Technologies and Potential Technologies for Removing Thallium from Process and Process Water, JEMEP, Volume

2, No. 1, 2002, pp 1-10.

POTENTIAL TECHNOLOGIES FOR REMOVING THALLIUM FROM MINE AND

PROCESS WASTEWATER: AN ANNOTATION OF THE LITERATURE

L.G. Twidwell1 and C. Williams-Beam2

ABSTRACT

Thallium is more toxic to humans than mercury, cadmium, lead, copper or zinc. Its chemical behavior
resembles the heavy metal lead and the alkali metals (K, Rb, Cs). It occurs almost exclusively in
natural waters as monovalent thallium (Tl+1). The solubility of thallous compounds (e.g., thallous
hydroxide) is relatively high so that Tl+1 is readily transported through aqueous routes into the
environment. The major sources of thallium are the base metal sulfides and precious metal bearing
sulfides. Therefore, it has been shown to be a contaminant constituent in waters emanating from
heavy metal sulfide bearing deposits.

A comprehensive survey of the thallium literature was conducted to answer two questions:
 Is thallium contamination in mine and effluent wastewater a significant problem and, if so,
 What technologies are available for removing thallium from the waters to achieve current U.S.
effluent discharge regulations?

An annotation of the available literature, descriptions of potentially appropriate technologies, and

recommendations for future study are presented in this paper.

Keywords: technologies, extraction, precipitation, adsorption, and

1
POTENTIAL TECHNOLOGIES FOR REMOVING THALLIUM FROM MINE AND
PROCESS WASTEWATER: AN ANNOTATION OF THE LITERATURE

INTRODUCTION

Technology Literature Search

An extensive survey of the literature has been conducted related to technologies that have been
developed for thallium removal from wastewater. Only the publications concerned with the removal
of thallium from aqueous solutions have been reviewed and summarized in this presentation, i.e.,
publications concerned with health effects, general chemistry, geochemistry, toxicity, etc have not
been reviewed.

The information summarized in this presentation emphasizes possible mine wastewater treatment
technologies. However, some of the unit operations described in the literature for cleanup of
municipal wastewater, stream waters, metallurgical and chemical wastewater and process waste
solutions have been surveyed. Therefore, much of the additional information is presented here with
the idea that technology transfer may be possible. Because of the extensiveness (on a world-wide
basis) of the thallium literature a portion of the annotation comments are based on a review of
abstracts rather than a review of complete publications.

All of the following thallium bearing water sources have been included in the literature survey:
groundwater pumped to conduct mining operations, waters emitted from abandoned mines,
process waters used in mining and mineral processing operations (including milling, concentrating,
smelting and refining), and waters produced during mine closure (such as effluents from heap
leach rinsing).

The literature databases searched for thallium publications include: Applied Science Abstracts,
Chemical Abstracts, Chemical Engineering and Biotechnology, Enviroline, GeoRef, and Metadex.
Each database was searched for the entire dates available. However, because of space limitations
only those studies published during the last ten years will be included, except for several critical
publications. For complete coverage of the literature the author recommends that the reader refer to
the publication by the US EPA Mine Waste Treatment Program (2001).

Thallium In The Environment

A recent review of the occurrence of thallium in the environment has been edited by Nriagu [1]. A
summary of the review is presented in Table 1. Other extensive reviews for thallium occurrence in the
environment, the production and uses of thallium, the biological effects of thallium in humans,
animals, and thallium uptake in plants are included in bibliography [Bagat, et al (1997); Kazantzis
(1986); Kemper, et al (1991); Micke, et al (1983); Sabbioni, et al (1984); Sager (1994); Schoer
(1984); Smith, et al (1978); and, Zitko (1975)].

Table 1. Thallium in the Environment

1
  
g/L (ppb) g/kg (ppb)
Source
Drinking Water [61] 7.2
Groundwater, River Water, 20-24
Groundwater [42]
Marine Sediment [60] 200-5,700
Deep Sea Sediments [63, 64] 10-5,700
Deep Sea Manganese Nodules [14, 63] to 100,000
Coal Power Plants, kg/yr
599,000
Worldwide [8]
Lanmuchang Thallium Ores, Hg-Tl Water (Well, Spring, 720,000-
Stream, Minewater) [18] 0.4-27 3,800,000
Nanhua Thallium Ores, As-Tl Water (Spring, Minewater,
Slag water) [18] 0.1-16.5 960-1,900
Sulfide Minerals: Chalcopyrite [69] to 5%
Galena [60] 1,400-20,000
Sphalerite [60] 8,000-45,000
Pyrite [60] 5,000-23,000
15,500 in
Production from Sulfides (Worldwide), kg/yr [1]
1988
Entering Pb, Zn, Cu Smelting (Worldwide), kg/yr [5, 21] >160,000
Production from Iron Smelting (U.S.), kg/yr [8, 21] >140,000
Total World Mobilization, kg/yr [21] >2,000,000

Thallium Sources

Thallium is normally associated with sulfide minerals and is often found in mineralized areas
interspersed with sulfide deposits (Zitko, 1975). Thallium bearing sulfide minerals exist but they exist
in low concentrations, e.g., the following sulfide minerals have been identified: carlinite (Tl2S),
lorandite (TlAsS2), christite (TlHgAsS3), ellisite (Tl3AsS3), weissbergite (TlSbS2), galkhaite
(Tl(Hg,Cu,Zn)6(As,Sb)4S12) (Percival, et al, 1993), Tl2(As,Sb)8S13 (Wilson, et al, 1991), lorandite
(Tl2As2S3), Crookesite (Cu15Tl2AgSe9), Vrbaite (TlsS.2As2S3.Sb2S3), Hutchinsonite ((Ag,Tl)2S.As2S3)
(Shaw, 1952).

The ionic radii of Tl+1 is similar to K+1, i.e., [Tl+1=1.40Ao; K+1=1.33Ao]. Therefore, Tl+1,
isomorphically substitutes into potassium mineral structures. These isomorphic mineral phases are
sometimes present near or in oxidized regions near sulfide deposits. It is not unusual for thallium to be
present in mined sulfide materials processed for recovery of gold, copper, lead, zinc and uranium

2
[12]. The geochemistry of thallium is well established and a number of reviews have been published
[Shaw (1952, 57); Sahl (1978); Sager (1992); Moh (1993); and Percival and Radtke (1993)].

Ores are presently only mined for thallium in China [Zhang, et al, 1998]; i.e., Nanhua, Yunnan and
Lanmuchang, Guizhou. The Nanhua property is an As-Tl containing thallium up to 0.19%. The
Lanmuchang property is a Hg-Tl deposit containing up to 0.38%. Elevated thallium concentrations in
the areas surrounding the mining operations and in associated waters are a major health problem, e.g.,
thallium in soils surrounding the Lanmuchang mining operation range from 4-55 mg/kg, waste
residues contain 86-240 mg/kg; waters contain from 0.4-27 mg/liter.

Environmental Standards
The USEPA specifies that the Best Demonstrated Available Technology (BDAT) for the thallium
wastewater is oxidation of Tl+1 species followed by precipitation [19]. The BDAT for treating
wastewater must lower the thallium to <0.14 mg/L. Other environmental standards are presented in
Table 2.

