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Science of the Total Environment 420 (2012) 300312

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Science of the Total Environment


journal homepage: www.elsevier.com/locate/scitotenv

Arsenic encapsulation using Portland cement with ferrous sulfate/lime and


Terra-Bond technologies Microcharacterization and leaching studies
Paul M. Randall
U.S. Environmental Protection Agency, National Risk Management Research Laboratory, Land Remediation and Pollution Control Division, 26 W. Martin Luther King Drive, Cincinnati, OH
45268, United States

a r t i c l e

i n f o

Article history:
Received 13 June 2011
Received in revised form 24 December 2011
Accepted 28 December 2011
Available online 13 February 2012
Keywords:
Arsenic
Stabilization
Encapsulation
Leaching
X-ray absorption

a b s t r a c t
This work reports the results of an investigation on the treatment and encapsulation of arsenic-containing
materials by Portland cement with ferrous sulfate and lime (PFL) and Terra-Bond, a commercially available
patented technology. The arsenic materials included: chromated copper arsenate (CCA)-treated wood materials; scorodite-rich mine tailings from the La Trinidad Mine in California; and a soil/smelter dust mixture
from the Anaconda Superfund site spiked with monosodium methyl arsenate (MSMA) to simulate an organoarsenic soil material. SEM/EDS and XRD spectra of PFL treated samples showed similarity across all three
waste materials while Terra-Bond treated samples showed predominance of elemental sulfur. SEM/EDS of
PFL treated samples showed that calcium was imbedded in the structure while micrographs of Terra-Bond
treated samples showed the appearance of an epoxy material on the surface. The epoxy material appears
to be responsible for encapsulating and reducing the leachability of arsenic. XANES spectra for the PFL treatment of CCA-containing samples showed that arsenic has a predominant pentavalent form (As + 5), and the
PFL treatment process did not alter the arsenic oxidation state. But, distinct differences were observed for
XANES spectra of untreated and PFL treated scorodite-rich mine tailing which changed the arsenic coordination structure from a mixture of As (+ 3/+ 5) to exclusively As (+ 5). Both S/S techniques reduced the
amount of arsenic released in the leaching tests. Most cases show lower amounts of arsenic released from
wastes treated by the Terra-Bond technique when compared to the PFL technique. The pH of the solution
signicantly affected the leachability, with the amount of arsenic released increasing with pH. Sequential extraction results indicate that sodium hydroxide was favorable in releasing arsenic in the mine tailings. This is
due to ligand displacement reactions of hydroxyl ions with arsenic species and high pH conditions that prevent the readsorption of arsenic.
Published by Elsevier B.V.

1. Introduction
Arsenic speciation controls how it interacts with the environment
and how easily it is treated and stabilized. Arsenite and arsenate species
interchange oxidation states depending on redox potential (Eh), pH,
chemical composition of the environment, and the extent of biological
transformations. Arsenite (As +3) compounds are the dominant form
under reducing conditions; while arsenate (As +5) is generally the stable form in oxygenated/oxidizing environments. Understanding the biotic and abiotic processes that affect the partitioning of arsenic between
the mobile (i.e., the aqueous phase and mobile colloids) and the immobile phases (i.e., aquifer solids and immobile colloids) is crucial. Anionic
arsenic compounds adsorb to soils, clays, organic matter, and multiple
metal hydroxide/oxides (e.g., hydroxides of iron, manganese, and aluminum). The extent of adsorption and chelation depends on which

Tel.: + 1 513 569 7673.


E-mail address: randall.paul@epa.gov.
0048-9697/$ see front matter. Published by Elsevier B.V.
doi:10.1016/j.scitotenv.2011.12.066

arsenic species are present, the Eh, pH, other chemicals that are present
(e.g., phosphate, sulfate, sulde, carbonate), and the activity of arsenic
biotransformation converting arsenic between arsenate, arsenite,
methylated, and other organoarsenic species.
Arsenic is challenging to treat at many cleanup sites. Arsenic is commonly found at U.S. Superfund National Priorities List (NPL) sites. Arsenic is also naturally present at high concentrations in some
groundwaters in the US (Smedley and Kinniburgh, 2002). The EPA has
estimated that there are approximately 800 sites in the U.S. which contain arsenic out of a total of 1753 NPL sites (U.S.EPA, 2011). A variety of
technologies are available to cleanup arsenic-bearing waste or arseniccontaminated soils and sediments. Cleanup methods may include site
isolation, physical separation, bioremediation, washing, heating
methods, electrokinetics, solidication and stabilization (S/S) or in a
few cases in-situ vitrication. Most often, the ultimate, cost effective solution for land remediation involves stabilization and solidication (S/S)
technologies that chemically changes arsenic and encapsulates it to a
less mobile and less toxic species. S/S technologies have an extensively
documented history to reduce the mobility of arsenic in soils and

P.M. Randall / Science of the Total Environment 420 (2012) 300312

other solids by using Portland cement, lime, ferrous sulfates and other
binders (Camacho et al., 2009; Dermatas et al., 2004; Fuessle and
Taylor, 2004; Kim et al., 2003; Kundu and Gupta, 2008; Leist et al.,
2003; Mollah et al., 2004; Moon and Dermatas, 2003; Moon et al.,
2010, 2004; Paria and Yuet, 2006; Phenrat et al., 2008; Qiao et al.,
2006; U.S.EPA, 2002; Zhao et al., 2010). Additives and binders act to oxidize As +3 to As +5, which can either form insoluble complexes or become immobilized due to the formation of strongly adsorbed species; or
form insoluble co-precipitates with calcium and/or iron. According to
stoichiometry, 1 mol of arsenic is retained per mole of calcium, however,
a substantial reserve of Ca (OH)2 is desirable because of other
environmentally-conditioned reactions which consume Ca (OH)2 (i.e.
carbonation). Dutre (Dutre and Vandecasteele, 1998) solidied and stabilized waste y ash (containing 23% to 47% wt of arsenic) using cement
and pozzolanic material. The factor that determines this reduction in arsenic concentration is the excess of lime leading to the optimal pH at a
high concentration of Ca 2+ ions in the solution. In another study
(U.S.EPA, 1996), the EPA data indicated that ferrous sulfate with lime
can successfully immobilize arsenic through precipitation of an arseniciron phase. Furthermore, Artiola et al. (1990) showed that ferrous
sulfate could achieve over 95% stabilization of arsenic-contaminated
soils. They speculated that the processes rely upon precipitation of
FeAsO4 as limiting arsenic mobility and also cementation as a physical
encapsulation process limiting arsenic mobility. Artiola speculated that
the mechanism for stabilization of arsenic by iron in solution is chemical
bonding (inner-sphere) between the dissolved iron and the AsO43 rather than anion exchange at surface sites of iron oxides (outer-sphere).
Voigt et al. (1996) was able to show that soil contaminated from industrial arsenic could be successfully treated using Portland cement with
ferrous sulfate and lime (PFL).
After the EPA's extensive screening of available S/S technologies, it
was decided to study two (2) S/S technologies: PFL and Terra-Bond,
a commercially available technology. Terra-Bond utilizes sulfur
chemistry to react with metals to physically encapsulate and form insoluble suldes (Pildysh, 2002). Overall objective of this project was
to examine the molecular structure and arsenic release of TerraBond and compare it to a modied PFL technology. Reasons and
novelty of this project include: 1. To date, there are limited data on
the performance of the Terra-Bond technology to treat arsenictype materials; 2. Little research data can be found concerning the
solid-state speciation of CCA-treated wood, mine tailings, or organoarsenic materials; 3. With the CCA-treated wood phase-out in the
U.S. residential sector in 2004, alternatives to management are limited; 4. Limited data is found on the sequential fractionation of arsenic;
and 5. Sulfur-treated matrices appear to have better characteristics in
strength, durability, and nonleachability than other binder systems,
so from a sustainability perspective, a sulfur-type technology has
the potential to address the reuse of huge amounts of excess sulfur
available from many petroleum reneries. This paper reports on the
assessment of these technologies using untreated and treated
arsenic-bearing materials.
2. Materials and methods
2.1. Sample collection and preparation
Table 1 shows the experimental sample matrix. Three (3) types of
arsenic-contaminated materials were selected: CCA-treated wood
waste, mine tailings from the La Trinidad Mine (referred to as La Trinidad mine tailings), and smelter dust/soil from a Superfund site in Anaconda, Montana. Smelter dust/soil was mixed with monosodium
methyl arsenate (MSMA) to derive an organo-arsenic type sample
for testing (referred to as Montana soil). Each of the three materials
collected were air-dried and sieved through 40 mesh (nominal sieve
opening 0.420 mm) to remove large chunks, pebbles, and woody materials. Samples were prepared by using sample size reduction tools

