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Love is in the Earth: A review of tellurium (bio)geochemistry in

Earth surface environments

O.P. Missen, R. Ram, S.J. Mills, B. Etschmann, F. Reith, J.

Shuster, D.J. Smith, J. Brugger

PII: S0012-8252(19)30699-3
DOI: https://doi.org/10.1016/j.earscirev.2020.103150
Reference: EARTH 103150

To appear in: Earth-Science Reviews

Received date: 24 October 2019

Revised date: 21 February 2020
Accepted date: 7 March 2020

Please cite this article as: O.P. Missen, R. Ram, S.J. Mills, et al., Love is in the Earth:
A review of tellurium (bio)geochemistry in Earth surface environments, Earth-Science
Reviews(2019), https://doi.org/10.1016/j.earscirev.2020.103150

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© 2019 Published by Elsevier.

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REVISION 2.1

Love is in the Earth: a review of tellurium (bio)geochemistry in Earth

surface environments

O.P. Missen a,b,* , R. Ram a, S.J. Mills b, B. Etschmann a, F. Reith c,d† , J. Shuster c,d, D.J.

Smith e, J. Brugger a,*

f
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a
School of Earth, Atmosphere and Environment, 9 Rainforest Walk, Monash University,

Clayton 3800, Victoria, Australia

b pr
Geosciences, Museums Victoria, GPO Box 666, Melbourne 3001, Victoria, Australia
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c
School of Biological Sciences, The University of Adelaide, Adelaide, SA 5005, Australia
d
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CSIRO Land and Water, Contaminant Chemistry and Ecotoxicology, PMB2, Glen Osmond,

SA 5064, Australia
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e
School of Geography, Geology & the Environment, University of Leicester, Leicester, UK
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*Corresponding authors’ e-mails: omissen@museum.vic.gov.au, joel.brugger@monash.edu

†
Passed away prior to completion of the manuscript

Keywords: Tellurium cycling, environments, (bio)geochemistry, mobility, mineralogy

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ABSTRACT

Tellurium (Te) is a rare metalloid in the chalcogen group of the Periodic Table. Tellurium is

regularly listed as a critical raw material both due to its increased use in the solar industry,

and to the dependence on other commodities in its supply chain. A thorough understanding of

the geo(bio)chemistry of Te in surface environments is fundamental for supporting the search

for future sources of Te (geochemical exploration); developing innovative processing

techniques for extracting Te; and quantifying the environmental risks associated with rapidly

increasing anthropogenic uses. The present work links existing research in inorganic Te

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geochemistry and mineralogy with the bio(geo)chemical and biological literature towards

developing an integrated Te cycling model.

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Although average crustal rocks contain only a few µg/kg of Te, hydrothermal fluids and
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vapours are able to enrich Te to levels in excess of mg/kg. Tellurium is currently recovered as
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a by-product of base- metal mining; in these deposits, it occurs mainly in common sulphides

substituting for sulphur. Extreme Te enrichment (up to wt.%) is found in association with the
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precious metals Au and Ag in the form of telluride and sulphosalt minerals. Tellurium also
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forms a large variety of oxygen-containing secondary minerals as a result of weathering of

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Te-containing ores in (near-)surface environments. Anthropogenic activities introduce

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significant amounts of Te into surficial environments, both through processing materials that

contain minor Te, and through breakdown of used Te-containing materials. Additionally,
132
radioactive Te is produced in nuclear reactors, and can contaminate surrounding and distal

environments.

Environmental contamination of Te poses concern to organisms due to the acute toxicity of

some Te compounds, especially the soluble tellurite and tellurate anions. A small percentage

of microorganisms, however, are able to tolerate elevated levels of Te by detoxifying it

through precipitation or volatilisation. Bioaccumulation of Te compounds can occur in some

plants of the garlic family. A variety of interlinked organic and inorganic processes governs
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Te environmental chemistry. The Te cycle in surface environments incorporates (oxidative)

dissolution of Te from primary ore minerals, inorganic precipitation and redissolution

processes in which secondary minerals are formed, and bioreductive reprecipitation and

volatilisation processes governed mainly by microbes. Our integrated Te cycling model

highlights the interplay between anthropogenic, geochemical and biogeochemical processes

on the distribution and mobility of Te in surface environments.

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HIGHLIGHTS

 Tellurium has a complex environmental geochemistry



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The many modes of Te bonding govern its surface behaviour
Outcropping Te deposits are an analogue for anthropogenic contamination
 We propose a cycling model for tellurium in surface environments
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 We highlight future areas for tellurium biogeochemical research
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TABLE OF CONTENTS

ABSTRACT 2

HIGHLIGHTS 3

TABLE OF CONTENTS 4

1. INTRODUCTION 5

2. PHYSICAL A ND CHEMICAL PROPERTIES OF TELLURIUM 9

3. TELLURIUM MINERA LOGY 11

4. TELLURIUM DISTRIBUTION AND ORE DEPOSITS 13

4.1 Overview of tellurium distribution in the Earth’s crust 13
4.2 Tellurium ore deposits 15

5. TELLURIUM IN THE ENVIRONMENT 22

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5.1 Tellurium in the oxidation zone of primary Te-rich ores 22

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5.2 Tellurium deportment in soils and deeper regolith environments 25
5.3 Anthropogenic tellurium 25
5.4 Tellurium toxicity 28

6. BIOGEOCHEMISTRY OF TELLURIUM
6.1 Biooxidation (bioleaching)
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31
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6.2 Biosorption 33
6.3 Bioreduction 34
6.4 Bioaccumulation 41
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6.5 Applications 42

7. A TELLURIUM BIOGEOCHEMICAL CYCLING MODEL 44

7.1 An integrated Te cycling model – comparison with Se 44
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7.2 Tellurium dispersion around Au-Te deposits 46

8. CONCLUSIONS 48
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ACKNOWLEDGEMENTS 49
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FOOTNOTES 49
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REFERENCES 51

TABLES 70

FIGURES A ND CAPTIO NS 79
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1. INTRODUCTION

Tellurium (Te) was discovered in 1783 by Franz Joseph Müller von Reichenstein, but fully

publicised only over a decade later by Martin Heinrich Klaproth, who named the new

element after the Latin word for "earth", tellus (Emsley, 2011; Klaproth, 1798). With an

estimated crustal abundance of ~5 µg/kg (reported range 1 to 27 µg/kg; Emsley, 2011;

Vaigankar et al., 2018; Wedepohl, 1995), it is one of the least abundant elements in the

lithosphere and comparable to crustal abundances of precious metals gold (Au) and platinum

(Pt) (Emsley, 2011). Recently, Te has come into prominence due to new industrial

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applications, including in cadmium telluride (CdTe) solar panels (Diso et al., 2016; Goldfarb,

2014; Reese et al., 2018), thermoelectric devices (Bae et al., 2016; Knockaert, 2011; Lin et al.,
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2016), batteries (Ding et al., 2015; He et al., 2016; He et al., 2017), and nanomaterials like
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CdTe quantum dots (Mahdavi et al., 2018). Furthermore, the recent nuclear incident at
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Fukushima led to severe contamination by the radioisotope Te, renewing interest in the
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biogeochemical mechanisms involved in Te transport in the environment (e.g. Gil-Díaz, 2019;

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Tagami et al., 2013).

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Tellurium is distributed unevenly through the Earth’s crust. Hydrothermal and magmatic
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processes are the key mechanisms leading to high Te concentrations and the formation of
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primary Te minerals (Brugger et al., 2016). Tellurium is an essential element in over 180

minerals, making it the most anomalously diverse element in mineralogy, i.e. it forms the

greatest number of minerals relative to its crustal abundance (Christy, 2015; Pasero, 2020).

Tellurides are primary minerals containing reduced Te (formal oxidation state -II to 0; e.g.,

calaverite, krennerite, sylvanite; Figure 1a-c) and elemental tellurium (Figure 1d); secondary

minerals comprise tellurites (oxidation state +IV) and tellurates (+VI) (e.g., teineite,

zemannite, and jensenite, Figure 1d- f). The designations ‘primary’ and ‘secondary’ minerals

relate to formation conditions. Primary minerals form deeper in the crust under anoxic

conditions from hydrothermal fluids or silicate melts (Ciobanu et al., 2006; Zhang and Spry,
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1994); whereas secondary minerals form via weathering of primary minerals under the

oxidising conditions of near-surface environments (Christy et al., 2016a). Some tellurites and

tellurates possess non- linear optical properties (Norman, 2017; Weil, 2018; Yu et al., 2016)

with potential applications in the electronics industry. Nonetheless, most industrial

applications for Te utilise tellurides (Amatya and Ram, 2012; Woodhouse et al., 2013; Yeh et

al., 2008).

In 2010, the US Department of Energy classified Te as a critical metal with an anticipated

global supply shortfall by 2025 (Bauer et al., 2010), and Te remains on the list of critical

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metals published by the US Department of the Interior in 2018 (USDOI, 2018). The global

Te industry is still in its infancy with a global production of 440 metric tonnes and estimated
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reserves of 31,000 metric tonnes from Te contained in copper ores (Anderson, 2019).
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Currently, >90% of Te (along with Se) is recovered from copper anode slimes as a by-
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product of the electrolytic refining of copper (Kyle et al., 2011; Makuei and Senanayake,

2018), and Te supply is thus intrinsically linked to the Cu mining industry. Recent advances
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in industrial uses of Te focus on CdTe solar panels, which currently supply five percent of the
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global solar panel market (USDOE, 2019). Due to a growing world population and
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concurrent attempts to limit man- made climate change, renewable energy industries including
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CdTe solar panels are growing in prominence (see Figure 2; Frishberg, 2017; Nuss, 2019;

Wang, 2011).

The increased demand for Te will inevitably result in increasing Te contamination around

mining and industrial sites (e.g. Kagami et al., 2012), and the decommissioning of CdTe solar

panels also has the potential to be a source of contamination, in particular to groundwater

(Fthenakis and Wang, 2006; Marwede and Reller, 2012; Ramos-Ruiz et al., 2017b; Xu et al.,

2018). Recent improvements to the detection of low levels of Te via cathodic stripping

voltammetry (Biver et al., 2015) and inductively-coupled plasma mass spectrometry (Filella

and Rodushkin, 2018) have been made, although further improvements in the detection limits
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of environmental Te are ideally required (Filella, 2019). Another short-term anthropogenic
132 129m
source of Te contamination are the radiogenic isotopes Te and Te released to the

environment in nuclear spills or explosions. This comprises both nuclear weapons testing

(particularly from the 1940s to the 1970s) and accidental spillage from power plant failure

such as the Chernobyl and Fukushima Daiichi nuclear disasters (Dickson and Glowa, 2019;
132
Yoschenko et al., 2018). The radioactive and biologically active decay product of Te, 132 I,

is of most concern, and a greater understanding of Te biogeochemical cycling could have

provided better and longer- lasting solutions for cleaning up radioactive materials following

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the Fukushima spill (Gil-Díaz, 2019).

Research in Te biogeochemistry remains overall in its infancy. The cycling of this element in
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near-surface environments is dynamic, as the transformation of Te oxidative states can form
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both inorganic and organic compounds (Belzile and Chen, 2015; Bonificio and Clarke, 2014;
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Chasteen et al., 2009). In terms of biogeochemical processes at the cellular level, mechanisms

for detoxifying often involve reduction of soluble Te oxyanions (i.e., tellurite and tellurate
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anions) (Piacenza et al., 2017; Taylor, 1996; 1999). These soluble Te oxyanions are toxic to
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most microorganisms at low concentrations, i.e., 1 mg/L or an equivalent 4 µM (Presentato

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et al., 2019), which are orders of magnitude less than cytotoxic concentrations of mercury or
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cadmium (Chasteen et al., 2009; Presentato et al., 2016). As such, Te solubility is a key factor

contributing to its toxicity; reduced Te compounds (e.g., meta llic Te) have low solubility and

are therefore considered less toxic as they are not bioavailable. Reduction of Te oxyanions by

microorganisms follows two major pathways, which may be either active or passive:

bioprecipitation and, to a lesser extent, biovolatilisation (Chasteen and Bentley, 2003). Active

bioprecipitation (also known as biomineralisation) results in the formation of nanoparticles of

elemental Te, and biovolatilisation in the formation of volatile, organic forms of Te such as

dimethyl telluride. In terms of passive bioprecipitation/biomineralisation, microorganisms as

well as other organic material, e.g., extracellular polymeric substances (EPS), can act as a
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sorbent material as well as a reductant for Te oxyanions. As such, the accumulation of

reduced Te can occur over time as long as Te oxyanions are supplied to the system and a

consistent presence of biomass is available to serve as a sorbent material and reductant

(Tanaka et al., 2010). Biooxidation of Te leading to its solubility (and intuitively, its mobility

in the environment) is the less-studied process of biogeochemical cycling relative to Te

oxyanion reduction. Metal-tolerant microorganisms are capable of indirectly oxidising

tellurides by producing an oxidant (e.g. Fe-oxidisers producing Fe3+) as a by-product of their

metabolism (Climo et al., 2000b). Collectively, the summation of reduction and oxidative

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processes contribute to the biogeochemical cycle of Te under near-surface environmental

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conditions and provide both organic and inorganic pathways for precipitation, sorption and

oxidation (Filella et al., 2019). pr

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Here we focus on the environmental (bio)geochemistry of Te, by first tying together existing
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research in mineralogy, geochemistry and microbiology – each discipline extensively studied

in their own right, but not often explicitly linked. Over the past decade, various aspects of the
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biosphere and lithosphere have been shown to influence the dissolution, re-precipitation and
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mobility of Se, the chalcogen element located above Te in the Periodic Table (Bailey, 2017;
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Nancharaiah and Lens, 2015; Sharma et al., 2015; Tan et al., 2016; Ullah et al., 2018). In
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addition, precious metals such as Au (Reith et al., 2013; Sanyal et al., 2019; Southam et al.,

2009) and Pt (Reith et al., 2014; 2016; 2019), which have had been generally considered to

be inert in the biosphere, have been shown to display complex biogeochemical cycling. To

our knowledge, an interdisciplinary research perspective of Te cycling is still lacking in the

literature; therefore, here we develop a model for a global biogeochemical cycling of Te in

near-surface environments. This Te biogeochemical cycling model helps to identify gaps in

our current understanding of Te biogeochemistry, and allows critical evaluation of var ious

environmental factors contributing to Te mobility, which is becoming increasingly important

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as anthropogenic activity associated with Te applications is a greater factor in environmental

contamination.

2. PHYSICAL AND CHEMICAL PROPERTIES OF TELLURIUM

Tellurium has the atomic number 52, belongs to the chalcogen group, and is located below

oxygen (O), sulphur (S; Kagoshima et al., 2015), and selenium (Se; Ullah et al., 2018), and

above radioactive polonium (Po; Ram et al., 2019) in the Periodic Table (see Supplementary

Table 1). Tellurium has 39 known isotopes, eight of which are naturally occurring. Half of

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those isotopes, 122 Te (natural abundance 2.5%), 124 Te (4.6%), 125 Te (6.9%), and 126 Te (18.7%),

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120 123
are stable. The other four naturally occurring isotopes are unstable, i.e., Te (0.09%), Te

(0.87%), 128
Te (31.8%) and 130
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Te (34.5%), but with long to extremely long half- lives of

~1016 , 9.2 × 1016 , 2.2 × 1024 (the longest known half- life of any isotope) and 7.9 × 1020 years,
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respectively (Emsley, 2011). The long- lived radioactive isotopes of Te are more abundant
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than the stable isotopes by a ratio of ca. 2:1. A ninth isotope, 132 Te (half- life 3.204 days), is of

considerable concern as a nuclear waste product and was the third most abundant element
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released by the Fukushima Daiichi nuclear disaster (Endo et al., 2018). Aside from trace
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132
levels found in U ores from natural nuclear fission events (Emsley, 2011), Te is of
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129m
anthropogenic origin. Additionally, Te (‘m’ indicating a metastable isotope with the
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nucleus in a long- lived excited state; 129m Te decays via gamma radiation to 129
Te with a half-

life 33.6 days) is produced in nuclear fission waste and spills (Watanabe et al., 2012; Endo et
127m 131m
al., 2018). The metastable isotopes Te and Te are also generated in smaller amounts
119m
by nuclear fission (Takahashi et al., 2019), and some other radioactive isotopes like Te

(half- life 4.70 days) are generated synthetically as precursors for medical uses (Bennett et al.,

2019).

