near Warrington, Cheshire (53 240 34.8000 N 2 280 38.8000 W), is an area adja-
and a ‘Rhizon’ soil pore water sampler inserted at a 45 angle. These consist of
cent to brickworks, where coal fly ash (CFA) and other industrial wastes have been
a porous polymer tube (10 cm) at one end that is inserted into the soil. This is
disposed of. CFA is alkaline and the main environmental problems are due to
connected to a PVC tube (10 cm) and a Luer-Lock connector, from which pore water
leaching of metal(loids) from the coal ash settling ponds, causing phytotoxicity
is obtained using a syringe and vacuum tube (Clemente et al., 2008). Pore water
(Prasad et al., 1996). Clay from the pits was used for brick making until the mid 1960s
samples were analysed for pH, WSOC, As, P (phosphorus) and Fe (iron) for all
(Warrington MBC Ranger Service, pers. comm.).
treatments and controls with the exception of the positive control.
Site 2 is located between two canals at Kidsgrove near Stoke-on-Trent (hereafter
referred to as Kidsgrove) (53 050 28.4600 N 2 15019.0300 W). Dredged sediment from
one canal has been deposited on the embankment that separates the two water- 2.4. Analytical methods
ways. This is contaminated with As and heavy metals, including Cu and Zn; the latter
may have originated from a pigment factory located further down the canal. The Soil pH, was determined using a 20 g dry sample mixed to a slurry with
origins of As in the sediment are not known. deionised water (50 ml). The supernatant was tested using a PHM85 precision pH
Site 3 is a former landfill site at Merton Bank, St. Helens, Merseyside (hereafter meter. Organic matter content was determined by loss-on-ignition (LOI) (450  C).
referred to as Merton Bank) (53 270 33.2100 N 2 420 50.1600 W). An alkali works oper- Available soil phosphate (PO4 3 ) in untreated soils was measured by the Olsen
ated on the site from 1873 within an industrial landscape, and subsequently the area method (Olsen et al., 1954). Pore water-soluble phosphorus (P) concentrations were
developed into a disused industrial waste site with shallow soils contaminated with determined by Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-
Le Blanc process waste (10–30 cm). Following remediation in the 1980s this 6.6 ha OES; Thermo Scientific, MA, USA). Soil samples for determination of pseudo-total As,
site is now intensively mown open grassland (mainly perennial Ryegrass (Lolium Cu, Zn, Cd and Ni (mg l1) concentrations were air-dried (25  C), sieved (<4 mm
perenne) and Yorkshire Fog (Holcus lanatus)) used for public recreation, within diameter) and aliquots (0.2 g) digested with Analar grade 15.55 M HNO3 (10 ml)
a residential and industrial area. using a CEM Mars Xpress microwave (Programme; 1600w 100% power 10 min; hold
at 160  C 20 min). Solutions were analysed by Inductively Coupled Plasma-Mass
2.2. Collection and preparation of soil samples Spectrometry (XSERIES 2 ICP-MS; Thermo Scientific, MA, USA). Accuracy was
checked regularly by reference to international certified standard water (NWRI-
Soil samples were collected following guidelines according to ISO 10381-1 and TMDA-62) and to digests of a standard reference soil (CMI7004). Dissolved organic
-2. Sampling was conducted using a non-systematic pattern (W formation) across carbon and nitrogen were determined using a TOC-VE Shimadzu water analyzer
the sites. Bulk (50 kg) surface soil samples (0–10 cm) were obtained from each site. (Shimadzu, Tokyo, Japan). Inorganic carbon and total carbon in solid samples were
Table 1 provides the main characteristics of the untreated soils. The samples were determined using a TOC-VE/SSM-5000A (900  C).
homogenised in the laboratory using a cement mixer. For each site, a sub-sample A sequential extraction specifically designed for As was carried out on the
was taken from the homogenised soil. These soil samples were air-dried for one equilibrated amended soils. All reagents used in the extraction procedures were
week. Dried soils were crushed and sieved to a particle size of <4 mm diameter, then analytical grade. Soil samples (1.00 g) were weighed into Nalgene polypropylene
pH, organic matter content, available P and pseudo-total metal concentrations were centrifuge tubes and all stages of the extraction procedure were carried out in the
determined for each soil prior to experimental use. Amendments were applied to tubes to minimise soil loss. The following five-step procedure, modified by Shio-
the homogenised soils at a rate of 30% v/v for GWC, and 20% v/v for BC. CL:AIRE watana et al. (2001) was used to evaluate the distribution of As in the treated soils:
(Contaminated Land: Applications in the Real Environment) recently conducted
a study using GWC at application rates of 25% and 50% (v/v) (CL:AIRE, SUB 10, 2008), (1) H2O (water soluble);
whilst at present there is no ideal application rate for BC. Amended soils were (2) 0.5 M NaHCO3 (surface-adsorbed);
homogenised thoroughly by hand, then moistened to 70% of the soil water holding (3) 0.1 M NaOH (Fe and Al-associated);
capacity (WHC) with distilled water and allowed to equilibrate in plastic bags at (4) 1 M HCl (carbonate bound);
room temperature for 14 days prior to being transferred to plastic pots (5 kg). (5) HNO3 (residual (pseudo-total); the original method used HNO3–HF).

