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Environmental Pollution 157 (2009) 847–856

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

Arsenic stability and mobilization in soil at an amenity grassland overlying

chemical waste (St. Helens, UK)
William Hartley a, *, Nicholas M. Dickinson a, Rafael Clemente b, Christopher French a,1,
Trevor G. Piearce c, Shaun Sparke a, Nicholas W. Lepp a
School of Biological and Earth Sciences, Liverpool John Moores University, Byrom Street, Liverpool L3 3AF, UK
Department of Soil and Water Conservation and Organic Waste Management, Centro de Edafologı́a y Biologı́a Aplicada del Segura, CSIC, Apartado 4195, 30080 Murcia, Spain
Biological Sciences Division, Lancaster Environment Centre, Lancaster University, Lancaster LA1 4YQ, UK

Stabilization of alkali industry waste requires careful management to minimise soil arsenic mobilization and dispersal to the wider environment.

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

Article history: A 6.6 ha grassland, established on a former chemical waste site adjacent to a residential area, contains
Received 23 June 2008 arsenic (As) in surface soil at concentrations 200 times higher than UK Soil Guideline Values. The site is
Received in revised form not recognized as statutory contaminated land, partly on the assumption that mobility of the metalloid
7 November 2008
presents a negligible threat to human health, groundwater and ecological receptors. Evidence for this is
Accepted 9 November 2008
evaluated, based on studies of the effect of organic (green waste compost) and inorganic (iron oxides,
lime and phosphate) amendments on As fractionation, mobility, plant uptake and earthworm commu-
nities. Arsenic mobility in soil was low but significantly related to dissolved organic matter and phos-
Phytoremediation phate, with immobilization associated with iron oxides. Plant uptake was low and there was little
Arsenic apparent impact on earthworms. The existing vegetation cover reduces re-entrainment of dust-blown
Soil particulates and pathways of As exposure via this route. Minimizing risks to receptors requires avoidance
Risk assessment of soil exposure, and no compost or phosphate application.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction volumes of waste containing arsenic as a major contaminant. Glass

wastes, known locally as Burgy Banks (St. Helens, 2007), have an
Two centuries of industrialization have created a considerable elevated As content because arsenic trioxide (As2O3) was added to
legacy of pollution in St. Helens in North West England. In 1862, this glass as a clarifying agent.
area around an alkali works near Merton Bank was described as St. Helens is also adjacent to large coal reserves that created
‘‘one scene of desolation [where] three-fourths of trees are totally considerable areas of spoil until mining ceased in the 1970s; in the
dead. Farms recently well-wooded, and with hedges in good last 20 years the colliery spoil heaps have been the focus of large
condition, have now neither tree nor hedge left alive; whole fields scale reclamation activity for environmental improvement and
of corn are destroyed . orchards and gardens have not a fruit tree revegetation in the context of UK community forestry (Hodge,
alive . pastures are so deteriorated that graziers refuse to place 1995; Rawlinson et al., 2004; Bell et al., 2007). Prior to this, in the
stock on them’’ (Brenner, 1974; Dingle, 1982). The Alkali Act of 1863 early 1980s, a former ill-defined chemical waste site at Merton
that resulted from this ‘‘scene of desolation’’ is recognized as the Bank (the location of the present study) in St. Helens was restored
first UK pollution control legislation (Hawes, 1995). Widespread to amenity grassland after more than a century of dereliction. Since
elevated soil arsenic (As) is a major component of this legacy, then, the site has been managed as intensively mown grass with
largely associated with development of the town around the open access that provides an important recreational area of urban
manufacture of glass, alkali chemicals, paints and numerous green space for local residents.
metallurgical industries. Both glass manufacture and soda ash For several years the Merton Bank site has provided a location
production (from the Le Blanc process) produced very large for research investigations into soil contamination, trace element
mobility (Hartley, 2002; Hartley et al., 2004; Clemente et al., 2008;
Hartley and Lepp, 2008a,b), brownfield land remediation (French,
* Corresponding author. Tel.: þ44 1 151 231 2224.
E-mail address: w.hartley@ljmu.ac.uk (W. Hartley).
2005; French et al., 2005) and evaluation of soil quality and health
Present address: Parsons Brinckerhoff Ltd, Manchester Technology Centre, (Dickinson et al., 2005; Hartley et al., 2008). Interest in the site has
Oxford Road, Manchester M1 7ED, UK. been related to the known elevated soil As concentrations, with