Of the chalcogens, Te has the highest melting and boiling points, at 449.5 and 988 °C,

respectively. However, in polymetallic systems, Te is one of the “low-melting point

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chalcophile metals” together with Ag, As, Au, Bi, Hg, Sb, Se, Sn, and Tl, forming melts at

metamorphic and hydrothermal temperatures between 500 and 600 °C, depending on

pressure (Frost et al., 2002; Tooth et al., 2011). Elemental Te is a semiconductor that is also

photoconductive (increased conductance when exposed to light; Liu et al., 2010), although Te

is more commonly combined with other elements in semiconducting applications (Marwede

and Reller, 2012).

In terms of its aqueous chemistry, Te is similar to Se, sharing fewer parallels with S and Po,

but previous studies have shown the danger of assuming that Te behaves analogous to other

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chalcogens (Chivers and Laitinen, 2015). Like S and Se, Te occurs in four main formal

oxidation states in aqueous solution: -II, +II (least stable and not known naturally), +IV and
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+VI. The +IV and +VI may coexist in the same solution due to slow reaction kinetics of
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aqueous Te oxidation and reduction (Filella and May, 2019). Reduced Te compounds (formal
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oxidation state -II and elemental Te) are typically poorly soluble; for example, the solubility

product (log Ksp ; reaction 2.1) for silver telluride (hessite) is -71.7 (Chen et al., 2002):
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Ag 2 Te(𝑠) ↔ 2Ag + (𝑎𝑞) + Te2− (𝑎𝑞), 𝐾sp = [Ag + ]2 [Te2− ] (2.1)

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Nonetheless, cadmium telluride, bismuth telluride and elemental Te were shown to be

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sparingly soluble in ambient conditions by Bonificio and Clarke (2014), diffusing across an

agar plate by a poorly understood mechanism.

The simplest Te anion is telluride (Te2-). Unsurprisingly, the Te2- anion (2.21 Å) has a larger

radius than the selenide (Se2-, 1.98 Å) and sulphide (S2-, 1.84 Å) anions. The difference in

radii is 11% for Se2- but 20% for S2-, exceeding the 15% limit of the Goldschmidt rule, and

meaning that Te2- substitution for S2- involves significant structural strain (Blundy and Wood,

1994; Shannon and Prewitt, 1969); yet sulphide minerals commonly can incorporate mg/kg

levels of Te (see Table 2). Additionally, as is the case for other p block elements, the hydride

(hydrogen telluride, H2 Te(g)) is volatile (Cooke and McPhail, 2001; Grundler et al., 2013),
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although, unlike Se, Te does not readily form a volatile chloride (Te 2+Cl2 ) when heated to

200°C in the presence of HCl with pH below 0 (Chen et al., 2016). Tellurium atoms often

polymerise to form more complex polytelluride anions with formal oxidation states between -

II and 0; the simplest aqueous polytelluride ion is the linear Te 2 2- ditelluride ion (Brugger et

al., 2012; Ruck and Locherer, 2015; Singh and Sharma, 2000). In minerals, Te participates in

varied forms of intermetallic bonding in tellurides (Bindi and Biagioni, 2018; Helmy et al.,

2007; Moëlo et al., 2008), for instance forming Te–Ag bonds in hessite; and Te–Au and Te–

Te bonds in calaverite (Figure 3). Te–Te bonds have metallic character, and metal–Te bonds

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tend to have strong covalent character due to the small difference in Pauling electronegativity

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between Te (2.1) and many metals such as Cu (1.90), Ag (1.93) and Pt (2.28). The non- metal

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O, by comparison, has a higher electronegativity of 3.44, allowing Te 4+ and Te6+ to form
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ionic bonds to O (Figure 3). Geometric arrangements of Te–O bonds around a Tem+ centre

form [Tem+On ]m-2n oxyanions (Christy et al., 2016a). Tetravalent Te has a stereochemically
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active lone electron pair, and as a result forms a variety of distorted (hemidirected)

coordination polyhedra (Christy and Mills, 2013), e.g., [Te 4+O 3 ]2-, [Te4+O4 ]4- and [Te4+O5 ]6-;
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sometimes there is more than one coordination in the same structure (Missen et al., 2019). In
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contrast, Te6+ lacks a lone electron pair, and occurs exclusively in minerals as Te6+O6
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octahedra (Christy et al., 2016a; Mills and Christy, 2013) (Figure 3). The structural diversity
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of Te–O compounds is further discussed in the following section.

3. TELLURIUM MINERALOGY

As a chalcophile element (Christy, 2018), Te typically occurs in sulphide ore deposits with

other chalcophile elements such as Ag, Cu and Pb (see Table 2). Rather than forming

separate telluride minerals, which tend to be minor phases in most deposits, the bulk of the

primary Te is typically found associated with sulphides, i.e., Te substitutes for S in common

sulphide minerals such as chalcopyrite, covellite, galena, pyrite, pyrrhotite and

sphalerite (Brugger et al., 2016; Dill, 2010; Hattori et al., 2002; Simon and Essene, 1996;
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Vikentyev, 2006). Pyrite is the most studied host sulphide for Te (Cook et al., 2009a;

Deditius et al., 2010, 2014; Dmitrijeva et al., 2020; Keith et al., 2018; King et al., 2014). The

mechanisms of Te incorporation in pyrite are complex and dynamic, involving for example

the preferential incorporation of Te on the (1 1 0) pyrite surface (Chouinard et al., 2005).

Tellurium minerals form in a variety of geological environments (see Section 4.2). As

previously discussed, Te mineralogy is the most ‘anomalously diverse’ of all elements

despite its low crustal abundance (Christy, 2015). As of 2020, the International Mineralogical

Association (IMA) recognises more than 180 Te minerals (Pasero, 2020), comprising almost

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equal numbers of primary (oxidation states almost entirely#1 -II to 0) and secondary

(oxidation states +IV and +VI) minerals. Important Te minerals are listed in Table 1, and a
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full current list is provided in Supplementary Table 2.
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Primary minerals form the bulk of Te minerals by weight/natural abundance. Gold and/or Ag
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tellurides are the most important primary Te minerals (See also Table 1). There are fourteen

Au–Te minerals, the most common being calaverite (AuTe 2 , Figure 1a), krennerite
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(Au3 AgTe8 , Figure 1b), sylvanite [(Au,Ag)2 Te4 , Figure 1c] and petzite (Ag3 AuTe2 ); and
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twenty-two primary Ag–Te minerals, the most common of which is hessite, Ag2 Te.
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Elemental Te is also a primary mineral in a few deposits (Figure 1d). There are 36 Bi–Te
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minerals (29 primary and 7 secondary minerals)#2 . Primary Bi–Te minerals are abundant in

some deposits (Ciobanu et al., 2009), for example tetradymite (Bi2 Te2 S) is the main Te ore

mineral in the Dashuigou deposit, China (Mao et al., 2002). Reliable thermodynamic data are

available for only a handful of telluride minerals, including calaverite (Mills, 1974) and two

Pt telluride minerals (Olivotos and Economou-Eliopoulos, 2016).

Secondary Te minerals develop in the topmost reaches of deposits, where primary minerals

come into contact with oxygenated groundwaters (Dill, 2010; Williams, 1990). Although

secondary minerals of some elements are prevalent enough to form economic deposits (e.g.,
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non-sulphide Zn deposits; Boni et al., 2003; Hitzman et al., 2003), secondary Te minerals are

rare and occur only in sub-economic amounts. Additionally, obtaining thermodynamic data

for these minerals is near impossible because of the difficulty in obtaining sufficient amounts

of pure material; synthesis usually leads to fine-grained mixtures.

Figure 4 shows the structural diversity of Te4+–O minerals, including isolated Te4+On

polyhedra, and Te4+On polyhedra linked in non-cyclic finite units, infinite chains, infinite

layers and infinite frameworks. This diversity explains the large amount of tellurite minerals,

and is due to the flexible and asymmetric coordination environment of the Te 4+ ion, which

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results from its lone electron pair (Christy and Mills, 2013). Similar structural diversity, from

units to frameworks, is possible for Te6+–O minerals, although most tellurate minerals
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contain Te6+O6 octahedra isolated from each other, with much of the structural diversity
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driven by the varied crystal chemistry of associated cations like Cu2+ (Christy et al., 2016b).
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Cyclic finite units of TeO n polyhedra are not yet known in any Te4+ or Te6+ mineral (Christy

et al., 2016a).
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4. TELLURIUM DISTRIBUTION AND ORE DEPOSITS

4.1 Overview of tellurium distribution in the Earth’s crust

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Tellurium is much more abundant in the solar system – 2.28-2.32 mg/kg Te based on C1

chondrite (Anders and Grevesse, 1989; Lodders, 2010) – than in the Earth’s crust (5 µg/kg).

The low crustal abundance of Te results from three processes active during the Earth’s

formative years. First, the Earth formed from Te- and other volatile-depleted chondritic

meteorites (Braukmüller et al., 2019). Second, volatile Te compounds such as hydrogen

telluride (H2 Te) formed and were subsequently lost to outer space during accretion (O'Neill

and Palme, 2008). Finally, Te acts as a siderophile under highly reducing conditions,

resulting in its sequestration with metallic Fe and Ni in the Earth’s core (Rose-Weston et al.,

2009; Wang and Becker, 2013). Hence, most Te in the crust is thought to have been added in
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a ‘late veneer’ (Wang and Becker, 2013), which over geologic timescales has differentiated

into the characteristic uneven distribution of Te known today.

The mobility of Te from the mantle to the atmosphere can be grouped according to prevalent

physical, geochemical and biochemical processes (Figure 5). Major Te sinks include mineral

deposits, weathered rocks, soils, and sediments, with the processes governing the interplay

between these sinks further discussed in Section 7.1. Tellurium is generally below the level of

ng/m3 in airborne particulates (Belzile and Chen, 2015), locally higher near Te-rich areas due

to release of volatiles. Tellurium is also highly depleted in seawater (<2 ng/L) and surface

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freshwater (<20 ng/L) compared to its crustal abundance (Table 3) (Belzile and Chen, 2015;

Emsley, 2011; Gil-Díaz et al., 2019a; Wedepohl, 1995). This is due to the strong sorption of
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Te(IV/VI) oxyanions onto mineral surfaces (Section 5.2; Qin et al., 2017), and as a result, Te
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tends to be enriched in soils (average around 35 µg/kg) (Figure 5); Te is particularly enriched
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locally near Te deposits and in ferromanganese nodules on the ocean floor (Baturin, 2012).

Ferromanganese nodules contain on average ~1 mg/kg Te, i.e. three orders of magnitude
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higher than the average crustal concentration, with some nodules containing over 200 mg/kg
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(Figure 5; Baturin, 2012; Hein et al., 2003). Elevated levels of Te are also found in red beds
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and black shales. Reduction spheroids in red beds (British Isles Triassic, Parnell et al., 2016;
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worldwide Mesoproterozoic, Parnell et al., 2018) commonly display average enrichment to 1-

10 mg/kg, and often contain micron-scale grains of telluride minerals. Neoproterozoic black

shales from the Gwna Group in the British Isles contain up to 30 mg/kg Te (Armstrong et al.,

2018).

Volcanoes are another source of environmental Te, where volatile forms of Te (e.g., H2 Te(g))

are released through eruptions, quiescent degassing (e.g., fumaroles), or hydrothermal

activity. For example, Te occurs at 10-1000 mg/kg levels in volcanogenic sulphur (Figure 5;

Yu et al., 2019). The high temperature (~600 ˚C) fumaroles at the Avacha Volcano,

Kamchatka, Russia, contain up to 15.9 mg/kg Te (Okrugin et al., 2017) (Table 3), and native
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Te has been identified in fumarolitic deposits from Vulcano, Italy (Fulignati and Sbrana,

1998). Deep-sea black-smoker massive-sulphide and volcanogenic-sulphur deposits typically

contain Te enriched by four orders of magnitude compared to average crustal levels (Butler

and Nesbitt, 1999; De Ronde et al., 2015; Greenland and Aruscavage, 1986; Yu et al., 2019).

Tellurium is also enriched in organic-rich rocks and coals (Belzile and Chen, 2015), with

concentrations up to 2 mg/kg in the pyritic coals of Brora, Scotland (Bullock et al., 2017).

Tellurium stored in coal is subsequently released into the atmosphere through the burning of

coal to produce energy (see Figure 5). There are relatively few studies on the Te content of

f
oo
crude oil and natural gas. Green (2011) calculated that 4 to 220 tonnes of Te were processed

during crude oil refinement in 2010, and <100 tonnes of Te processed during natural gas
pr
refinement, though the average amounts in each source are likely to be <1 mg/kg. Parnell et
e-
al. (2015) used pyrite Te levels as a proxy for Te content of natural oil reservoirs. The
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average Te content of pyrite associated with biodegraded palaeo-oil reservoirs is in the 100s

of µg/kg, as opposed to less than 30 µg/kg for other pyrites in central England (Parnell et al.,
al

2015).
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4.2 Tellurium ore deposits

u

4.2.1 Overview
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Tellurium is produced from only a handful of localities, and no deposit is currently mined

solely for Te. For instance, Te is recovered as a by-product of Au mining from the Kankberg

mine in Sweden (Goldfarb, 2014; Goldfarb et al., 2017), which has local epithermal- like

mineralisation in a volcanogenic massive sulphide district; and together with Au from the

epithermal vein deposits of Dashuigou and Majiagou in the Sichuan and Shaanxi provinces of

China (Mao et al., 2002). Additionally, the company Deer Horn Capital expects to begin

production of Te together with Au and Ag from the Deer Horn area of British Columbia,

Canada. The average Te grade at Deer Horn is 118 mg/kg Te, with an expected total amount
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of 67 tonnes recoverable (Meintjes et al., 2018). Other major producers of Te are the United

States, Canada, Peru and Japan (Anderson, 2019; Emsley, 2011). Although it is rarely

recovered, Te is enriched (100’s of µg/g to wt.%) in many base- and precious- metal deposits.

The largest reserves based on the amounts of Te produced by Cu mining are in China

(6,600 metric tons), Peru (3,600 metric tons) and the United States (3,500 metric tons)

(Anderson, 2019). Nonetheless, the disconnect between relatively large Te reserves and the

relatively small amounts actually produced means that Te is classified as a critical mineral

commodity (USDOI, 2018).

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The most important deposit types are of magmatic and hydrothermal origin. Note that in this

and the following sections, we list only the most Te-rich deposits, or those where Te is an
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important constituent of the economic mineral assemblage. Tellurium enrichment occurs in
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association with Au and/or Ag in many (usually hydrothermal) ore deposits, and with
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Platinum Group Minerals (PGMs) in a smaller number of deposits (usually magmatic, e.g.

Ciobanu et al., 2006; Keith et al., 2018; Pals et al., 2003). Several magmatic Copper–Nickel–
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Platinum- Group-Metal (Cu–Ni–PGM) sulphide deposits (e.g. Noril’sk (Genkin and

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Evstigneeva, 1986) and Kola Peninsula (Subbotin et al., 2019) in Russia; Bushveld in South
u

Africa (Kingston, 1966); and Sudbury in Canada (Dare et al., 2014)) are enriched in Te (e.g.,
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up to 150 mg/kg in chalcopyrite-rich massive sulphide ores from Sudbury; Dare et al., 2014).

The major sulphide minerals in Cu–Ni–PGM deposits are pyrrhotite, pentlandite and

chalcopyrite, which may host Te themselves (Table 2), although Te-rich Cu–Ni–PGM

deposits tend to contain small amounts of tellurides (Holwell et al., 2017). Even though Cu–

Ni–PGM sulphide deposits are the only non- hydrothermal Te deposit type, they host some of

the larger Te reserves.

Outside of magmatic deposits, the majority of Te deposits are hydrothermal in nature,

encompassing the following deposit types (Goldfarb et al., 2017); numbers in square brackets

refer to locality number in the map shown in Figure 6:

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 Epithermal deposits, e.g. Cripple Creek [49], Colorado, USA (Kelley et al., 1998;

Thompson et al., 1985), Emperor [4], Fiji (Pals and Spry, 2003; Pals et al., 2003),

Moctezuma mines [56], Mexico (Deen and Atkinson Jr, 1988) and Săcărâmb [37],

Romania (Ciobanu et al., 2004).