Table 1
Origin and physico-chemical characteristics of soils used in test study. Trace elements are pseudo-total concentrations (mg kg1 dry wt.) (n ¼ 3, with S.E.). Values followed by
the same letter are not significantly different (p < 0.05).

Merton Bank Kidsgrove Rixton


Origin Alkali waste from the Le Blanc industry Canal embankment augmented Coal fly ash
with dredged sediment
Soil classification Sandy loam/loamy sand Loamy sand Sandy clay loam
Sand (%) 82.71 83.42 48.26
Silt (%) 5.54 9.12 22.25
Clay (%) 11.75 7.46 29.25
pH 7.06  0.01 6.98  0.02 8.49  0.03
Loss-on-ignition (% OM) 17.75 16.46 8.68
Total carbon (%) 8.88 10.22 5.87
Inorganic carbon (%) 0.71 0.66 0.74
Organic carbon (%) 8.16 9.56 5.13
Water-soluble carbon (mg kg1) 365.9  3.13 375.9  7.53 201.77  6.37
Water-soluble organic carbon (mg kg1) 62  9.35 b 75  3.76 a 56  0.84c
Water-soluble nitrogen (mg kg1) 29.67  5.41 73.0  13.03 0
As (mg kg1) 71.9  9.48 b 59.5  6.91 a 78.0  15.53 b
Cu (mg kg1) 101.7  40.17 508.3  16.56 32.5  2.40
Zn (mg kg1) 117.9  33.36 114.1  0.40 68.7  2.84
Cd (mg kg1) 1.65  0.34 36.2  2.00 0.83  1.00
Ni (mg kg1) 29.88  2.64 44.3  7.37 25.70  2.17
Fe (%) 4.9 b 8.4 a 3.8 b
PO4
3 available (mg kg
1
) 39.0  4.2 a 11.4  5.2 b 18.3  5.6 c
2656 W. Hartley et al. / Environmental Pollution 157 (2009) 2654–2662

Table 2 particulate matter adhering to their surfaces. The material was then re-washed
Physico-chemical characteristics of the organic amendments (trace element (deionised water) and treated in the same way as the foliage.
concentrations are pseudo-total HNO3 digests unless otherwise stated) (n ¼ 3, with
S.E.). 2.7. Microwave digestion of plant material

Green waste compost Biochar


Plant samples were digested using a CEM Mars Xpress microwave digestion
pH 8.10  0.02 9.94  0.04 instrument. Dry, finely ground plant material was weighed (0.2 g) into a digestion
Loss-on-ignition (%) 23.13 55.50 vessel (120 ml) to which Analar grade 14 M HNO3 (10 ml) was added. Digests were
Total carbon (%) 13.06 88.38 carried out in triplicate and analysed via ICP-MS. Bowens Kale powder (Bowen, 1974;
Inorganic carbon (%) 0.73 2.42 Katz, 2002) was used as a standard reference plant material for QA purposes. Mean
Total organic carbon (%) 12.33 85.96 recovery for As was 124  9.7%.
Fe (%) 1.6 3.8b
P (%) 0.22b 0.43b 2.8. Statistical analysis
P (mg kg1) 49a  0.33 ndc
As (mg kg1) 4.24  0.28 ndd Statistical analyses were performed using SPSS Ver. 14. Dunnet’s test and GLM
Zn (mg kg1) 138  5.08 70b were used to test for differences in As uptake in Miscanthus between soil type and
Cu (mg kg1) 63.17  1.86 70b treatment type. One-way Anovas combined with Dunnet’s test were used to
Ni (mg kg1) 18.05  1.32 <3.2 determine differences between treatments and trace element mobility in pore water
a
Water-soluble phosphorus concentration extracted using ASTM leaching test samples.
(for ASTM methodology see Hartley et al., 2004).
b
XRF analysis. 3. Results
c
nd not determined.
d
nd not detected.
3.1. Soils and amendments