301

Table 1
Experimental sample matrix of wastes containing arsenic.
Type of arsenic waste

Location/site

Comments

Chromated copper arsenate


(CCA)a treated wood
waste samples
Scorodite-rich mine tailings

Osmose Wood
Preserving Division,
Grifn, GA
La Trinidad Mine,
North Fork American
River watershed,
California

Contains copper,
chromium, and arsenic

Mixture of organo-arsenic Smelter site in the


(monosodium methylarse- Butte/Anaconda area,
nate [MSMA]) and soil con- Montana
taining smelter dustb,c

Location: 39.2020432 N
latitude and 120.
4938989 W longitude
North American Datum
(NAD) 27, ~ 4000 ft mean
sea level
MSMA crabgrass killer
(manufacturer/
distributor Green Light,
San Antonio, TX) was
purchased from local
store

a
CCA treated wood waste samples contained selected ner fraction after discarding
larger sieved fractions and woody materials.
b
The smelter dust may contain other metal co-contaminants (cadmium, copper,
lead, zinc, mercury, manganese). However, this study focused on arsenic only.
c
To incorporate the inorganic and organic components of arsenic, the organoarsenic and smelter dust were mixed to obtain one composite waste sample.

(like a crusher/grinder) and used homogenization methods to select


suitable test samples. Contamination of samples was avoided by
using a clean and washed hammer, anvil, mortar, pestles, and nylon
screens for individual samples. EPA Quality Assurance/Quality Control
procedures were used. Duplicate analysis was conducted randomly
on 10% of the total samples and one matrix spike was conducted
per group of samples. U.S. EPA Method 6020 was used for determination of total arsenic via inductively coupled plasma-mass spectrometer (ICP-MS).
2.1.1. CCA-treated wood waste samples
CCA-treated wood waste samples were collected from a company
that has treated lumber for over 60 years. Since the CCA-treated wood
phase-out in the residential sector in 2004, there are concerns that
the amounts of CCA-treated wood will increase in landlls. Alternatives to management of CCA-treated wood include: incineration, stabilization/solidication, electrodialytic remediation, reconguration
and reuse, composting with decay fungi, and acid extraction and bioleaching of metals by bacteria (Clausen, 2004). In some circumstances
CCA-treated wood may be mixed with cement and utilized in construction materials (Gong, 2005). Disposal alternatives have their
problems and limitations. At the present time, landlling appears to
be the best disposal method in the U.S., Canada, and Australia. In Denmark, incineration of CCA-treated waste wood is not allowed; instead,
the wood is land-lled until new methods for handling the wood are
available (Pedersen et al., 2005).
With regard to stabilization effectiveness, solid-state speciation of
the metals in CCA-treated wood is an important factor. The active
composition of a typical CCA Type C formulation contains 47.5% hexavalent chromium as CrO3, 18.5% copper as CuO and 34.0% arsenic as
As2O5 (Lebow and Foster, 2005). Nico et al. (2004) studied new CCA
treated wood, aged CCA treated wood, and an easily dislodgeable residue removed from the surface of aged CCA treated wood. In all cases,
the dominant oxidation states of the two elements were found to be
arsenic (+5) and chromium (+3). The local chemical environment
of the two elements was best represented as a chromiumarsenic
cluster consisting of a chromium dimer bridged by an arsenic (+5)
oxyanion (Nico et al., 2004).
2.1.2. La Trinidad mine tailings
The ore contains suldes, including arsenopyrite (FeAsS), pyrite
(FeS2), chalcopyrite (CuFeS2) and galena (PbS). The high concentration of arsenic in the tailings is due to gold processing techniques

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P.M. Randall / Science of the Total Environment 420 (2012) 300312

employed at the mine, which extracted gold and disposed the arsenic,
iron and quartz (SiO2) into a tailings pile. As a result of weathering
and erosion of the tailings pile, iron and arsenic formed scorodite
(FeAsO42H2O). Scorodite can dissolve congruently or incongruently
depending on the pH. Congruent dissolution of scorodite releasing
equimolar concentrations of arsenic and Fe occurs at low pH by the
following reaction:

FeAsO4 2H2 O H H2 AsO4 FeOH

H2 O:

As higher pH values, scorodite dissolves incongruently forming


iron hydroxide and arsenate oxyanions (H2AsO4 or HAsO42):

FeAsO4 2H2 O H2 O H2 AsO4 FeOH3 s H

FeAsO4 2H2 O H2 O HAsO4 FeOH3 s 2H :

a polyvinyl chloride (PVC) monolithic sample holder (approximate


dimensions: 2 in. [diameter] 4 in. [length]. The sample holders
were lled to approximately 75% to allow room for any possible expansion. After the slurry was added to the open end of the sample
holder, the top open-ends were sealed with paralm and maintained
at room temperature during the 28-day cure time. After curing, the
samples were removed from the holder using disposable razors. Appropriate care was taken to avoid contamination of the samples. All
samples prepared in the above manner were used for the subsequent
leaching and characterization experiments. The prepared samples
produced homogeneous monoliths after seven days curing using the
PFL technique.

2.1.3. Smelter dust/soil mixed with MSMA (Montana soil)


Monosodium methyl arsenate (MSMA) was mixed with soil and
smelter dust obtained from Anaconda, Montana. MSMA is a herbicide
commonly used as a crabgrass killer, manufactured and distributed as
Green Light. The bottle label for this product indicated that it contains 48.3% MSMA and 51.7% inert ingredients, with 22.3% total arsenic (all in water soluble form), expressed as elemental arsenic. MSMA
is widely used to clear weeds from non-cropland areas, such as public
right-of-ways. There is little data concerning the leachability, fate and
transport of this herbicide, or the toxicity when present in contaminant mixtures typical of industrial waste streams.
To prepare the samples, native Anaconda smelter and soil sample
(without the addition of MSMA) was analyzed to contain 2350 mg/kg
arsenic. To thoroughly mix the soil with the MSMA, a sample of the
soil and smelter dust (2340 g) was added to a 2 L high density polyethylene (HDPE) container with a wide mouth screw cap with
200 mL of MSMA solution. Approximately 1000 mL of deionized
Millipore water was also added to the container to make a homogenized paste. This paste was transferred into a baking pan and air
dried under a hood. The air-dried soil was sieved through 40 mesh
to obtain soil materials less than 0.42 mm in size. The MSMAtreated soil and smelter dust mixture is sometimes referred to in
this paper as Montana soil or organo-arsenic soil mixture.
2.2. Treatment methods
2.2.1. Portland cement with ferrous sulfate and lime (PFL)
PFL method was selected to encapsulate the arsenic material in a
cement matrix. In this study, Type 1 Ordinary Portland Cement
(OPC) manufactured by the Quikrete Company, Inc. was used to prepare samples. The chemical oxide components of the OPC was CaO
(6167%), SiO2 (1724%), Al2O3 (38%), Fe2O3 (16%), MgO
(0.14%), Na2 + K2O (0.51.5), SO3 (13%). Type 1 OPC complies
with the American Society for Testing and Materials (ASTM) C-150
and federal specications for Portland cement No. 1124.
To prepare the PFL treated samples, a chemical mix design described by Voigt et al. (1996) was followed. Each of the three sieved,
untreated, air-dried samples (689 g) were transferred to 2 L HDPE
containers with wide mouth screw caps. Approximately 311 mL of
water were added to produce a slurry, to which 100 mL of a concentrated solution of ferrous sulfate (500 g/L) was added. The slurry mixture was allowed to settle for 20 min. In a separate container, 30 g of
Portland cement, 90 g calcium hydroxide (Ca (OH)2) and 180 mL of
water were mixed and poured into the ferrous sulfate-sample slurry.
The samples in the HDPE containers were mixed thoroughly in a rotary apparatus for 24 h. After mixing, the samples were transferred into