 Orogenic gold deposits, e.g. Sunrise Dam [78], Australia (Sung et al., 2007, 2009) and

Ashanti [13], Ghana (Bowell, 1992).

 Volcanogenic Massive Sulphide (VMS) deposits; Ural Mountains [28], Russia is by

far the best described (Vikentyev, 2006).

f


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Iron Oxide-Copper-Gold (IOCG) deposits, e.g. Olympic Dam [1], Australia (Rollog et

al., 2019).

 pr
Porphyry deposits, e.g. Almalyk [19], Uzbekistan (Cheng et al., 2018) and Mount
e-
Milligan [74], British Columbia, Canada (LeFort et al., 2011).


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Intrusion-related Au deposits, e.g. Dongping Au-Te field [79] in Hebei, China

(Sillitoe and Thompson, 1998) and Bjorkdal [81], Sweden (Roberts et al., 2006).
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 Skarn deposits, e.g. Ortosa [49], Spain (Cepedal et al., 2006) and Geodo, [16A] South
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Korea (Kim et al., 2012b).

 Carlin-type gold deposits, e.g. Deep Star [69], Nevada, USA (Fleet and Mumin, 1997;
u
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Heitt et al., 2003) and Zarshuran [31], Iran (Asadi et al., 2000; Mehrabi et al., 1999).

As the majority of Te deposits are hydrothermal, and indeed hydrothermal processes are key

to determining the modern surface distribution of Te, the hydrothermal geochemistry of Te is

discussed in the following section.

4.2.2 Hydrothermal geochemistry of tellurium

In contrast to surface waters, hydrothermal fluids can be enriched in Te, although few data

are currently available. Waters from modern geothermal systems routinely carry Te at the

µg/L level (seawater <2 ng/L), and fluid-inclusions from Te-rich epithermal and porphyry

systems may carry as much as 100’s of mg/L Te (Table 3). Tellurium transport in
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hydrothermal fluids remains “incompletely understood” (Goldfarb et al., 2017) due to the

paucity of experimental data at elevated temperatures. The seminal work of McPhail (1995)

still provides an extensive review of Te thermodynamic data at room temperature, as well as

isocoulombic extrapolations, allowing prediction of Te transport and deposition in waters and

vapours to 350˚C. Experimental studies by Brugger et al. (2012), Grundler et al. (2013) and

Etschmann et al. (2016) provide the only direct evidence of the nature and geometry of Te

complexes at elevated temperatures, as well as updated thermodynamic properties for a

number of key complexes. Filella and May (2019) provide a modern reassessment of the

f
available thermodynamic properties for the Te–O–H system at 25 ˚C; we chose to retain the

oo
properties of McPhail (2005) and Grundler et al. (2013), because (i) the choice of properties

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changes little in the speciation diagram shown in Figure 7A; (ii) these properties allow
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calculations at elevated temperatures; (iii) they are freely available for use (supplementary

material in Ram et al. 2019); and (iv) they more accurately reproduce the few available
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experimental data (Figure 8). A list of recommended thermodynamic properties is listed in

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Table 4.
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Tellurium is generally extremely poorly soluble under reducing conditions, in the form of

tellurides (e.g., Te2- and HTe-) and polytelluride (e.g., Te2 2-) complexes (Figure 7). Brugger et
u
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al. (2012) showed that polytelluride species are stable to high temperatures (599 °C; 800 bar),

and are thus expected to be an important form of Te in basic fluids at high temperatures (e.g.,

CO2-rich fluids) (Cook et al., 2009c; Cooke and McPhail, 2001; Gao et al., 2017; Grundler et

al., 2013; Keith et al., 2018). Brugger et al. (2012) also showed that branched polytelluride

species are stable at low temperature, but only the Te2 2- dimer remains at high temperature.

Under more oxidising conditions, the tellurite complexes H2 TeO 3 (aq), HTeO 3 -, and TeO 3 2-

become increasingly stable as temperature increases (Figure 7). At 300˚C, they are stable

close to the hematite/magnetite buffer (Figure 7), leading Grundler et al. (2013) to propose

that these complexes account for Te transport in some Te-rich systems (e.g., porphyry-
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epithermal systems). In situ XAS measurements by Grundler et al. (2013) showed that these

tellurite complexes share a trigonal pyramidal [TeO 3 ] geometry (with Te at the apex and the

three O atoms at the vertices), and the electron lone pair above the pyramid. The one-sided

geometry of Te4+ complexes plays a key role in their interaction with other species. In general,

Au and Te tend to have higher solubility in basic fluids (Brugger et al., 2012; Figures 7,8),

meaning that alkaline and silica-undersaturated host rocks support more efficient transport

and enrichment of Te and Au (Smith et al., 2017). In contrast to S and Se, Te can form

complexes with halides (metal- like behaviour). Etschmann et al. (2016) showed that the

f
square pyramidal [TeCl4 (aq)] complex occurs in very acidic brines, but this complex is likely

oo
to play a minor role in natural environments. Figure 7 also illustrates that tellurate complexes

pr
[typically octahedral, e.g. H6 TeO 6 (aq)] exist only at low temperature in the presence of
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significant amounts of molecular oxygen, and hence are important only in (near)-surface

environments.
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An important aspect of the hydrothermal geochemistry of Te is the fact that Te partitions

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strongly into the vapour phase upon separation under reducing conditions in the form of
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H2 Te(g), leading to relative enrichment of Te in the vapour phase. These volatile phases are

believed to play an important role in the formation of “bonanza” Au–Te ores in epithermal
u
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systems (Cook et al., 2009c; Cooke and McPhail, 2001; Gao et al., 2017; Grundler et al.,

2013; Keith et al., 2018).

Finally, as a “low-melting point chalcophile metal”, Te will also be enriched together with Ag,

As, Au, Bi, Hg, Sb, Se, Sn, and Tl in melts at temperatures between 500 and 600 °C (Frost et

al., 2002; Tooth et al., 2011). These melts can play a key role in Te enrichment and Au-Ag

mineralisation, either via physical migration (Tomkins et al., 2006), via interaction with

hydrothermal fluids (McFall et al., 2018; Tooth et al., 2008; 2011), or with magmatic vapours

(Okrugin et al., 2017; Yu et al., 2019).

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4.2.3 Distribution of Te deposits

Figure 6 shows the worldwide distribution Te deposits with respect to the underlying crustal

provinces. Localities are itemised in Supplementary Table 3. The majority of Te deposits

occur in Phanerozoic Orogenic belts, which reflects the predominance of epithermal and

porphyry-type deposits, the role of subduction in the formation of these deposits, and the

destruction of these shallow deposits by erosion in older terrains (Kesler and Wilkinson,

2008). This relation is particularly noticeable on the western side of North America and

through the central Orogen provinces of Eurasia. Links between magmatic Cu–Ni–PGM

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deposits and porphyry or epithermal Cu–Au(–Te) deposits have recently been determined,

with Te a useful tracer of the metallogenic continuum between these deposit types (Holwell

et al., 2019). pr
e-
Epithermal Au and Te deposits are some of the largest and highest grade Te resources.
Pr

Epithermal deposits are typically associated with alkaline volcanic rocks, and although

limited in their spatial distribution, they are economically important (du Bray, 2017).
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Tellurium- rich epithermal deposits typically contain abundant tellurides that can host a large
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proportion of the precious metals Au and Ag, as well as heavy metals such as Pb (e.g., altaite),
u

Bi (e.g., tetradymite) and Hg (e.g., coloradoite) (Dill, 2010). Telluride minerals typically
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form late in the paragenesis, after the bulk of associated S has been removed from solution to

form sulphide minerals (Watterson et al., 1977).

Porphyry Cu–Au–Te deposits are mainly found in western North America in the Orogenic or

Extended Crust provinces, and include famous localities like Bingham Canyon, Utah and the

world-class but not yet producing Pebble deposit in remote western Alaska.

Although many orogenic gold deposits contain minor amounts of telluride minerals, a few

have significant amounts of Au bound to Te; these include California’s gold-rush deposits in

the Mother Lode region, and Sunrise Dam in Western Australia (Sung et al., 2009; 2007).
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Note that the genesis of the Te-rich mineralisation in some orogenic Au deposits remains

controversial; the most famous example is the giant Golden Mile deposit, Western Australia

(Bateman and Hagemann, 2004; Shackleton et al., 2003), in which the Te-rich ores have been

attributed to an epithermal- like genesis (Clout et al., 1990), but more recently have been

linked to higher temperature (400˚C) deep magmatic-derived fluids (Mueller et al., 2020).

Tellurium- rich skarns are rare and feature only a handful of examples, spread across several

continents, from Geodo in South Korea (Kim et al., 2012b) to Hedley in British Columbia,

Canada (Ray et al., 1987). Gold tends to be the main commodity in Te-bearing skarns, with

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lower levels of Te associated with skarn Au deposits than in other deposit types.

pr
Volcanogenic massive sulphide (VMS) deposits only comprise a handful of Te-rich examples,

including the Central Asian Au mines of Almalyk, Uzbekistan (Cheng et al., 2018) and Zod,
e-
Armenia (Konstantinov and Grushin, 1970), with the Te associated with the sulphide
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minerals. Kankberg, Sweden produces around 10% of the world’s Te as a by-product of Au

processing and occurs in a VMS region, but the local mineralisation at Kankberg itself is
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epithermal (Goldfarb et al., 2017).

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A handful of Carlin- type and intrusion-type Au deposits also contain small amounts of Te.
u

Aside from a cluster of three Carlin-type deposits in Nevada (Getchell, Meikle and Deep
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Star), which contain up to a maximum of 200 mg/kg Te in the ores, the only other Carlin

deposit with significant Te is the Zarshuran deposit in Iran (Asadi et al., 2000).

Perhaps the most unusual Te deposit is the IOCG deposit of Olympic Dam, Australia – the

world’s largest IOCG deposits. The ore contains ~2.5 mg/kg Te, which translates into

~24,000 tons of Te out of 9,576 Mt ore (Ehrig et al., 2012; Rollog et al., 2019).

Magmatic deposits commonly occur in Shield and Platform geologic provinces, which

encompass areas with relatively flatter terrain than the Orogenic provinces. Montana’s

Stillwater complex is the only exception, being located in the Rocky Mountains on the
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boundary of the Orogenic and Large Igneous provinces. Te whole rock grades at the

Stillwater complex are relatively low, not exceeding 20 mg/kg (Zientek et al., 1990), but still

exceeding baseline Te levels by four orders of magnitude.

4.2.4 Tellurium as a tool in mineral exploration

The enrichment of Te in precious and base metal deposits, coupled with its occurrence in

distinctive zones around ore deposits, means that it may be used as a geochemical tracer in

mineral exploration. Watterson et al. (1977) showed that proximal haloes containing at least

100 µg/kg Te extend up to 10 km away from central orebodies in the United States, with

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proximal concentrations in excess of 10 mg/kg. For instance, the Ely Au-Cu-Ag porphyry

deposit in Nevada also has a Te-containing halo, with an average of 100 mg/kg Te recorded
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in the jasperoids, gossans, and highly altered sedimentary carbonates in the mineralised zone
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of the district. The levels of Te actually increase toward the boundaries of the Ely deposit,
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which in total encompasses around 40 km2 surface area and approximately 60 km3 of Te-

enriched rock (Gott and McCarthy, 1966; Watterson et al., 1977). However, the use of Te in
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geochemical exploration for base and precious metals remains limited, possibly because its
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usefulness is limited by our poor understanding of Te dispersion processes.

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5. TELLURIUM IN THE ENVIRONMENT

5.1 Tellurium in the oxidation zone of primary Te-rich ores

The preservation of secondary minerals in the oxidation zone provides a window into the

dissolution process, allowing us to see secondary minerals that record processes and

conditions when the original hypogene ore is at complete equilibrium with atmospheric

oxygen (Williams, 1990). Overall, an improved understanding of the deportment of Te from

exposed Te deposits will also provide a useful analogy for anthropogenic Te-contamination

(Filella et al., 2019). The first step in generating secondary Te minerals is the release of Te

oxyanions into solution via dealloying of tellurides and/or the oxidation of other primary Te-
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bearing minerals, predominantly sulphides (Table 2). Solubilised Te oxyanions may

precipitate by reaction with other solubilised cations of metals like Fe 3+, Zn2+, Cu2+, UO 22+

and/or Pb2+ (Christy et al., 2016b; Figure 9A), and dealloying often leaves behind the

precious (and less soluble) metals in native form (Okrugin et al., 2014; Figure 9B-D).

Secondary minerals often surround primary minerals as coatings or halos (Figure 1d). The

exact formation conditions and crystallisation processes of individual secondary minerals are

not fully understood, although contributing factors include local chemical environment, pH

and redox potential (Christy et al., 2016b). A lack of thermodynamic data (due in part to the

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lack of synthetic analogues) on Te minerals contributes to the difficulty in understanding

their geochemical formation conditions (Christy et al., 2016b; Filella and May, 2019). Upon
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deeper weathering, as observed above the high- grade Bambolla vein at Moctezuma, Mexico,
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Te occurs predominantly in association with Fe-(Mn)-oxy-hydroxides (Figure 10),
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presumably in sorbed forms (Hayes and Ramos, 2019).

Several studies have addressed the weathering of tellurides under mild (mostly ≤ 220˚C)
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hydrothermal conditions; under these conditions the reaction occurs over a time-scale of
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hours, whereas at ambient conditions months to years are required (Tenailleau e t al., 2006).
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Studied minerals include calaverite, AuTe2 (Zhao et al., 2009; Equation 5.1); krennerite,
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Au3 AgTe8 (Xu et al., 2013; Equation 5.2); and sylvanite, (Au,Ag)2 Te4 (Zhao et al., 2013;

Equations 5.3, showing dissolution of sylvanite, and 5.4 showing the coupled precipitation of

calaverite-I). The oxidation of these tellurides leads to the formation of “mustard gold”

(Figure 9C,D) through dissolution of the parent telluride, subsequent reprecipitation of gold

(or gold-silver alloy) and diffusion of the aqueous Te away from the reaction front in the

solution (Altree-Williams et al., 2015; Zhao et al., 2009; Figure 9B). Although to date these

reactions have been studied in abiotic conditions, in the weathering environment they may be

microbially mediated.
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AuTe2 (𝑠) + 2O2 (𝑎𝑞) + 2H2 O ↔ 2H2 TeO3 (𝑎𝑞) + Au(𝑠) (5.1)

Au3.28 Ag 0.72 Te8 (𝑠) + 8.05O2 (𝑎𝑞) + 7.89H2 O + 0.23HCl(𝑎𝑞)

↔ 3.77Au0.87 Ag 0.13 (𝑠) + 0.23AgCl(𝑠) + 8H2 TeO3 (𝑎𝑞) (5.2)

Aux Ag 2−𝑥 Te4 (𝑠) + 4.5O2 (𝑎𝑞) + 2HCl(𝑎𝑞) + 3H2 O

↔ 𝑥AuCl(𝑎𝑞) + (2 − 𝑥 )AgCl(𝑎𝑞) + 4H2 TeO3 (𝑎𝑞) (5.3)

(1 − 𝑥 )AuCl(𝑎𝑞) + 𝑥AgCl(𝑎𝑞) + (2 − 𝑥 )H2 TeO3 (𝑎𝑞)

↔ (Au1−𝑥 Ag 𝑥 )Te2−𝑥 (𝑠) + HCl(𝑎𝑞) + (1.5 − 𝑥 )H2 O

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+ (2.25 − 𝑥 )O2 (𝑎𝑞) (5.4)

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Some of the best-known secondary Te mineral localities are relatively small epithermal Au

and/or Ag deposits or prospects that are also rich in Te, most notably the Moctezuma mines,
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Sonora, Mexico (21 new Te minerals; Jacobson et al., 2018; see Figure 6, locality 56) and the
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Otto Mountain mines (16 new exclusively Te–O minerals; Christy et al., 2016b), California,

United States; locality 59). The prevalence of these deposits and description of many rare
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secondary minerals on the western side of North America is partly due to avid mineral
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collector interest in the area, meaning that most potential Te mineral localities have been
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extensively explored (Localities 49-71 in Figure 6). Many secondary Te minerals are known
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from just one locality, indicating that highly specific conditions are required for the fo rmation

of some of these phases (Christy et al., 2016a; Kampf et al., 2016).