Table 3 Arsenic concentrations were similar in the three soils, varying


Organic matter (% LOI) changes to soils after amendment additions. between 60 and 72 mg kg1 (Table 1). Carbon was largely present in
Treatment organic form in the three soils; together with P and Fe, concen-
trations were generally in the mid-range for mineral (but not
Untreated GWC (30%) BC (20%)
organic) soils in the UK (Allen, 1989). Soil from Rixton had a higher
Merton Bank 17.75 28.05 25.82
Kidsgrove 16.46 23.28 20.71
clay content and higher pH, but less sand and lower OM, water-
Rixton 8.68 12.81 10.88 soluble C and N. Kidsgrove soil had higher Fe. Amendments
(Table 2) increased organic carbon in all soils (Table 3). Both GWC
and BC are well known to vary according to feedstock and
production process; in this case, the BC had total carbon (TC)
2.5. Plant growth and uptake studies
similar to typical values of 75% (Lehmann, 2007) but higher P than
Plastic pots (5 kg capacity; 32 cm diameter) filled with polluted soils prepared as the value given by Lehmann (2007) for adsorption of phosphate
described above (Section 2.2) were planted with Miscanthus x giganteus rhizomes. (approximately 0.03%). Biochar-amended soils were more alkaline
Rhizomes originated from Johannes Falk, Nordic Biomass, Denmark (1 year old) and
than unamended controls (Fig. 7).
were supplied by John Amos & Co. (Leominster, Herefordshire, UK). Rhizomes were
washed (tap water) and cleaned to remove any residual peat-based compost, then
a single piece containing 2–3 buds was planted into each pot (10 cm long). Each 3.2. Plant yield and As uptake
treatment was carried out in triplicate. Pots were placed on plastic saucers to
prevent leachate draining from the soils and the trials were carried out in
Green waste compost substantially increased Miscanthus yield
a controlled greenhouse environment (21  2  C; 60% R.H.; 12 h light) with regular
daily watering (tap water). Plants were grown for a period of 8 months. but there was little effect of BC (Table 4). The inhibitory effects of
the As-enriched soils on biomass production were evident in
comparison with a reference peat-based compost in which yield
2.6. Harvesting of shoot/rhizome/root material
was nearly double that of the Kidsgrove soil amended with GWC.
Miscanthus foliage was harvested by cutting stems 1 cm above the soil using The beneficial effects of GWC on plant growth, and absence of any
stainless steel scissors. The material was washed with deionised water to remove effect with BC, were reflected in the leaf chlorophyll content [data
soil residues from the base of the stems, blotted with tissue paper until dry, weighed not shown].
fresh then oven dried at 35  C for five days. Dried biomass was re-weighed then There was no clear effect of either amendment on As uptake into
ground in a stainless steel Fritsch cutting mill (Pulverisette 15). Ground samples
were stored in polyethylene containers prior to analysis.
Miscanthus, although concentrations in foliage were marginally
Rhizomes and roots were removed from the soil, separated and washed with lower in Kidsgrove soil compared to the other soils (Fig. 1b).
deionised water. They were then placed into a sonic bath to remove any fine However, substantially more As entered the roots and rhizomes in

Table 4
Total yield (n ¼ 3, with S.E.), As concentration (n ¼ 3, with S.E.) and As uptake in Miscanthus foliage grown in the three test soils.

