Tellurium Distribution and Speciation in Contaminated Soils from

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Tellurium Distribution and Speciation in Contaminated Soils from Abandoned Mine Tailings: Comparison with Selenium Hai-Bo Qin, Yasuo Takeichi, Hiroaki Nitani, Yasuko Terada, and Yoshio Takahashi Environ. Sci. Technol., Just Accepted Manuscript • Publication Date (Web): 20 Apr 2017 Downloaded from http://pubs.acs.org on April 21, 2017

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Environmental Science & Technology

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Tellurium Distribution and Speciation in Contaminated Soils from Abandoned

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Mine Tailings: Comparison with Selenium

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Hai-Bo Qin,*,†,‡ Yasuo Takeichi,§ Hiroaki Nitani,§ Yasuko Terada,∥

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and Yoshio Takahashi*,‡

6

†

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Chinese Academy of Sciences, Guiyang 550081, China

8

‡

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University of Tokyo, Hongo 7-3-1, Bunkyo-ku, Tokyo 113-0033, Japan

State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry,

Department of Earth and Planetary Science, Graduate School of Science, The

10

§

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Organization (KEK), 1-1 Oho, Tsukuba, Ibaraki 305-0801, Japan

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∥

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Sayo-cho, Sayo-gun, Hyogo 679-5148, Japan

Institute of Materials Structure Science, High Energy Accelerator Research

Japan Synchrotron Radiation Research Institute (JASRI), SPring-8, 1-1-1 Kouto,

14 15 16 17 18 19

Corresponding authors:

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*Phone: +86-85-85895787; fax: +86-851-85891334; e-mail: [email protected]

21

(Hai-Bo Qin)

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*Phone: +81-3-5841-4517; fax: +81-3-5841-8791; e-mail: [email protected]

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(Yoshio Takahashi)

24 1

ACS Paragon Plus Environment


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ABSTRACT

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The distribution and chemical species of tellurium (Te) in contaminated soil were

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determined by a combination of micro focused X-ray fluorescence (µ-XRF), X-ray

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diffraction (µ-XRD), and X-ray absorption fine structure (µ-XAFS) techniques. Results

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showed that Te was present as a mixture of Te(VI) and Te(IV) species, while selenium

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(Se) was predominantly present in the form of Se(IV) in the soil contaminated by

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abandoned mine tailings. In the contaminated soil, Fe(III) hydroxides were the host

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phases for Se(IV), Te(IV), and Te(VI), but Te(IV) could be also retained by illite. The

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difference in speciation and solubility of Se and Te in soil can result from different

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structures of surface complexes for Se and Te onto Fe(III) hydroxides. Furthermore, our

35

results suggest that the retention of Te(IV) in soil could be relatively weaker than that of

36

Te(VI) due to structural incorporation of Te(VI) into Fe(III) hydroxides. These findings

37

are of geochemical and environmental significance for better understanding the

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solubility, mobility, and bioavailability of Te in the surface environment. To the best of

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our knowledge, this is the first study reporting the speciation and host phases of Te in

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field soil by the µ-XRF-XRD-XAFS techniques.

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2


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TOC/Abstract Art

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3



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INTRODUCTION

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Tellurium (Te) has attracted increasing attention due to its wide industrial

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applications such as improving optoelectronic and thermal properties of steel and glass,

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developing new materials (e.g., CdTe thin-film solar panels), as well as producing

50

fluorescent probes.1-4 As expected, the expanded use of Te can lead to environmental

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pollution and induce acute and chronic Te poisoning to human (e.g., the degeneracy of

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liver and kidney).2,5 The Occupational Safety and Health Administration (OSHA) has set

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the permissible exposure limit for workers to Te compounds in the workplace as 0.1 mg

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m-3 over an 8-hour workday.5 In addition, radiotellurium including 127mTe, 129mTe, 131mTe,

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and 132Te may be released into the environment in the case of the nuclear accidents (e.g.,

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Fukushima Daiichi Nuclear Power Plant accident in March 2011), which are severely

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harmful to human health through inhalation and ingestion of contaminated crops.6,7

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Tellurium is one of the least abundant elements in the earth’s crust, but it is

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considerably enriched in marine ferromanganese crusts.1,8,9 The environmental fates and

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biogeochemical behaviors of Te are still poorly known, although its chemical and

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physical properties are generally considered to be similar to those of selenium (Se) in the

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same Group 16 of the periodic table. It was recently suggested that the distribution

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behavior between Te and Se is significantly different in a laboratory soil-water system,10

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but similar studies in natural systems are lacking due to extremely low Te concentration

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in geological, environmental, and biological samples.