Despite the prevalence and diversity of secondary Te minerals in some localities, others

display little or no secondary Te mineralisation. For example, secondary Te minerals are

virtually unknown in Australia, despite a number of Te-rich deposits and occurrences

(Figure 6). These deposits occur in old cratons, and have been subjected to weathering since

at least the Mesozoic. This suggests that climate, intensity of weathering, and the metallic

elements in the parent tellurides play an important role in controlling the paragenesis of
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secondary Te minerals. Extreme, prolonged weathering results in the dispersion of Te: deep

weathering generates large amounts of Fe oxides, and these scavenge Te via sorption,

limiting Te solubility and precipitation of secondary Te minerals (Hayes and Ramos, 2019;

Figure 10). In young (<~10 My) deposits, weathering is limited, and although some

secondary Te minerals do form, for example at the Late Miocene (6.9–7.1 My) Aginskoe

deposit, Kamchatka, Russia (Andreeva et al., 2013; Takahashi et al., 2013; Figure 9), the

extent of the secondary Te mineral occurrence is highly limited (Okrugin et al., 2014). Mills

and Christy (2019) dated the secondary U-tellurite minerals schmitterite and moctezumite

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from the Tertiary Moctezuma deposit, Mexico, to 436.5 ±27.1 and 502.8±46.0 (schmitterite)

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and 31.9±0.2 and 274.8±9.1 (moctezumite) ky old. These data suggest that erosion rate and

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climate play a key role in the development and preservation of secondary Te minerals.
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5.2 Tellurium deportment in soils and deeper regolith environments
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In the regolith, immediately following the dissolution of tellurides, Te is generally bound by

sorption onto clay-sized soil particles rather than in minerals (Fairbrother et al., 2012;
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Goldfarb et al., 2017; Hayes and Ramos, 2019). In particular, a strong association has been
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observed between Fe3+ oxide minerals and Te (Qin et al., 2017). Te6+ can be incorporated
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into the structures of Fe3+ oxides, whereas Te4+ tends to be bound more weakly to Fe3+ oxides
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by surface interactions only (Qin et al., 2017). Both Qin et al. (2017) and Hayes and Ramos

(2019) studied Te speciation in tailings piles, meaning that subsequent studies are required to

analyse Te behaviour in different contexts, namely sites which are less contaminated by

anthropogenic activities.

5.3 Anthropogenic tellurium

To date, the major anthropogenic activities involving Te are mining and ore processing (Te

being a by-product of Cu mining in particular) and fossil fuel burning, with emission

concentrations of Te on the order of mg/kg (Figure 5). Given the ~five-fold increase in Te
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usage since 1940 (Nuss, 2019), environmental release of Te from Te-producing processes,

manufacturing Te-bearing industrial products, and subsequent decommissioning of these

products is expected to escalate. Highly toxic Te was also released during the Chernobyl and

Fukushima nuclear disasters; this is covered in the following section.

Currently, the production of CdTe solar cells consumes 40% of global Te output. Other

applications include thermoelectric production (30%), metallurgy/alloys (15%), rubber (5%),

and as a paint or pigment for glasses, enamels, and plastics (Anderson, 2019). Further uses of

Te include manufacture of CdTe quantum dots, readily synthesised by pyrolysis (Murray et

f
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al., 1993). The semiconducting properties of these quantum dots make them useful for a wide

variety of medical (William et al., 2006) and electronics (Kumar and Kumar, 2015)
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applications. CdTe solar panels have their CdTe firmly encapsulated in protective casing,
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meaning that the operational risk of toxic exposure to humans is virtually zero (Biver and
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Filella, 2016).

Nearly 90% of Te is produced by extraction from anode slimes using a series of

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pyrometallurgical and hydrometallurgical operations to remove Se, Te and other precious

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metals (Kyle et al., 2011; Makuei and Senanayake, 2018). The mined ore is subjected to
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milling, flotation, smelting, casting and finally electrolysis in which Te is separated from Cu
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and collects alongside other impurities as tellurides in the anode slime, now enriched 10 5

times compared to the Te concentration in the Cu ore (Makuei and Senanayake, 2018). The

methods for recovering Te from the slimes are determined by chemical and phase

composition and content of associated metals. The tellurides are subjected to

hydrometallurgical treatment either by direct leaching of the raw slimes with sulphuric acid

in the presence of oxygen (pressure) or aeration (atmosphere), or by pressurised leaching in

alkaline solution. Tellurium has also been extracted from lead(–zinc) smelting processes

(Makuei and Senanayake, 2018). Other potential sources for Te extraction are flue dusts and

gases generated during the smelting of bismuth, copper, and gold ores (Kyle et al., 2011).
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Tellurium contamination is commonly a by-product of the processing of Te-bearing raw

materials via Te-rich wastewaters (e.g. Cu-processing, Kagami et al., 2012; Shibasaki et al.,

1992; sulphuric acid production, Zonaro et al., 2017) or emissions from smelters (Chien and

Han, 2009; Perkins, 2011). Mining activities and in particular tailings piles and dams may

also leach Te, especially from Au mining, or even the mining of o ther sulphide deposits, for

instance at the Kawazu mine, Shizuoka, Japan (Qin et al., 2017; see Figure 6, locality 18) and

at Rodalquilar, Spain (Wray, 1998; see Figure 6, locality 34). Tellurium contamination also

results from electronics waste processing and recycling (Shuva et al., 2016). Sorption of Te is

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one method which may be used to remediate a Te-contaminated site or waterway, through

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carbon-based sorbents (Dimpe and Nomngongo, 2017) or biosorption (Piacenza et al., 2017),

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potentially recycling the sorbed Te for future use. In this manner current sources of Te
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contamination may be transformed into future sources of Te (Shuva et al., 2016).
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CdTe has a band gap of 1.45 eV at 300 K, making it perfectly matched to the peak of the

solar spectrum (Wu, 2004), leading to ever- increasing use in the solar panel industry.
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Discarded cadmium telluride (CdTe) solar panels and to a lesser extent, other thermoelectric
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materials like Bi2 Te3 (with specific uses in the electronics industry) are likely to increase the
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anthropogenic output of Te into the environment (Cyrs et al., 2014; Marwede and Reller,
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2012; Zeng et al., 2015). The dissolution of commonly used tellurides must be understood so

that the Te (and associated elements) do not become environmental contaminants (Ramos-

Ruiz et al., 2017b). Dealloying of CdTe occurs most efficiently when the decomposing solar

panels are exposed to oxidising, acidic conditions (Ramos-Ruiz et al., 2017b), with the

reduction rate decreasing monotonically with increasing pH (Biver and Filella, 2016). Unlike

for some chalcogenides, the CdTe dissolution rate does not stop completely under anoxic

conditions, and increases near-linearly with increasing dissolved oxygen. Bi2 Te3 behaves

markedly differently, with no oxygen dependence, and a minimum rate of reduction at pH 5.3

(Biver and Filella, 2016). These two examples show the importance of understanding the
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dissolution regimes of individual tellurides, which may vary markedly from telluride to

telluride.

5.4 Tellurium toxicity

132
Soluble Te oxyanions, the short- lived radioactive isotope Te, and nanoparticles of both

elemental Te and cadmium telluride (CdTe) are the most common toxic forms of Te. Soluble

forms of Te are more toxic than their insoluble counterparts based on the increased

bioavailability of Te from soluble compounds, with toxicity beginning at extremely low

levels for microbes (1 mg/L for tellurite; Presentato et al., 2019). In general, the tellurate

f
oo
anion is 2-10 times less toxic than tellurite (Cunha et al., 2009). Both soluble oxyanions are

most likely to be encountered in contaminated wastewaters or around the weathering zone s of

Te deposits.
pr
e-
For humans, ca. 90% of ingested Te accumulates in the bones (Gerhardsson, 2015), while
Pr

accidental ingestion of microgram amounts o f TeO 2 or Na2 TeO 3 results in body odour and

garlic breath due to the metabolism of the Te 4+ oxysalts to gaseous dimethyl telluride,
al

(CH3 )2 Te (Cunha et al., 2009; Gerhardsson, 2015). Te is expected to be processed in a similar

rn

manner to Se, although unlike Se, Te is not an essential micronutrient (Ogra, 2009;
u

Presentato et al., 2019). No cases of severe Te poisoning have been recorded, though workers
Jo

at a Canadian silver refinery exposed to Te during their work tended to report experiencing

garlic odour when their Te content surpassed 1 µmol Te per mol creatinine (Berriault and

Lightfoot, 2011). The late Alan Criddle (mineralogist at the Natural History Museum,

London) contracted one of the few documented recent cases of tellurium breath following a

visit to the Au–Te deposit at Moctezuma, Mexico. “[He] breathed in dust rich in the

secondary tellurate ochres that occur there. He said his breath stank so bad that dogs would

run howling from him. He found it difficult to live with himself for a few days ” (oral

communication, Ben Grguric).

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One of the most toxic forms of Te is the short- lived, anthropogenically produced, radioactive

isotope, 132 Te. 132 Te is a component of nuclear disaster contamination, and was the third-most

released radionuclide following the Fukushima Daiichi accident (Figure 11), with the total

released activity of 180 petabecquerel (PBq) only less than that from 131 I and 133 Xe (Gil-Díaz,

2019). 132 Te is a β-particle emitter with a half- life of 3.2 days, decaying to 132 I, which itself is

radioactive with a half- life of <3 hours and releases a β-particle to form the stable 132 Xe. The

main toxicity mechanism of 132 Te is the in corpore formation of the thyroid-critical element I,
132 132
as radioactive I. The I is subsequently transported to the thyroid, where it decays,

f
132
causing radiation damage (Drozdovitch et al., 2019). Exposure to Te is believed to have

oo
contributed to the high incidence of thyroid cancers in people directly exposed to radiation

pr
after the Fukushima Daiichi nuclear disaster (Drozdovitch et al., 2019). Additionally, 129m
Te
e-
is also produced in nuclear waste, and was detected in aerosols around Fukushima following

the meltdown (Foreman, 2015; Kanai, 2015) and may also be transported aqueously (Gil-
Pr

129m 129
Díaz et al., 2019b). Te decays via gamma radiation to Te, then follows a similar decay
132 129 129 129
Te, i.e. via two β-particles to form stable
al

path to Xe via radioactive I. However, I

has a half- life of 1.58 × 107 years, meaning 129

I and thus 129m
Te are of considerably less
rn

132 132 129m 132

concern biologically than Te and I, with Te instead finding application as a Te
u

129 129m
signaller (Tagami et al., 2013). The long half- life of I means most Te produced in
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anthropogenic nuclear reactions remains either in storage or in the environment today.

Although less toxic than their soluble and bioavailable oxyanion counterparts, Se and Te

nanoparticles are themselves toxic to many microorganisms. Many Te-resistant

microorganisms actively produce Te nanoparticles from Te oxya nions as a detoxifying

mechanism (see Section 6.3). The toxicity mechanism for non-resistant microorganisms is

(1) believed to be due to reaction of the nanoparticles with intracellular thiols, producing

reactive oxygen species (ROS) causing oxidative stress, much like the oxyanions of Se and

Te (e.g. Zonaro et al., 2015), and (2) may contribute to functional damage of cell membranes
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by changing their composition (Pi et al., 2013). An advantage of nanoparticles over

traditional antimicrobial agents is that their high surface-to-volume ratios provide a larger

area of interaction with biological systems (Zonaro et al., 2015). Selenium and Te

nanoparticles are particularly noted for their antibiofilm ability, as many conventional

antibiotics are more effective against planktonic than biofilm bacteria, a problem which Se

and Te nanoparticles readily overcome (e.g. Zonaro et al., 2015, Vaigankar et al., 2018).

Tellurium nanoparticles produced from Bacillus sp. BZ have been documented for their

antifungal properties against the fungus Candida albicans (Zare et al., 2014). Tellurium and

f
Se nanoparticles could thus have future antimicrobial and/or antifungal roles, with different

oo
morphologies to target different classes of organism (Abo Elsoud et al., 2018; Estevam et al.,

pr
2017; Tran and Webster, 2013; Vaigankar et al., 2018; Zonaro et al., 2015).
e-
A different type of toxic Te-containing nanoparticle comes in the form of CdTe quantum dots,
Pr

which are now known to be cytotoxic (Chen et al., 2012; Lovrić et al., 2005). The formation

of ROS when CdTe nanoparticles interact directly with the plasma membrane, mitochondria
al

and nucleus of cells is a key factor in their toxicity (Lovrić et al., 2005). Other toxicity factors
rn

are the release of soluble Cd2+ ions and the overall intracellular distribution of the quantum
u

dots (Chen et al., 2012). Consequently, CdTe quantum dots must either be firmly
Jo

encapsulated in protective coatings for safe usage (e.g. glutathione ; Zheng et al., 2007), and

CdTe quantum dots have sometimes been replaced by quantum dots formed from other

materials (Li et al., 2009; Pons et al., 2010).

6. BIOGEOCHEMISTRY OF TELLURIUM

Many essential processes in the biosphere are carried out by microbes, which generally

operate on quicker timescales than purely inorganic processes (Ehrlich and Newman, 2009;

Figure 12). Tellurium, unlike the other non-transient chalcogens, is not known to be an

essential biological nutrient (Ogra, 2017), but Te is occasionally found substituting for S in
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the two sulphur-containing amino acids cysteine and methionine (Anan et al., 2013; Ramadan

et al., 1989). Additionally, some microorganisms can respire Te oxyanions (e.g. Yurkov et al.

1996; further detail provided below); this suggests that Te should possibly be included in the

list of biological trace elements. In the environment, microorganisms typically interact with

part per trillion levels of Te, given its extreme rarity – especially in surface waters (see

Section 4.1). Tellurium has more similarity to S than other common biologically active

elements – especially when present in high concentrations, where it can interact with

sulphate-specific enzymes such as sulphate reductases (Ottosson et al., 2010) and transporters

f
(Goff and Yee, 2017). More recently, Te toxicity has been explored at a more detailed

oo
biochemical level, examining the speciation of Te in different biological environments (e.g.

pr
Ogra, 2017; Turner et al., 2012). While there is still conjecture on Te microbiology as applied
e-
to natural (including mineral transformation) contexts, specific aspects of Te microbiology

are well understood, particularly its bioreduction. This has been extensively investigated by
Pr

several researchers including Taylor (1999), Zannoni et al. (2007), Turner et al. (2012) and
al

Presentato et al. (2019).

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Broadly, Te biogeochemistry may be divided into biooxidation, biosorption/bioaccumulation,

u

and bioreduction (Figure 12). Biooxidation typically results in species which are more
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soluble and toxic than their (usually solid) precursors. Coping mechanisms for dealing with

high concentrations of Te oxyanions include biosorption, as well as bioprecipitation and

biovolatilisation, which are both forms of bioreduction.

6.1 Biooxidation (bioleaching)

Although there is no current evidence for direct environmental biooxidation of Te, recent

characterisation of ‘Se-oxidising bacteria’ and their role in biogeochemical Se cycling

(Nancharaiah and Lens, 2015) suggests that there may be ‘Te-oxidising bacteria’ in certain

Te-rich (micro)-environments. Se-oxidising bacteria are mostly chemautotrophs, often

thiobacilli. Biooxidation processes for Se are typically 3-4 times slower than reduction,
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meaning that biologically mediated processes alone result in locally greater amounts of

reduced Se species (Nancharaiah and Lens, 2015). Se oxidisers may themselves be capable of

oxidising Te and tellurides to release Te oxyanions back to the environment, but to our

knowledge this potential process has not been studied.