2.2.2. Terra-Bond technology


The Terra-Bond process, a proprietary treatment technology developed by Pildysh Technologies, Inc, is designed to encapsulate materials in a stable thermoplastic, polymeric, sulfur-based material
matrix. Pildysh Technologies reported that the Terra-Bond process
was tested on arsenic-contaminated dust, containing 15 to 20%
(mass) arsenic trioxide. The leachable arsenic content, according to
the manufacturer, from these stabilized pellets was 1 to 3 mg-As/L
(Pildysh, 2002). The arsenic-containing materials were treated by
the Terra-Bond process at Pildysh Technology's facility in Calgary,
Alberta Canada because the process requires specialized proprietary
equipment and materials. An EPA representative was present. The
Terra-Bond process involved mixing an amount of the arsenic material into a molten sulfur binder such that the material is substantially coated by the molten sulfur binder to produce an encapsulated
product. The molten sulfur binder was cooled to produce a hard encapsulated material. The encapsulated waste material was then separated into discrete particles having a size suitable for use as an
aggregate. The pelletizing process (rolling technique) was used for
separating the encapsulated arsenic material into the desired discrete
spherical pellets. The ow chart for the Terra-Bond process is
shown in Fig. 1.
2.3. SEM/EDS and XRD
A JEOL JSM-840A scanning electron microscope (SEM) with an attached Oxford INCA 300 Energy Dispersive Spectrometer (EDS) was
used for semiquantitative surface analysis. A fully automated Rigaku
D-Max-B powder X-ray diffractometer system was used to analyze
bulk sample mineralogy. SEM/EDS has a maximum resolution of approximately 6 nm, and magnications ranging from 10 to 300,000.
Unpolished mounts coated with carbon were examined threedimensionally. Small fragments (representative of the sample) were
carefully adhered to double-sided carbon tape which was attached
to a one inch carbon planchette. Images were obtained using secondary and backscattered electrons at magnications of either 78 to 1200
times. Semi-quantitative chemistry information (elemental identication and approximate abundance) was collected on various areas
of interest using the Oxford EDS.
2.4. EXAFS and XANES
Arsenic K-edge absorption spectra (EXAFS [Extended X-ray Absorption Fine Structure] and XANES [X-ray Absorption Near-Edge
Structure]) were recorded for the untreated and treated samples.
Spectra of two model compounds, sodium arsenite (NaAsO2) and sodium arsenate (Na2HAsO4) were also recorded as references of different arsenic oxidation states (As (+3) and As (+ 5) respectively). Xray absorption spectroscopy spectra were recorded at the Stanford
Synchrotron Radiation Laboratory (SSRL) beamline 11-2. To support
these experiments, Beam Line 11-2 is equipped with collimating
and focusing optics, a double double Si(220) LN-cooled monochromator, and a 30-element solid state Ge detector array. EXAFS is the

P.M. Randall / Science of the Total Environment 420 (2012) 300312

Coarse
Filler
Material

Arsenic containing
Waste Material
(untreated)

Molten
Sulfur

303

Drying/pre-heating

Surface
Treatment

Compounding

Proprietary
Hydrocarbon
based (Inter-Bond)

Proprietary
Functional Filler

Pellet Forming
(Primary Encapsulation)

Pellet Cooling

Proprietary
Hydrocarbon
based Filler

Pellet Sealing
(Secondary Encapsulation)

Sealant Rapid Curing

Pellet Containment
Fig. 1. Process ow chart for stabilization/encapsulation of arsenic-containing materials by Terra-Bond technology.

oscillating part of the X-ray absorption spectrum that extends to


about 1000 eV above the absorption edge of a particular element in
a solid sample. These oscillations can be used to determine the atomic
number, distance and coordination number of the atoms surrounding
the element where the absorption edge is being examined. XANES is
part of the X-ray absorption spectrum that extends over a range of
about 100 eV, between the edge region and the EXAFS region.
XANES can provide information about vacant orbitals, electronic conguration and site symmetry of the absorbing atom. Different arsenic
species can be identied in solid samples by the EXAFS or XANES
spectra through linear combination of several model compounds
(i.e. sodium arsenite, sodium arsenate). EXAFS data were analyzed
using the computer program EXAFS-PAK. EXAFS raw spectra were
normalized using Victorian function and spline-tted to extract
EXAFS signals. Structural information for the sorption complexes
was then determined by tting the unknown spectra with nonlinear least-squares methods, using phase and amplitude parameters
obtained from theoretical calculation results of FEFF8.0 simulation
software. Least-square ttings of each shell resulted in the determination of the coordination number (CN) and the bonding distance (R).
The DebyeWaller factor, 2, and Eo (Eo is dened as the energy at
which the photoelectron wave vector, k, is equal to 0) were allowed
to vary during the optimization of CN and R. The resulting CN and R,
based on this tting procedure, are expected to be accurate to
10% and 0.02 , respectively, for the rst shell when single absorberscatterer paths are t.
2.5. Measurement of arsenic release-leaching methods
Untreated and treated arsenic-contaminated materials were subjected to dissolution/leaching tests. The physical process of leaching

is when a material (treated or not), is exposed to a liquid solution


and a rate of dissolution is measured. EPA interest is in the rate at
which arsenic is removed or released from the untreated and treated
materials and which could be released into the environment as leachate. Leaching involves a number of different processes, including initial loss of surface deposits and unxed components, penetration of
solutions into substrate pore-space with hydrolysis or dissolution of
xed (or complexed) components, and migration of stabilizers to
the surface .
A number of standard protocols exist for conducting laboratory
leaching studies. In this study, the U.S. EPA Toxicity Characteristic
Leaching Procedure (USEPA Method 1311) was used which is the
most commonly-employed leaching test used in the U.S. (U.S.EPA,
2011). Since the leaching behavior of arsenic is more complex than
could be determined by a single batch test, other leaching and analytical methods of untreated and treated samples were performed such
as a pH-based leaching method and a modied sequential extraction
procedure. These methods are described next.
2.5.1. Arsenic solubility and release as a function of pH
These tests were conducted on both treated and untreated solid
samples to determine the effect of pH on the different sample material and how the release of arsenic is affected by the surrounding
pH. Kosson and Sanchez have developed a leaching protocol for
obtaining leachability information as a function of pH for granular
waste materials and sludges (Kosson et al., 2002; Sanchez et al.,
2003). In this study, a series of parallel extractions of nely crushed
waste material was prepared in a liquid-to-solid ratio (L/S) of
10 mL/1 g dry sample. Size reduction (b2 mm) of the solid material
was used in this test. The aqueous extractants were pH adjusted
with nitric acid (HNO3) or sodium hydroxide (NaOH) to achieve

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P.M. Randall / Science of the Total Environment 420 (2012) 300312

nal solution pH of 2, 9, and 12, for a total of three pH leaching tests.