Table 2. Environmental Standards

Source
Standard, g/L

USEPA Primary Drinking Water Regulations, (MCL) 2

Human Health Effects in Seawater 4

Wastewater (for USEPA RCRA categories: P113, P115, U214,

U215, U216, and U217) BDAT 140

Soils, Federal Republic Germany 1 mg/kg

Environmental Threshold Exposure to Thallium Compounds in

U.S., Federal Republic Germany, Switzerland 0.1 mg Tl/m3

DESCRIPTION OF THALLIUM REMOVAL TECHNOLOGIES

Adsorption processes

A large number of investigations have focused on surface adsorption as a means of removing metals,
arsenic, and selenium from aqueous phase solutions, e.g., adsorption on ferric hydroxides, aluminum
hydroxides, alumina, activated carbon, clays, etc. However, much less has been published concerning
thallium removal by adsorption. Adsorption phenomena on ferric surfaces has been the emphasis of
most of the investigations for metals, arsenic, and selenium but most of the thallium adsorption
literature is based on manganese dioxide adsorption.

Manganese dioxide adsorption-A number of studies have been directed toward evaluating the
adsorptive power of a variety of types of manganese dioxide for thallium and heavy metals: natural
and chemically precipitated manganese dioxide, e.g., Bidoglio, et al (1993); Grossl, et al (1994);
Flegal, et al (1989); electrolytic manganese dioxide, e.g., Dahal, et al (1996, 98); and manganese
3
dioxide sludge, e.g., Jibiki (1995).

Chemically precipitated manganese dioxide-Bidoglio, et al (1993) have reviewed adsorption of

thallium on chemically precipitated manganese dioxide (-MnO2). These authors also conducted
experimental work comparing the adsorption of thallium on -MnO2 (190 m2/g), SiO2 (200 m2/g), and
-Al2O3 (130 m2/g). They found complete thallium adsorption (from solutions containing 24 g/L to
41mg/L thallium) on -MnO2 at pH levels of 4.7-8.5. The mechanism for removal was surface
adsorption of Tl+1 with subsequent oxidation to Tl2O3. Comparative tests using -Al2O3 and SiO2
showed essentially no thallium adsorption over the same pH range.

Means, et al (19xx) conducted a literature review of manganese dioxide adsorption that provides a
number of reasons why it is a good adsorbent for cations. Their points include: Manganese dioxides
are much better heavy metal scavengers than other surfaces, e.g, the degree of adsorption is
manganese oxide>organic matter>iron oxides>clay minerals. Surface areas of manganese minerals,
like birnessite -MnO2, range up to 350 m2/g. The pzc (point of zero charge) is unusually low, i.e.,
pH=1.5-2. Therefore, the surface is negatively charged for pH conditions of many waters which
provides electrostatic attraction for cations. The cation exchange capacity is relatively large, e.g., 1.5
equivalents/100 g (compares to 0.1 equivalents/100 g of montmorillonite clays) at a pH of 8.5.

Electrolytic manganese dioxide (EMD)-EMD is commercially formed by electrolytic oxidation of

manganese sulfate solution under acidic conditions at temperatures near the boiling point (Dahal,
1996, 98). Its major use is in disposable and rechargeable batteries. Conditions for complete removal
of thallium were not specified, i.e., manganese loading, pH, time, temperature, influence of other
solution species.

Adsorption on EMD is normally a function of initial ion concentration, presence of other ions, and
solution pH. Dahal, et al (1996, 98) demonstrated that adsorption of metal ions follows the simple
Langmuir adsorption equation. The order of specie adsorption from solutions (10-2,000 mg/L) was
shown to be (pH<2): Bi+3~Pb+2>Tl+1>Cr+3>Cu+2 and (pH 4), Pb+2>Cu+2>Tl+1>>Cr+3.

Manganese dioxide sludge-Manganese dioxide sludge produced during zinc electrowinning has been
shown to be very effective in removing thallous ions from zinc process waters and from lead smelting
effluent wastewater. Jibiki 1995) has demonstrated thallium removal from lead smelting effluent
waters to less than 100 g/L (12.5 mg/L thallium initial). His recipe includes the following, i.e.,
electrolytically formed manganese dioxide is required (manganese ores, mineral forms of MnO2 and
chemically precipitated manganese dioxide were not as effective as the electrolytically produced
manganese sludge); -400 mesh particles are recommended; a dose of one gpl; a pH of <4 is desirable;
and a residence time in a stirred reactor of one half to one hour. The loaded manganese dioxide can
be treated to recover the thallium, e.g., the manganese dioxide can be leached in a weak acidic
solution in the presence of a reducing agent such as sulfur dioxide, sulfite chemicals, ferrous
chemicals. The thallium can then be recovered from solution by precipitating elemental thallium using
zinc dust.

Ferrihydrite adsorption of thallium-Ferric precipitation as ferrihydrite has been extensively covered

in the literature. In fact, there is a recipe book (Swertzmann and Fechter, 1995) on how to prepare
hydrated iron oxides. All of the iron oxides are crystalline except Ferrihydrite. Ferrihydrite is

4
normally of low crystallinity and is actually a range of compounds that exhibit different degrees of
structural order. In general, ferrihydrites are characterized according to the number of broad X-ray
peaks, e.g., 2-line (completely amorphous) and 6-line (semi-crystalline). The generally accepted
formula for ferrihydrite is 5Fe2O3.9H2O (Schwertmann and Cornell, 1991).

There has not been a through experimental investigation of the adsorption of thallium on ferrihydrite.
What little data exists is based on phenomenalogical observations that thallium concentrations
(mostly as thallic ions) in sediments appear to higher in ferrihydrite and manganese dioxide bearing
sediments. Other evidence for believing that ferrihydrite is effective for adsorbing thallium is
provided by surface adsorption modeling work by Lin and Nriagu (1998). They have modeled the
adsorption of Tl+1 and Tl+3 on ferrihydrite by using the MINEQL calculational two-layer adsorption
model. Their results predict that the order of adsorption effectiveness for thallium on ferrihydrite at
pH 6 is Tl+1>Tl+3>Pb+2>Cu+2>>Zn+2>Cd+2.

Kikuchi, et al (1990) demonstrated the removal of thallium from synthetic and process solutions.
They demonstrated that thallium could be effectively removed by doping the solution with iron
powder, then oxidizing with hydrogen peroxide, then raising the pH. The proposed removal
mechanism was a combination of thallic hydroxide precipitation and thallium aqueous specie
adsorption on freshly formed ferrihydrite. The authors treated thallium solutions containing 100-500
mg/L with an iron dosage 12.5 g/L and a peroxide dosage of 100 cm3 of 30% H2O2/L for 15 minutes
and achieved removal to 1-20 mg/L.

Brewster and Passmore (1994) developed a similar process called the Andco Process. Their process
utilizes an iron scarifical anode to produce ferrous ions in the wastewater which are then oxidized to
form ferrihydrite for adsorption of aqueous ionic species. This process has not been applied
industrially for thallium removal but it has been applied industrially for the removal of arsenic [42].
They demonstrated complete (<5 µg/L) thallium removal in a pilot plant study (28,336 gallons) for a
superfund landfill site water containing 32 g/L thallium.

Loux, et al (1989) modeled the results of previous experimental test work on Wisconsin aquifer
materials containing ferrihydrite. The order of predicted adsorption was found to be the same as the
observed, i.e., Pb>Cu, Be>Zn>Cd>Tl>Ni, Ba.

