Subscriber access provided by UNIVERSITY OF WISCONSIN-MILWAUKEE
Article
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
Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Environmental Science & Technology is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
Page 1 of 35
Environmental Science & Technology
1
Tellurium Distribution and Speciation in Contaminated Soils from Abandoned
2
Mine Tailings: Comparison with Selenium
3 4
Hai-Bo Qin,*,†,‡ Yasuo Takeichi,§ Hiroaki Nitani,§ Yasuko Terada,∥
5
and Yoshio Takahashi*,‡
6
†
7
Chinese Academy of Sciences, Guiyang 550081, China
8
‡
9
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
§
11
Organization (KEK), 1-1 Oho, Tsukuba, Ibaraki 305-0801, Japan
12
∥
13
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:
20
*Phone: +86-85-85895787; fax: +86-851-85891334; e-mail: qinhaibo@vip.gyig.ac.cn
21
(Hai-Bo Qin)
22
*Phone: +81-3-5841-4517; fax: +81-3-5841-8791; e-mail: ytakaha@eps.s.u-tokyo.ac.jp
23
(Yoshio Takahashi)
24 1
ACS Paragon Plus Environment
Environmental Science & Technology
25
ABSTRACT
26
The distribution and chemical species of tellurium (Te) in contaminated soil were
27
determined by a combination of micro focused X-ray fluorescence (µ-XRF), X-ray
28
diffraction (µ-XRD), and X-ray absorption fine structure (µ-XAFS) techniques. Results
29
showed that Te was present as a mixture of Te(VI) and Te(IV) species, while selenium
30
(Se) was predominantly present in the form of Se(IV) in the soil contaminated by
31
abandoned mine tailings. In the contaminated soil, Fe(III) hydroxides were the host
32
phases for Se(IV), Te(IV), and Te(VI), but Te(IV) could be also retained by illite. The
33
difference in speciation and solubility of Se and Te in soil can result from different
34
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
38
solubility, mobility, and bioavailability of Te in the surface environment. To the best of
39
our knowledge, this is the first study reporting the speciation and host phases of Te in
40
field soil by the µ-XRF-XRD-XAFS techniques.
41
2
ACS Paragon Plus Environment
Page 2 of 35
Page 3 of 35
Environmental Science & Technology
42
TOC/Abstract Art
43
44 45
3
ACS Paragon Plus Environment
Environmental Science & Technology
46
INTRODUCTION
47
Tellurium (Te) has attracted increasing attention due to its wide industrial
48
applications such as improving optoelectronic and thermal properties of steel and glass,
49
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
51
pollution and induce acute and chronic Te poisoning to human (e.g., the degeneracy of
52
liver and kidney).2,5 The Occupational Safety and Health Administration (OSHA) has set
53
the permissible exposure limit for workers to Te compounds in the workplace as 0.1 mg
54
m-3 over an 8-hour workday.5 In addition, radiotellurium including 127mTe, 129mTe, 131mTe,
55
and 132Te may be released into the environment in the case of the nuclear accidents (e.g.,
56
Fukushima Daiichi Nuclear Power Plant accident in March 2011), which are severely
57
harmful to human health through inhalation and ingestion of contaminated crops.6,7
58
Tellurium is one of the least abundant elements in the earth’s crust, but it is
59
considerably enriched in marine ferromanganese crusts.1,8,9 The environmental fates and
60
biogeochemical behaviors of Te are still poorly known, although its chemical and
61
physical properties are generally considered to be similar to those of selenium (Se) in the
62
same Group 16 of the periodic table. It was recently suggested that the distribution
63
behavior between Te and Se is significantly different in a laboratory soil-water system,10
64
but similar studies in natural systems are lacking due to extremely low Te concentration
65
in geological, environmental, and biological samples.