Merton Bank Kidsgrove Rixton

Yield (g/pot) Arsenic concentration Plant Yield (g/pot) Arsenic concentration Plant Yield (g/pot) Arsenic concentration Plant
in foliage (mg kg1 uptake in foliage (mg kg1 uptake in foliage (mg kg1 uptake
dry wt.) (mg/pot) dry wt.) (mg/pot) dry wt.) (mg/pot)
Treatment
Untreated 53.5  6.79 0.6  0.11 0.03 134.5  8.61 0.06  0.02 0.008 29.7  11.19 0.67  0.22 0.02
GWC 133.77*  15.76 0.54  0.38 0.07 203.62*  2.14 0.12  0.05 0.02 132.86*  2.59 0.39  0.19 0.05
BC 55.63  2.32 0.54  0.12 0.03 142.52  8.78 0.07  0.11 0.01 27.35  3.7 0.62  0.16 0.02
Peat-based 380  11.75 nd nd 380  11.75 nd nd 380  11.75 nd nd
compost

*p < 0.001.
nd ¼ not determined.
W. Hartley et al. / Environmental Pollution 157 (2009) 2654–2662 2657

a 10 Root
1600 Residual
Carbonate-bound
Rhizome
1400 Fe & Al- associated
8 Foliage
surface-adsorbed
1200 water soluble
As (mg kg-1)

6
1000

As (mg kg-1)
4
800

2 600
a

400
0

b 10 200

0
8

140
As (mg kg-1)

6
120

4 a
100
a
2
As (mg kg-1)

80

0
60
c 10
40

8
20
As (mg kg-1)

6
0

4 100

a
2 80
a

0
As (mg kg-1)

60
Untreated GWC BC
Treatment
Fig. 1. Arsenic uptake in Miscanthus roots, rhizomes and foliage as affected by green 40
waste compost (GWC) and biochar (BC) when grown in (a) Merton Bank (b) Kidsgrove
and (c) Rixton soils (n ¼ 3, S.E.) (a ¼ p < 0.001).

20
Merton Bank soil and approximately 10% of the As pool was
transferred to foliage (as in Kidsgrove soil). Higher As transfer to
foliage in Rixton soil, despite low uptake to roots, confounded this
0
pattern.
Untreated GWC BC
Treatment
3.3. As mobility in soil Fig. 2. Arsenic fractionation (Shiowatana extraction) from Merton Bank (a), Kidsgrove
(b) and Rixton (c) soils and treated with green waste compost (GWC) and biochar (BC)
Incorporation of GWC increased As lability, with higher (mean values, n ¼ 3). Order of sequential fractions: I ¼ water soluble, II ¼ surface-
concentrations recorded in water soluble and surface-adsorbed adsorbed, III ¼ Fe- and Al-associated, IV ¼ carbonate bound, and V ¼ residual.
2658 W. Hartley et al. / Environmental Pollution 157 (2009) 2654–2662

3
0.2
0.2 Untreated
GWC

Fe (mg l-1)
As (mg l-1)
As (mg l-1)

0.1
0.1
1

0 0 0

0.2 3
0.2 Untreated
Biochar

Fe (mg l-1)
2
As (mg l-1)
As (mg l-1)

0.1 0.1

0 0 0
0 50 100 0 1 2 3 0 50 100
WSOC (mg l-1) Fe (mg l-1) WSOC (mg l-1)

Fig. 3. Relationship between concentrations of untreated (B) and GWC treated (:) pore water As (p  0.001), Fe (p  0.001) and water-soluble organic carbon (WSOC) and BC-
treated (-) pore water As (p ¼ 0.226), Fe (p ¼ 0.142) and water-soluble organic carbon (WSOC) in Merton Bank soil collected over the time period of the investigation (n ¼ 48).

fractions (Fig. 2). Biochar had little significant effects on As in foliage were 5.25, 21.7 and 2.94 mg kg1 respectively. The same
mobility. Concentrations of phytotoxic trace elements in Mis- fractionation procedure showed that these potentially phytotoxic
canthus foliage were within the normal range in uncontaminated trace elements (Cu, Zn and Ni) were largely (>40%) bound to
plant materials. Highest concentrations of Cu, Zn and Ni recorded carbonate in all the soils [data not shown]; limited mobility

0.016 0.016 2
Untreated
1.6 GWC
0.012 0.012
As (mg l-1)