0269-7491/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
848 W. Hartley et al. / Environmental Pollution 157 (2009) 847–856

hotspots above 4000 mg kg1 dry wt. that critically exceed the UK until the 1980s, and (ii) the likelihood that future use of the site or
Contaminated Land Exposure Assessment (CLEA) Soil Guideline differing management practices may alter As mobility and transfer
Value (SGV) of 20 mg kg1 total inorganic As for residential land use to receptors such as humans, groundwater or soil biota.
(DEFRA, 2002b) as well as the SGV of 500 mg kg1 that applies to
commercial and industrial land uses. Concentrations of As in 2. Methods
uncontaminated UK soils are generally in the range of 2–
53 mg kg1 [median 10 mg kg1] (Archer and Hodgson, 1987). The 2.1. Study site
metalloid is a USEPA Group A human carcinogen, with soil inges-
The site at Merton Bank, 16 km east of Liverpool, is situated in an urban resi-
tion being a critical issue in assessing health risks. Baseline risk dential housing area bounded by the Sankey Brook (a tributary of the River Mersey),
assessment studies use the assumption that As is bioavailable a Phragmites wetland and a small industrial and commercial area (Fig. 1). In 1849,
although it is known, for example, that both soil pH and speciation this was the site of a reservoir that supplied water to nearby mills that was later
significantly affect this property (Datta and Sarkar, 2005). drained. An alkali works was present on part of the site in 1873, although this had
been removed some 20 years later. It is reported that, on cessation of production,
This paper is a collation of data obtained from Merton Bank that
‘‘the site consisted of two large conical tips of alkali waste with a central area of
assesses the significance of elevated As concentrations in surface rubble . and has remained untreated for over 70 years’’ (Murphy, 1979). There is
soil and questions the assumption that As has low mobility and a history of refineries, alkali, other chemical and copper (Cu) works in the immediate
bioavailability. This is the first paper that focuses specifically on this vicinity of the site, but declining industrial activity and a conversion to residential
particular site. We evaluate (i) the consequences of Monitored development occurred in the area during the 1960s. In 1978, the alkali waste was
leveled and used to contour the site which is now raised up to 15 m above
Natural Attenuation (relying on natural processes to reduce the
surrounding land with slopes of 4–12 . A 20 cm layer of imported acidic colliery
mobility and concentration of contaminants) and aftercare spoil was then applied to the surface to ameliorate extreme alkalinity after which
following typical methods of landscape engineering used in the UK the surface was ripped to 60 cm. A thin layer of soil (apparently limited to about 5 cm

Fig. 1. Merton Bank in St. Helens, Merseyside, with three experimental plots marked. The site is bordered to the north by a footpath and brook (above Plot 2) and to the south by the
strip of shrubs and trees (W of Plot 2).
W. Hartley et al. / Environmental Pollution 157 (2009) 847–856 849

depth) and fertilizers were applied to the soil in 1980 prior to seeding of the site for
amenity grassland, with small patches of trees and shrubs planted in deeper soil
(Murphy, 1979). The site has no formal drainage system but appears to be generally
well drained, at least partially into the adjacent watercourse.
No anoxic conditions were encountered when trial pits were dug and oxygen
values above 10% were recorded to depths of 1 m, suggesting that the most domi-
nant As species in the soil was arsenate (AsV). Surface soil was characterized as silt
loam (70% of samples), sandy silt loam (18%) loamy sand (10%) or clay loam (2%); the
latter used for one of the more recent detailed studies of As (Hartley and Lepp,
2008b). Total nitrogen concentrations (range between plots ¼ 0.22–0.30%) were
typical for mineral soils. Extractable phosphate was particularly low (0.5 mg,
100 g1 in 73% of samples, n ¼ 33) for UK soils (Allen, 1989) although higher values
were determined in one study, carried out after green waste compost (GWC) had
been applied.

2.2. Site investigation and sampling

A site investigation was carried out in 1999 (The Mersey Forest, 1999); 35 trial
pits (all dimensions 1.5 m) were dug to provide descriptive profiles, with 1 kg bulk
soil samples removed for analysis (0–15 cm and two lower depths). Additional soil
sampling was carried out using hand augers to obtain 1 kg bulk samples to 7.5 cm
depth (25 samples) and 15 cm depth (10 samples). Early in 2000, three experimental
plots of short-rotation coppice woody plants were established at the site (Fig. 1). The
plots were rotovated, followed by a glyphosate weed control treatment. Soils were
then sampled, using an auger, to 30 cm depth in a herringbone sampling design
(DoE, 1994); 72 samples per plot allowed identification of 1% hotspots (3 m  3 m).
The planting of Salix and Populus taxa, Betula pendula, Alnus incana and
Larix  eurolepis was part of a wider experimental trial at five brownfield sites,
reported elsewhere (French et al., 2005). Collections of soil for laboratory analyses
were obtained from hotspots within these plots (Fig. 2), following guidelines ISO
10381-1 and -2 (International Standards Organisation). Another post-graduate
(Ph.D.) laboratory-based project was also completed using soils from this site
(Hartley, 2002).
In 2002, earthworms were sampled within each of the three experimental
blocks by digging and hand sorting from 25  25 cm pits. In late 2005 further studies
focusing on a range of biological descriptors (Dickinson et al., 2005) were initiated,
including a comparison of Merton Bank with 9 other remediated sites in North West
England (Hartley et al., 2008). In the latter study, sampling areas delineated by
0.25  0.25 m quadrats were excavated until there was no further evidence of
earthworm activity, sometimes at a depth of as little as 0.15 m. Numbers, weights
and functional groupings of earthworms [epigeics, non-burrowing in surface litter
and organic horizons; endogeics, sub-surface dweller in branching, horizontal
burrows; anecics, surface litter feeders in deep vertical burrows] (Bouché, 1977)
were recorded.
In early 2005, the experimental blocks were coppiced and GWC of accredited UK
standard (BSI, 2005) was applied as a mulch, to a depth of 20 cm, in randomly placed
(approximately 5 m) strips. In 2007, rhizon samplers were inserted at varying depths
to 20 cm in pits within composted and non-composted sections of the experimental
plots for monitoring of soil pore water, using methods reported elsewhere (Clem-
ente et al., 2008).