Dutizac (1997) and Zinck and Dutrizac (1998) have demonstrated that thallium (10-3000 mg/L) is
not effectively removed from high zinc (75 g/L zinc, pH 2.5-4.5, 40o-75oC) bearing solutions by
ferrihydrite adsorption. The thallium removal that did result (even though only a small fraction was
removed at the lower temperatures) was identified to be removed via thallium jarosite precipitation
[TlFe3(SO4)2(OH)6]. However, this work does not negate the possible effectiveness of ferrihydrite
adsorption of thallium under other conditions, i.e., this study was conducted in the presence of high
concentrations of zinc cations which likely saturate the available adsorption sites thus precluding the
adsorption of thallium aqueous species.

xxZeolite Adsorption-Eyde, et al, [46, 47] have applied zeolite (CABSORB ZS500RW) to the
removal of thallium from actual minewater. The authors treated a western gold mining company's
mine closure drainage and process waters containing 50-1000 µg/L thallium in bench scale and pilot
scale studies by their zeolite adsorption technology. The treatment lowered the thallium to <1.7
µg/L. The pilot scale treatment was conducted in upflow fluidized bed packed columns using a single
5
pass exposure system at flowrates of 15-25 gallons/minute. The closure technology chosen by the
mining company consisted of reverse osmosis followed by zeolite adsorption polishing. In 1998 over
11 million gallons of RO permeate were polished by the zeolite system to a thallium of <2 µg/L. The
<2 µg/L was achieved in the first column utilizing a five minute retention time. Over 22,000 bed-
volumes passed through the original bed without need for replacement of the zeolite. A pilot scale
demonstration (fluid bed adsorber) at the ASARCO lead smelter using their water treatment thickener
overflow water successfully reduced the thallium to less than their effluent standard, i.e., <56 µg/L.
However, the process was not selected for use because manganese was not successfully lowered to
the desired limit.

Activated carbon adsorption-There have not been very many studies on the effectiveness of carbon
for thallium removal. Rivera-Utrilla, et al [48] studied the adsorption of Cs+1, Tl+1, Sr+2, and Co+2 on
activated carbons from aqueous solutions. They used three carbon types, e.g., two were produced
from almond shells and one purchased from a commercial source. The exposure conditions consisted
of adding 0.1 gram of carbon/4 milliliters of 7-10 molar solution of Tl+1 at a pH of 6. The results of
their work showed greater than 98% of the thallium was removed, regardless of carbon type or
content. They also found that thallium was not removed when carbon was not present. The
conclusion that the authors presented is that Tl+1 was adsorbed but then was oxidized to relatively
insoluble thallium hydroxide or oxide.

Sheya and Palmer [49] investigated (US Bureau of Mines) the effect of metal impurities (including
thallous ions) on adsorption of gold by activated carbon (coconut) in cyanide solutions over the pH
range 6.4-12.5. Experiments were conducted in solutions with and without gold and cyanide present.
One gram of activated carbon was added to 250 milliliters of 150 mg/L of thallium and 0.5 g/L of
free cyanide. Thallium showed increased adsorption with an increase in pH, e.g., 14% at a pH of 6.8
and 55% at a pH of 12.5. In the presence of gold (150 mg/L) thallium was more strongly adsorbed,
e.g., 22% at a pH of 6.8 and 70% at a pH of 12.3.

Other Absorbents-Rauws and Canton [50] suggest that potassium ferricyano ferrate (prussian blue)
absorbs thallium ions almost quantitatively. Prussian blue is an antidote for thallium poisoning in
several European countries. The solution conditions, doping concentrations, cost, and final
achievable thallium concentrations were not presented.

Srivastava, et al [51, 52] investigated the use of chromium ferrocyanide gel for removal of heavy
metals. They found that the gel had a great affinity for heavy metals, including thallium. The order of
affinity for metals (pH 2-3) was Ag+1>Tl+1, Cu+2>Co+2>Cd+2>Zn+2>Mn+2>Pb+2>Mg+2, Fe+3>Al+3. The
loading capacity for heavy metals was 3.65 milliequivalence/gram of gel.

Precipitation

Thallium is recovered from process solutions [53] at the Sumitomo Harima Works (lead/zinc smelter
complex) for market. This is one of the few plants that recover thallium for the marketplace. Zinc and
lead concentrates are roasted in a sintering operation. The thallium is volatilized along with the
cadmium. The thallium and cadmium are scrubbed from the gas phase. The cadmium is removed by
ion exchange (thallium follows the cadmium). The concentrated cadmium solution is precipitated as a
cadmium carbonate. The solution phase contains the thallium as thallous ions. The thallous ions are
oxidized and thallic hydroxide precipitates. The resulting sludge contains from 25-37% thallium. The
6
thallium sludge is releached in hydrochloric acid containing sodium bisulfite and is reduced to thallous
chloride. This solution is then treated with zinc dust to reduce the thallous to elemental thallium. The
final solution contains approximately 1 g/L thallium.

EPA's BDAT is oxidation and chemical precipitation [19]. Th process consists of the steps: lime or
caustic is added to a mix tank to raise the pH to 8-10. If thallous ions are present sodium hypochlorite
is added as a preliminary step to oxidize the thallous specie to the thallic form. Thallic hydroxide
precipitates along with other metal hydroxides. The slurry is then treated by conventional
coagulation, settling devises.

Ion Exchange (IX)

IX is widely used in hydrometallurgical applications for treatment of solutions containing uranium,

chromium, platinum group metals. However, its application as a treatment technology for removing
thallium has not been extensively investigated.

Albert and Masson patented [54] a process utilizing IX. Their patent covers the extraction of thallium
from acidic solutions by use of an IX resin containing thiol; stripping of the thallium into a relatively
concentrated solution and subsequent recovery of metallic thallium as a marketable product. The
treatment can be performed in the presence of arsenic, cadmium and zinc and can be made selective
for thallium by controlling the solution pH and potential, e.g., 0.6 volts at pH <1 up to 0.2 volts at pH
6. Krakowiak, et al [55] patented an IX process for treating complex metal bearing solutions. The
ion exchange is accomplished by using an oxygen donor macrocyclic polyether crypt and ligand
covalently bonded to an inorganic solid support. Thallium can be extracted from mg/L or µg/L to
<detection limits. The resin is then stripped using strong acids, e.g., 1M HNO 3 or 1M HCl.

Solvent Extraction( SX)

Sato, et al [56-59] have investigated SX of Tl+3 ions from aqueous solutions. They have considered
the extraction by common SX reagents, including tributyl phosphate (TBP), trioctyl phosphine oxide
(TOPO), trioctylamine (TOA), di 2-ethylhexyl phosphoric acid (DEHPA), 2-ethylhexyl 2-ethylhexyl
phosphoric acid (EHEHPA) and 5,8-diethyl-7-hydroxy-6dodecanoneoxime (LIX 63). They found
that thallium is effectively extracted by TOPO in benzene (at 25oC) from hydrochloric acid solutions.
The thallium can be recovered from the organic phase by stripping in 0.1 M sodium hydroxide. The
order of extraction of the Group IIIB elements is Tl>Ga>In. Hasegawa, et al (60) also investigated
the use of TOPO for extracting group IIIB elements (including thallium+3, 20.4 mg/L) from
hydrochloric acid. Their results are in approximate agreement with Sato, et al (56). The order of
extraction using TBP was the same as the order for TOPO. Sato, et al (56, 57) considered the
extraction of group IIIB elements from hydrochloric acid solutions by DEHPA and EHEHPA. They
found that the order of extraction of the group IIIB elements was In>Ga>Tl>Al (at <0.4 moles
HCl/liter); In>Tl>Ga>Al (at 0.4-5 moles HCl/liter); and Tl>Ga>In>Al (at >5 moles HCl/liter); by
both DEHPA and EHEHPA, but the extractions were higher in the DEHPA tests. Sato, et al (56)
considered the extraction of group IIIB elements from hydrochloric acid solutions by LIX 63. They
found that the order of extraction of the group IIIB elements is Tl>In>Ga (at <3 M HCl) and
Tl>Ga>>In (at >3 M HCl). The thallium can be recovered from the organic phase by stripping in 1 M
sodium carbonate solution.