The nal L/S sample for leachability tests included deionized water,
the added acid or base, and the amount of moisture inherent to the
waste matrix as determined by moisture content analysis. Samples
were leached for 24 h (pH 2 and 12) or 48 h (pH 9) on a rotary
(end-over-end) apparatus (Model 3740-12-BRE, Associated Design
& Mfg. Co, VA). Rapid and continuous tumbling is maintained
throughout the experiment (30 +/ 2 rpm) by the rotary apparatus
at room temperature. Leachates were then ltered through a
0.45 m membrane by vacuum ltration. Times of extraction were selected to approximate the timeframe of the TCLP extraction procedure. Afterwards, the pH of the leachate was measured then
acidied with nitric acid (pH b 2) for total arsenic analysis by ICP-MS.
2.5.2. Sequential extraction procedure (SEP)
Sequential extraction procedures (SEP) are used to determine the
solid-phase association in which elements of interest exist in a variety
of different matrices. Foundation work for SEP was provided by Tessier in the late 70s (Tessier et al., 1979). A modied sequential extraction (Ko et al., 2003; Pandey et al., 2004; Van Herreweghe et al., 2003)
was used. The chemical fractionation procedure is included in Table 2.
Three sets of samples were prepared for sequential extraction: 1)
CCA-treated wood waste samples untreated and treated with PFL
and Terra-Bond; 2) La Trinidad mine tailings untreated and treated
with PFL and Terra-Bond; and 3) Montana soil untreated and treated with PFL and Terra-Bond. For each sample, 0.5 g was initially
collected in a 50 mL capacity container (Oak Ridge polysulfonate, Nalgene round bottom centrifuge tube) and reacted for the specied
time interval as indicated in the fraction sequence. Particle size reduction was not used in the test. After equilibration, the suspensions
were centrifuged at 3000 rpm for 5 min. The leachate was then ltered using a 0.2 m Supor-200 (Gelman Laboratory) membrane lter. The residuals were washed with deionized reverse osmosis (RO)
Millipore quality water to remove the reagent and then taken to the
next step of the extraction. Lastly, the supernatant liquid was sent for
total arsenic analysis by ICP-MS.
2.5.3. Measurement of leachability index and Fickian diffusion models
In addition to the above leaching data, kinetics data was also collected to attempt to understand the diffusion phenomena inside the
untreated and treated materials. Arsenic leaching data as a function
of time was collected at pH 9(2, 7, 14, and 28 days). Kinetic leaching
data was used for incorporation into a one dimensional Fickian

Table 2
Modied sequential extraction procedure for arsenic-bearing solid phases (Ko et al.,
2003; Pandey et al., 2004; Van Herreweghe et al., 2003).
Fraction Chemical agent added to the solid Duration
sample/residue

Target phase

Fraction
1
Fraction
2
Fraction
3
Fraction
4

Water extractable As

30 ml DI water

30 ml 0.5 M ammonium uoride


(NH4F)
30 ml 0.1 M sodium hydroxide
(NaOH)
30 ml 0.5 M sodium citrate
(C6H8O7Na3) and 2.5 ml 1 M
sodium bicarbonate (NaHCO3)
(85 C) while adding 0.5 g sodium
sulfate (Na2SO42H2O)
Fraction 20 ml 8.8 M hydrogen peroxide
5
(H2O2) (acidied to pH 2 with
nitric acid [HNO3]); heat (85 C)
until dry and then redissolve with
HNO3 (30 ml of 0.02 M strength)
Fraction Aqua regia (HCl:HNO3 = 3:1)
6

12 h
shaking
12 h
shaking
12 h
shaking
15 min
heating

As bound to Al-oxides
As bound to Fe oxides
or hydroxides
Reducible fraction

J De

C
x

where C = concentration of component, [M/L 2T], and De = effective


diffusivity [L 2/T]. For the solid/leachant system, with a semi-innite
solid of rectangular geometry in an innite bath and Fickian diffusion,
the material balance takes the form of:
C
C
De
R
t
x

where R = net rate of production of the mobile contaminant [M/TL 3].


When applied to a solid of rectangular geometry where the transport mechanism is strictly Fickian, the equation describing diffusion
takes the form of Fick's second law to incorporate time (Batchelor,
1998):
C
2 C
De 2 R
t
X

where R is the rate of transfer from the mobile to immobile phase and
X is the distance into the solid.
Using Fick's second law of diffusion, a widely accepted general
model was developed by Crane (1980) and further used by Kim and
Batchelor (2001). The data generated from the standard dynamic
leach tests was inputted into this model:
Mt

Mo

4De
L2

0:5
t

0:5

where
Mt
Mo
Mt/Mo
L
De

amount of contaminant leached at time t


fraction of contamination initially available for leaching
fraction of contaminant leached at time t
ratio of volume to surface area of the solid
effective diffusivity.

The effective diffusion coefcient can thus be calculated from the


slope of the plot of Mt/Mo over the square root of time. Then, the
leachability index (LI) can be used to evaluate the relative mobility
of arsenic on a uniform scale that varies from 5 to 15 m with arsenic
mobility decreasing with increasing scale value.
LI

logb
De

where b = 1 cm 2/s.
3. Results and discussion
3.1. Physical and chemical properties

Evaporating Oxidizable fraction


and 12 h
shaking

diffusion model in order to make predictions about arsenic leaching


from solidied waste material over a specic time scale. The mass
ux (J) of the constituents through the solid at high concentration
to areas of low concentration can be described in one dimension by
Fick's rst law:

Remaining refractory
As minerals (or
residual fraction)

Table 3 shows the total concentrations of selected metals (arsenic,


mercury, barium, cadmium, chromium, lead, selenium, and silver) on
a dry weight basis. Total arsenic concentrations in the untreated samples ranged from 28,500 ppm in the MSMA spiked Montana soil to
186,000 ppm in the La Trinidad mine tailings. Table 4 shows the physical and chemical characteristics of both untreated and treated samples. Each sample was analyzed for its moisture content,
compressive strength, particle size, and bulk density. The treated

P.M. Randall / Science of the Total Environment 420 (2012) 300312


Table 3
Selected metals concentrations in untreated samples.
Metals

Table 5
Dimensions of treated samples.

Untreated samples
CCA-treated wood
waste
a

Arsenic
Mercury
Barium
Cadmium
Chromium
Lead
Selenium
Silver

95,900 7000
1.7
338
NDc
54,700
477
6.5
NDe

Weight Dimensions2
(g)
(cm cm)

Sample description
La Trinidad mine
tailings
186,000 7780
177
8
2.9
NDd
2850
29.1
12.9

305

Montana soil (MSMA


spiked)
28,500 1190
5.7
330
7.6
6.0
1330
2.09
19.7

CCA-treated wood waste (PFL 100.66


treated)
103.1
CCA-treated wood waste
(Terra-Bond treated)

8.85
6.7

La Trinidad
treated)

tailings

(PFL 148.95

Average and standard deviation values calculated from two samples.


Sample was determined to contain 2350 mg/kg arsenic present in the native Anaconda smelter soil (without addition of MSMA).
c
Cadmium method detection limit and reporting limit for this sample was 1.4 mg/kg
(dry) and 4.23 mg/kg (dry), respectively.
d
Chromium method detection limit and reporting limit for this sample was 5.1 mg/
kg (dry) and 20.5 mg/kg (dry), respectively.
e
Silver method detection limit and reporting limit for this sample was 1.4 mg/kg
(dry) and 2.82 mg/kg (dry), respectively.

145.27

samples were analyzed to determine only their arsenic content. The


moisture content of the untreated arsenic-contaminated samples varied from 15% to 36%. The moisture content of treated samples was less
than that of the untreated samples, with samples treated using the
Terra-Bond technique containing the least amount of moisture (between 0.2% and 0.3%). Correspondingly, the bulk density of the TerraBond-treated samples was higher than the untreated samples and
the samples treated with PFL. Table 5 shows the dimensions, surface
area, volume of the treated samples, and the control sample.

La Trinidad tailings (TerraBond treated)

17.54
16

Montana soil (PFL treated)

130.63
146.55

Montana soil (Terra-Bond


treated)

17.65
14.83

PFL treated control

108.92

Terra-Bond treated control

327

4.63
(dia.) 9.05 (L)
4.60 (dia.) 9.3
(L)
1.73, 2.1, 2.27,
1.66 (dia.)
1.57, 1.28, 2.06,
1.67 (dia.)
4.78
(dia.) 7.15 (L)
4.8 (dia.) 7.1
(L)
2.49, 2.01, 2.18,
2.58 (dia.)
1.84, 2.46, 2.25,
2.05 (dia.)
4.55
(dia.) 7.59 (L)
4.5 (dia.) 8.3
(L)
2.63, 2.12, 2.51,
2.22 (dia.)
2.37, 2.03, 2.69,
1.99 (dia.)
5.45 (dia.) 6
(L)
5.1 (L)

Surface
area (cm2)

Volume
(cm3)

165.2

152.3

167.6

154.5

11.8

3.8

8.5

2.3

143.2

128.2

143.2

128.4

16.8

6.5

14.5

5.2

140.9

123.3

149.1

131.9

17.6

7.0

16.2

6.1

149.3

139.9

156.1

132.7

1: The dimensions are reported as average and standard deviation values calculated
from four spherical Terra-Bond treated samples and two cylindrical PFL treated samples. One control sample data was reported for control samples.
2: The diameters (cm) were measured for four different orientations of spherical
samples.