2.3. Laboratory and glasshouse investigations

Sub-samples of field-collected bulk soils were homogenized in the laboratory by

hand mixing. Air-dried soil was crushed and sieved (<4 mm), prior to determination
of pH, organic matter content (loss-on-ignition) and total organic carbon (Carbon
Analyzer) and available phosphate using the Olsen method (Allen, 1989). Soil
samples were also variously amended with a range of iron oxides (1% w/w), lime
(1% w/w), phosphate (0.4% w/w) and GWC (at 30 and 50% v/v). Treated soils were left
to equilibrate for 1 month prior to investigations at 20  C. Leaching studies involved
modified Dutch (3 week test in which soil is leached with water at a rate of
1 ml min1 upward through a column) and ASTM (American Society of Testing and
Materials procedure whereby soil (25 g) is shaken for 48 h in 100 ml water)
procedures; methodologies are reported in detail elsewhere (Hartley et al., 2004).
Prior to determination of pseudo-total metal(loid) concentrations, soil samples were
oven-dried (40  C), sieved (<2 mm) and microwave digested using 14 M HNO3/HCl
(USEPA, 1994). Determination of trace elements in soil and plant samples was
carried out variously using AAS, HG-AAS, ICP-OES or ICP-MS, with these and other
physico-chemical parameters determined using standard methodologies reported
elsewhere (Hartley et al., 2004; French, 2005; Clemente et al., 2008).
A sequential extraction with 0.01 M CaCl2 followed by 0.05 M EDTA was used
during the early investigations followed later by a modified sequential extraction
scheme developed by Shiowatana et al. (2001). The modified Dutch Leaching Test Fig. 2. Dispersion of As in surface soils in the three experimental plots at Merton Bank.
(NEN 7343) was used to assess amendment efficacy over a greater timescale, and to Different shading categories are arbitrary and operationally defined using ArcView GIS
simulate the long-term behavior of As in soils under more natural conditions; 3.2; spatial interpolation of inverse distance weighted (IDW) was applied with 12
effectively the standard test was modified to simulate excessive leaching and a worst neighbouring samples for estimation of each grid point. Maximum values (darkest
case scenario (Hartley et al., 2004). shading) in the range of 5000–5500 mg kg1 (Plot 1, 30 m  30 m) 4500–
Glasshouse pot experiments were also carried out in which Lolium perenne c.v. 5000 mg kg1 (Plot 2, 21 m  21 m) and 2500–3000 mg kg1 (Plot 3, 30 m  30 m)
Elka (ryegrass) was grown in pots (5 kg capacity; 32 cm diameter; 20 g seeds pot1) [data redrawn from French (2005), not drawn to scale].
filled with iron oxide and lime amended contaminated soil and harvested every
850 W. Hartley et al. / Environmental Pollution 157 (2009) 847–856

three weeks from May to September, providing five successive harvests. Plant Table 2
growth trials were carried out in a controlled glasshouse environment (21  2  C; Soil descriptors at the Merton Bank sites from French (2005)1, Hartley and Lepp
60% R.H.; 12 h light) with regular daily watering (distilled water) as required. The (2008a,b)2 and The Mersey Forest (1999)3. Analyses are ICP-MS-pseudo-total.1,2
soils were also used to grow two species of vegetable crop (data not shown in this
paper, Hartley and Lepp, 2008a). Physico-chemical property Source Mean (s.e.)
Further pot trials (5 kg capacity; 32 cm diameter) investigated the effect of GWC pH 1 7.25
incorporation on water soluble organic carbon (WSOC) concentrations and arsenic 2 6.47
mobility. Green waste compost was applied to the soil at a rate of 30% v/v. Amended 3 7.50
soils were homogenized thoroughly by hand, moistened to 70% of the soil water LOI (%) 1 10.1 (0.42)
holding capacity (WHC) with distilled water and allowed to equilibrate in plastic 2 14.0 (1.07)
bags at room temperature for 1 month prior to being transferred to the pots. 3 11.0 (0.74)
Untreated soils were used as controls. Once filled with soil, a hole was drilled in the Soil classification 2 Sandy loam/loamy sand
side of each plastic pot (10 cm below the lip) and a ‘rhizon’ soil pore water sampler Sand (%) 2 82.71
was inserted at a 45 angle. Samples were collected every 4 weeks over a 6-month Silt (%) 2 5.54
period and analysed for dissolved organic carbon (DOC) and As. Clay (%) 2 11.75
Accuracy of trace element concentrations in soils and soil extracts from previ- As (mg kg1) 1 1386
ously unpublished analytical data was routinely checked by reference to interna- 2 71.96 (9.48)
tional certified standard water (NWRI-TMDA-62) and to digests of a standard Zn (mg kg1) 1 261 (35.7)
reference soil (CMI7004). 2 171 (53.9)
Cu (mg kg1) 1 150 (20.3)
2.4. Statistical analysis 2 222.8 (122.6)
Cd (mg kg1) 2 30.0 (0.13)
Statistical analysis was carried out using Minitab Ver. 15. One-way ANOVAs and Pavailable (mg kg1)a 2 39.0 (4.2)b
GLMs combined with Dunnet’s Test were used to test for statistical significance. 3 4.49 (0.730)
Fe (%) 2 3.544 (0.94)
S (%) 2 0.379 (0.006)
3. Results and discussion
Available P determined by the Olsen method (Allen, 1989).
Data obtained after GWC application.
3.1. Contamination at Merton Bank