7
Summary

Very few technologies appear to hold promise for application to minewaters for removing thallium to
<2 g/L. A summary of the technologies recommended for further evaluation (either laboratory or
pilot scale evaluation) is presented in Table 2.

Table 2. Summary of Technologies Recommended for Further Evaluation

Technology Description Precautions Product
MnO2 MnO2 adsorption of heavy Most test work has been directed Thallium loaded
Adsorption metals has been extensively toward adsorption of thallium from MnO2, or if the
investigated. Conditions the solution phase; very little thallium can be
+1
for Tl removal can be information is available as to the effectively
specified. Other aqueous extraction of thallium from the stripped from the
species in the solution will adsorbent and the possibility of MnO2, elemental
likely influence the removal reuse of the MnO2, in order, to thallium.
of thallium, i.e, the order minimize adsorbent cost. The
of adsorption (at pH 4) has technology has not advanced to
been shown to be; pilot or full scale utilization.
+2 +2 +1 +3
Pb >Cu >Tl >>Cr .
Ferrihydrite Surface adsorption This technology has not been Ferrihydrite
Adsorption modeling suggest that experimentally demonstrated to be sludge. The
ferrihydrite may be very effective for adsorption of sludge would
effective at pHs>6. The thallium. Successful application to have to be
predicted order of a variety of mine waters needs to handled as a
effectiveness for thallium be demonstrated. hazardous waste.
on ferrihydrite at pH 6 is
Tl+1 >Tl+3>Pb+2>Cu+2>>
Zn+2>Cd+2.
Metal This process is based on The product from this treatment The product
Reduction industrial practice for cannot be disposed of in tailings from this
treating process solutions, ponds. The extent of thallium treatment is
i.e., the process is zinc removal is unknown, i.e. it is metallic zinc
reduction of thallium ions. unknown whether thallium in containing
Other cementing reagents solution can be lowered to the thallium. The
may be effective, e.g., iron g/L range. thallium content
or aluminum scrap. can be built up to
relatively high
levels, i.e.,
several percent.
The product
should be
marketable.

Acknowledgments

The authors gratefully acknowledge the financial support of the USEPA, MWTP Activity IV, Project
8
12, EPA/DOE IAG No. DW89935117-01-0.

DESCRIPTION OF THALLIUM REMOVAL TECHNOLOGIES

Adsorption Processes
A large number of investigations have focused on surface adsorption as a means of removing metals,
arsenic, and selenium from aqueous phase solutions, e.g., adsorption by ferric hydroxides, aluminum
hydroxides, alumina, activated carbon, clays, etc. However, much less has been published concerning
thallium removal by adsorption. Adsorption phenomena on ferric surfaces has been the emphasis of
most of the investigations for metals (Twidwell, 1995), arsenic (Twidwell, 1995, 1999), and selenium
(Twidwell, 1997, 1999, 2000). However, most of the thallium adsorption literature is based on
manganese dioxide adsorption.

Manganese Dioxide Adsorption: Chemically Precipitated Manganese Dioxide-A

relatively large number of studies have been directed toward evaluating the adsorptive power of
natural and chemically precipitated manganese dioxide for heavy metals, e.g., Chao and Theobald
(1976); Means, et al (1978); Mckenzie (1979); Bidoglio, et al (1993); Grossl (1994); Flegal, et al
(1989); electrolytic manganese dioxide for heavy metals and thallium, e.g., Dahal, et al, (1996, 98);
and manganese dioxide sludge for metals and thallium, e.g., Jibiki (1995).

Bidoglio, et al (1993) have reviewed adsorption of thallium on chemically precipitated manganese

dioxide (similar in structure to natural Birnessite, -MnO2). The authors also conducted experimental
work comparing the adsorption of thallium on -MnO2 (190 m2/g, the authors experiments were
conducted using surface areas of 20 and 500 m2/liter), SiO2 (200 m2/g, the authors experiments were
conducted using a surface area of 500 m2/liter), and Al2O3 (130 m2/g, the authors experiments were
conducted using a surface area of 650 m2/liter). The authors found complete thallium adsorption
(from solutions containing 24 ppb to 41 ppm thallium) on -MnO2 (using only 20 m2/liter) at pH
levels of 4.7 and 8.5. The thallium was initially present in the aqueous phase as Tl (+1). The
mechanism for removal was surface adsorption of Tl (+1) with subsequent oxidation to Tl2O3 (which
has an exceeding low solubility, e.g., the thallium concentration was calculated to be 5x10-11
moles/liter at pH 4.7 by Bidoglio). Comparative tests using -Al2O3 and SiO2 showed essentially no
thallium adsorption over the same pH range. -Al2O3 showed a trend of increasing adsorption from
pH 8 (approximately 10% adsorption) to pH 12 (approximately 80% adsorption).

Means, et al (1978) conducted a literature review of manganese dioxide adsorption and their review
provides a number of reasons why it is such a good adsorbent for cations. Some of their points are
summarized below:

 Manganese dioxides are considerably better heavy metal scavengers than iron oxides. The
degree of adsorption onto common soil constituents follows the order: Manganese
oxide>organic matter>iron oxides>clay minerals.
 Surface areas of manganese minerals, like birnessite -MnO2, range up to 350 m2/g.
 The pzc (point of zero charge) is unusually low, i.e., pH=1.5-2. Therefore, the surface is
negatively charged for pH conditions of many waters. This provides an electrostatic attraction
for cations.
 The cation exchange capacity is relatively large, e.g., 1.5 equivalents/100 g (compares to 0.1

9
 equivalents/100 g of montmorillonite clays) at a pH of 8.5.

Manganese Dioxide Adsorption: Electrolytic Manganese Dioxide (EMD)-EMD is

commercially formed by electrolytic oxidation of manganese sulfate solution under acidic conditions
at temperatures near the boiling point of the solution (Ward, et al, 1992). Its major use is in
disposable and some rechargeable batteries. It is a non-stoichiometric compound having an
exchangeable hydrogen ion, e.g., a typical composition is MnO1.96H0.08. Its general structure is a
microtwinned intergrowth of birnessite and pyrolusite with cation vacancies present (Pannetier,
1992). The adsorption capacity of EMD materials appear to be a function of the hydrogen content.
Conditions for complete removal of thallium were not specified, i.e., manganese loading, pH, time,
temperature, influence of other solution species.