66
In the natural environment, Te occurs in several oxidation states (-II, 0, IV, and VI)
67
both in organic and inorganic forms.1,2 Oxyanion tellurate (Te(VI)) is the predominant
68
species of Te in hydrosphere.9,11 Tellurite (Te(IV)) is another soluble form, but its toxicity 4
ACS Paragon Plus Environment
Page 4 of 35
Page 5 of 35
Environmental Science & Technology
69
is 10-fold higher than Te(VI).12 Te(IV) is toxic to bacteria even at a low concentration, yet
70
some Te-resistant bacteria that can reduce Te(IV) and Te(VI) to elemental Te(0) have
71
been found in nature.13-15 Elemental Te(0) is insoluble in water, and thus has less mobility
72
and toxicity. These microorganisms could be used to relieve excessive Te in aquatic
73
environment via microbial reduction from Te oxyanions to precipitated Te(0).14,15 Various
74
telluride minerals such as calaverite (AuTe2), rickardite (Cu7Te5), and sylvanite
75
(Ag3AuTe2) often coexist in gold (Au) deposits,1,16 while organic forms of Te (e.g.,
76
dimethyl telluride, telluro-cystine, and telluro-methionine) are mainly related to
77
biological activities.1,2 Thus, Te speciation is crucial for better understanding its
78
distribution, bioavailability, toxicity, and mobility in the environment, because different
79
forms show the unique biogeochemical properties.
80
However, research regarding the distribution and chemical speciation of Te in field
81
soil has been scarcely attempted, owing to challenging analytical methods for Te
82
speciation.17 In the past few decades, X-ray absorption fine structure (XAFS) method that
83
consist of X-ray absorption near edge structure (XANES) and extended X-ray absorption
84
fine structure (EXAFS) spectroscopy has been widely utilized to nondestructively
85
identify metal(loid)s speciation in solid samples.10,18-21 Nevertheless, Te speciation in
86
common soil containing low Te content could not be determined by XAFS technique with
87
reasonably high detection limit. Furthermore, the absorption energies of the K-edge and
88
LIII-edge of Te are 31814 eV and 4341 eV, respectively, but both energies are
89
inaccessible at many traditional XAFS beamlines in the world. The consequence is that
90
synchrotron based XAFS measurement is difficult to be carried out even if Te content in
91
solid sample is high enough to collect the XAFS spectra of Te. 5
ACS Paragon Plus Environment
Environmental Science & Technology
92
The Kawazu Mine located at Shimoda City, Shizuoka Prefecture, Japan, is famous
93
for the occurrence of Au-Ag-Te-Mn veins, where a unique Te mineral named Kawazulite
94
(Bi2Te2Se) has been discovered.22-24 However, Te level and speciation in the soil around
95
Kawazu Mine are largely unknown. In this study, we have investigated Te concentration
96
in the soils from abandoned Kawazu Mine tailings. Furthermore, the chemical speciation
97
and host phases of Te in the contaminated soil have been identified using powerful micro
98
focused XAFS (µ-XAFS), X-ray fluorescence (µ-XRF), and X-ray diffraction (µ-XRD)
99
techniques. The aims of this study were (i) to clarify the distribution and speciation of Te
100
in the contaminated soil and (ii) to further provide valuable insights into the migration,
101
bioavailability, and potential risk assessment of Te in the surface environment.
102 103
MATERIALS AND METHODS
104
Sample Collection and Preparation. The soil samples were collected around
105
Hinokizawa pithead (34.41° N, 138.55° E) of Kawazu Mine (Figure S1), details on its
106
geology and ore deposit are given in the Supporting Information (SI). In the laboratory,
107
soil samples, free of plant roots and detritus, were air-dried and then ground with an agate
108
mortar for chemical and speciation analysis. Furthermore, a thin section of the soil
109
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
ACS Paragon Plus Environment
Page 16 of 35
Page 17 of 35
Environmental Science & Technology
345
hydroxides have high affinities (> 98.4% of Te was adsorbed) for both Te(IV) and Te(IV)
346
under common environmental conditions. In terms of Te species, the logKd levels of
347
Te(IV) were clearly greater than those of Te(VI) adsorption on ferrihydrite and goethite
348
except for strong alkaline environments (e.g., pH=11), implying that Te(IV) seems to be
349
readily adsorbed by Fe oxides. Hein et al.9 suggested that Te(IV) in seawater is
350
preferentially scavenged by FeOOH at the surface of ferromanganese crust, which results
351
in the fact that the thermodynamically more stable Te(IV) is less abundant by factors of 2
352
to 3.5 than Te(VI) in ocean water. In addition, larger logKd values were observed for
353
ferrihydrite relative to goethite in either Te(IV) or Te(VI) system, which is probably
354
ascribed to the higher Brunauer-Emmett-Teller surface area for ferrihydrite (330 m2 g-1)
355
than that for goethite (20 m2 g-1).40,41 These results are consistent with the fact that Fe(III)
356
hydroxides are the host phase of Te in solid samples demonstrated by spectroscopic
357
methods, which is highly reasonable because oxyanions are readily adsorbed by
358
positively-charged Fe(III) hydroxides.