3.2. XRD results


The untreated CCA-treated wood waste showed dominance of calcium chromate hydrate (CaCrO42H2O) and quartz (SiO2). The CCAtreated wood waste which was treated with PFL showed dominance
of calcite (CaCO3), thaumasite or hydrated calcium silicon carbonate
sulfate hydroxide (Ca3Si[CO3][SO4][OH]6 12H2O) and copper dichromate dihydrate (CuCr2O7(H2O)2), lammerite (Cu3(AsO4)2, and
arsenic-oxides. Additional peaks were found at d-spacings 4.49, 3.62
and 2.19 and were attributed to the formation of calcium hydrogen
arsenate. The d-values were in good agreement with literature data
presented by Mollah et al. (1998).
The peaks at d-spacings 9.65 and 5.60 were attributed to an
AsO43 substituted ettringite analog. Thaumasite is structurally

related to ettringite, a common product from the hydration of tricalcium aluminate in the presence of sulfate ions in Portland cement.
Though the mechanism of thaumasite formation is not clearly understood, thaumasite forms as a replacement of ettringite at temperatures about 15 C, and can exist as a solid solution series with
ettringite, in which silicon atoms are replaced by aluminum in these
octahedral sites. The anion substitutions are, however, more complex
as the charge has to be reduced to compensate for the lower oxidation
state of Al(III) compared with that of Si(IV). In ettringite, one quarter
of the available anion sites are lled by water molecules; while in
thaumasite, an ordered arrangement of equal number of sulfate and
carbonate ions occupies the anion sites. At each corner of the unit
cell of ettringite, there is a cylindrical column of composition Ca3

Table 4
Physical and chemical properties of untreated and treated samples.
Parameters

Arsenic (mg/kg dry)

Untreated

PFL treated

Terra-Bond treated

CCA wood
treater waste

La Trinidad
mine tailings

Montana soil
(MSMA spiked)

CCA wood
treater waste

La Trinidad
mine tailings

Montana soil
(MSMA spiked)

CCA wood
treater waste

La Trinidad
mine tailings

Montana soil
(MSMA spiked)

95,900
7000
0.67 0.000
36.2 1.55
420.0 10 4

186,000
7780
1.14 0.000
14.7 0.14
55.3 10 4

28,500 1190a

52,200 212

20,500 140

11,200 330

32,900 200

5160 375

0.71 0.000
10.4 0.21
34.8 10 4

0.70 0.005
9.6 0.16
4.6 (dia.) 9
(l)

160,000
5670
1.15 0.021
8.2 0.028
4.8 (dia.) 7.1
(l)

1.08 0.036
14.1 8.2
4.5 (dia.) 7.9
(l)

2.60 0.4
0.34 0.004
1.8d 0.3

2.89 0.3
0.30 0.10
2.2d 0.3

2.48 0.08
0.23 0.016
2.3d 0.3

NA

NA

33 2.2c

21 3.945

52 6.014

NA

NA

NA

Bulk densityb (g/cm3)


Moisture contentc (%)
Particle size (cm) or
monolith dimension
(cm cm)
Compressive strength NA
(psi)

NA = not applicable.
a
Sample was determined to contain 2350 mg/kg arsenic present in the native Montana/Anaconda smelter soil (without addition of MSMA).
b
Average and standard deviation values calculated from ve samples.
c
Average and standard deviation values calculated from two samples.
d
The dimensions of the Terra-Bond treated spherical samples were average and standard deviation values from three samples.

306

P.M. Randall / Science of the Total Environment 420 (2012) 300312

[Al(OH)612H2O] 3+ that runs parallel to the c-axis which is based on


the atomic coordinates provided by Torres et al. (2004). The sulfate
anions and the remaining water molecules lie in channels running
parallel to these columns. Thaumasite is comprised of similar columns and channels to those found in ettringite, except that silicon replaces aluminum in the columns, while 2(SO4) 2 and 2(CO3) 2
replace 3(SO4) 2 and 2H2O in the channels. The smaller silicon
atoms are stabilized in octahedral coordination by charge transfer
through the hydroxyl groups to the calcium ions (in eightfold coordination) and onward to the water molecules that are hydrogen bonded to the sulfate and carbonate anions. Positive identication of
thaumasite easily can be confused with ettringite. Comparison of
XRD patterns also shows some similarities between thaumasite and
ettringite, particularly in the intensity of the primary Bragg angle
peaks where the primary peaks at about 8 to 9 are almost identical,
thus leading to uncertainty whether thaumasite or ettringite, or both,
are present. Secondary XRD peaks provide better distinction between
the two minerals and can be used to identify the mineral in question.
However, several of the minor peaks for ettringite were not present in
the PFL treated samples. It appears that the thaumasite played an important role in interacting with arsenic present in the CCA-treated
wood samples. Similar formation of thaumasite was also identied
in two other PFL treated wastes by XRD. The CCA-treated wood
waste that was treated with Terra-Bond showed predominantly
sulfur and quartz. The presence of additives signicantly contributed
to the strong intensities in the treated samples. Also, XRD conrmed
the predominance of scorodite in untreated La Trinidad mine tailings.
Overall, the XRD spectra illustrate the chemical composition of the
waste and how it changes with treatment. No other XRD analyses
were conducted on other samples considering the dominance of
treatment additives, where diffraction spectra of PFL treated samples
display remarkable similarity across all three waste materials. For
Terra-Bond treated samples, the low waste content (b20%) results
in the predominance of sulfur in the diffraction spectra and does
not reveal signicant information regarding arsenic bonding. The
spectrum for untreated Montana soil was not acquired given the
high concentration of the arsenic additive, relative to native arsenic
present in the sample.
3.3. SEM/EDS results
Using the SEM/EDS system, the scanning electron micrographs of
untreated and treated wastes containing arsenic were obtained at
varying magnications (see Fig. 2). Spot chemical analysis of samples
was conducted by the EDS and the quantication of the peak intensities revealed that the most prevalent elements detected in the
untreated CCA-treated wood waste were arsenic, chromium, copper,
and oxygen(Fig. 2A). Upon PFL treatment of the CCA-treated wood
waste samples, EDS peaks of calcium were observed, indicating that
calcium is imbedded in the structure (Fig. 2B). Micrographs of samples treated using the Terra-Bond technique show the appearance
of an epoxy material on the surface and it is believed that this
epoxy material coating is responsible for reducing the leachability of
arsenic from the treated samples by encapsulation (Fig. 2C). Similar
observations were made with La Trinidad mine tailings and Montana
soil samples (Fig. 2DF).
3.4. EXAFS and XANES results
Arsenic EXAFS and Fourier transforms (FTs) of treated and
untreated samples are presented in Fig. 3. Only selected samples
were analyzed because of limited X-ray beam time available. In the
FT magnitudes, analysis showed that arsenic has an AsO coordination of CN 4 and R 1.68 , and AsFe/Cu coordination of CN 1
and R 3.28 (Table 6). In general, one cannot distinguish backscattering atoms with a difference of an atomic number less than 5.