The surface soil at Merton Bank is highly polluted with As Arsenic adsorption is affected by the surface charges on iron
(Table 1), with a heterogeneous dispersion of hotspots of up to oxides, and the quantity of anions adsorbed is related to the pHpzc
5000 mg kg1 (Fig. 2). Elevated concentrations of As were found at (point at which there is a net zero charge on the mineral surface)
all locations sampled. In the most detailed survey (French et al., (Sadiq, 1997). Many iron oxide surfaces are altered by pH, being
2005) arithmetic means varied between 642 and 879 mg As kg1 positively charged in acid conditions changing to negatively
within the 3 plots. However, As tends to be relatively immobile in charged when conditions are alkaline (Parfait, 1980). Alkaline pH
soil (Langdon et al., 1999; Milton and Johnson, 1999); for example, causes desorption of AsV and sometimes arsenite (AsIII) (Jain et al.,
soils and mine spoils in SW England contain respectively <1.2% and 1999). For iron oxides, the pHpzc is usually in the range 7–10
<0.3% of total As in water-extractable fractions (Kavenagh et al., (Alloway, 1995), and therefore pH is of importance in regulating As
1997). Soil concentrations of heavy metals were lower, with only bioavailability (Marin et al., 1993; Mitchell and Barr, 1995). Arsenic
marginally elevated hotspots of lead (Pb) (only 1 plot was signifi- is known to be less mobile in acidic soils due to the adsorption
cantly contaminated with Pb in 59% of samples (Table 1) (SGV effect on iron oxide surfaces (Madejón and Lepp, 2007). Soil pH
450 mg kg1)), with cadmium (Cd), zinc (Zn), nickel (Ni), and values of 6.5–7.6 at Merton Bank may enhance the risk of As
copper (Cu) also detected (Table 2). mobility. In soil solution, As is present as negatively charged oxy-
anions, existing in several oxidation states and forms; AsIII is much
3.2. As mobility and inorganic amendments more toxic than arsenate AsV. Oxidation from AsIII to AsV tends to
occur quickly, especially in the presence of manganese (Mn) oxides,
Several physical and chemical properties are known to affect the enhancing soil sorption (Sparks, 1995). Waterlogging of soil can
sorption of As in soil with as much as 90% found to be associated influence oxidation status, producing more toxic AsIII, but the
with the clay fraction (Johnson and Hiltbold, 1969). The sandy loam Merton Bank site appears to be well drained.
surface soils, apparently dominant at Merton Bank, have a relatively Chemical tests that estimate bioaccessibility of trace elements
low clay content of 12% (Table 2), although these are higher in some are valuable in terms of providing broad comparisons between the
areas of the site that have clay loams (Hartley and Lepp, 2008b). soluble metal(loid) fractions of contaminated soils. Sequential
Arsenic has been shown to have a high affinity for oxidic surfaces, extraction protocols (Ure, 1990; Ure and Davidson, 2002) use
attaching itself preferentially to iron oxides (Atkins and Lewis, chemical fractionation to reveal the ease of release of trace
1976) which adsorb anions such as arsenate (AsV) from the soil elements from the soil to solution phase using increasingly
solution. aggressive digestion reagents (Kumpiene et al., 2008). The greatest
proportion (w60%) of As at Merton Bank was bound to the Fe- and
Table 1 Al-associated phase (also referred to as the reducible fraction as
Arsenic and lead recorded in soils at various locations across the Merton Bank site. arsenic associated with it would be mobilized if reducing condi-
Most data were from hand-augered samples to a maximum of 30 cm depth, but in
tions occurred; Bacon and Davidson, 2008), with less than 5% being
many cases soil coverage was noted to be much shallower.
surface-adsorbed or water soluble in untreated soil (Fig. 3). It is well
Trace Mean pseudo-total EDTA-extractable CaCl2-extractable established that iron oxides show greatest potential for As
element (mg kg1) (mg kg1) (mg kg1)
adsorption in soils (Lumsdon et al., 1984; Waychunas et al., 1993;
Mean Range Mean % Pseudo-total Mean % Pseudo-total Mench et al., 1998; Verkleij et al., 1999); iron oxides applied to
Asa 1386 4.9–5266 35.4 2.6 3.1 0.23 garden soils have produced reductions of up to 50% in water-
Asb 849 53–8076 nd nd nd nd extractable As concentrations, with concomitant reductions in As
Pba 2088 38.6–3640 645.6 30.9 0.1 <0.1 uptake by lettuce (Mench et al., 1998). Arsenic mobility is reduced
Pbb 603 94–6503 nd nd nd nd by the formation of amorphous ironIII arsenate (FeAsO4$H2O)
Analyses are ICP-MS-pseudo-total. (Carlson et al., 2002) and various surface complexes are formed
Data from a consultant’s report (The Mersey Forest, 1999). with hydrous metal oxides; for example arsenate forms isolated
W. Hartley et al. / Environmental Pollution 157 (2009) 847–856 851