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In the natural environment, Te occurs in several oxidation states (-II, 0, IV, and VI)

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both in organic and inorganic forms.1,2 Oxyanion tellurate (Te(VI)) is the predominant

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species of Te in hydrosphere.9,11 Tellurite (Te(IV)) is another soluble form, but its toxicity 4


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is 10-fold higher than Te(VI).12 Te(IV) is toxic to bacteria even at a low concentration, yet

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some Te-resistant bacteria that can reduce Te(IV) and Te(VI) to elemental Te(0) have

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been found in nature.13-15 Elemental Te(0) is insoluble in water, and thus has less mobility

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and toxicity. These microorganisms could be used to relieve excessive Te in aquatic

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environment via microbial reduction from Te oxyanions to precipitated Te(0).14,15 Various

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telluride minerals such as calaverite (AuTe2), rickardite (Cu7Te5), and sylvanite

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(Ag3AuTe2) often coexist in gold (Au) deposits,1,16 while organic forms of Te (e.g.,

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dimethyl telluride, telluro-cystine, and telluro-methionine) are mainly related to

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biological activities.1,2 Thus, Te speciation is crucial for better understanding its

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distribution, bioavailability, toxicity, and mobility in the environment, because different

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forms show the unique biogeochemical properties.

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However, research regarding the distribution and chemical speciation of Te in field

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soil has been scarcely attempted, owing to challenging analytical methods for Te

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speciation.17 In the past few decades, X-ray absorption fine structure (XAFS) method that

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consist of X-ray absorption near edge structure (XANES) and extended X-ray absorption

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fine structure (EXAFS) spectroscopy has been widely utilized to nondestructively

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identify metal(loid)s speciation in solid samples.10,18-21 Nevertheless, Te speciation in

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common soil containing low Te content could not be determined by XAFS technique with

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reasonably high detection limit. Furthermore, the absorption energies of the K-edge and

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LIII-edge of Te are 31814 eV and 4341 eV, respectively, but both energies are

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inaccessible at many traditional XAFS beamlines in the world. The consequence is that

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synchrotron based XAFS measurement is difficult to be carried out even if Te content in

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solid sample is high enough to collect the XAFS spectra of Te. 5



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The Kawazu Mine located at Shimoda City, Shizuoka Prefecture, Japan, is famous

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for the occurrence of Au-Ag-Te-Mn veins, where a unique Te mineral named Kawazulite

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(Bi2Te2Se) has been discovered.22-24 However, Te level and speciation in the soil around

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Kawazu Mine are largely unknown. In this study, we have investigated Te concentration

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in the soils from abandoned Kawazu Mine tailings. Furthermore, the chemical speciation

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and host phases of Te in the contaminated soil have been identified using powerful micro

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focused XAFS (µ-XAFS), X-ray fluorescence (µ-XRF), and X-ray diffraction (µ-XRD)

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techniques. The aims of this study were (i) to clarify the distribution and speciation of Te

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in the contaminated soil and (ii) to further provide valuable insights into the migration,

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bioavailability, and potential risk assessment of Te in the surface environment.

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MATERIALS AND METHODS

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Sample Collection and Preparation. The soil samples were collected around

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Hinokizawa pithead (34.41° N, 138.55° E) of Kawazu Mine (Figure S1), details on its

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geology and ore deposit are given in the Supporting Information (SI). In the laboratory,

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soil samples, free of plant roots and detritus, were air-dried and then ground with an agate

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mortar for chemical and speciation analysis. Furthermore, a thin section of the soil

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sample that has been firstly sieved to eliminate large particles ( 4.5) were found in the systems of both Te(IV) and Te(VI) adsorption on ferrihydrite and goethite under neutral pH (Figure 5), suggesting that Fe(III) 16