Environmental oxidative processes initiated by microbes are commonly caused by ‘indirect’

mechanisms. One common way metals are released from insoluble minerals in local (micro-

)environments is that the bacteria use an ‘inert’ substrate to grow, and EPS or other biogenic

molecules produced as the colony grows slowly dissolve the surface of the

f
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substrate (Fairbrother et al., 2009; Reith et al., 2009; 2019). Another common pathway occurs

by the production of an oxidant in situ. Only a handful of acidophilic chemolithotrophic

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bacteria – all S- and/or Fe-oxidisers that produce inorganic oxidants as a by-product of their
e-
metabolism – have been studied for their oxidising behaviour applied to Te compounds, with
Pr

almost all of these studies aiming to enhance bioleaching (Choi et al., 2018; Climo et al.,

2000a; 2000b; Guo et al., 2012a; 2012b; Kim et al., 2015). Bioleaching is an attractive
al

method for extracting metals from sulphide ores as it uses gentler chemicals than traditional
rn

leaching (Khaing et al., 2019). The leaching bacteria do not directly oxidise Te, but instead

Fe-oxidising bacteria oxidise Fe2+ to Fe3+ ions. In the presence of S-oxidising bacteria, which
u
Jo

tend to produce pH- lowering H+, the Fe3+ ions are then able to oxidise tellurides, releasing the

constituent metals into solution (Climo et al., 2000b). Equation 6.1 shows the

thermodynamically favourable (log K = 25.7 at 25°C, increasing to 29.0 at 60°C) oxidation of

calaverite by (biologically produced) ferric ions:

AuTe2 (𝑠) + 8Fe3+ (𝑎𝑞) + 6H2 O ↔ Au(𝑠) + 2H3 TeO3+ (𝑎𝑞) + 6H + (𝑎𝑞) + 8Fe2+ (𝑎𝑞) (6.1)

The most common S- or Fe-oxidising bacteria are capable of Te ore bioleaching, as discussed

in the following papers:

 Acidothiobacillus ferrooxidans (Choi et al., 2018; Kim et al., 2015)

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 Leptospirillum ferrooxidans (Climo et al., 2000b)

 Thiobacillus ferrooxidans (Climo et al., 2000b; Guo et al., 2012b), T. thiooxidans, T.

caldus (Climo et al., 2000b)

In conclusion, in natural environments, Te and tellurides may be oxidised either inorganically

(e.g. in the presence of an oxidant like Fe 3+) or organically (by as yet-uncharacterised Te

oxidisers). Currently, inorganic oxidation of tellurides is the best-defined way of releasing Te

to the environment, but the oxidants may be produced by biological means; Fe and S

oxidisers are both capable of leaching Te from tellurides in anthropogenic contexts. To date,

f
oo
no microorganism has been described as purposefully dissolving tellurides or metallic Te via

a direct biooxidative process (Bonificio and Clarke, 2014).

6.2 Biosorption
pr
e-
Biosorption of Te is typically a precursor to bioreductive or bioaccumulative processes, as
Pr

microorganisms remove (soluble) Te from the environment in a process which begins with

the interaction of EPS with Te oxyanions (Figure 12). The biosorption mechanisms of soluble
al

Te oxyanions are not fully understood. One pathway for E. coli involves the tellurate anion
rn

entering E. coli cells via the SulT-type sulphate transporter CysPUWA (Goff and Yee, 2017).
u

Removing the CysPUWA transporter in mutant strains of E. coli resulted in the accumulation
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of less cellular Te, and higher resistance to Te compared to the wild-type strain (Goff and

Yee, 2017). The tellurite anion appears to enter cells via different transporters, e.g. phosphate

transporters move tellurite into E. coli (Borghese et al., 2016a). Tellurite enters Rhodobacter

capsulatus cells via acetate permease RcActP2, and expressing RcActP2 of R. capsulatus

results in a fourfold increase in the rate of tellurite uptake in E. coli (Borghese et al., 2016a).

In case of fatal Te poisoning, Te may be bound in the dead microorganism’s biomass,

preventing it from interacting with other microorganisms. There is little prior literature

examining the biosorption of Te as a biochemical process, other than acknowledging that it is

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a precursor to bioreduction (Section 6.3) and bioaccumulation (Section 6.4). More commonly,

biosorption (followed by bioaccumulation) is simply discussed as a method of bioremediation

of areas Te-contaminated areas (Piacenza et al., 2017; see Section 6.5).

6.3 Bioreduction

Tellurium bioreduction comes in two main forms, namely bioprecipitation and

biovolatilisation, with the former being the more common Te detoxification mechanism.

Bioprecipitation of Te oxyanions to metallic Te was first noticed over a century ago ; indeed,

the black precipitate produced remains in use to test for the presence of certain Te-resistant

f
oo
strains (Corper, 1915; King and Davis, 1914). Biovolatilisation of Te oxyanions was also first

noticed in the 19th century due to the potent smell of volatile Te compounds. The conversion
pr
of Te oxyanions to alkylated, gaseous Te compounds is mediated by S-adenosyl- methionine
e-
(SAM), as described by the Challenger mechanism (Basnayake et al., 2001). Early
Pr

experiments suggesting that S-adenosyl methionine (SAM) would bind to a telluro- methylase

enzyme (TehB) as part of the volatilisation process (Liu et al., 2000; Presentato et al., 2019)
al

were verified by the crystal-structure determination of TehB isolated from E. coli

rn

(Choudhury et al., 2011). Simplified versions of the two main bioreduction types are given
u

here using the soluble tellurite anion as the starting material:

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𝐁𝐢𝐨𝐩𝐫𝐞𝐜𝐢𝐩𝐢𝐭𝐚𝐭𝐢𝐨𝐧 𝐨𝐯𝐞𝐫𝐚𝐥𝐥 (𝐮𝐧𝐛𝐚𝐥𝐚𝐧𝐜𝐞𝐝): 𝐓𝐞𝐎𝟑𝟐− (𝒂𝒒) ↔ 𝐓𝐞𝟎 (𝒔) (𝟔. 𝟐)

𝐁𝐢𝐨𝐯𝐨𝐥𝐚𝐭𝐢𝐥𝐢𝐬𝐚𝐭𝐢𝐨𝐧 𝐨𝐯𝐞𝐫𝐚𝐥𝐥 (𝐮𝐧𝐛𝐚𝐥𝐚𝐧𝐜𝐞𝐝): 𝐓𝐞𝐎𝟑𝟐−(𝒂𝒒) ↔ (𝐂𝐇𝟑 )𝟐𝐓𝐞(𝒈) (𝟔. 𝟑)

The importance of determining the mechanism of tellurite toxicity is growing as

anthropogenic uses of Te increase (Ottosson et al., 2010); as a result, Te bioreduction has

entered a scientific ‘Renaissance period’ over the past decade (Goff and Yee, 2017;

Presentato et al., 2019; Turner et al., 2012). Figure 12 shows our summary of the currently

known and postulated biogeochemical processes for Te.

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6.3.1 Mechanism of Te bioprecipitation

Bioprecipitation provides a method for removing toxic soluble Te oxyanions from the

environment, depositing Te as (relatively) inert nanoparticles (Figure 12). The environmental

fate of these nanoparticles is not well understood, with a paucity of studies on Te

nanoparticles in the environment. Tellurium-resistant microorganisms are in general not

adversely affected by the nanoparticles they produce, even though the nanoparticles

themselves are toxic for many microorganisms (Presentato et al., 2019). Bioprecipitation can

occur as a result of microorganisms respiring Te oxyanions in anaerobic respiration processes:

f
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some microorganisms are able to use either the tellurite or tellurate anions as terminal

electron acceptors. Under anoxic conditions, both Bacillus selenitireducens and

pr
Sulphurospirillum barnesii are capable of respiring the Te oxyanions anaerobically, turning a
e-
fatal concentration of Te oxyanions for many microorganisms into an evolutionary advantage
Pr

(Baesman et al., 2007).

Microorganisms capable of reducing the oxyanions of Te occur in a variety of extreme

al

environments, and a selection of the most important are listed in Table 5. A community of
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123 separate Te-resistant bacteria was isolated from the Antarctic peninsula (Arenas et al.,
u

2014), where the resistance to Te oxyanions is thought to be endowed by cross-resistance to

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other ROS generators like UV light. Other Te-resistant microorganisms were isolated from

the extreme high pressure and temperature environment of the Juan de Fuca Ridge black

smoker field, in the depths of the Pacific Ocean (Maltman et al., 2016; 2017). Tellurium and

selenium reducing bacteria are thought to have a symbiotic relationship with the tube worms

which they associate with near the Juan de Fuca Ridge black smoker field (Maltman et al.,

2016; 2017). Vent chimneys are a rich natural Te source (see Table 3), therefore

microorganisms from these environments are more likely to be Te resistant (Bonificio and

Clarke, 2014). Similar communities of Te oxyanion-reducing bacteria occur in a variety of

anthropogenically contaminated sites (Chien and Han, 2009; Kagami et al., 2012; Qin et al.,
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2017; Zonaro et al., 2017; Table 5). Highly saline lakes or springs like California’s Mono

Lake (Figure 12; Baesman et al., 2006; 2007; 2009) or Iran’s Neidasht spring (Etezad et al.,

2009; Soudi et al., 2009) also harbour Te-resistant organisms. The diversity of these localities

shows that bacterial communities with varying degrees of Te resistance (for instance,

different rates of reduction and minimum inhibitory concentrations) exist in a large variety of

terrestrial environments.

The majority of microorganisms capable of reducing Te oxyanions are Gram- negative

bacteria, along with some alpha-Proteobacteria, Gram-positive bacteria (Presentato et al.,

f
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2016) and fungi (Abo Elsoud et al., 2018; Gharieb et al., 1999). Interestingly, as well as

containing more representative species which can reduce Te oxyanions, Gram- negative
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bacteria are in general more susceptible to Te oxyanion (especially tellurite) toxicity (Castro
e-
et al., 2008), as the peptidoglycan-based cell wall of Gram-positive bacteria is better able to
Pr

prevent Te oxyanions from entering the cells.

The Gram- negative Te-sensitive E. coli was used in studies of how non-Te resistant
al

microorganisms cope with high levels of soluble Te (e.g. Wang et al., 2011). Some strains of
rn

E. coli have higher levels of resistance to Te oxyanions than others, and genes encoding
u

resistance in other microorganisms have been expressed successfully in E. coli – giving the
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modified E. coli greater resistance to Te oxyanions (e.g. Castro et al., 2009). The effects of

elevated tellurite in E. coli include decreased dNADH/NADH (Nicotinamide Adenine

Dinucleotide) dehydrogenase activity, alteration of oxidases, augmented lipid peroxidation,

and Fe–S centre dismantling (Díaz-Vásquez et al., 2015). Exposure to elevated levels of Te

oxyanions for non-resistant organisms usually proves fatal due to the generation of ROS and

to an unbalancing of the thiol:redox cell buffering system, (e.g. Arenas et al., 2014; Díaz-

Vásquez et al., 2015). One method of reducing tellurite toxicity is by exposure to the less

toxic selenite, which protects E. coli from tellurite damage in certain situations (Vrionis et al.,

2015). Microorganisms which have been conditioned (i.e. pre-exposed to low level
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concentrations of Te oxyanions) also tend to survive better when exposed to larger levels of

tellurite (Presentato et al., 2016).

Like E. coli, other microorganisms also use a NADH-dependent pathway to reduce tellurite

e.g. Salinicoccus iranensis (Alavi et al., 2014). Some Te-resistant microorganisms may have

specific tellurite reductases such as the E3 (dihydrolipoamide dehydrogenase) component of

a pyruvate dehydrogenase of Aeromonas Caviae (Castro et al., 2008; 2009), the zinc- (Zn)

and molybdenum- (Mo) containing enzyme of B. sp. STG-83 (Etezad et al., 2009) and the

two distinct enzymes responsible for Te and Se oxyanion reduction in the ER-Te-48 strain of

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bacteria isolated from the Juan de Fuca Ridge black smokers (Maltman et al., 2017). The

exact structure of specific Te-reducing enzymes is not fully understood. One tellurate
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reductase enzyme in E. coli is likely to contain molybdopterin, as mutants with genes deleted
e-
in the molybdopterin synthesis pathway were unable to reduce tellurate (Theisen et al., 2013)
Pr

– potentially this molybdopterin is the Mo-containing unit postulated by Etezad et al. (2009)

in B. sp. STG-83. Resistance to Te and other metals may also be associated with antibiotic
al

resistance due to co-resistance (i.e. genetic linkage) between the resistance genes (Argudín et
rn

al., 2018).
u

Unsurprisingly, Te oxyanion-reducing bacteria operate best when in the presence of a reliable

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source of organic carbon, typically also an electron donor which facilitates bioreductive

processes (e.g. acetate, lactate and pyruvate). The presence of redox mediator molecules

(generally quinone-based) typically results in greater efficiency of Te oxyanion reduction as

they can quickly transport electrons from cells to oxidised compounds (Ramos-Ruiz et al.,

2016; Van der Zee and Cervantes, 2009). The presence of other anions or molecules may also

alter the rates of Te oxyanion reduction. The pathways for reduction of selenite and tellurite

are typically rather different. Microorganisms that were studied for Te or Se oxyanion

reduction activity alone are expected to also reduce the other, but with different efficiencies

and maximum allowable concentrations of the oxyanions – as shown by comparative studies

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(e.g. Etezad et al., 2009). The reduction rates of tellurite and tellurate anions are generally

also different for this reason. Tellurite is typically reduced faster, as the transition to

elemental Te requires two less electrons per Te atom than the reduction of tellurate. For

instance, the tellurite anion reduction rate by the methanogenic microbial consortium studied

by Ramos-Ruiz et al., (2016) is seven times faster than the rate for tellurate: the reduction of

tellurate to tellurite is the rate-limiting step.

The presence of selenite increases tellurite reduction 13- fold in some bacterial cultures (Bajaj

and Winter, 2014) due to stimulation of tellurite reduction by parallel reduction with selenite.

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Conversely, a mixture of selenite and tellurite has a more prohibitive effect on growth of the

white-rot fungus Phanerochaete chrysosporiumhan than either anion alone, indicating that
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reduction mechanisms are organism-specific (Espinosa-Ortiz et al., 2017). In Shewanella
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oneidensis MR-1, elemental chalcogen precipitates are produced extracellularly for Se, and
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intracellularly for Te (Klonowska et al., 2005).

Some fungi and yeasts are also capable of bioreducing Te oxyanions. Gharieb et al. (1999)
al

found that a species of Fusarium reduced tellurite to elemental Te, and in the same study
rn

noted that Penicillium citrinum reduced tellurite to both elemental Te nanoparticles and also
u

to a volatile Te species (see Section 6.3.3) The previously mentioned white-rot fungus, P.
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chrysosporium, is capable of reducing both Se and Te oxyanions (Espinosa-Ortiz et al., 2017).

Abo Elsoud et al. (2018) analysed six different fungal isolates, and found that all were

capable of producing elemental Te, and new Te-reducing fungi are regularly identified (Liang

et al., 2019). It is likely that many more fungi will reduce Te oxyanions, particularly in

telluriferous areas. Some fungi are particularly noted for their biovolatilisation (see Section

6.3.3).

6.3.2 Morphology of biogenic Te nanoparticles

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The morphology of precipitates formed via microbial reduction of Te oxyanions varies

considerably (Figure 14), and includes both intracellular and extracellular Te nanoparticles,

typically as rods or spheres (e.g. Baesman et al., 2009; Sepahei and Rashetnia, 2009;

Figure 14a). The mediating factors controlling whether the Te is produced intracellularly

and/or extracellularly seem to be organism-dependent, although in general the particles are

produced near the cytoplasm (White et al., 1995). Kagami et al. (2012) found that elemental

Te produced extracellularly can migrate away from the parent cell once produced. The size of

the nanoparticles often exceeds 100 nm (Jain et al., 2014)#3 . Redox mediators tend to promote

f
the production of extracellular Te nanostructures (Borghese et al., 2016b; Ramos-Ruiz et al.,

oo
2016; Wang et al., 2011). Most studies describe Te oxyanion reduction under anoxic

pr
conditions, where the reduction of an alternative oxidant to oxygen is preferable; however,
e-
Presentato et al. (2016) describes the reliable synthesis of Te nanorods by an aerobic

mechanism (Figure 14b). Bioprecipitated compounds aside from elemental Te have only
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rarely been reported, for instance the extracellular Se–Te composite nanoparticles formed by
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reduction of a mixture of selenite and tellurite (Bajaj and Winter, 2014; Figure 13c).
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6.3.3 Mechanism of Te biovolatilisation

u

Alkylation of p block elements (in particular methylation) is a common method by which

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cells metabolise metals (Fatoki, 1997; Frankenberger Jr, 1993), and is a key method of

releasing Te to the atmosphere (Figure 5). Biovolatilisation typically accounts for less than 5%

of total Te oxyanion conversion, with the remainder of the Te bioprecipitated (Figure 12;

Ollivier et al., 2008), i.e. there are no specific Te biovolatilisers. Biovolatilisation produces

volatile, smelly gases containing covalent Te–C or Te–S bonds, the simplest of which is

dimethyl telluride [DMTe; (CH3 )2 Te]. Dimethyl ditelluride (DMDTe; CH3 TeTeCH3 ) is also

common, while dimethyltellurenyl sulphide is rarer (DMTeS; CH3 TeSCH3 ) (see Figure 12;

Ollivier et al., 2008; Zonaro et al., 2015). Organosulphur compounds like dimethyl sulphide

are also produced during the biovolatilisation processes producing organotellurium

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compounds (Ollivier et al., 2008). Biovolatilisation thus results in the release of Te to the

atmosphere. This process may occur in areas naturally rich in Te, or at contaminated

anthropogenic sites.