a 1200 was applied to Merton Bank soil there was an 8% reduction in As

leached. This may be due to As binding with calcium (Ca2þ), and
thus reducing mobility (Hartley et al., 2004).
1000 Preliminary studies and analyses of soil pore water, collected
using rhizon samplers directly from the site at two soil depths
(15 cm and 30 cm), showed As concentrations to be in the range of
800 40–189 mg l1, which represents <0.02% of pseudo-total soil
concentrations, based on 500 mg As kg1 (Clemente et al., 2008).
As (mg kg-1)

Maximum pore water concentrations and those obtained from

standard leachate tests can be further extrapolated using a crude
worst case scenario mass balance calculation: annual rainfall in the
area of about 800 mm potentially could mobilize 0.12–0.8% of the
total mass of soil As (calculated to 30 cm depth). Current UK
guideline values take no account of the biological availability or
200 mobility in soil, although advances have been made in under-
standing oral bioaccessibility in humans, with estimates ranging
from 0.5 to 45% (median 11%) for UK soils (Cave et al., 2002).
0 Phosphate (P) and arsenate (AsV) are chemical analogues that
exhibit similar chemical behavior, competing directly for binding
Water Sodium bicarbonate (0.5 M) Sodium hydroxide (0.1 M)
sites within the soil (Davenport and Peryea, 1991; Zhang and Selim,
Hydrochloric acid (1 M) Nitric acid (14 M)
2008). It has been demonstrated that As may be mobilized in
phosphorus-amended soils (Qafoku et al., 1999) largely due to
b 20 competitive anion exchange (Peryea, 1998). In the present study,
addition of phosphate as phosphorous pentoxide (P2O5) 18% (7.2% P
soluble in water) at an extreme rate of 0.4% (w/w), revealed a 13-
15 fold increase in leachable As compared to untreated soil following
extraction using the ASTM leaching test (Fig. 4).
As (mg kg-1)

3.3. Arsenic mobility and organic amendments

Organic matter also affects As mobility, competing for sorption

sites and displacing As from iron oxides (Redman et al., 2002) with
AsV having high lability and solubility in contaminated humus-rich
acid soils (Tye et al., 2002). However results have been controver-
e ite rit e e sial with some researchers witnessing reductions in plant uptake
ted Lim eth im im
trea Go nG I)+L II)+L (Cao and Ma, 2004) whilst others have observed increases in As
Un Iro e(I e(I
F F leaching from soils amended with compost (Mench et al., 2003),
Treatment partly brought about by changes in pH and the type of compost
applied. At slightly acidic pH (5.5) As sorption is high but, at neutral
Fig. 3. a. Arsenic fractionation in Merton Bank soil amended with iron oxides and lime
(1% w/w), using the method of Shiowatana et al. (2001) [from Hartley and Lepp, 2008b, pH, AsV may be reduced to AsIII thereby increasing metalloid
with permission]. The extractants approximate to water soluble-extractable (water), mobility in compost-amended soil (Shiralipour et al., 2002).
surface-adsorbed (NaHCO3), Fe- and Al-associated (NaOH), carbonate bound (HCl) and
residual (HNO3), and b. Changes in labile As in Merton Bank soil as a function of
amendments (1% w/w), assessed using the modified Dutch Leaching Test 3
(means  s.d., n ¼ 3, from Hartley et al., 2004, with permission).

inner-sphere complexes on ferrihydrite (HFO), with binuclear

bidentate complexes or mononuclear monodentate complexes
forming at high or low surface coverage respectively (Mench et al.,
1998). Amendment of Merton Bank soil with iron grit redistributed
As (mg kg-1)