Adsorption on EMD is normally a function of initial ion concentration, presence of other ions, and
solution pH. Dahal, et al (1996, 1998) demonstrated that adsorption of metal ions follows the simple
Langmuir adsorption equation. The order of specie adsorption from solutions containing from 10-
2,000 ppm (using 0.200 grams of EMD/20 ml solution, i.e., for the quoted surface area of 34
m2/gram the experiments were performed using 6.8 m2 of EMD surface/20 ml or 340 m2/liter of
solution) was shown to be (at pH <2): Bi+3~Pb+2>Tl+1>Cr+3>Cu+2 and at pH 4,
Pb+2>Cu+2>Tl+1>>Cr+3. Information was not provided concerning the final thallium solution
concentration achievable during the adsorption experiments.

Manganese Dioxide Adsorption: Manganese Dioxide Sludge-Manganese dioxide sludge

produced during zinc electrowinning has been shown to be very effective in removing thallous (+1)
ions from zinc process waters and from lead smelting effluent wastewaters. Jibiki (1995) has
demonstrated thallium removal from lead smelting effluent waters to less than 100 ppb (from waters
containing 12.5 mg/L thallium). His recipe includes the following, i.e., electrolytically formed
manganese dioxide is required (manganese ores, mineral forms of MnO2 and chemically precipitated
manganese dioxide were not as effective as the electrolytically produced manganese sludge); -400
mesh particle size is recommended; a dose of approximately one gram per liter is necessary (higher
doses may be required for higher thallium bearing solutions); a pH of <4 is desirable; and a residence
time in a stirred reactor is from one half to one hour. The thallium loaded manganese dioxide can be
treated to recover the thallium, e.g., the manganese dioxide can be leached in a weak acidic solution
in the presence of a reducing agent such as sulfur dioxide, sulfite chemicals, ferrous chemicals. The
thallium can then be recovered from solution by precipitating elemental thallium using zinc dust.

Ferrihydrite Adsorption-Ferric precipitation has been characterized in the literature under

the names ferric hydroxide, amorphous ferric hydroxide, hydrous ferric oxide, amorphous iron
oxyhydroxide, amorphous ferric oxyhydroxide, hydrolyzed ferric iron, ferrihydrite and ferric
oxyhydroxide precipitation. All of these products will be referred to in this report as ferrihydrite.
Much of the literature deals with metals, arsenic and selenium removal from solution but there has
also been some consideration for thallium removal.

Ferric precipitation as ferrihydrite has been extensively covered in the literature. In fact, there is a
recipe book (Schwertmann and Cornell, 1991) on how to prepare hydrated iron oxides (even a color
chart is presented distinguishing the various forms of iron hydroxides) including: Goethite (alpha
FeOOH), Akaganeite (beta FeOOH), Lepidocrocite (gamma FeOOH), Feroxyhyte (delta FeOOH),
Ferrihydrite (Fe5HO8.4H2O), Hematite (alpha Fe2O3), Maghemite (gamma Fe2O3), Magnetite (Fe3O4).
10
 All of the listed iron oxides are crystalline except Feroxyhyte and Ferrihydrite. Ferrihydrite is
normally of low crystallinity and is actually a range of compounds that exhibit different degrees of
structural order. In general, ferric oxyhydroxides are characterized according to the number of broad
X-ray peaks, e.g., 2-line (completely amorphous) and 6-line (semi-crystalline). Several formulae for
ferrihydrite have been proposed, e.g., 5Fe2O3.9H2O (Schwertmann and Fechter, 1982; Eggleton,
1988); Fe5O8.4H2O (Towe and Bradley, 1967); and Fe6(O4H3)3 (Chukhrov, et al, 1973).

Ferrihydrite Adsorption: Thallium-There has not been a through experimental investigation

of the adsorption of thallium on ferrihydrite. What little data exists is based on phenomenalogical
observations that thallium concentrations (mostly as thallium +3) in sediments appear to higher in
ferrihydrite (or ferric oxyhydroxide) and manganese dioxide bearing sediments. Other evidence for
believing that ferrihydrite is effective for adsorbing thallium is provided by surface adsorption
modeling work, e.g., Lin and Nriagu (1998) have modeled the adsorption of thallium (+1) and
thallium (+3) on ferrihydrite by using the MINEQL calculational two-layer adsorption model
(Schecher, 1991). Their results predict that thallium (+1) will begin to adsorb at a pH of 3 and will be
completely adsorbed by pH 6; thallium (+3) will begin to significantly adsorb at a pH of 4.6 and will
be completely adsorbed by pH 6.5. The predicted order of adsorption effectiveness for thallium on
ferrihydrite at pH 6 is

Tl(+1)>Tl(+3)>Pb(+2)>Cu(+2)>>Zn(+2)>Cd(+2).

Kikuchi, et al (1990) demonstrated years ago (patents were obtained in 1955, 60) the removal of
thallium from synthetic and process solutions. They demonstrated that thallium could be effectively
removed by doping the solution with iron powder, then oxidizing with hydrogen peroxide, then
raising the pH. The proposed removal mechanism was a combination of thallic hydroxide
precipitation and thallium aqueous specie adsorption on freshly formed ferric hydroxide. The authors
treated solutions containing 100-500 mg thallium/liter with an iron dosage 12.5 g/liter and a peroxide
dosage of 100 cm3 of 30% H2O2/liter solution for 15 minutes and achieved removal to1-20 mg/liter
thallium.

Brewster and Passmore (1994) developed a similar process called the Andco Process. Their process
utilizes an iron scarifical anode to produce ferrous ions in the wastewater solution which are then
oxidized to form ferric hydroxide for adsorption of aqueous ionic species. This process has not been
applied industrially for thallium removal but it has been applied industrially for the removal of arsenic
(McCloskey, 1998). They demonstrated complete (to <5 µg/liter) thallium removal in a pilot plant
study (28,336 gallons) for a superfund landfill site water containing 32 g/L thallium.

Loux, et al (1989), modeled the results of previous experimental test work on Wisconsin aquifer
materials containing ferrihydrite. The order of predicted adsorption was found to be the same as the
observed, i.e., Pb>Cu, Be>Zn>Cd>Tl>Ni, Ba.

Dutizac (1997) and Zinck and Dutrizac (1998) have demonstrated that thallium (10-3000 mg/L) is
not effectively removed from high zinc (to 75 g/L zinc, pH 2.5-4.5, 40o-75oC) bearing solutions by
ferrihydrite adsorption. The thallium removal that did result (even though only a small fraction was
removed at the lower temperatures) was identified to be removed via thallium jarosite precipitation
[TlFe3(SO4)2(OH)6]. However, this work does not negate the possible effectiveness of ferrihydrite
adsorption of thallium under other conditions, i.e., this study was conducted in the presence of high
11
concentrations of zinc cations which likely saturate the available adsorption sites thus precluding the
adsorption of thallium aqueous species.

Zeolite Adsorption: Thallium-Eyde, et al (1998) have applied zeolite (CABSORB

ZS500RW) to the removal of thallium from actual minewaters. The authors treated a western gold
mining company's mine closure drainage and process waters containing 50-1000 µg/L thallium in
bench scale (900 µg/L thallium) and pilot scale (50 µg/L thallium) by their zeolite adsorption
technology. The treatment lowered the thallium concentration to <1.7 µg/L (effluent standard
required by the state). The pilot scale treatment was conducted in upflow fluidized bed packed
columns using a single pass exposure system at flowrates of 15-25 gallons/minute. The closure
technology chosen by the mining company (now in active closure) consisted of reverse osmosis
(which does not completely remove the thallium) followed by zeolite adsorption polishing (two 5000
pound zeolite columns). In march, 1998 over 11 million gallons of RO permeate had been polished
by the zeolite system to a thallium concentration of <2 µg/L. The <2 µg/L was achieved in the first
column utilizing a five minute retention time. Over 22,000 bed-volumes passed through the original
bed without need for replacement of the zeolite.