Specific organisms which display natural volatilising behaviour, listed by alphabetical order

of genus then by species, are listed in Table 2 (DMTe, DMDTe and DMTeS in second

column from right). Penicillium molds are some of the only fungi studied for their

biovolatilising behaviour (White et al., 1995), with Penicillium citrinum biovolatilising as

well as bioprecipitating Te (Gharieb et al., 1999). One unexpected source of Se and Te

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volatiles (along with volatile compounds of five other heavy metals) in certain local areas is

duck manure compost, the microbes in which proved capable of methylating and/or
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ethylating Se and Te (Pinel-Raffaitin et al., 2008).
e-
It is unclear whether biovolatilisation is truly a detoxification measure for microorganisms
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which convert soluble Te to volatile forms, as unlike elemental Te, volatile organotellurium

compounds are not necessarily less toxic than their soluble Te oxyanion counterparts (White
al

et al., 1995). Nonetheless, even if the toxicity is similar, volatile compounds do have more
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chance of migrating away from the microbes, suggesting that this mechanism is overall a
u

detoxification measure (Basnayake et al., 2001). In highly Te-rich areas, the smell of onions
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or garlic may be detected in the air from the action of bioreducing microbes.

6.3.4 Other mechanisms of Te detoxification

Bioreduction is the most common method of Te detoxification, but it is not the only method

by which microorganisms process high levels of soluble Te. Some bacteria (e.g.

Erythromicrobium ezovicum and Roseococcus thiosulphatophilus) have been found to

process Te oxyanions without using a reduction pathway, depending on the source of organic

carbon available (Yurkov et al., 1996). These alternative methods of Te detoxification

include tellurite efflux or complexing (Sepahei and Rashetnia, 2009; Yurkov et al., 1996),
 Journal Pre-proof
with complexing of Te oxyanions being a possible precursor to their bioaccumulation. The

existence of microorganisms that resist high levels of Te oxyanions without using

bioreductive mechanisms adds a further layer of complexity to the biogeochemistry of Te

(Turner, 2001).

6.4 Bioaccumulation

Bioaccumulation begins for Te at the smallest biological level as Te-resistant microbes

absorb soluble Te oxyanions and convert them to elemental Te by bioreduction. Elemental Te

may accumulate in Te-resistant cells as Te nanoparticles or as Te bound in proteins.

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Tellurium nanoparticles are typically produced near cell boundaries (Turner et al., 2012), and

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some are released extracellularly (e.g. Bajaj and Winter, 2014; Borghese et al., 2016b) and

may act as toxins for other microorganisms – in a different fashion to the toxicity mechanism
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for soluble Te oxyanions (e.g. Abo Elsoud et al., 2018). In general, heavy metals and other
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toxins are concentrated up the food chain; plants and animals have higher levels of Te than

the surrounding environment.

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Some onion and garlic family (Allium) plants owe their distinctive smell to organosulphur

compounds – and to lesser extents to organoselenium and organotellurium compounds.

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Although Te conversion in these species is not an essential feature of their metabolism, plants

like Allium sativum are capable of incorporating Te into two usually S-containing amino

acids, cysteine and methionine (Anan et al., 2013), with some plants in the Allium family

containing extreme levels of Te enrichment up to 300 mg/kg (Dunn, 2011). However in

general, Te levels in plants do not exceed 1 mg/kg, even in telluriferous soils (Cowgill, 1988),

and commonly plants contain less than 0.02 mg/kg Te (Dunn, 2011). The flowers of plants

generally contain the most Te, and tree leaves contain more Te than branches (Cowgill, 1988;

Dunn, 2011).
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Bioaccumulation of Te provides one potential sink for Te in the natural environment. The

rarity of Te means that natural bioaccumulation only occurs to a significant extent in areas

with naturally or anthropogenically raised levels of Te. As a relatively reactive element, Te is

unlikely to remain bioaccumulated for long periods of time, especially as biogenically

produced nanoparticles (see below).

6.5 Applications

All of the common biotransformations of Te have some practical uses, which are briefly

discussed in this section. Biooxidation of gold tellurides has become a relatively common

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pre-treatment step in gold mining. Gold tellurides host a significant amount of the gold grade

in many deposits, but traditional leaching using cyanide, thiourea, or ammoniacal thiosulfate
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solutions are not efficient for gold tellurides; thus pre-treatment stages have been introduced
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prior to leaching, the most commonly used being energy intensive high temperature roasting
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(Zhao et al., 2010). Adding a culture of oxidising microbes to Au-telluride ore piles may

allow release of higher amounts of metals than would otherwise be possible (Climo et al.,
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2000a; 2000b), while at the opposite end of the process, adding a culture of reducing
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microbes to waste streams could allow recovery of toxic elements, preventing them from
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becoming pollutants (Ramos-Ruiz et al., 2017a).

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Biosorption of a variety of heavy metals has been discussed as an environmentally friendly

method for their remediation (Alluri et al., 2007; Banerjee et al., 2018; Dhankhar and Hooda,

2011; Gavrilescu, 2004; Piacenza et al., 2017; White et al., 1995). Using either living or dead

biomass to entrap metals from polluted streams is particularly viable for large-scale low-level

contamination, when sorption using more toxic chemicals is less effective (Gavrilescu, 2004).

Currently, such techniques have not been implemented for Te sorption on an industrial level

However, the most likely area of future application involves the biosorption of Te (and Cd)

released from decommissioned CdTe solar panels (Alluri et al., 2007; Dhankhar and Hooda,

2011; Rajwade and Paknikar, 2003). Biosorption may one day be used for both remediation
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of a contaminated area and recycling, by collecting the sorbed nanoparticles and repurposing

them for other uses (Dhankhar and Hooda, 2011; Piacenza et al., 2017). Two studies

published near-concurrently in 2017 both outlined a preliminary design for an Upflow

Anaerobic (granular) Sludge Bed (UASB) for Te biosorption. Both papers theorised that their

model reactor beds could be scaled up to recycle Te-containing wastewaters as nanoparticles

of elemental Te (Mal et al., 2017; Ramos-Ruiz et al., 2017a). The UASBs provide a double

benefit of cleaning the wastewater and also potentially result in a recycled supply of Te. Mal

et al. (2017) found that their model reactor was able to remove 90% of the tellurite from

f
20 mg/L tellurite solutions, with most of this Te associating with the granular sludge as

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elemental Te. 78% of this Te was reclaimed from the sludge by an EPS method. Ramos-Ruiz

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et al. (2017) obtained comparable percentages (83-96%) of continuous removal of Te from
e-
20 mg/L tellurite solutions without a redox mediator to assist in the electron transfer, and

greater than 99.5% efficiency with the redox mediator (riboflavin, better known as vitamin
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B2). Similar UASBs have also been designed and described for Se alone (e.g. Jain et al.,
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2016). More recently, Wadgaonkar et al. (2018a) described a UASB capable of bioreducing

selenite and tellurite simultaneously. Biosorption – and often subsequently, bioprecipitation –

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thus forms an intermediate step in the removal of soluble Te from the environment, and on a
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larger scale may gain prominence in future as a method of removing and recycling Te from
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waste materials (Nancharaiah et al., 2016).

Tellurium and Se nanoparticles can be produced via bioreduction in morphologies that can be

difficult to obtain via inorganic means (Bansal et al., 2012; Zonaro et al., 2017). Biosynthesis

also has environmental advantages, typically requiring lower amounts of toxic chemicals than

alternative methods (Presentato et al., 2016). As well as antimicrobial applications (Section

5.4), the nanoparticles may potentially be used in a variety of highly accurate detecting

applications, such as for detecting hydrogen peroxide (Manikandan et al., 2017; Wang et al.,

2010), chlorine gas (Sen et al., 2009) and Hg2+ cations (Wei et al., 2011). Further applications
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of Se and Te nanoparticles make use of their ability to photocatalytically degrade organic

pollutants such as methylene blue in the presence of sunlight (Vaigankar et al., 2018). Overall,

these applications already show the versatility of Te biotransformations, and we predict that

future study of Te biogeochemistry will lead to many more.

7. A TELLURIUM BIOGEOCHEMICAL CYCLING MODEL

7.1 An integrated Te cycling model – comparison with Se

An integrated Te cycling model is presented in Figure 5, linking inorganic and organic

f
processes. Our Te cycle is based on those known for other elements, especially Se, and on

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our current understanding of the geochemistry and microbial ecology of Te. Elemental

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cycling has long been known for biologically essential elements, most notably the carbon (C),
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nitrogen (N) and sulphur (S) cycles. Even elements which were long assumed to be

geochemically inert are involved in complex biogeochemical cycling (Stolz, 2017), including
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Au and Pt (Reith et al., 2014; 2007). Te is the last non-transient chalcogen (any attempts to
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define such a cycle for polonium (Po) would be essentially meaningless) without a detailed

biogeochemical cycling description, following the description of the Se cycle by Nancharaiah

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and Lens (2015).

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The Te cycle begins with the transformation of Te-rich crustal rock through either

magmatism or hydrothermal processes (Figure 5), leading to the formation of Te-rich rocks

and deposits (Section 4). The ore from these deposits may be processed by mining and

smelting, most likely for the Au or Cu content rather than for recovery of Te itself, or the Te

may be released to the environment by weathering processes, especially if anthropogenic

activities have exposed more of the ore (Figure 5). Weathering and emission of Te to the

environment during mining, usage and recycling/breakdown may lead to solid, aqueous or

gaseous forms of Te, depending on the processes involved. Solid forms include Te sorbed

onto clays and Fe oxides in soils, oxidative dissolution leads to aqueous Te oxyanions, and
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volatilisation (mostly biological, except at high temperatures during earlier smelting or

mining processing steps) leads to gaseous forms of Te (Figure 5). Deposition into sediments

and dissolution into groundwater result in higher Te concentrations than occur in freshwater

and ocean water (Figure 5). Te also sparingly enters biomass through microorganisms,

though as Te is nonessential for life, its intake is incidental compared to the minute but

essential amounts of Se that all organisms must absorb. The breakdown of these organisms

over millions of years leads to the presence of Se and Te in coal at levels greater than their

crustal abundances, and burning coal is one mode of Te and Se release to the atmosphere

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(Figure 5).

The bacterium in Figure 12 shows the biogeochemical processes present for Te in full.
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Nancharaiah and Lens (2015) postulate that Se is cycled between oxic and anoxic
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environments in natural environments, and influences carbon and nitrogen mineralisation
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processes through bacterial anaerobic respiration. As is the case for Te, Se bioreduction

converts Se from soluble Se oxyanions to elemental Se and volatile organo-selenium

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compounds. Selenium oxidisers provide one method of release of Se from elemental Se and
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selenides, allowing solubilised Se to again travel in waterways until a reduction source

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(selenium resistant microbes and soluble inorganic cations which precipitate Se oxyanions) is
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encountered, whereas Te oxidisers are currently only postulated to exist. The relation

between the Te and Se cycles may be even closer, with some microorganisms capable of

acting in similar ways on both Se and Te species – for instance Se and Te reducers both

produce either elemental chalcogen nanoparticles or volatile organochalcogens (Wallschläger

and Feldmann, 2010). In summary, the processes governing the Te biogeochemical cycle are

clear, but the extent to which microbially-catalysed pathways for reduction, oxidation or

other processes predominate in surficial environments is not yet known, and will form the

core of future work on the environmental geochemistry of Te.

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7.2 Tellurium dispersion around Au-Te deposits

In Figure 15, we apply our cycling model to the example of elemental dispersion of Te

around a Au–Te deposit. We have chosen to discuss this example of Te cycling, as (1) Te and

Au are typically found together, in association with metal sulphides; (2) the Au cycle is

already well understood (Rea et al., 2018; Sanyal et al., 2019; Shuster and Reith, 2018),

(3) Te may be used as a pathfinder for Au through application of their linked biogeochemical

cycles, and (4) this is an important analogue for predicting the fate of anthropogenic Te

contamination.

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This model describes the movement of Te and Au through the environment around a buried

Au–Te hydrothermal vein. Gold and Te occur as gold tellurides, along with small Au nuggets,
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‘invisible Au’ associated with other primary minerals, and elemental Te (Sung et al., 2009).
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Once these minerals reach the surface and interact with groundwater within the saprolith,
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they may begin to undergo dissolution reactions, in particular inorganic acidic weathering

(see Section 5.1). Passive oxidation by different classes of microorganisms may also have an
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effect on the release of Au and Te to the soil. As soluble species, Au and Te in surface
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aqueous solutions are toxic to macro- and microorganisms in sufficiently high concentrations.
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Once solubilised, reprecipitation and dissolution reactions occur in a cyclical fashion, and
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other chemical species such as Cu2+, Pb2+, Fe3+, Cl- interact with soluble forms of Te.

Tellurium released into natural waters as tellurite may undergo further oxidation to tellurate.

As mobile Te oxyanions, Te may be transported away from the weather ing zone of the Te

deposit by groundwater. Eventually, Te may be removed from environmental aqueous

solution by three major methods:

(1) Purely inorganic methods (precipitation by a cation, possibly leading to secondary

mineralisation). This scenario is especially prominent if pH levels increase towards neutral

further from weathering sites, lowering the solubility of soluble Te oxyanions.

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(2) Microbial bioreduction (formation of Te nanoparticles or gaseous organotellurium

compounds, especially in areas where the microorganisms display Te resistance). Some

microorganisms have been shown to successfully detoxify both Se and Te oxyanions,

suggesting that this is one area where the Se and Te cycles may overlap (Bajaj and Winter,

2014; Espinosa-Ortiz et al., 2017). The plethora of studies on how microorganisms interact

with soluble Te in controlled laboratory settings gives us an insight into how such

microorganisms might interact with soluble Te in natural environments. Bioprecipitated Te

nanoparticles are relatively reactive, although if they aggregate together the rate of reaction is

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slowed. The elemental Te nanoparticles produced by bioprecipitation may remain insoluble,

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or depending on conditions could be oxidised again to soluble Te species. Alkylated forms of

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Te produced by biovolatilisation, although produced as minority products in bioreductive
e-
processes, can travel as airborne material (although organotellurium compounds are denser

than air, meaning these compounds are unlikely to travel long distances), spreading Te away
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from natural or anthropogenic Te rich areas. Other methods of Te release to the atmosphere
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include anthropogenic methods (e.g. burning Te-containing coal) and the release of Te-

containing volcanic gases.

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(3) Removal of Te and Au from aqueous solutions by macrobiota, although in sufficient

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amounts this may result in health problems for the new host organisms. This effect is most

prominent in metal-rich haloes around ore deposits.

Eventually Te returns to the regolith, either as atmospheric organotellurium compounds

interacting with soils to form aqueous or solid forms of Te, or by release of Te and Au from

their hosts. Microbes and fungi are likely to be involved in these conversion steps, from

where Te may continue its biogeochemical cycle. Thus, through a variety of inorganic and

biological processes, Te may be cycled through the environment, with these cycles especially

active near locally Te-rich areas (e.g. Au mining sites) or anthropogenically contaminated

areas (e.g. Cu refining plants or sulphuric acid factories). We expect that future advances in
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this area will lead to a more complete description of the biogeochemical Te cycle, including

the percentage split between inorganic and biological pathways for the same processes, thus

providing valuable insight into the environmental mobility of a rare, yet important element.