As (mg l-1)

Fe (mg l-1)

1.2
0.008 0.008
0.8

0.004 0.004
0.4

0 0 0

2
0.016 0.016 Untreated
Biochar
1.6
0.012 0.012
As (mg l-1)

Fe (mg l-1)
As (mg l-1)

1.2
0.008 0.008
0.8

0.004 0.004
0.4

0 0 0
0 50 100 150 0 1 2 0 50 100 150
WSOC (mg l-1) Fe (mg l-1) WSOC (mg l-1)

Fig. 4. Relationship between concentrations of untreated (B) GWC treated (:) pore water As (p  0.001), Fe (p  0.001) and water-soluble organic carbon (WSOC) and BC-treated
(-) pore water As (p  0.001), Fe (p ¼ 0.207) and water-soluble organic carbon (WSOC) in Kidsgrove soil collected over the time period of the investigation (n ¼ 48).
W. Hartley et al. / Environmental Pollution 157 (2009) 2654–2662 2659

0.6 Untreated
0.6 1.5
GWC

0.4
As (mg l-1)

As (mg l-1)
0.4 1

Fe (mg l-1)
0.2 0.2 0.5

0 0 0
0.6
1.5 Untreated
0.6
Biochar

0.4
As (mg l-1)

Fe (mg l-1)
As (mg l-1) 0.4

0.2 0.2 0.5

0 0 0
0 100 200 300 0 0.5 1 1.5 0 100 200 300
WSOC (mg l-1) Fe (mgl-1) WSOC (mg l-1)

Fig. 5. Relationship between concentrations of untreated (B) and GWC treated (:) pore water As (p  0.001), Fe (p ¼ 0.005) and water-soluble organic carbon (WSOC) and BC-
treated (-) pore water As (p  0.001), Fe (p ¼ 0.436) and water-soluble organic carbon (WSOC) in Rixton soil collected over the time period of the investigation (n ¼ 48).

would have mitigated further against detrimental effects on increased availability of P limiting As uptake; the chemical simi-
growth and uptake. larity and behaviour of phosphate (PO3 4 ) and As means they may
Pore water WSOC significantly increased (p  0.001) following compete with each other for uptake sites (Adriano, 2001). When
incorporation of GWC to the test soils as did water-soluble Fe phosphate is limited, As is taken up into plants at higher rates due
concentrations (p  0.001) (Figs. 3–5). Pore water As increased in all to the stimulation of the phosphate uptake system under low
test soils following GWC-amendment, but most significantly in phosphate status (Thompson et al., 1990). Low P conditions that
Kidsgrove soil; the labile As pool increased threefold compared to would enhance uptake did not exist in the present study even in
untreated soils (Fig. 4). In comparison to untreated soils, P untreated soils. Higher rates of As uptake into roots at Merton Bank,
concentrations significantly increased (p  0.001) in Kidsgrove and where soil P was highest, require a different explanation. One
Rixton soils following GWC-amendment (Fig. 6). Biochar amend- possibility may be due to differences in soluble metal(loid)–organic
ment had a strong effect on increasing As mobility in Rixton soil complexes that are known to enter the root free space, but are not
(Fig. 5) but not otherwise; there was no relationship between necessarily translocated to the foliage. Therefore, As may be
WSOC, As and Fe with BC-amendment. Iron concentrations in all mobilised in pore water in GWC phosphorus-enriched soils (Qafoku
BC-treated soils were reduced compared to untreated soils. Mis- et al., 1999; Hartley et al., 2009) largely due to competitive anion
canthus had no measurable effect on As mobility when compared to exchange (Peryea, 1991), but without increasing uptake by plants.
soils without Miscanthus growing in them [data not shown]. Water-soluble organic carbon is the most mobile fraction of
organic ligands that exist in soils and may assist in the transfer of
4. Discussion metal(loids) through soil as organic complexes (Cao et al., 2003).
Whilst organic matter is generally beneficial to degraded soils,
In spite of similar As concentrations in the three test soils, there is some concern that contaminant solubility may also be
inherent differences existed between them in terms of As mobility increased through the formation of soluble organic complexes due
and bioavailability. This was probably a product of the different to incorporation of carbon-rich composts (Zhou and Wong, 2001;
sources of contamination, and particularly differences in P, pH, Fe, Mench et al., 2003). In the present study, soil pore water As was
OM and WSOC concentrations that existed between them before significantly increased in all test soils treated with GWC. Besides
and after amendment additions (Tables 1 and 3). Both BC and GWC the role of P enrichment, as discussed above, there is probably
represent the introduction of large pools of organic carbon that may a significant additional influence of soluble Fe and complex organic
have substantial further impact. As far as the authors are aware, BC acids on As lability.
has not previously been applied to As-polluted soils to evaluate its In a recent laboratory investigation, Wang and Mulligan (2009)
effect on retention and mobility of the metalloid. It is already well observed that mobilization of As was closely related to mobilization
established that DOC may reduce or increase metal adsorption onto of Fe in mine tailings treated with humic acid. They found that
soil surfaces by either (i) being preferentially surface-adsorbed presence of humic acid promoted formation of aqueous Fe–humate
rather than the metal(loid) it is competing with or (ii) by forming complexes preventing iron hydroxides forming and thereby
soluble organo-metallic complexes with the metal(loid) and hence reducing As retention in the tailings. Addition of GWC to the
increasing its mobility (Guisquiani et al., 1998). polluted soils in the present study resulted in significantly higher
In the present study, neither GWC nor BC substantially altered concentrations of Fe in pore waters compared to untreated soils
As uptake into Miscanthus foliage. One explanation may be (Figs. 3–5). Solubilisation of Fe in pore water may have affected the
2660 W. Hartley et al. / Environmental Pollution 157 (2009) 2654–2662