A pilot scale demonstration (fluid bed adsorber) at the ASARCO lead smelter using their water
treatment thickener overflow water successfully reduced the thallium concentration to less than their
effluent standard, i.e., <56 µg/L. However, the process was not selected for use because manganese
was not successfully lowered to the desired limit.

Relevant properties of the zeolite are include: surface area, 521 m2/gram; exchange capacity, 2.5
meq/gram; stability, pH 3-12; cost, approximately $1/lb; effective pore diameter, 4.3 Ao; density, 36
lbs/ft3; exchange selective, Tl+1>Cs+1>K+1>Ag+1>Rb+1>NH4+1>Pb+2 >Na+1
=Ba+2>Sr+2>Ca+2>Li+1 (Eyde, 1993).

Alumina/Silica Adsorption-Very little data are available for the adsorption of thallium by
alumina or silica surfaces. Bidoglio, et al (1993) have reviewed adsorption of thallium on chemically
precipitated manganese dioxide (similar in structure to natural Birnessite, -MnO2). The authors also
conducted experimental work comparing the adsorption of thallium on -MnO2 (190 m2/g, the
authors experiments were conducted using surface areas of 20 and 500 m2/liter), SiO2 (200 m2/g, the
authors experiments were conducted using a surface area of 500 m2/liter), and Al2O3 (130 m2/g, the
authors experiments were conducted using a surface area of 650 m2/liter). The authors found
complete thallium adsorption (from solutions containing 24 g/L to 41 mg/L thallium) on  -MnO2
(using only 20 m2/L) at pH levels of 4.7 and 8.5. The thallium was initially present in the aqueous
phase as Tl (+1). The mechanism for removal was surface adsorption of Tl (+1) with subsequent
oxidation to Tl2O3 (which has an exceeding low solubility, e.g., the thallium concentration was
calculated to be 5x10-11 moles/liter at pH 4.7 by Bidoglio). Comparative tests using -Al2O3 and
SiO2 showed essentially no thallium adsorption over the same pH range.  - Al2O3 showed a trend
of increasing adsorption from pH 8 (approximately 10% adsorption) to pH 12 (approximately 80%
adsorption). The experimental results are not very encouraging for the development of an industrial
treatment technology.

Jinzhou, et al (1997) determined the distribution of many species from the solution phase to either
alumina or bentonite (50 mg adsorbent/4 ml of solution). The authors defined a distribution constant,
Kd:
12
 Kd=Tlmass in solid/Tlmass in solution
The Kd values were 4x104 for thallium adsorbed on both alumina and bentonite.

Activated Carbon AdsorptionThere have not been very many studies on the effectiveness of
carbon for thallium removal. Rivera-Utrilla, et al (1984) studied the adsorption of Cs+1, Tl+1, Sr+2,
and Co+2 on activated carbons from aqueous solutions. They used three carbon types, e.g., two were
produced from almond shells and one purchased from a commercial source. The exposure conditions
consisted of adding 0.1 gram of carbon/4 milliliters of 10-7 molar solution of thallium (+1) at a pH of
6. The results of their work showed greater than 98% of the thallium was removed, irregardless of
carbon type or content. They also found that no thallium was removed when carbon was not present.
The conclusion that the authors presented is that thallium (+1) was adsorbed but then was oxidized
to relatively insoluble thallium hydroxide or oxide.

Sheya and Palmer (1986) investigated (for the U.S. Bureau of Mines) the effect of metal impurities
(including thallous ions) on adsorption of gold by activated carbon (coconut) in cyanide solutions
over the pH range 6.4-12.5. Experiments were conducted in solutions with and without gold and
cyanide present. One gram of activated carbon was added to 250 milliliters of 150 mg/liter of
thallium and 0.5 g/liter of free cyanide. The pH was adjusted to the desired value using sodium
hydroxide. Thallium showed increased adsorption with an increase in pH, e.g., 14% at a pH of 6.8
and 55% at a pH of 12.5. In the presence of gold (150 mg/liter) thallium was more strongly
adsorbed, e.g., 22% at a pH of 6.8 and 70% at a pH of 12.3.

Other Absorbents-Rauws and Canton (1976) suggest that potassium ferricyano ferrate
(prussian blue) absorbs thallium ions almost quantitatively. Prussian blue is an antidote for thallium
poisoning in several European countries. The solution conditions, doping concentrations, cost, and
final achievable thallium concentrations were not presented.

Arginbaev, et al (1984) considered the use of titanium containing absorbents. They purified sulfate
solutions containing arsenic and thallium using titanyl and ammonium sulfate. Titanium arsenates
formed and it was found that they had a great affinity for thallium, e.g., 62-63 mg thallium/g of
titanium arsenate. This, of course, is not a practical technology to be applied to thallium bearing
solutions.

Srivastava, et al (1980) investigated the use of chromium ferrocyanide gel for removal of heavy
metals. They found that the gel had a great affinity for heavy metals, including thallium. The order of
affinity for metals in acidic solutions (pH=2-3) is Ag+1>Tl+1,
Cu+2>Co+2>Cd+2>Zn+2>Mn+2>Pb+2>Mg+2, Fe+3>Al+3. The loading capacity for heavy metals is 3.65
milliequivalence/gram of gel.

Precipitation
Only thallium (+3) can be removed via precipitation, i.e., thallic hydroxide/thallic oxide show
relatively low solubilities whereas thallium (+1) hydroxide is highly soluble. See Figures 11
(concentration/pH diagram) and 3 (EH/pH diagram). It appears possible to achieve thallium aqueous
specie concentrations of less than 100 µg/L. This requires that the solution conditions be highly
oxidizing.

Thallium is recovered from process solutions (Minami, 1990) at the Sumitomo Harima Works
13
(lead/zinc smelter complex) for market. This is one of the few plants that recovers elemental thallium
for the marketplace. Zinc and lead concentrates (<100 mg thallium/kg concentrate) are roasted in a
sintering operation. The thallium is volatilized along with the cadmium. The thallium and cadmium
are scrubbed from the gas phase. The cadmium is removed by ion exchange (thallium follows the
cadmium). The concentrated cadmium solution is precipitated as a cadmium carbonate. The solution
phase contains the thallium as thallous ions. The thallous ions are oxidized and thallic hydroxide
precipitates. The resulting sludge contains from 25-37% thallium. The thallium sludge is releached in
hydrochloric acid containing sodium bisulfite (a reducing agent). The thallium is reduced to thallous
chloride. This solution is then treated with zinc dust to electrochemically reduce the thallous ions to
elemental thallium metal. The final solution contains approximately 1 g/L thallium.

EPA's Best Demonstrated Available Technology is oxidation and chemical precipitation. This
wastewater treatment technology is briefly described by Rissmann and Schwartz (1990): the process
consists of the following generic steps: lime or caustic is added to a mix tank to raise the pH to 8-10.
If thallous ions are present sodium hypochlorite is added as a preliminary step to oxidize the thallous
specie to the thallic form. Thallic hydroxide precipitates along with other metal hydroxides. The
slurry is then treated by conventional coagulation, settling devises. The production of thallium
bearing sludges are undesirable, i.e., they are hazardous wastes that are costly to produce and they
contain only minor concentrations of non-recoverable thallium.