As to the residual fraction (Fig. 3a). However, incorporation of FeII

sulphate plus lime increased the concentration of As bound to the
Fe and Al fraction, thereby increasing the stabilization of the
metalloid in the soil, reducing potential mobility and hence soil–
plant transfer. 1
Whilst differences between treatments using sequential
extractions were marginal (Fig. 3a), longer-term leaching studies
(Fig. 3b) show much more significant differences. The modified
Dutch Leaching Test showed that FeII and FeIII sulphates plus lime
significantly reduced the amount of As leached from Merton Bank
soil (Fig. 3b). The most effective treatment was amendment with 0
FeIII plus lime; leaching of untreated soil was reduced from Untreated Phosphate
14,680 mg kg1 to 1110 mg kg1, equivalent to a 92% reduction in Soil Treatment
leachable As (Hartley et al., 2004). Other treatment formulations Fig. 4. Change in As mobility as affected by phosphate addition (4000 mg kg1) to
also reduced As in leachates, but to a lesser degree; for example, Merton Bank soil (n ¼ 3, s.e.), using the ASTM leaching test [previously unpublished
reductions of 56% with goethite and 17% with iron grit. When lime data].
852 W. Hartley et al. / Environmental Pollution 157 (2009) 847–856

Reduction of AsV to AsIII is dependent on both pH and redox

a 1000
potential. In an oxidized soil, such as this, H2AsO
4 would change to
HAsO2 4 as pH increases, their concentrations being equal at pH
6.76. Sorption of arsenate then decreases as pH increases as is 800
known to occur for phosphate. Fulvic acid has been shown to
increase As leaching by out-competing the metalloid for binding

As (mg kg-1)
sites such as ferrihydrite whilst humic acid was suggested not to be 600
involved in As leaching (Grafe et al., 2002). Hence the degree of
organic matter humification will affect As mobility due to the
presence of either high or low molecular weight organic acids 400
having either low or high solubility respectively (Kumpiene et al.,
The current requirement to divert biodegradable wastes from 200
landfill has led to increased use of GWC as a mulch and soil-forming
material on brownfield land (Saebo and Ferrini, 2006; Gadepalle
et al., 2007; van Herwijnen et al., 2007a; Sere et al., 2008). Whilst 0
generally beneficial to degraded soils, there is some concern that Untreated GWC
contaminant solubility may be increased through the formation of Water Sodium bicarbonate (0.5 M)
soluble organic complexes due to incorporation of carbon-rich
Sodium hydroxide (0.1 M) Hydrochloric acid (1 M)
composts (Zhou and Wong, 2001; Mench et al., 2003; van Her-
Nitric acid (14 M)
wijnen et al., 2007b). Negatively charged dissolved organic
substances appear to have higher potential to compete with As for
adsorption sites in soils, leading to increased As mobility (Lin et al., b 50
2008). It has also been suggested that added organic matter acts as a
a food source for microbes that enhance As leaching as the
metalloid is biotransformed and reduced to AsIII (Mandl et al., 1992; 40
Turpeinen et al., 1999), although rates of formation are likely to be
small in most circumstances (DEFRA, 2002b). Conversely, others
have found reduced mobility after compost application (Xu et al.,
As (mg kg-1)

30 a
1991; Cao and Ma, 2004; Perez-de-Mora et al., 2007). The effect of
pH is a major controlling factor and it has been reported that in the
presence of organic matter, oxyanion adsorption is increased as pH
decreases (Sposito, 1989). In the present study where the soil pH of
6.5–7.6 was already relatively high, addition of GWC (30% v/v)
appears to release a proportion of the bound As from the Fe and Al
oxide fraction which is redistributed to less strongly bound phases 10
(surface-adsorbed and water soluble), thereby increasing As in
these fractions by more than 10% (Fig. 5a).
Incorporation of larger amounts of GWC (50% v/v) doubled the 0
leachable As concentrations in the last four fractions of the modi- 1 2 3 4 5 6 7
fied Dutch Leaching Test (Fig. 5b). Overall, GWC increased the Fraction (K)
amount of As leached by 18%, thought in this case to be possibly due
Fig. 5. a. Arsenic fractionation in Merton Bank soil amended with green waste
to increased fulvic and humic acids (Kumpiene et al., 2008). The
compost (GWC, 30% v/v), using the method of Shiowatana et al. (2001) [previously
present findings suggest that release of As from sorption sites may unpublished data], key as in Fig. 3a, and b. Changes in labile As in untreated Merton
not occur immediately within the soil, as this test attempts to Bank soil , and Merton Bank soil amended with green waste compost (50% v/v) ,
simulate trace element leaching over a greater timescale (upwards assessed during the modified Dutch Leaching Test (n ¼ 3,  standard deviations)
of 3 years) implying that application of GWC may affect As mobi- [previously unpublished data].

lization in the long term. Results from short-term pot trials show
GWC-treated soil to increase WSOC together with slightly elevated
As concentrations (Fig. 6). It has been observed that a small but
substantial increase in arsenic mobility in wetland soils is associ-
ated with high DOC, brought about by formation of aqueous
arsenic/dissolved organic matter (DOM) complexes either by
positively charged amino groups in DOM (Saada et al., 2003) or by
As (mg l-1)

metal cation bridges (Redman et al., 2002).