a 1 0.12
P
a 9 Untreated
Fe Biochar
As GWC
0.1 8.5
0.8
P (mgl-1) Fe (mg l-1)

0.08 8

pH
As (mg l-1)
0.6 a
7.5
0.06

0.4
7
0.04

0.2 6.5
0.02

b 9
0 0

8.5
b 1
a
0.01

a 8

pH
0.8 0.008
P (mgl-1) Fe (mg l-1)

7.5
As (mg l-1)

0.6 a 0.006
a 7
a
0.4 0.004
6.5

0.2 0.002 c 9

0 0 8.5

c 2.5 b 0.3 8
pH

a 7.5
2
P (mgl-1) Fe (mg l-1)

0.2 7
As (mg l-1)

1.5

6.5
1 1 2 3 4 5 6 7
0.1 Monthly sampling

Fig. 7. Change in pore water pH over the time period of the investigation as affected by
0.5 organic treatments in (a) Merton Bank, (b) Kidsgrove and (c) Rixton soils.
a

0 0 sites such as ferrihydrite (Grafe et al., 2002). Large concentrations of


Untreated GWC BC WSOC from GWC may have further enhanced As mobility due to
Treatment competition for sorption sites, displacing As from iron oxides
Fig. 6. Water-soluble phosphorous, arsenic and iron in pore water samples from
(Redman et al., 2002). These negatively-charged dissolved organic
(a) Merton Bank, (b) Kidsgrove and (c) Rixton treated with green waste compost (GWC) substances appear to have higher potential to compete with As for
and biochar (BC) (n ¼ 3, S.E.) collected at the beginning of the investigation adsorption sites in soils leading to increased As mobility (Lin et al.,
(a ¼ p < 0.001, b ¼ p < 0.05). 2008). Thus, dissolved organic carbon may play an important role
in mobilizing As in soil (Grafe et al., 2001).
mechanisms of adsorption and co-precipitation of As, through the
formation and mobilization of soluble arsenic–metal–organic
Table 5
complexes (Lombi et al., 2000; Lin et al., 2002; Wang and Mulligan,
Arsenic transfer coefficients in Miscanthus foliage.
2009). Highest pore water As concentrations were observed in
Merton Bank and Kidsgrove soils which contained the largest pools Merton Bank Kidsgrove Rixton
of Fe (Table 1). Untreated 0.014 0.001 0.009
Fulvic acids but not humic acids have also been shown to GWC 0.008 0.002 0.005
BC 0.008 0.001 0.008
increase As leaching by out-competing the metalloid for binding
W. Hartley et al. / Environmental Pollution 157 (2009) 2654–2662 2661

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