Therefore, it is difcult to assign which is the backscatterer (Fe or


Cu) based on the EXAFS study alone. However, reported AsFe distances fall in the range of R = 3.05 to 3.09 and R = 3.34 to 3.39
for arsenic sorbed on various iron oxides. The atomic distance
obtained from this work (R = 3.28 ) is shorter than the expected
AsFe distances. This shorter distance may be a good indication that
arsenic is actually bonded with a copper-substrate (e.g., copper oxides) or that there is a formation of AsCu co-precipitate since copper
is abundant. However, the possibility that arsenic forms surface complexes with both copper and iron substrates cannot be ruled out. No
matter what the neighboring atoms are, EXAFS results strongly suggest that the treatment process does not alter the arsenic coordination structure among these CCA samples.
XANES results for CCA-treated wood waste samples, La Trinidad
mine tailings and Montana soil samples (untreated and PFL-treated)
are illustrated in Fig. 4. In Fig. 4A (CCA-treated wood), both untreated
and treated samples have almost identical XANES spectra indicating
that arsenic coordination with the nearest neighboring atoms is not
changed due to the treatment process. While there is a distinct shift of
absorption edge to higher energy of the model compounds representing
a change of oxidation states (from As (+3) to As (+5)), the arsenic Kedge of CCA samples matches with that of the As (+5) model compound. The result suggested that arsenic in the CCA-treated wood samples has a predominant oxidation state of As (+5), and the treatment
process did not alter the arsenic oxidation state.
In the mine tailing samples, distinct differences were observed for
XANES spectra of untreated and PFL treated samples (Fig. 4B). The
peak for untreated samples was observed to have a lower slope on
the right edge compared to the other samples. A shoulder on the absorption edge (at about 11,872 eV) can also be observed. This shoulder feature has been reported by different researchers as a result
from a combination of As (+3) and As (+5) oxidation states. Samples with PFL treatment (Fig. 4A), on the other hand, have an edge energy identical to that of the As (+5) model compound. Thus, it may
be surmised that PFL treatment of mine tailing samples not only
changed arsenic coordination structure, but also oxidized arsenic
from a mixture of As (+3)/(+5) to exclusively As (+5). Furthermore, the considerable shift of absorption edges suggested that
there are signicant amounts of other type of arsenic species contained in the sample. This supports XRD and SEM/EDS analysis that
the untreated mine tailings contain signicant amounts of scorodite.
EXAFS analysis of the PFL treated sample indicates that arsenic is coordinated with four oxygen at R = 1.69 and with two iron at
R = 3.38 . In comparison, scorodite has a coordination structure of
AsO: CN = 6.45, R = 1.68 , and AsFe: CN = 4, R = 3.36 . While
the atomic distances are comparable between the treated sample
and scorodite for both AsO and AsFe, the treated sample has a
smaller coordination number of both paths than that of scorodite.
The structural parameters of the treated sample are actually more
similar to that of amorphous ferric arsenate (AsO: CN = 4,
R = 1.7 ; AsFe: CN = 1.23; R = 3.37 ). Thus, it is plausible from
the treatment process that As (+5) may form some amorphous coprecipitate with iron. However, further investigation is needed to determine the actual composition of arsenic species.
XANES spectra were also collected for untreated Montana soil samples and for treated samples (PFL technique and Terra-Bond technique) (Fig. 4C). The absorption edge of the Montana soil samples falls
between that of As (+3) and As (+5) model compounds. Therefore,
the spectra indicate that there is a combination of oxidation states in
the samples. An attempt to t the sample XANES spectra with the spectra
from model compounds to deduce the proportion of As (+3)/As (+5) in
the samples was unsuccessful due to the limited number of standards
collected. It may be due to the fact that the spectra of model compounds
have broader white lines compared to those of the samples. Therefore, it
is difcult to t the sample spectrum with linear combinations of spectra
from model compounds collected at this stage.

P.M. Randall / Science of the Total Environment 420 (2012) 300312

307

BEI @ 1000X

BEI @ 400X

EPOXY

BEI @ 200X

BEI @ 400X

BEI @ 78X

BEI = 50m

Fig. 2. Scanning electron micrographs of untreated and treated arsenic-containing materials; A untreated CCA-containing wood waste, B PFL treated CCA-containing wood
waste, C Terra-Bond treated CCA-containing wood waste, D PFL treated La Trinidad mine tailings, E Terra-Bond treated La Trinidad mine tailings, F Terra-Bond treated Montana soil. Spot microanalysis was done by EDS.

The absorption edge shifted to higher energy when comparing


XANES spectra of untreated samples and PFL treated samples, suggesting that some As (+3) was converted to As (+5) during/after
the treatment process. It should also be noted that the XANES spectra
show distinctly different features among these two samples between
the energy range of 11,880 and 11,900 eV. These differences indicate
an arsenic coordination structure change due to the PFL treatment. On
the contrary, Terra-Bond-treated samples show no difference from
the untreated samples in terms of oxidation states and XANES features. Therefore, the Terra-Bond treatment process did not signicantly change the arsenic coordination structure in these samples.
3.5. Leaching behavior and arsenic release results
3.5.1. Assessment of pH-based results
In Fig. 5, the leach test data is illustrated for the untreated and
treated samples. For both CCA-treated wood samples and La Trinidad

mine tailings, increasing the pH to 12 signicantly increased the release of arsenic from the untreated materials. In contrast, lower leaching numbers were observed for the untreated CCA and mine tailing
samples at pH 9, respectively, and even less at pH 2. Though mine tailings treated by both the Terrabond and PFL methods behaved similarly, more arsenic was released from CCA-treated wood samples
stabilized using Terrabond than with PFL at pH of 12. With regard
to the Montana soil mixture, it leached a much higher percentage of
arsenic in all cases relative to the CCA and mine tailing material. In
general, the overall quantity of arsenic leached was observed to be
dependent upon both the stabilization technique and pH. The amount
of arsenic released from untreated samples was signicant at all pH
values, approaching quantitative leaching of all arsenic at pH 12.
Comparing across stabilization methods, greater quantities of arsenic
were released from samples stabilized with PFL compared to TerraBond under acidic conditions, at pH 2 and also when extracted
with acetate (pH ~4.9, TCLP). Under alkaline conditions (pH 9 and

308

P.M. Randall / Science of the Total Environment 420 (2012) 300312

Fig. 3. Arsenic EXAFS spectra and Fourier transform magnitudes of untreated and treated materials. Model compounds sodium arsenite and arsenate are also shown. Fourier transform magnitudes are on the right. An EXAFS spectrum is used to distinguish the coordination environment of arsenic in each of the materials. Peak positions in FTs are not corrected
for phase shift effects.

12), greater quantities of arsenic were leached from the Terra-Bond


stabilized Montana soil samples than the PFL treated material. However, in general, both treatments released greater quantities of arsenic with increasing pH for PFL stabilized Montana soil and for TerraBond stabilized Montana soil.

3.5.2. Assessment of sequential extraction results


Sequential extractions were performed on untreated and treated
samples of CCA-treated wood samples, La Trinidad mine tailings material, and Montana soil. The purpose of the sequential extraction experiment is to illustrate the distribution of different arsenic forms to
the six different leaching fractions. The total arsenic concentration released to each leaching fraction is provided in Table 7. Untreated CCA
wood waste material, in contrast to untreated La Trinidad or Montana
soil, cumulatively leached 39% of the total arsenic contained within
the waste material. This gure is reected in the Terra-Bond treated
CCA material, which cumulatively leached 32%. Upon treatment of the
CCA waste material with PFL, ultimately all of the arsenic contained
within this waste material (114%) was leachable. For both untreated
and Terra-Bond treated CCA material, the fraction containing the
greatest concentration of arsenic was the FeO and organic matter
fraction (sodium hydroxide extractable arsenic). Treatment of CCA
material with PFL rendered the arsenic waste stable against sodium
hydroxide. The chemical reagent most effective at leaching the

Table 6
EXAFS tting results of arsenic samples.
Sample

CCA-treated Wood wasteuntreated


CCA-treated Wood wastetreated by S/S
Montana
soil
(MSMA
spiked)-untreated
Montana
soil
(MSMA
spiked)-treated by S/S
La Trinidad mine tailingsuntreated
La Trinidad mine tailingstreated by S/S