3.4. Biological impacts

Sufficient experimental work has been carried out at Merton

Bank to allow a preliminary evaluation of potential ecotoxicology of
As at the site. Glasshouse plant investigations using L. perenne (the 0
0 50 100
dominant grass species at Merton Bank) showed that As concen-
trations in plants were not raised substantially above background WSOC (mg l-1)
concentrations of 0.1–1.0 mg kg1 (Fig. 7) normally expected at Fig. 6. Relationship between concentrations of pore water As and water soluble
uncontaminated sites (Allen, 1989). Arsenic uptake was highest in organic carbon in untreated (B) and GWC (30% v/v) treated (:) Merton Bank soil
soil amended with lime (1% w/w) but soil–plant As transfer [previously unpublished data].
W. Hartley et al. / Environmental Pollution 157 (2009) 847–856 853

1st Harvest
2nd Harvest

Arsenic (mg kg-1)

3rd Harvest
4th Harvest

2 5th Harvest

Compost Untreated Lime Goethite Iron Grit Fe(II) + Fe(III) +
reference Lime Lime
Fig. 7. Uptake of As by ryegrass (Lolium perenne var. Elka) from Merton Bank soil with inorganic amendments in pot experiments (n ¼ 3, s.e.) [Hartley and Lepp, 2008b, with
permission]. Compost reference refers to plants grown in compost only.

coefficients (Tc) for ryegrass grown in untreated soil were low abundance and diversity was in the intermediate range of several
(0.01) (Hartley and Lepp, 2008a) and at the lower end of published brownfield sites in the region (Table 4). A scoring system provided
typical transfer values of between 0.01 and 0.1 (Kloke et al., 1984), an index of combined assays, allocating Merton Bank a score of 73%
and 0.0007 and 0.032 (Warren et al., 2003). Overall, Fe-oxides were of the biological quality achieved by a particularly successful
shown to be effective in situ amendments that reduced As landfill site remediation in the region (Hartley et al., 2008).
bioavailability, although soil–plant transfer of As was not
completely halted by any amendment (Hartley and Lepp, 2008a).
3.5. Risk assessment
Mortality of woody biomass species at Merton Bank was the
highest, and productivity was the lowest, when comparing 5
Part IIA of the UK Government’s Environmental Protection Act of
brownfield sites located in North West England that were studied
1990 requires a risk-based approach to the assessment and
intensively by French et al. (2005). Varying yields of 1.5, 3.5 and
management of potentially contaminated sites. The existing
5.5 dry t ha1 annum1 in the 3 plots probably reflecting higher
predominantly intensively mown grassland cover at Merton Bank
production on north-facing slopes with less sun exposure and less
appears to be a healthy sward giving full soil coverage that
water shortage during the summer. Uptake of As into foliage and
undoubtedly restricts the re-entrainment of dust-blown particu-
woody stems of plants was insignificant (<2 mg kg1), with the
lates. The site is extensively used for dog-walking, casual sports and
exception of Larix where up to 14 mg kg1 As was recorded in
recreation by local residents, and it would seem likely that any
foliage, although survival of this species was low at all 5 sites (mean
human exposure pathways would be through direct ingestion of soil
11%) and may not be related to particular conditions at this site.
or inhalation of wind blown or otherwise re-entrained particulates.
Earthworm activity plays an important functional role in soils
Soil-to-plant uptake is low (as observed in the ryegrass study) and
through comminution, mixing and aeration, stimulation of micro-
there is a negligible food chain risk through this route. However,
bial activity and enhancement of decomposition and nutrient
long-term and repeated exposure through unwashed hand-to-
cycling (Edwards and Bohlen, 1996). Earthworms are potentially
mouth transfer and inhalation requires further consideration.
valuable indicators of soil health (Langdon et al., 2003). The overall
UK CLEA guidance (DEFRA, 2002a) utilizes statistical tools or
abundance and species diversity of earthworms was found to be
‘mean value tests’ when examining heterogeneously contaminated
moderate in the experimental plots in a survey conducted in 2002.
land. If the calculated upper 95th percentile (US95) is less than the
Eight species of earthworms were found; 81 individuals of 6 species
SGV, then contamination may be judged not to be an issue for
on As hotspots (>300 mg kg1), and 200 earthworms of 7 species in
purposes of human health risk assessment. Using this criterion, all
less contaminated areas of the plots (As warm spots,
three plots were significantly As-contaminated, with more than
<300 mg kg1) (Table 3). Allolobophora chlorotica was the most
abundant earthworm in the ‘hotspots’ whilst Aporrectodea cal-
iginosa was dominant in the less contaminated areas. The largest Table 3
earthworm species, Lumbricus terrestris and the smallest species, Differences between soil sampled within 0.25  0.25 m quadrats in hotspots
(n ¼ 20) and warm spots (n ¼ 18) across the three experimental plots (s.e.)
Murchieona minuscula, were only found in the less contaminated
[previously unpublished data].
‘warm spots’. There are few records of M. minuscula, making it an
interesting find, its small size allowing it to be easily overlooked Hot spot Warm spot
when sampling, and perhaps misidentified in the laboratory. Total As (mg kg1) 2287  417 301  6.12
Endogeic species were the most numerous ecological group pH 7.5  0.10 6.9  0.16
Moisture (%) 25.9  0.68 23.3  0.59
with the largest combined weight. In areas amended with compost, Loss-on-ignition (%) 13.0  0.73 11.8  0.67
there was a clear increase in earthworm abundance; anecic species, Total number of earthworms 81 200
with lower reproduction rates, increased most in terms of biomass, Mean number of earthworms per quadrat 4.1  2.19 11.1  1.78
but endogeics increased most in number (Fig. 8). Earthworms have Total number of epigeics 35 94
Total number of endogeics 36 92
been previously observed to inhabit arsenic-rich soils and to evolve
Total number of anecics 10 14
tolerance to the metalloid (Morgan et al., 1993; Langdon et al., Total number of species 6 7
2001). There was no evidence of toxicity or other detrimental
Epigeics: Lumbricus castaneus (3), Lumbricus rubellus (46), Lumbricus festivus (80).
effects on earthworm communities at Merton Bank. Recent Endogeics: Allolobophora chlorotica (43), Aporrectodea caliginosa (81), Murchieona
assessment of other biological descriptors in the most As- minuscula (4).
contaminated experimental plot (Plot 2), showed that earthworm Anecics: Lumbricus terrestris (21), Allolobophora longa (3).
854 W. Hartley et al. / Environmental Pollution 157 (2009) 847–856