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hydroxides have high affinities (> 98.4% of Te was adsorbed) for both Te(IV) and Te(IV)

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under common environmental conditions. In terms of Te species, the logKd levels of

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Te(IV) were clearly greater than those of Te(VI) adsorption on ferrihydrite and goethite

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except for strong alkaline environments (e.g., pH=11), implying that Te(IV) seems to be

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readily adsorbed by Fe oxides. Hein et al.9 suggested that Te(IV) in seawater is

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preferentially scavenged by FeOOH at the surface of ferromanganese crust, which results

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in the fact that the thermodynamically more stable Te(IV) is less abundant by factors of 2

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to 3.5 than Te(VI) in ocean water. In addition, larger logKd values were observed for

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ferrihydrite relative to goethite in either Te(IV) or Te(VI) system, which is probably

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ascribed to the higher Brunauer-Emmett-Teller surface area for ferrihydrite (330 m2 g-1)

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than that for goethite (20 m2 g-1).40,41 These results are consistent with the fact that Fe(III)

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hydroxides are the host phase of Te in solid samples demonstrated by spectroscopic

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methods, which is highly reasonable because oxyanions are readily adsorbed by

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positively-charged Fe(III) hydroxides.

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In contrast, lesser degree of Te adsorption was found for illite relative to iron oxides

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regardless of Te species and pH condition. The negatively-charged illite, a 2:1 layer type

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clay mineral, basically exhibit three types of sorption sites: sites on the basal planar,

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interlayer sites, and hydroxyl groups on the sheet edges. The first and second sites exhibit

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negative charge, which are specifically responsible for pH-independent adsorption of

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cations such as cesium.42,43 However, sorption on the hydroxyl group sites is

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pH-dependent because of its amphoteric nature, which is speculated to be the most

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relevant adsorption mechanism for anions. Recently, the complexation models involving

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mechanism related to surface functional groups have been successfully utilized to 17



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simulate the adsorption of Se on illite.44,45 Furthermore, much larger amounts of Te(IV)

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were adsorbed by negatively-charged illite compared with Te(VI) under a relatively lower

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pH (Figure 5). This is likely to be partially explained since the possible species of Te(IV)

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such as TeO-OH+ and/or H2TeO3 show some cationic properties, while Te(VI) is mainly

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present in the forms of anionic H2TeO4 and/or HTeO4- under low pH conditions (Figure

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S4).31,32 These results confirm the observation that more Te(IV) was found in the hotspots

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(e.g., Spots 6 and 8) containing more illite in the contaminated soil from abandoned

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tailings by the µ-XRF-XRD-XAFS technique.

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Comparison between distribution and speciation of Te and Se in soil. For comparison

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with the distribution and speciation of Te, a similar data set for Se was simultaneously

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obtained in the soil thin section (e.g., Figures 1D and 1E). The distribution of Se was

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almost identical to that of iron according to the µ-XRF mapping data (Figure S5), as

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shown for Te distribution pattern in the same soil grains (Figure 1). Combining with

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µ-XRD results for these particles (Figure S3) suggests that Fe(III) hydroxides can be the

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host phases for Se and Te in the soil contaminated by waste tailings. This finding is

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confirmed by the fact that added Te and Se are mainly associated with Fe(III) hydroxides

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in incubated soil in the laboratory experiment.10

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Selenium K-edge µ-XANES spectra for Se hotspots were very similar to that of

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NaHSeO3 (Figure S5), suggesting that Se(IV) is the predominant form in the

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contaminated soil from abandoned tailings, which is in line with the observation that

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Se(IV) is one of major species in soil developed on reclaimed mine lands.46 However, a

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mixture of Te(VI) and Te(IV) was present in the same soil particles obtained from Te 18


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K-edge µ-XANES results (e.g., Spots 7, 8, 9, and 10 in Figure 2). This significant

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difference in speciation of Se and Te in contaminated soil can be well explained by

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different structures of surface complexes for Se and Te on Fe(III) hydroxides, which has

394

been documented by theoretical prediction and spectroscopic analysis. As shown in

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Figure 4, the p Κ a values for conjugated anions of Se and Te present an order of Te(VI) >

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Te(IV) > Se(IV) > H2WO4 >> Se(VI), indicating that Te(VI), Te(IV), and Se(IV) prefer to

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form stable inner-sphere complexes on the surface of Fe(III) hydroxides, whereas Se(VI)

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forms less stable outer-sphere complex. These predictions have been well demonstrated

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by EXAFS results.10,18,47 Thus, Se(VI) has a lower affinity to soil particles and is readily

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leached from soil into aquatic environment, which can be responsible for the much lesser

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presence of Se(VI) in the contaminated soil.