ArsenicO

arsenic within the PFL-stabilized CCA waste was observed to be the


acid-soluble/oxidizable extraction (hydrogen peroxide/nitric acid).
With regard to the La Trinidad mine samples, most of the arsenic
was leached with sodium hydroxide (i.e. fraction F3) for both PFL
and Terra-Bond treatments in addition to the untreated samples. In
La Trinidad mine tailing samples, untreated La Trinidad mine waste
was observed to leach most of the arsenic contents with sodium hydroxide because of the high solubility of scorodite at high pH. For
both the untreated and treated samples of La Trinidad mine waste
material, the cumulative amounts of arsenic released by this sequential extraction method was quantitative in the case of untreated
(123%) and PFL treated (103%) samples or nearly quantitative (91%)
as in the case of the Terra-Bond treated material.
With regard to the Montana soil samples spiked with MSMA, sequential extraction data shows a high degree of leaching of the arsenic contained within this material, for treated and untreated material
alike. After only the second extraction, the untreated material had
leached 82% of the total arsenic, the PFL treated material leached
77% and the Terra-Bond material leached 63%. These data demonstrate, not the principle forms, or reservoirs, or arsenic within these
three waste materials, but rather the nature of the articial arsenic
amendment to the Montana soil. Referring to Table 2, the native arsenic concentration of this soil was determined to be 2350 mg-As/kg, or
only 8% of the nal arsenic concentration, with the amendment being
MSMA, an organo-arsenate, likely to have signicantly different reactivity compared to inorganic forms of arsenic. Thus, it is difcult, if not
impossible, to surmise details of arsenic speciation or bonding environment from sequential extraction data where nearly all the arsenic
is leached after only the second (of six) extractions.

ArsenicFe/Cu

CN
R ()
10% 0.02

2
(2)

4.6

1.69

0.0029 1.1

3.29

0.0037

4.3

1.68

0.0027 0.9

3.28

0.0028

4.1

1.69

0.0047 0.7

3.34

0.0061

4.7

1.69

0.0048 1.0

3.21

0.0092

4.3

1.69

0.0027 1.8

3.38

0.0039

CN
R ()
10% 0.02

2
(2)

CN coordination number, R interatomic distance, 2 DebyeWaller parameter.

3.5.3. Kinetics and diffusion results


Kinetic leaching experiments of La Trinidad Mine waste, CCAtreated wood waste and Montana soil were conducted at pH 9, with arsenic measurements taken at four time points: 2, 7, 14 and 28 days.
Untreated samples, for all three waste materials, leached signicantly
greater amounts of arsenic. La Trinidad untreated material was observed to leach arsenic nearly exponentially from 2 to 28 days. Similarly, the trend of arsenic leaching as a function of time for the CCA
material increased from 2 to 28 days, although the trend was more linear than that observed for the La Trinidad material. In both La Trinidad
and CCA treated samples (PFL and Terra-Bond), arsenic leaching was
signicantly suppressed, and the overall increased arsenic leaching at
28 days above that extracted after 2 days was observed to be small relative to the untreated material. Using PHREEQC-2, a hydrogeochemical

P.M. Randall / Science of the Total Environment 420 (2012) 300312

309

observations: (1) iron concentration decreased over 28 days of solution


contact with the untreated material, which would be expected to occur
should a solid-phase iron-bearing mineral precipitate; and (2) the arsenic concentrations decreased, which would also be expected to occur as
arsenic is known to be adsorbed by iron oxide minerals. No follow-up
experiments were performed for Montana soil samples in order to corroborate the formation of a discrete iron oxide phase during the timecourse of the kinetic leaching experiment; however, the decline in soluble iron is a strong indication of the precipitation of an iron hydroxide
phase.
Assuming that mass transfer is the principle factor for these results, the empirical data was taken from the pH 9 kinetic leaching
tests and inputted into the Fickian diffusion model. The Fickian diffusion model to nd the mass of arsenic released per mass of material is
shown in Eq. (7) assuming a spherical geometry. The leachability
index was then calculated for each time point using Eq. (8).
In this experiment, the materials were pulverized, sieved, added
to an aqueous solution and pH adjusted to 9, on a daily basis; nally,
the leachate was removed and analyzed at discrete time points. Due
to the simple batch-style leaching experiments used in this study,
the one dimensional Fickian diffusion model was considered the
most appropriate model for estimating and contrasting arsenic leachability from all materials tested. Table 8 shows De calculated from the
slope of the trend lines; the results show low values for the leachability indices (LI) which indicate that the treatments may not be suitable
for disposal. Generally, when the LI 9 the performance can be considered controlled. When the LI b 8, it is considered to be unsuitable
for disposal (Dermatas et al., 2004). One possible explanation for the
low values of the LIs is that the batch recipes need to be optimized
(e.g. higher Fe/As ratios).
3.6. Discussion

Fig. 4. Arsenic XANES spectra of untreated and treated samples; A XANES spectra for
untreated and PFL treated CCA-containing wood waste; B XANES spectra of
untreated and PFL treated La Trinidad mine tailings; C XANES of untreated and
PFL/Terra-Bond treated Montana soil samples.

modeling program, saturation indices for iron and arsenic bearing minerals were computed for the solution phase species measured for day 2
and day 28 for the untreated Montana soil extractions. These results indicate that the soluble metal concentrations for arsenic and iron at day 2
are over-saturated with respect to iron oxide phases but not scorodite
(an ironarsenate oxide mineral), and precipitation of ferrihydrite
was predicted. This prediction is consistent with the following

In La Trinidad mine tailing samples, XRD and SEM micrographs


showed that the mine tailings were predominantly the mineral scorodite (FeAsO4). Over an environmentally important pH range of 59,
dissolution of scorodite is found to be slow by Bluteau and
Demopoulos (2007). Our results conrm that the dissolution of scorodite is a slow process over this pH range. Incongruent dissolution of
scorodite is very slow leading to the formation of a highly metastable
nano-crystalline ferrihydrite phase and simultaneous release of arsenic into solution. The solubility of scorodite at 22 C was determined
to be in the order of 1 mg/L As (+5) at pH 6 and stabilized at
24 weeks at 5.9 mg/L As (+5) at pH 7. Higher solubility values were
observed in the alkaline region. Total dissolved arsenic concentrations were limited by two factors: (1) total available scorodite and
(2) the precipitation of new Fe(III) phases subsequent to scorodite
dissolution (e.g., amorphous iron hydroxides and hematite) which
serve as effective sorbent surfaces for arsenate at pH b pHpzc.
From the sequential extraction tests, this study found hydroxide to
be an effective extractant of arsenic from the La Trinidad mine tailings
samples. These results are likely due to electrostatic repulsion between the negatively charged arsenic species (i.e. arsenate) and negatively charged Fe oxide surfaces. Arsenic readsorption on Fe oxide
surfaces is less favorable due to the increased OH\ concentration
and increased competition for ligand-exchange sites. At extreme
low pH (i.e. pH = 1), arsenate is fully protonated and positive charges
are predominant on the Fe oxide sites. Consequently, there is less impact of electrostatic attraction on arsenic retention. Also, ligand exchange rates would be enhanced by protonation of oxygen at the
FeOAs sites resulting in reduced strength of arsenate bonding at
the Fe oxide surface.
The most important factors in determining the leachability of arsenic from CCA-treated wood waste material is the concentration
and type of arsenic contained within the specic preservative, the
drying and storage conditions, and the choice of wood species.

310

P.M. Randall / Science of the Total Environment 420 (2012) 300312

1000000

La Trinidad MineTailings

100000
100000

CCA-Treated Wood Samples

Arsenic,mg/kg

Arsenic,mg/kg

10000
Total
1000
TCLP
pH2

100

pH9

10000
Total
TCLP

1000

pH2
pH9
100

pH12

pH12

10

10

1
CCA/Untreated

100000

CCA/PFL

CCA/Terra-Bond

Trinidad/Untreated

Trinidad/PFL Trinidad/Terra-Bond

Montana Soil with MSMA spike

Arsenic,mg/kg

10000

Total

1000

TCLP
pH2

100

pH9
pH12

10

1
Soil/Untreated

Soil/PFL

Soil/Terra-Bond

Fig. 5. Leach test data-CCA-treated wood, LaTrinidad mine tailings, Montana soil with MSMA spiked-all treated with PFL or Terra-Bond method.