1.2 risks between 2.7  104 and 6  105 (DEFRA, 2002a,b). An Index
Dose of minimal risk is derived from combined oral and inhalation
pathways of 0.302 mg kg1 body weight day1. In practical terms
1 this dosage would require a daily ingestion of just 0.04 g Merton
Bank soil day1 (from 500 mg As kg1 hotspots, by a 70 kg adult).
The difficulty of digesting soil and absorbing As from the digestive
Earthworm weight (g)

0.8 system mitigates to some degree against this concern.

The potential for increased exposure of human, groundwater
and ecological receptors in the future largely depends on the long-
0.6 term stability of As in surface soils and underlying wastes. At
present, UK guidance only considers ecological receptors at sites
with designated nature conservation status. Currently, however,
0.4 the soil at Merton Bank appears to support a diverse community of
b soil fauna. The site is free draining with no evidence of water-
logging and, together with a low soil phosphate status (with the
0.2 exception of the plots treated with GWC), this would help to
immobilize the metalloid; the grassland is not irrigated or routinely
fertilized. Relatively high soil pH (6.5–7.6) may enhance the
mobility of As.

4. Conclusion

b A realistic interpretation of the evidence is that surface soil at

80 Merton Bank is significantly contaminated with As, but currently
appears to be relatively stable in terms of environmental mobility
of this element. The metalloid generally is not mobile and is
Earthworm number

strongly adsorbed in soil. The current extremely high As content of

shallow surface soils must reflect mixing and some degree of
upward movement of contaminants from underlying wastes during
site engineering and the first 25 years of pedogenesis, even though
40 a generally low clay content would suggest restricted binding sites
in the surface soils.
The reclamation carried out at Merton Bank in 1980 falls below
b acceptable modern standards (Fox et al., 1998; Wong and Bradshaw,
2002), but the site appears to have remained relatively stable for
the past 28 years. In common with many brownfield sites in this
region and elsewhere in the UK, the approach to management is
0 through Monitored Natural Attenuation (Environment Agency,
Untreated soil Soil+GWC 2004). Natural processes are unlikely to adequately resolve the
Soil Treatment pollution issues, but there is no evidence that suggests any exac-
Fig. 8. Mean biomass and number of earthworms within ecological groupings in
erbation of risk. This site is not currently monitored in any form.
Merton Bank plots amended with GWC (n ¼ 3, s.e.). Endogeics are represented by Surface soils will naturally accumulate organic matter from
spotted bars, epigeics, solid grey bars and anecics, dashed bars [previously unpublished vegetation over time and potentially this could increase As
data]. mobility. Amending the site with recycled GWC or fertilizing with
phosphate would not appear to be sensible options for sustainable
99% of samples exceeding SGVs for As of 20 mg kg1 for residential site management. In terms of future management, iron oxides are
land uses (DEFRA, 2002b). Less conservative SGVs are set for worth considering as an amendment to reduce As mobilization to
commercial and industrial land uses at 500 mg As kg1. Further the wider environment. To date, As mobility into deeper layers of
statistical guidance on comparing soil contamination data with the waste has not been investigated which is a major shortcoming
critical concentrations has been provided more recently (CL:AIRE, of the existing site characterization. More detailed studies of
2008). downward As migration, particulate re-entrainment and ecological
There are uncertainties about the human health risks of As monitoring are required.
ingestion from soil. UK guidance uses an estimate that a daily
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