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Furthermore, approximately 0.1% of Se and less than 0.001% of Te in the same soil

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sample were leached by water, respectively, implying that Se is much more soluble (>100

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times) than Te in soil (Table S4). Similarly, the laboratory study10 also showed that the

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distribution of Se to water is much higher than that of Te in the synthetic soil-water

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system. It has been further documented that the larger affinity of Te for soil in originates

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from the formation of the inner-sphere complexes of Te(IV) and Te(VI) on Fe(III)

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hydroxides, while higher distribution of Se to water was ascribed to highly soluble Se(VI)

409

and its weak outer-sphere complex as shown for dominant Se(VI) in water phase.10

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Therefore, the difference in the speciation and solubility of Se and Te in contaminated

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soils from abandoned mine tailings can be strongly confirmed by the distribution

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behaviors of Se and Te observed in the laboratory study.

413 19



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Environmental Implications. It has been suggested that numerous ions (e.g., Zn2+, Cr3+,

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Ge4+, As5+, and Sb5+) can be structurally incorporated into Fe(III) site of iron

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oxides.18,41,48,49 Compared with surface adsorption, structural incorporation cannot be

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greatly affected by environmental factors such as pH, ionic strength, and competitive

418

ions, resulting in the relatively low solubility and mobility in the environment. Similarly,

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Te(VI) in soil can be expected to be relatively stable and difficult to mobilize if Te(VI) is

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structurally incorporated into Fe(III) oxides in soil as demonstrated for ferromanganese

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crust, although chemical processes for Te enrichment in contaminated soil could be more

422

complicated due to various affecting factors. However, Te(IV) was also an important

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chemical species in addition to Te(VI) in the contaminated soil. Unlike Te(VI), Te(IV)

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can be adsorbed by illite and Fe(III) hydroxides in soil via the formation of surface

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complexes. Thus, the retention of Te(IV) in soil could be less stable than with that for

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Te(VI), possibly resulting in easier release and migration for Te(IV) in soil under suboxic

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conditions.

428

In the study area, the total Te concentrations in fern and moss species were 0.13 and

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1.26 mg kg-1, respectively. In comparison with a recent investigation,7 these values are

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greatly higher than Te levels in Japanese crops ranging from 0.0001 to 0.12 mg kg-1 with

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a geometric mean of 0.0018 mg kg-1, but the soil-to-crop transfer factors (TFs) of Te in

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our study are within the range of TFs in various crops (1.3×10-3-2.3×10-1). These facts

433

suggest that plant uptake of Te is likely to depend on its bioavailable fraction in soil, as

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documented for other trace elements like Se.50,51 It has been assumed that Te in paddy

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soil could be reduced to highly mobile HTeO3- under flooded condition, resulting in

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higher Te concentration in brown rice than that in upland crop.7 However, further study is 20


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necessary to clarify the bioavailability of every Te speciation in soil to different plant

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species.

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Our study clarifies the chemical speciation and host phases of Te in the

440

contaminated soil by the µ-XRF-XRD-XAFS techniques. These findings are of

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significant importance for better understanding the solubility, mobility, and

442

bioavailability of Te in contaminated soil environment, which also can be extended to

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similar surface environments. As Te concentration in common sample is much lower than

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the level required for XAFS analysis, it is needed to develop the modeling of solid-water

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distribution of Te to extend the speciation results of Te to much lower Te level in

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environment.

447 448 449

Supporting Information

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Complementary materials including figures (S1-S5), tables (S1-S4), as well as

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several supplemental texts for the materials and methods section. Figures showing the

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location of study area, total Te concentration in soil, µ-XRD patterns of Te hotspots,

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Eh-pH diagram for Te, and the distribution and speciation of Se in contaminated soil.