8. CONCLUSIONS

Tellurium biogeochemistry is a fascinating and under-studied area of research.

Tellurium is regularly listed as a critical raw material both due to its increased use in the solar

industry, and to the dependence on other commodities in its supply chain. As Te usage

f
increases and our exposure to Te correspondingly rises, a thorough understanding of the

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geo(bio)chemistry of Te in surface environments is fundamental for supporting the search for

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future sources of Te (geochemical exploration); developing inno vative processing techniques

for extracting Te; and quantifying the environmental risks associated with new anthropogenic
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uses. The present work links existing research in inorganic Te geochemistry and mineralogy
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with the bio(geo)chemical and biological literature towards developing an integrated Te

cycling model.
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A key challenge to understanding the dynamics of Te mobility in the environments in

the quantification of the role of microbes. Although microbes capable of bioreduction of Te

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compounds have been well-studied in laboratory contexts and can be used in bioremediation,

their role in environmental systems currently remains poorly quantified. In particular, it is

noticeable that metallic Te nanoparticles have not been reported from the environment to date.

Similarly, biooxidation of Te compounds has only been observed occurring indirectly, yet it

is likely that direct Te oxidisers exist but have not yet been effectively characterised. Since

Te in present in reduced, insoluble forms in ores, its oxidatio n is the first step in its liberation.

Coupled to both of these processes is the need to better understand the biosorption and

bioaccumulation of Te, in particular, the fate of Te nanoparticles (presumably produced by

Te bioreduction) in the environment. Quantification of these fundamental processes is

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required to decipher the interplay between anthropogenic, geochemical and biogeochemical

processes and its role on the distribution and mobility of Te in surface environments.

ACKNOWLEDGEMENTS

The authors acknowledge support funding provided to OPM by an Australian

Government Research Training Program (RTP) Scholarship, a Monash Graduate Excellence

Scholarship (MGES) and a Monash-Museums Victoria Scholarship (Robert Blackwood). The

authors further acknowledge The Ian Potter Foundation grant ‘tracking tellurium’ to SJM.

f
Further funding support was provided Natural Environment Research Council (UK) grant

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NE/M010848/1 in the Security of Supply of Minerals programme to DJS. The authors would

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like to acknowledge the ARC Research Hub on Australian Copper-Uranium (project number:

IH130200033), funded by the Australian Research Council, BHP Olympic Dam and the
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South Australian Department of State Development; for their support and assistance. We are
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grateful to Brent Thorne (Figure 1), Georges Favreau (Figure 2b), Victor Okrugin (Figure 9a)

and Stefan Ansermet (Figure 10c) for providing images.

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FOOTNOTES
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#1
The only exception to this rule is goldfieldite, Cu10 Te4 S13 , which has Tellurium (IV)
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surrounded by three S atoms.

#2
Note that all numbers of total minerals in this section include overlaps as some Te minerals

have complex chemical compositions. Montbrayite, for instance, has the recently revised

formula [(Au,Ag,Sb,Pb,Bi)23 (Te,Sb,Pb,Bi)38 ; Bindi et al., 2018].

#3
When studying applications for biogenic Te nanoparticles, dimensions less than 30 nm can

be desirable due to the large increases in surface area achievable with a given mass of

nanoparticles, compared to, for example, the same mass of nanoparticles which exceed 100

nm in at least one dimension.

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TABLES

Table 1: Selected Te minerals (including wt% to nearest % of Te for tellurides). A full table
of Te minerals is presented in Supplementary Table 1.

Mineral name Ideal chemical formula Crystal Ideal Wt%

symmetry Te*
PRIMARY (TELLURIDES)
Altaite PbTe Isometric 38 %
Calaverite AuTe2 Monoclinic 56 %
Cervelleite Ag4 TeS Monoclinic 22 %
Coloradoite HgTe Isometric 39 %

f
Empressite AgTe Orthorhombic 54 %

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Frohbergite FeTe2 Orthorhombic 82 %
Goldfieldite Cu10 Te4 S13 Isometric 33 %
Hessite
Kawazulite
Ag2 Te
Bi2 Te2 Se
pr Monoclinic
Trigonal
37 %
34 %
e-
Kostovite CuAuTe4 Orthorhombic 66 %
Pr

Krennerite Au3 AgTe8 Orthorhombic 59 %

Melonite NiTe2 Trigonal 81 %
Montbrayite (Au,Ag,Sb,Bi,Pb)23 - Triclinic 45-50 %
al

(Te,Sb,Bi,Pb)38
Muthmannite AuAgTe2 Monoclinic 46 %
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Nagyágite [Pb3 (Pb,Sb)3 S6 ](Au,Te)3 Monoclinic ~30 %

u

Petzite Ag3 AuTe2 Isometric 33 %

Jo

Rickardite Cu7 Te5 Orthorhombic 59 %

Rucklidgeite PbBi2 Te4 Trigonal 45 %
Stützite Ag5-xTe3 ; Hexagonal
43 %
0.24 ≤ x ≤ 0.36
Sylvanite (Au,Ag)2 Te4 Monoclinic 60-61 %
Tellurobismuthite Bi2 Te3 Trigonal 48 %
Tetradymite Bi2 Te2 S Trigonal 36 %
(ELEMENTAL)
Tellurium Te Trigonal
SECONDARY (TELLURITES)
Emmonsite Fe3+2 (Te4+O 3 )3 ·3H2 O Triclinic
3+
Mackayite Fe (Te4+2 O 5 )(OH) Tetragonal
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Magnolite Hg1+2 Te4+O3 Orthorhombic
Moctezumite Pb(UO 2 )(Te4+O3 )2 Monoclinic
Paratellurite α-Te4+O 2 Tetragonal
Spiroffite Mn2+2 Te4+3 O 8 Monoclinic
Teineite CuTe4+O 3 ·2H2 O Orthorhombic
Tellurite β-Te4+O 2 Orthorhombic
3+ 4+
Zemannite Mg0.5 ZnFe (Te O3 )3 Hexagonal
·(3+n)H2 O; 0 ≤ n ≤ 1.5
(TELLURATES)
Burckhardtite Pb2 (Fe3+Te6+)[AlSi3 O 8 ]O6 Trigonal
6+
Dugganite Pb3 Zn3 (AsO 4 )2 (Te O 6 ) Trigonal

f
Jensenite Cu3 Te6+O6 ·2H2 O Monoclinic

oo
6+
Khinite PbCu3 (Te O 6 )(OH)2 Orthorhombic
6+
Markcooperite Pb2 UO2 (Te O6 ) Monoclinic
Mcalpineite 6+
Cu3 (Te O6 )
6+
pr Isometric
e-
Ottoite Pb2 Te O5 Monoclinic
6+
Quetzalcoatlite Zn6 Cu3 (Te O6 )2- Trigonal
Pr

(OH)6 ·AgxPbyClx+2y
Timroseite Pb2 Cu5 (Te6+O6 )2 (OH)2 Orthorhombic
Xocolatlite Ca2 Mn4+2 (Te6+O6 )2 ·H2 O Monoclinic
al

(MIXED-VALENCE)
Carlfriesite CaTe4+2 Te6+O8 Monoclinic
rn

Tlapallite (Ca,Pb)3 CaCu6 - Trigonal

[Te4+3 Te6+O 12 ]2-
u

(Te4+O3 )2 (SO 4 )2 ·3H2 O

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Table 2: Quantification of amounts of Te associated with common sulphides. Some
measurements are averages across a range of samples, others particular to a specific locality.

Ideal Te content
Mineral name chemical Detail/locality average Reference
formula (mg/kg)
Covellite CuS Average Up to 430 (Dill, 2010)

Chalcopyrite CuFeS2 Average Up to 70 (Dill, 2010)

(George et al.,
Average <1
2018)
Broken Spur vent, (Butler and
45
Mid-Atlantic Ridge Nesbitt, 1999)
Baita Bihor; (George et al.,
1.9

f
epithermal 2018)

oo
Kanmantoo;
(George et al.,
metamorphosed 1.9
2018)
sulphide ore

Galena PbS Average

pr Up to 200 (Dill, 2010)
e-
Pyrite FeS2 Average Up to 70 (Dill, 2010)
Pr

Volcanogenic
massive sulphide
Up to 860, often (Belousov et al.,
average, Yilgarn
less than 2 2016)
Craton, Western
al

Australia
Orogenic average,
rn

Up to 710, often (Belousov et al.,

Yilgarn Craton,
less than 100 2016)
Western Australia
u

Pyrite,
arsenian pyrite FeS2 ,
Jo

(Keith et al.,
and Fe(S,As)2 Carlin average 573
2018)
arsenopyrite and FeAsS
compilation
Epithermal high
(Keith et al.,
sulphidation 343
2018)
average
Epithermal low
(Keith et al.,
sulphidation 600
2018)
average
Epithermal alkaline (Keith et al.,
546
average 2018)
(Keith et al.,
Orogenic average 306
2018)
(Keith et al.,
Porphyry average 26.3
2018)
Pyrite, As- Dongping, China, 4.0-20823 (i.e. (Cook et al.,
FeS2
deficient alkaline epithermal microinclusions 2009a)
 Journal Pre-proof
of tellurides)
Huangtuliang, 3.0-18285 (i.e.
(Cook et al.,
China, alkaline microinclusions
2009a)
epithermal of tellurides)
Hougou, China, (Cook et al.,
2.6-19.6
alkaline epithermal 2009a)

Pyrrhotite Fe1-xS Average Up to 60 (Dill, 2010)

(Cook et al.,
Sphalerite ZnS Average < 0.05
2009b)
Magura epithermal
(Cook et al.,
Au deposit, 16-665
2009b)
Romania

f
oo
pr
e-
Pr
al
u rn
Jo
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Table 3: Concentrations of dissolved Te in geothermal and hydrothermal fluids.

Te
Temperature
Locality concentration Comments Reference
(˚C)
(µg/L)
Three samples
Reykjanes geothermal with chlorinity
(Hardardóttir
system, Iceland, at 284-295 16.5 to 18.5 close to that of
et al., 2009)
1350– 1500 m depth seawater (0.51-
0.53 M).
Lihir geothermal
Lihir water also
system, Papua New (Simmons and
260 Up to 4 contained up to
Guinea, at depth Brown, 2006)
13 µg/L Au.
550 m
Wairakei geothermal
Used as a field (Simmons and
 255

f
system, New Zealand, Up to 0.4
blank sample Brown, 2006)

oo
at depth 950 m
Based on
Pacmanus seafloor hot extrapolations
springs field, Papua from samples (Binns et al.,
New Guinea, at depth
130 m
 55 pr
3 to 18
heavily
contaminated by
2004)
e-
seawater (88%)
233-255 Liquid-vapour
Up to 14,000
(homogenisation T) inclusion
Pr

Au–Te epithermal Unique liquid-

358 340,000 (Wallier et al.,
system of Roşia vapour inclusion
2006)
Montană, Romania Two co-existing
al

5,500 and low-density

ND
180,000 vapour
rn

inclusions
The final stage
Porphyry Cu–Mo–Au of this
stage and transitional
u

mineralizing
quartz–sericite–pyrite (Pudack et al.,
278  23 Up to 670,000 system is a Te-
Jo

stage of the Nevados de 2009)

rich high
Famatina deposit
sulphidation
(northwest Argentina) system
High-
temperature gas
High temperatures condensate
fumaroles at the contained ca. (Okrugin et
Avacha Volcano,  600 Up to 16,000
100 times more al., 2017)
Kamchatka Peninsula, Te than low-
Far East Russia
temperature
condensates
Te in scarcely
hydrothermally
High-sulphidation
altered rocks in
hydrothermal system (Fulignati and
250–520 5000-19,000 correspondence
of the La Fossa volcano Sbrana, 1998)
to the highest-
(Vulcano, Italy) temperature
fumarolic vents
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Table 4: Thermodynamic properties for Te aqueous species, minerals, and vapor species adapted from selected references.

Temperature [ºC]
Reaction Reference
25 50 60 100 150 200 250 300 350
Aqueous Species
H2 Te(aq) + 1.5O2 (g) = H2 TeO3 (aq) 99.06 90.59 87.57 77.09 66.81 58.72 52.21 46.87 42.46 McPhail (1995)
HTe- + H+ + 1.5O2 (g) = H2 TeO3 (aq) 101.70 93.30 90.32 80.10 70.24 62.67 56.75 52.16 48.88 McPhail (1995)
Te2- + 2H+ + 1.5O2 (g) = H2 TeO3 (aq)
Te2 2- + 2H+ + H2 O(l) + 2.5O2 (g) = 2H2 TeO3 (aq)
H3 TeO3 + = H2 TeO3 (aq) + H+ (log K a0 )
113.86
151.77
–2.79
105.04
139.20
–2.43
101.90
139.74
–2.31
91.45
119.47
–1.88
81.36
104.79
–1.46
o f
73.85
93.55
–1.14
68.14
84.83
–0.87
63.89
78.14
–0.62
61.31
73.54
–0.32
McPhail (1995)
McPhail (1995)

o
Grundler et al. (2013)

r
H2 TeO3 (aq) = HTeO3 - + H+ (log Ka1 ) –5.22 –5.57 –5.69 –6.07 –6.39 –6.61 –6.84 –7.17 –7.98 Grundler et al. (2013)
HTeO3 - = TeO3 2- + H+ (log K a2 ) –10.07 –9.89 –9.83 –9.58 –9.29 –9.04 –8.86 –8.84 –9.25

p
Grundler et al. (2013)

-
H6 TeO6 (aq) = H2 TeO3 (aq) + 2H2 O(l) + 0.5O2 (g) -2.77 -1.97 -1.67 -0.58 0.57 1.56 2.42 3.17 3.81 McPhail (1995)
H5 TeO6 - + H+ = H6 TeO6 (aq)

e
7.70 7.40 7.31 7.01 6.81 6.76 6.85 7.14 7.73 McPhail (1995)

r
H4 TeO6 2- + H+= H5 TeO6 - 10.95 10.57 10.46 10.16 10.05 10.12 10.37 10.84 11.72 McPhail (1995)
Minerals
Te(s) + H2 O(l) + O2 (g) = H2 TeO3 (aq)
TeO2 (s) + H2 O(l) = H2 TeO3 (aq) (log K s )
42.6
–4.61

l
38.6
–4.21
P37.2
–4.07
32.3
–3.59
27.4
–3.14
23.5
–2.77
20.5
–2.44
18.0
–2.07
16.2
–1.53
Robie & Hemingway (1995)
Grundler et al. (2013)
AuTe2 (s) (calaverite) + 1.5H2 O(l) + 2.25O2 (g) + H+
= 2H2 TeO3 (aq) + Au +

n a74.4 67.5 65.0 56.4 47.9 41.3 36.0 31.8 28.8 Mills (1974)

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+ + Mills (1974), Afifi et al.
Ag 2 Te(s) (hessite) + 2H + 1.5O2 (g) = 2Ag + 2H2 TeO3 (aq) 49.8 45.4 43.7 38.2 32.9 28.8 25.5 22.9 21.1
(1988)

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Echmaeva & Osadchii,
Ag 3 AuTe2 (s) (petzite) + 4H+ + 3O2 (g)
86.8 78.9 76.1 66.3 56.9 49.4 43.6 – – ( 2009), from Grundler et al.