Dutrijac (1997) demonstrated that a thallium jaosite [TlFe3(SO4)2(OH)6] forms under the same
conditions for removing iron as a jarosite from zinc leach solutions (T>75oC, 75 g/L Zn) prior to zinc
recovery by electrolysis. Thallium jarosite forms in preference to sodium [NaFe 3(SO4)2(OH)6] or
ammonium [NH4Fe3(SO4)2(OH)6] jarosites. The rapid formation of thallium jarosite requires a
temperature>75oC. The formation appears to be independent of thallium concentration over the
range 0-3000 mg/L.

Oxidation
The oxidation of thallium to its trivalent state has been investigated by several researchers, e.g., Byers
(1984); FMC (1983, 84); Fruse (1969); Hill (1964); Hirose, et al (1965); MacLean, et al (1966);
McEuen and Norris (1984); Walker (1980). Thallic oxidation of organics is widely practiced and,
therefore, there has been a lot of attention applied to the oxidation of thallous (the normal valence
state in most natural waters) to thallic with subsequent recycle within the process for further organic
oxidation. Several patents recommend that relatively strong oxidizing agents are required to
accomplish the oxidation, especially in acidic solutions. Examples are presented below:

MacLean, et al (1966) recommend electrolytic oxidation. Others recommend molecular oxygen, e.g.,
Johnson (1978), Naglieri, et al (1978), and Johnson (1980). The disadvantages of these processes
include the requirement that the oxidation be performed in the presence of catalysts or in autoclave
reactors; both add extra expense to the oxidation process.

Walker (1980) suggested the use of organic hydroperoxide in the presence of a noble metal catalyst.
However, the formation of an organic acid product required that a separate separation process be
employed to remove the product organic acid. Also, the expense of the noble metal cayalyst is a
deterrent to the use of this technology.

McEuen and Norris (1984) and Byers (1984) proposed that relatively inexpensive hydrogen peroxide
14
(inexpensive compared to the use of a catalyst, high temperature and/or special acids) could be used.
Prior to this patent hydrogen peroxide was considered ineffective for thallium oxidation in acidic
solutions below pH 9-10. Hydrogen peroxide was known to be effective in highly basic solutions.
The basis for the McEuen patent was that the oxidation reaction could be enhanced by removing the
product thallic ions from solution by any of a number of techniques, e.g., solvent extraction or ion
exchange of the thallic ions, reaction with organics, or dissolution in another solvent. The removal of
the oxidation reaction product then stimulates further thallous oxidation. The effectiveness (60-80%
conversion in 4-6 hours) of the process is described in the patent by several examples.

Ion Exchange (IX)

Ion exchange (IX) is widely used in hydrometallurgical applications for treatment of solutions
containing uranium, chromium, platinum group metals. Ion exchange is similar in principal to solvent
extraction except the exchanger is present attached to a solid phase rather than as a dissolved
constituent in an organic liquid phase, i.e., the technology for solvent extraction requires handling two
liquid phases (in mixer/settlers); the technology for ion exchange requires handling a solid and a liquid
phase (in columns or in recirculating beds). Ion exchangers are widely used industrially for removing
low concentration impurities from concentrated acidic solutions (like electrowinning and
electrorefining electrolytes) and also for treating dilute metal bearing waste waters (usually used as a
final solution polishing operation).
Ion exchange is used widely for cleaning up drinking waters, dilute metal bearing solutions,
wastewater, and groundwater. However, its application as a treatment technology for removing
thallium has not been extensively investigated.

Albert and Masson (assigned to Metaleurop, S.A.) have patented (1994) a process utilizing ion
exchange. Their patent covers the extraction of thallium from acidic solutions containing low
concentrations of the element by use of an ion exchange resin containing thiol groups (thioalcohol or
thiophenol groups, e.g., IMAC TMR marketed by Duolite), the stripping of the thallium into a
relatively concentrated solution and subsequent recovery of metallic thallium as a marketable product.
The treatment can be performed in the presence of arsenic, cadmium and zinc and can be made
selective for thallium by controlling the solution pH and potential, e.g., 0.6 volts at pH <1 up to 0.2
volts at pH 6. The quoted examples show that for a solution (pH ~2) containing Cd (6.3 g/L), As
(0.82 g/L), Zn (2.1 gg/L), Tl (0.34 g/L), using two stages of contact the thallium was lowered to
6,000 µg/L. Another example illustrated the removal at pH 8. Thallium at 240 mg/L was lowered to
<1 mg/L. The required strip solution is a concentrated acid, e.g., 20 g/L sulfuric acid.

Krakowiak, et al (1995) patented an ion exchange process for treating complex metal bearing
solutions. The ion exchange is accomplished by using an oxygen donor macrocyclic polyether
cryptand ligand covalently bonded to an inorganic solid support. Thallium can be extracted from
ng/liter or µg/liter to <detection limits. The resin is then stripped using strong acids, e.g., 1M HNO3
or 1M HCl.

Solvent Extraction
Sato, et al (1989, 1992, 1996, 1997) have investigated the solvent extraction of thallium (+3) ions
from aqueous solutions. They have considered the extraction by common solvent extraction reagents,
including tributyl phosphate (TBP), trioctyl phosphine oxide (TOPO), trioctylamine (TOA), di 2-
ethylhexyl phosphoric acid (DEHPA), 2-ethylhexyl 2-ethylhexyl phosphoric acid (EHEHPA) and 5,8-
diethyl-7-hydroxy-6dodecanoneoxime (LIX 63).
15
Sato, et al (1996) considered the extraction of group IIIB elements (including thallium (+3)) from
hydrochloric acid solutions. They found that thallium is effectively extracted by TOPO in benzene (at
25oC) from hydrochloric acid solutions. See Table 10. The thallium can be recovered from the
organic phase by stripping in 0.1 molar sodium hydroxide. The order of extraction of the Group IIIB
elements is Tl>Ga>In. Hasegawa, et al (1980) also investigated the use of TOPO for extracting
group IIIB elements (including thallium (+3), 20.4 mg/L) from hydrochloric acid. Their results are in
approximate agreement with Sato, et al (1996).

Table 10. Extraction of Thallium (+3) from Hydrochloric Acid Solutions Using TOPO (thallium
initial concentration=1g/L)
TOPO, HCl, Ea=Tlin organic/Tlin aqueous HCl, Ea=Tlin organic/Tlin aqueous
moles/L moles/L moles/L
0.005 0.02 48 5 95
0.004 0.02 14 5 30
0.003 0.02 6 5 9

The order of extraction using TBP was the same as the order for TOPO. However, data were not
presented for TBP extractions in their 1996 paper. The results for TBP were presented in a later
paper by Sato, et al (1997). Also, the extractions by TOA were considered in the latter paper. The
1997 results are summarized in Table 11.