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Tables showing the geochemical characteristics of studied samples, the best fitting results

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for Te k-edge µ-XANES spectra of Te hotspots, structural parameters of EXAFS spectra

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for the Te hotspot in soil and adsorbed samples, and leached results for the contaminated

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soil using water.

458 459

21



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Acknowledgments

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This work was supported by Grants-in-Aid for Scientific Research from the Japan

462

Society for the Promotion of Science (Nos. 16K13911, 16K12627, 16H04073, 15H02149,

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and 24110008), the National Natural Science Foundation of China (41303099), Chinese

464

Academy of Sciences “Light of West China” Program, and State Key Laboratory of

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Environmental Geochemistry (SKLEG2015201). This study was performed with the

466

approval of JASRI/SPring-8 (2015B0118, 2015B0127, 2016A0118, and 2016A0127) and

467

Photon Factory (2016G632 and 2015G664).

468

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Environ. Int. 2013, 52, 66-74.

607

29



608

Captions

609

Figure 1. µ-XRF maps of selected areas in contaminated soil. The upper figures are

610

optical image of five interested areas (A-E), while the middle and lower figures show the

611

maps of Te and Fe, respectively. The open circles in Te maps indicate interested hotspots

612

for further µ-XAFS measurement.

613

Figure 2. Te K-edge µ-XANES spectra (solid lines) of interested hotspots in soil grains

614

marked by open circles in Figure 1. Red dotted lines on each spectrum are simulation

615

spectra obtained from the best LCF results by combining Na2TeO3 and Na2H4TeO6 in the

616

range of 31800-31835 eV.

617

Figure 3. Te K-edge EXAFS spectra of hotspots in soil grains and adsorbed samples: (A)

618

k3-weighted x(k) spectra, and (B) their RSFs (phase shift not corrected). Solid lines are

619

spectra obtained by experiments, and red dash lines are calculated spectra by curve-fitting

620

analysis.

621

Figure 4. Relationship between pKa values and attachment modes on ferrihydrite for

622

various oxyanions. The pKa1 and pKa2 values are obtained from the reference.33

623

Figure 5. Adsorption envelopes for Te(IV) and Te(VI) on ferrihydrite (Fh), goethite (Goe)

624

and illite as a function of pH. Diamond, triangle and circle represent ferrihydrite, goethite

625

and illite, respectively. Solid and dotted lines indicate Te(IV) and Te(VI) species,

626

respectively.

627

30


Page 30 of 35

Page 31 of 35


628

629 630 631 632 633 634 635

Figure 1. µ-XRF maps of selected areas in contaminated soil. The upper figures are optical image of five interested areas (A-E), while the middle and lower figures show the maps of Te and Fe, respectively. The open circles in Te maps indicate interested hotspots for further µ-XAFS measurement.

31



636

637 638 639 640 641 642

Figure 2. Te K-edge µ-XANES spectra (solid lines) of interested hotspots in soil grains marked by open circles in Figure 1. Red dotted lines on each spectrum are simulation spectra obtained from the best LCF results by combining Na2TeO3 and Na2H4TeO6 in the range of 31800-31835 eV.

32


Page 32 of 35

Page 33 of 35


643

644 645 646 647 648 649

Figure 3. Te K-edge EXAFS spectra of hotspots in soil grains and adsorbed samples: (A) k3-weighted x(k) spectra, and (B) their RSFs (phase shift not corrected). Solid lines are spectra obtained by experiments, and red dash lines are calculated spectra by curve-fitting analysis.

33



650

651 652 653 654

Figure 4. Relationship between pKa values and attachment modes on ferrihydrite for various oxyanions. The pKa1 and pKa2 values are obtained from the reference.33

34


Page 34 of 35

Page 35 of 35


655

656 657 658 659 660 661 662

Figure 5. Adsorption envelopes for Te(IV) and Te(VI) on ferrihydrite (Fh), goethite (Goe) and illite as a function of pH. Diamond, triangle and circle represent ferrihydrite, goethite and illite, respectively. Solid and dotted lines indicate Te(IV) and Te(VI) species, respectively.

35


Tellurium Distribution and Speciation in Contaminated Soils from

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