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= 3Ag + + Au + + 2H2 TeO3 (aq)
( 2013)*
Gaseous species
H2 Te(g) + 1.5O2 (g) = H2 TeO3 (aq) 98.1 88.9 85.7 74.4 63.3 54.7 47.7 41.9 (37.1) McPhail (1995)
Te2 (g) + 2H2 O(l) + 2O2 (g) = 2H2 TeO3 (aq) 102.9 92.9 89.3 77.0 64.9 55.3 47.6 41.2 (35.9) McPhail (1995)
H2 TeO3 (aq) = TeO2 (g) + H2 O(l) –31.1 –28.0 –26.8 –22.9 –19.0 –16.0 –13.5 –11.6 –10.3 Barin (1995)
H2 TeO3 (aq) = TeO2 (H2 O)(g) –20.5 –17.6 –16.5 –13.1 –9.90 –7.56 –5.83 –4.58 –3.81 Grundler et al. (2013)
H2 TeO3 (aq) + H2 O(l) = TeO2 .2(H2 O)(g) –38.5 –31.4 –29.1 –21.3 –14.7 –10.3 –7.31 –5.31 –4.14 Grundler et al. (2013)
* Grundler et al. (2013) have a typo in their Table 13 – the properties for petzite are listed using O 2 (aq), rather than O 2 (g).
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Table 5: Microbiological identities, locations, and produced Te nanoparticle morphology for selected Te oxyanion-reducing forms of bacteria

Product of reduction,
Genus and species, with strain Taxonomic
Location collected (if applicable) nanostructure size in nm Reference
or enzyme (if applicable) designation
if applicable
Aeromonas caviae ST Gram-negative rod Previously isolated Te0 (Castro et al., 2008)
0
Aspergillus welwitschiae Sources such as rotting garlic, kitchen Te nanospheres and
Fungus (Abo Elsoud et al., 2018)

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sink slime nanoellipsoids (~60)
Gram-positive rod, Sediment slurries from Mono lake, Te0 nanospheres and

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Bacillus beveridgei (Baesman et al., 2009)
facultative anaerobe California, USA nanorods
Bacillus filicolonicus, B.
laterosporus
Gram-positive rods,
facultative anaerobes
Sarcheshme copper mine in Kerman
Province, Iran

r o Te0 nanospheres (Sepahei and Rashetnia, 2009)

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Mud samples from salt marsh bordering
Intracellular Te0 nanorods

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Bacillus halodenitrificans Gram-positive rod,
the Indian River inlet, in Rehoboth Beach, (Ollivier et al., 2008)
facultative anaerobe (<100)

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Delaware, USA

Bacillus pumilis
Gram-positive rod,
facultative anaerobe
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Anzali Lagoon in Gilan province, Iran
and the Neidasht spring in the north of

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Iran
Te0 ; volatilisation of
unspecified gases
(Soudi et al., 2009)

Bacillus selenitireducens
Gram-positive rod,
facultative anaerobe l
Sediment slurries from Mono lake,

a California, USA
Extracellular Te 0 nanorods
(<200) clustered into larger
rosettes
(Baesman et al., 2006;
Baesman et al., 2007)

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Bacillus species, Enzyme STG- Gram-positive rod, Neidasht spring in the north of Iran (also
Te0 (Etezad et al., 2009)
83 facultative anaerobe see above)
Gram negative
Extracellular Se0 –Te0
Duganella violacienigra

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heterotrophic non-
halophilic and aerobic
proteobacterium
Obligate aerobic
Se-rich soils from agricultural fields in
India
composite nanoparticles
(~100)
(Bajaj and Winter, 2014)

Erythrobacter litoralis photosynthetic Previously isolated Intracellular Te0 (Yurkov et al., 1996)
bacterium
Obligate aerobic Intracellular Te0 or resistant
Erythromicrobium ezovicum photosynthetic Previously isolated but no apparent reduction, (Yurkov et al., 1996)
bacterium depending on carbon source
Erythromicrobium
Obligate aerobic
hydrolyticum, E. ramosum, E. Previously isolated Intracellular Te0 (Yurkov et al., 1996)
photosynthetic bacteria
sibiricum, E. ursincola
Magnetospirillum magneticum Facultative anaerobic Coprecipitated Te 0 and
Previously isolated (Tanaka et al., 2010)
strain AMB-1 magnetotactic spiral magnetite nanocrystals
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Drainage water from a metal refining Extracellular Te 0 (100) and

Ochrobactrum anthropi TI-2
Gram-negative rod(s) plant in Amagasaki City, Hyogo DMTe, DMDTe and (Kagami et al., 2012)
and TI-3
Prefecture, Japan DMTeS
Gram-negative rod,
Dump of roasted (arseno)pyrites from
Ochrobactrum sp. MPV1 Aerobic Intracellular Te0 (Zonaro et al., 2017)
near a factory in Tuscany, Italy
α-proteobacterium
Sediment from the Er-Jen River in Tainan
Paenibacillus Sp. Strain TeW Gram-positive rod County, Taiwan, contaminated by run-off Te0 (Chien and Han, 2009)

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from electroplating factories and smelters
Pseudoalteromonas sp. strain Gram-negative aerobic
EPR3 rods
Previously isolated from volcanic vents

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Te0 ; DMTe (Bonificio and Clarke, 2014)

ro
Gram-negative
Pseudomonas Kesterson Reservoir in the San Joaquin
fluorescens K27 facultative anaerobic Te0 ; DMTe and DMDTe (Basnayake et al., 2001)
Valley of California, USA

-p
rod
Pseudomonas mendocina MCM
Gram-negative rod Previously isolated Te0 (Rajwade and Paknikar, 2003)

re
B-180
Photosynthetic Gram-
Intracellular Te0 nanorods
Rhodobacter capsulatus negative anaerobic α-

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Previously isolated (Borghese et al., 2016)
(200-700)
proteobacterium
Rhodococcus aethivorans BCP1
Aerobic Gram-positive
sphere

a l
Previously isolated
Intracellular Te0 non-
aggregated nanorods (<700)
(Presentato et al., 2016)

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Mud samples from salt marsh bordering
Obligately aerobic,

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Rhodotorula mucilaginosa the Indian River inlet, in Rehoboth Beach, Te0 (Ollivier et al., 2008)
Gram-positive rods
Delaware, USA
Intracellular Te0 or resistant

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Obligately aerobic
Roseococcus thiosulfatophilus Previously isolated but no apparent reduction, (Yurkov et al., 1996)
photosynthetic sphere

Salinicoccus iranensis
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Gram-positive
halophilic sphere
Gram-positive
Previously isolated
Salty environments including saline or
depending on carbon source
Te0 (Alavi et al., 2014)

Salinicoccus sp. QW6 hypersaline soils, hypersaline brackish Intracellular Te0 (Amoozegar et al., 2008)
halophilic sphere
water and textile factory effluents of Iran
Facultative Gram- Water from the Zuari Estuary, Goa state, Te0 nanorods (8-75
Shewanella baltica (Vaigankar et al., 2018)
negative anaerobic rod India diameter)
Kim: Intracellular Te 0
Facultative Gram- nanorods (100-200); (Kim et al., 2012a; Klonowska
Shewanella oneidensis MR-1 Previously isolated
negative anaerobic rod Klonowska: also et al., 2005)
intracellular (size
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unspecified)
Pages: Te0 intracellularly;
Pages: Isolated from contaminated
Kagami: Te0 intracellularly
Pseudomonas cultures; Kagami: Drainage
Stenotrophomonas maltophilia and extracellularly (200- (Kagami et al., 2012; Pages et
Gram-negative rod water from a metal refining plant in
300) and DMTe and al., 2011; Zonaro et al., 2015)
Amagasaki City, Hyogo Prefecture,
DMDTe; Zonaro: Te0 (75-
Japan; Zonaro: Environmental isolates
80)
Extracellular Te0

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Sulphurospirillum barnesii Sediment slurries from Mono lake, nanospheres (<50)
Anaerobic spiral (Baesman et al., 2006)
California, USA coalescing into larger

o ocomposites

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Abbreviations: Te0 – solid elemental tellurium, DMTe – gaseous dimethyl telluride, DMDTe – gaseous dimethyl ditelluride and DMTeS –

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gaseous dimethyl tellurenyl sulphide. Ordered by scientific name.

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FIGURES AND CAPTIONS

(a) (b)

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Figure 1: Visual and chemical diversity of Te minerals. Three primary minerals: (a)
Calaverite (AuTe2 ) from Cripple Creek, Colorado, USA, field of view (FOV) 1.3 mm, (b)
Krennerite (Au3 AgTe8 ) also from Cripple Creek, FOV 3 mm and (c) Sylvanite [(Au,Ag) 2 Te]
from Emperor Mine, Viti Levu, Fiji, FOV 5 mm. (d) One example of elemental Te with the
wsecondary mineral, teineite (CuTe4+O3 ·2H2 O) from Teine Mine, Japan, FOV 3 mm. Finally,
two secondary minerals: (e) Zemannite [Mg0.5 ZnFe3+(Te4+O3 )3 ·(3+n)H2 O)], from Moctezuma
mines, Mexico, FOV 2 mm and (f) Jensenite (Cu2+3 Te6+O6 ·2H2 O) from Centennial Eureka
Mine, Utah, USA, FOV 1 mm. Images credit: Mr. Brent Thorne (Utah, USA, private
collection).
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Figure 2: a) World consumption of Te, showing the dramatic growth in Te usage over the
past decade in thermoelectric devices and photoreceptors, with cadmium telluride (CdTe)
solar panels one of the main drivers. a) Reproduced from Nuss (2019) with permission from
CSIRO Publishing. b) One of the many new CdTe solar panel arrays: a solar-powered pump
in the village of Angarf, Ouarzazate Province, Morocco. Image credit: Mr. Georges Favreau
(Aix-en-Provence, France, private collection).
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Figure 3: The wide variety of bonding Te participates in contributes to its rich surface
chemistry. Te participates in intermetallic bonding between elements like Ag, Au, and other
Te atoms in primary minerals. Te also forms a variety of arrangements with oxygen, with
different bonding modes for Te4+ and Te6+. The bonding arrangements between Te and O are
further explored in Figure 4.
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Figure 4: Various Te–O bonding networks as illustrated by Te4+ minerals (see Supp. table 1 for formulae). The bonding networks vary from
simple, finite units to complex, three-dimensional structures. All structures except cyclo are known in minerals, with the simplest neso
compounds forming the largest number of structures across both Te4+ and Te6+ minerals. Although other ligands may bind to Te 4+ and Te6+ in
synthetic contexts, in minerals, all strong bonds are to oxygen atoms.
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Figure 5: Tellurium environmental cycling schematic, bringing together the various sinks of
Te (highlighted in green) and the processes and transformations which occur between
different Te reservoirs (highlighted in pink). Particularly high concentrations of Te are found
in volcanogenic sulphur, some ore deposits and in Cu conce ntrates and anode slimes during
some Cu processing. The complex biological interactions shown in the top part of the
diagram are further explored in Section 6. a (Anders and Grevesse, 1989); b (McDonough and
Sun, 1995); c (Hattori et al., 2002); d (Hu and Gao, 2008); e (Dill, 2010); f (Maslennikov et al.,
2013); g (Hein et al., 2003); h (Goldfarb et al., 2017); i (Makuei and Senanayake, 2018); j
(Kavlak and Graedel, 2013); k (Nuss, 2019); l (Filella et al., 2019); m (Belzile and Chen,
2015); and n (Ba et al., 2010).
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Figure 6: World map showing locations of selected tellurium-enriched mineral occurrences, by deposit type. The deposit types shown here are
classified as follows: volcanogenic massive sulfide (VMS), iron oxide-copper-gold (IOCG), orogenic gold, porphyry, epithermal, skarn, Carlin-
type gold, magmatic copper–nickel–platinum- group metal (Cu-Ni-PGM), and other deposit types (43, 46 and 50, Te-rich waste from massive
sulphide ores; 79 and 81, Intrusion-related Au deposit). Adapted from mindat.org, Goldfarb et al. (2017) and Keith et al. (2018), using the crust-
type world map template of the USGS (https://earthquake.usgs.gov/data/crust/type.html).
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Figure 7: Solubility of various Te species at ~1 (solid red lines) and 100 ppb levels (dashed
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red lines) as a function of pH and oxygen fugacity at (a) 25 and (b) 300 °C and water-
saturated pressures, using thermodynamic properties collected by McPhail (1995) and
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Grundler et al. (2013). The Fe diagram in a Fe-S-Cl-O-H system is drawn as blue dashed
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lines for reference (conditions listed in the legend inset). The S diagram is shown as purple
dashed lines. Abbreviations in top two diagrams: py - pyrite; hm - hematite; mt - magnetite;
po – pyrrhotite. Horizontal dotted lines at the top and bottom of the two diagrams indicate the
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stability field of H2 O.
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Figure 8: Solubility of tellurite (TeO 2 ) at 25˚C calculated at ionic strength = 1, using the
properties of Grundler et al. (2013) and Filella and May (2019) using Geochemist’s
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Workbench (Bethke, 2008). The tellurite solubilities measured by Grundler et al. (2013) are
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shown using circles; unfilled circles correspond to solutions of buffer-only (ionic strength
<0.5), and filled circles to solutions with ~1 m NaCl and ~0.2 m buffer.
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Figure 9: Formation of secondary Te minerals at the young (6.9–7.1 My) Aginskoe deposit,
in the active volcanic arc in the Kamchatka Peninsula, Russia. (A) Rich assemblage of
secondary Te minerals are found in a restricted part of the oxidation zone. (B) Weathering of
a chalcopyrite grain containing petzite inclusion. The rim (labelled o-cpy) consists of poorly
crystallised, inhomogeneous and Te-bearing Fe-Cu-oxy-hydroxides, containing inclusions of
fine-grained native gold. (C,D) Microporous gold resulting from the dealloying of primary Te
minerals, most likely calaverite; some of the pores are filled with a Te-rich phase, probably
tellurite. Image credits: (A) Prof. V. Okrugin (Institute Of Volcanology And Seismology,
Russian Academy of Science, Petropavlovsk-Kamchatsky, Russia); (B-D) Copyright
permission received from Okrugin et al. (2014).
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Figure 10: Moctezuma, Sonora, Mexico, is famous for the abundance and diversity of
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tellurium minerals. (A) On the first few meters below the surface, intense weathering results
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in the formation of abundant Fe(Mn)-oxy- hydroxides; these are shown by portable-XRF to

contain high amounts of Te (>>100 ppm); however, no visible secondary mineral was
observed. Below this level, native tellurium was observed undergoing weathering to tellurite
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(TeO 2 ) and probably other secondary minerals in smaller amounts. (B) Native tellurium (here
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in a calcite matrix) is the most prominent primary (hydrotherma l) Te mineral. (C) Tellurite is
one of the most prominent secondary minerals, here in millimetre-size blades. Image credit:
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(C) Stefan Ansermet (Musée cantonal de géologie, Lausanne, Switzerland).

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132
Figure 11: Log scale Te concentration contour maps in the eastern part of Fukushima Prefecture showing the distribution of the
132
anthropogenic and radioactive isotope Te around the Fukushima Daiichi Nuclear Power Plant (FDNPP) (decay-corrected to March 11, 2011)
132
showing (a) Measured Te; (b) estimated from 129m Te, and (c) all data including MEXT. Copyright permission received from Tagami et al.
(2013).
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Figure 12: A schematic of a ‘super- microorganism’ capable of mediating the key processes microbes participate in with Te that control its
immobilisation and mobilisation; these include bioaccumulation, bioprecipitation, bioreduction, biovolatilisation and biooxidation. Biosorption
controls the initial step of interaction between any microorganism and Te, while bioreduction is the most common detoxification step.
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Figure 13: Mono Lake, California. Three Te-oxyanion reducing bacteria (Bacillus beveridgei,
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B. selenitireducens and Sulphurospirillum barnesii, see Table 2) have been found from the
saline and alkaline waters of this lake (Baesman et al., 2006; Baesman et al., 2009; Baesman
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et al., 2007). Note that the salinity is so high that evaporites precipitate onto the rocks sitting
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above the water line. Image licensed under a Creative Commons Attribution-Share Alike 3.0
Unported license (https://commons.wikimedia.org/wiki/File:Mono_Lake_Tufa.JPG).
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Figure 14: Te nanostructures produced by bioprecipitation. (a) SEM micrographs of Te

nanospheres and a cluster of Te nanorods produced by Bacillus beveridgei. Copyright
permission received from Baesman et al. (2009). Licence no.: 4761590947824. (b) TEM
micrograph of Te nanorods produced aerobically by Rhodococcus aetherivorans, visible
protruding outwards from a single cell. Reproduced from Presentato et al. (2016). (c) SEM
micrographs of SeTe nanospheres produced by Duganella violacienigra (C4 label on right
hand side indicates culture number in original paper). Reproduced from Bajaj and Winter
(2014).
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Figure 15: Postulated model for Te and Au cycling in the regolith, modified after the gold dispersion model from Figure 2 of Rea et al. (2016).
Licence no.: 4761590226366. Note the major difference between the two elements is that Te can be made airborne by microbes in the form of
dimethyl telluride or other alkylated forms of Te, whereas Au remains in the soil or groundwater.
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Declaration of interests

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the

work reported in this paper.

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