Table 11. Extraction of Thallium (+3) from Hydrochloric Acid Solutions Using TBP and TOA
(thallium initial concentration=1g/L)
HCl, Organic, Ea=Tlin organic/Tlin aqueous Organic, Ea=Tlin organic/Tlin aqueous
moles/L volume % volume %
TBP
0.01 1.9 0.8 4.7 4.8
1 1.9 0.1 4.7 0.7
10 1.9 1.5 4.7 9
TOA
0.2 0.1 moles/L 0.05
1 0.1 moles/L 0.8
10 0.1 moles/L 10

Sato, et al (1988, 89) considered the extraction of group IIIB elements (including thallium (+3)) from
hydrochloric acid solutions by DEHPA and EHEHPA. They found that the order of extraction of the
group IIIB elements is In>Ga>Tl>Al (at <0.4 moles HCl/liter); In>Tl>Ga>Al (at 0.4-5 moles
HCl/liter); and Tl>Ga>In>Al (at >5 moles HCl/liter); by both DEHPA and EHEHPA, but the
extractions were higher in the DEHPA tests. See Table 12 for the distribution ratios. The thallium

16
can be recovered from the organic phase by stripping in 1 molar hydrochloric acid solution.

Table 12. Extraction of Group IIIB Elements from Hydrochloric Acid Solutions Using DEHPA
(thallium initial concentration=1g/L; 0.5 moles DEHPA/L)
HCl, moles/L Ea=Ga,In, or Tlin organic/Ga,In, or Tlin aqueous
Ga In Tl
0.2 1.54 Very large 0.20
5 0.22 0.14 0.95
8 1.94 0.05 3.94

Sato, et al (1989) considered the extraction of group IIIB elements (including thallium (+3)) from
hydrochloric acid solutions by LIX 63. They found that the order of extraction of the group IIIB
elements is Tl>In>Ga (at <3 moles HCl/liter) and Tl>Ga>>In (at >3 moles HCl/liter). See Table 13
for the distribution ratios. The thallium can be recovered from the organic phase by stripping in 1
molar sodium carbonate solution.

Table 13. Extraction of Thallium (+3) from Hydrochloric Acid Solutions Using LIX 63 (thallium
initial concentration=1g/L; 0.32 moles LIX 63/L)
HCl, moles/L Ea=Tlin organic/Tlin aqueous
0.3 0.10
1 1.3
5 20

Reddy and Reddy (1983) investigated the solvent extraction of thallium (+3) (100 mg/liter thallium)
from hydrochloric acid using sulphoxides, e.g., di-n-pentyl sulphoxide (DPSO), di-n-octyl sulphoxide
(DOSO), diphynyl sulphoxide (DPHSO), and tri-n-octyl phosphine oxide (TOPO). The extraction of
thallium was a function of extractant type and extractant concentration. The amount of reagent
required at a fixed extraction distribution ratio (15.8) was as follows (in moles/liter): DPHSO=1,
DOSO=DPSO=0.06, TOPO=0.001. The order of extraction at the same organic concentration is:
DOSO=DPSO>TOPO>>DPHSO.

SUMMARY

Very few technologies appear to hold promise for application to minewaters for removing thallium to
the low ppb range, e.g., <2 g/L. A summary of the technologies recommended for further
evaluation (either laboratory or pilot scale evaluation) is presented in Table 14.

Table 14. Summary of Technologies Recommended for Further Evaluation

Technology Description Precautions Product

17
Manganese Manganese dioxide
Dioxide adsorption of heavy metals
Adsorption has been extensively
investigated. Conditions
for thallium (+1) removal
from solution can be
specified. The presence of
other aqueous species in
the solution to be treated
will likely influence the
removal of thallium, i.e,
the order of adsorption (at
pH 4) has been shown to
be; Pb+2>Cu+2>Tl+1>>Cr+3.
Most of the experimental test work Thallium loaded
has been directed toward manganese
adsorption of thallium from the dioxide or, if the
solution phase; very little thallium can be
information is available as to the effectively
extraction of thallium from the stripped from the
adsorbent and the possibility of manganese
reuse of the manganese dioxide, in dioxide,
order, to minimize adsorbent cost. elemental
Also, only laboratory studies have thallium.
been performed. The technology
has not advanced to pilot or full
scale utilization.

Ferrihydrite Surface adsorption This technology has not been Ferrihydrite

modeling suggest that experimentally demonstrated to be (ferric
ferrihydrite adsorption may very effective for adsorption of oxyhydroxide)
be effective at pH levels thallium. sludge. This
greater than approximately sludge should be
6. The predicted order of Successful application to a variety considered a
adsorption effectiveness of minewaters needs to be hazardous
for thallium on ferrihydrite demonstrated. material. The
at pH 6 is sludge would
Tl(+1)>Tl(+3)>Pb(+2)>Cu have to be
(+2)>>Zn(+2)>Cd(+2). treated for
proper disposal
(probably as a
hazardous
waste).

18
Metal This process is based on The product from this treatment The product
Reduction industrial practice for cannot be disposed of in tailings from this
treating process solutions, ponds. treatment is
i.e., the process is zinc elemental zinc
electrochemical reduction The extent of thallium removal is containing
of thallium ions ( zinc unknown, i.e., it is unknown deposited
cementation of thallium). whether thallium concentrations in elemental
solution can be lowered to the ppb thallium. The
Other cementing reagents range. thallium
may be effective, e.g., iron concentration
or aluminum scrap or can be built up to
powders. relatively high
levels, i.e.,
several percent.
The product
should be
marketable as a
source of
thallium.

ACKNOWLEDGEMENTS

The authors gratefully acknowledge the financial support of the USEPA, MWTP Activity IV, Project
12, EPA/DOE IAG No. DW89935117-01-0.

BIBLIOGRAPHY

Albert, L., H. Masson (Assigned to S.A. Metaleurop), Thallium Extraction Process, U.S. Patent 5,296,204, July
1992, 6 p.

Allison, J.D., D.S. Brown, K.J. Novo-Gradac, MINTEQA2/PRODEFA2, A Geochemcial Assessment Model for
Environmental Systems: Version 3.0 User's Manual, EPA/600/3-91/021, March 1991, 105 p.

Amer, S., Solvent Extraction Applications to Hydrometallurgy: Part 4. Iron, Beryllium, Aluminum, Gallium,
Indium, and Thallium, Rev. Metal. (Madrid), Vol. 17, No. 2. 1981, pp. 109-30.

American Water Works Association, Standard Methods for the Examination of Water and Wastewater, 19th
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 LIST OF TABLES

1 Thallium in the Environment

2 Environmental Standards
3 Solution Treatment Technologies Potentially Applicable to Minewater
4 Summary of Technologies Recommended for Further Study

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 LIST OF FIGURES

1 EH/pH diagram for the thallium (50 ppm)-water system at 25oC

2 EH/pH diagram for the thallium-sulfur-water system (50 ppm Tl, 500 ppm S)
at 25oC
3 EH/pH diagram for the thallium-water system at low thallium concentrations
(50 ppb) at 25oC
4 EH/pH diagram for the thallium-sulfur-water system at low thallium
concentrations (50 ppb Tl, 500 ppb S) at 25oC
5. EH/pH diagram for the thallium-chloride-water system
(Tl=50 ppb, Cl=18980 ppm)
6 Thallium-water system: aqueous thallous (+1) specie distribution as a
function of pH
7 Thallium-water system: aqueous thallic (+3) specie distribution as a
function of pH
8 Thallium-seawater system: aqueous thallic (+3) specie distribution
as a function of pH (Cl=18,980 ppm)
9 Thallous carbonate solubility as a function of pH (P CO2=0.00034 atm)
10 Thallous sulfide solubility as a function of pH
11 Thallic hydroxide solubility as a function of pH in the thallium-sulfate-water
system
12 Thallic hydroxide solubility as a function of pH in the thallium-chloride-water
ystem

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