Other factors inuencing leachability are the metal xation on wood


surface, ion-exchange xation capacity of metal, the natural pH, and
the chemical composition and anatomy of the wood. During sequential extractions of the untreated CCA-treated wood material, only 40%
of the total arsenic was ultimately extracted, with the majority of extractable arsenic associated with organic matter and iron hydroxides
(sodium hydroxide extraction). In the Terra-Bond treated CCA
waste, the majority of arsenic also remained unextracted (~ 68%),
with the majority of extractable arsenic being leached with aqua
regia (hydrochloric acid/nitric acid). In the case of PFL treated

waste, the majority of arsenic was extracted during the acid soluble
or oxidizable fraction. Overall, the water soluble, iron or aluminum
bound, and reducible fractions accounted for the least amount of arsenic extracted in the untreated or treated CCA treater wood waste.
Also, the predominant extraction phase changed, suggesting that
the arsenic form changed depending on the waste treatment, whether it was untreated, Terra-Bond, or PFL. The implication is that the
highly organic nature of the untreated wood sample retains arsenate
through interactions which may be disrupted by hydroxide ion. The
Terra-Bond treated material was remarkably stable across the

Table 7
Arsenic released by sequential extraction.
Units

Total As
content

Water soluble
(F1)

Al- and Caassoc. (F2)

FeO and organic matter


assoc. (F3)

Reducible
(F4)

Acid soluble/
oxidizable (F5)

Residual
(F6)

Sum

mg/kg

mg/kg

mg/kg

mg/kg

mg/kg

mg/kg

mg/kg

mg/kg

309
42
30

2313
3186
89

12,750
3414
948

5898
5241
105

8456
37,007
12

7435
10,705
2445

37,161
38.7
59,595 114.2
3629
32.4

3
1143
24

938
15,556
54

170,440
118,800
24,350

17,330
4409
2082

288
4592
3

5991
16,230
3266

194,990 122.6
160,730 103
29,779
90.5

16,320
5769
1923

7110
9090
1323

3735
3003
1095

575
177
196

186
350
97

422
1214
719

28,348
99.5
19,603
95.6
5353 103.7

CCA-treated Wood Untreated


95,900
waste
PFL
52,200
Terra11,200
Bond
La Trinidad mine
Untreated 159,000
tailings
PFL
156,000
Terra32,900
Bond
Montana soil
Untreated
28,500
(MSMA-spiked) PFL
20,500
Terra5160
Bond

All data are in units of mg/kg dry weight. Mass normalized data are relative to whole-stabilized waste and are not normalized to the actual mass of the waste material within the
stabilized matrix. Cumulative leaching data which exceed 100% simply reect the combination of multiple analytical error terms inherent within the sum of arsenic leached within
all six fractions.

P.M. Randall / Science of the Total Environment 420 (2012) 300312


Table 8
Effective diffusivity and leachability indices from graphical analysis.
S/S treatment type

Slope of the plot CFR vs. t (De)

LI

La Trinidad mine tailings


Untreated
Terra-Bond
PFL

7.39E06
4.80E07
1.10E07

5.1
6.3
7

CCA
Untreated
Terra-Bond
PFL

6.64E06
3.88E06
3.10E07

5.2
5.4
6.5

Montana soil (MSMA spiked)


Untreateda
Terra-Bond
PFL

1.13E04
1.07E04
5.09E05

4
4.3

De effective diffusivity coefcient.


LI leachability index.
a
Cannot compute LI based on a negative slope.

initial ve extractions, with the majority leached under extreme acidic and oxidizing conditions, indicating that Terra-Bond is preferable
to PFL for the containment of arsenic.
With the Montana soil, there were approximately 28,000 mg/kg of
total arsenic in the untreated Montana soil, although a majority of this
was added as MSMA. Both untreated and treated samples contained signicant amounts of water soluble arsenic in the untreated sample,
Terra-Bond treated, and PFL treated sample. In the PFL treated sample, the greatest amount of arsenic was extracted with NH4F, which relates to iron or aluminum bound arsenic. It is evident that PFL treatment
promoted formation of iron-bound arsenic, increasing from 25.3% to
46.4%. Recalcitrant forms of arsenic (i.e., organic matter and iron hydroxides bound) were released by NaOH extraction at 15.3%. It is important not to draw too many conclusions regarding the bonding
environment of the treated Montana soils due to the observation that
a majority of the total arsenic was leached following only the third extraction. An interpretation of the high leachability of the arsenic in
this series of samples (treated and untreated) is the addition of the
MSMA amendment which was not chemically bonded or physically encapsulated to a signicant extent by either treatment and, therefore,
does not represent an accurate reection of arsenic-containing waste
materials which are aged in the natural environment.
In all three untreated arsenic contaminated waste materials, the
sequential extractions indicated that leachability depends on the
chemical nature of arsenic present in the material. In CCA-treated
wood waste material, there was a complex mixture of metals xated
on organic matter and soil residues. In La Trinidad mine tailings, the
majority of arsenic was also associated with organic matter and iron
hydroxides. In Montana soils, the majority of arsenic was easily
extracted in the water soluble phase. These results illustrate that different arsenic-containing materials may contain different forms of arsenic, and each specic material requires consideration prior to
selection of the most appropriate S/S technology.

311

the arsenic oxidation state. But, there were distinct differences observed
for XANES spectra of untreated and PFL treated scorodite-rich mine tailing which changed the arsenic coordination structure from a mixture of
As (+3/+5) to exclusively As (+5). These results are consistent with
previous analyses ((Jing et al., 2005; Yoon et al., 2010). Further research
should be expanded to study the speciation of organoarsenical species
in solid phases and elucidate the complexation mechanisms between
them and solid surfaces.
In all three untreated arsenic contaminated waste materials, sequential extraction showed that arsenic species were tightly bound
to the organic matter/Fe hydroxide fraction. In CCA-treated wood
waste samples, there was a complex mixture of metals xated on organic matter and soil residues. In La Trinidad mine tailings, the majority of arsenic was present as the mineral scorodite and also associated
with iron hydroxides. In Montana soils, the majority of arsenic was
easily extracted in the water soluble phase, presumably due to the articial enrichment of arsenic in this sample (in the form of MSMA).
Terra-Bond treated samples of CCA-containing samples and La Trinidad mine tailings passed the TCLP arsenic standard of 5.0 mg/l. The
soil samples (spiked with MSMA) were signicantly reduced in all
samples but did not meet the TCLP. Terra-Bond treated samples released signicantly more mass of arsenic at higher pH (e.g. pH = 12).
Both treatment methods reduced the arsenic released, but the effectiveness of these treatments varied signicantly. Effective diffusivities indicate that the treatments may not be suitable for disposal. But
another researcher (Moon et al., 2010) has shown that quicklime-sulfate method may show good results. More data is needed on other
contaminants present in the untreated materials (e.g. chromium, copper) to provide information on the main controlling species and the
effectiveness of the treatment with other contaminants. This is critical
since a treatment process that shows promise for arsenic may result
in a poor choice for other contaminants. Further research and more
renement of the technology recipes are needed to assure longterm containment of the arsenic.
Acknowledgements
The U.S. Environmental Protection Agency through its Ofce of Research and Development funded and managed the research described
here. Part of this research was carried out at the Stanford Synchrotron
Radiation Lightsource (SSRL) a national user facility operated by Stanford University on behalf of the U.S. Department of Energy. I am grateful to Battelle Labs in Columbus, OH for analytical work and Dr. ChiaChen Chen (University of Texas) for assistance with the EXAFS and
XANES work. I am also grateful to Roger Yeardley for graphics assistance and to the anonymous reviewers who improved upon this
work. This research has not been subjected to Agency review and
therefore does not necessarily reect the views of the Agency. Mention of trade names and products should not be interpreted as conveying ofcial EPA approval, endorsement, or recommendation.
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