359
In contrast, lesser degree of Te adsorption was found for illite relative to iron oxides
360
regardless of Te species and pH condition. The negatively-charged illite, a 2:1 layer type
361
clay mineral, basically exhibit three types of sorption sites: sites on the basal planar,
362
interlayer sites, and hydroxyl groups on the sheet edges. The first and second sites exhibit
363
negative charge, which are specifically responsible for pH-independent adsorption of
364
cations such as cesium.42,43 However, sorption on the hydroxyl group sites is
365
pH-dependent because of its amphoteric nature, which is speculated to be the most
366
relevant adsorption mechanism for anions. Recently, the complexation models involving
367
mechanism related to surface functional groups have been successfully utilized to 17
ACS Paragon Plus Environment
Environmental Science & Technology
368
simulate the adsorption of Se on illite.44,45 Furthermore, much larger amounts of Te(IV)
369
were adsorbed by negatively-charged illite compared with Te(VI) under a relatively lower
370
pH (Figure 5). This is likely to be partially explained since the possible species of Te(IV)
371
such as TeO-OH+ and/or H2TeO3 show some cationic properties, while Te(VI) is mainly
372
present in the forms of anionic H2TeO4 and/or HTeO4- under low pH conditions (Figure
373
S4).31,32 These results confirm the observation that more Te(IV) was found in the hotspots
374
(e.g., Spots 6 and 8) containing more illite in the contaminated soil from abandoned
375
tailings by the µ-XRF-XRD-XAFS technique.
376 377
Comparison between distribution and speciation of Te and Se in soil. For comparison
378
with the distribution and speciation of Te, a similar data set for Se was simultaneously
379
obtained in the soil thin section (e.g., Figures 1D and 1E). The distribution of Se was
380
almost identical to that of iron according to the µ-XRF mapping data (Figure S5), as
381
shown for Te distribution pattern in the same soil grains (Figure 1). Combining with
382
µ-XRD results for these particles (Figure S3) suggests that Fe(III) hydroxides can be the
383
host phases for Se and Te in the soil contaminated by waste tailings. This finding is
384
confirmed by the fact that added Te and Se are mainly associated with Fe(III) hydroxides
385
in incubated soil in the laboratory experiment.10
386
Selenium K-edge µ-XANES spectra for Se hotspots were very similar to that of
387
NaHSeO3 (Figure S5), suggesting that Se(IV) is the predominant form in the
388
contaminated soil from abandoned tailings, which is in line with the observation that
389
Se(IV) is one of major species in soil developed on reclaimed mine lands.46 However, a
390
mixture of Te(VI) and Te(IV) was present in the same soil particles obtained from Te 18
ACS Paragon Plus Environment
Page 18 of 35
Page 19 of 35
Environmental Science & Technology
391
K-edge µ-XANES results (e.g., Spots 7, 8, 9, and 10 in Figure 2). This significant
392
difference in speciation of Se and Te in contaminated soil can be well explained by
393
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
395
Figure 4, the p Κ a values for conjugated anions of Se and Te present an order of Te(VI) >
396
Te(IV) > Se(IV) > H2WO4 >> Se(VI), indicating that Te(VI), Te(IV), and Se(IV) prefer to
397
form stable inner-sphere complexes on the surface of Fe(III) hydroxides, whereas Se(VI)
398
forms less stable outer-sphere complex. These predictions have been well demonstrated
399
by EXAFS results.10,18,47 Thus, Se(VI) has a lower affinity to soil particles and is readily
400
leached from soil into aquatic environment, which can be responsible for the much lesser
401
presence of Se(VI) in the contaminated soil.
402
Furthermore, approximately 0.1% of Se and less than 0.001% of Te in the same soil
403
sample were leached by water, respectively, implying that Se is much more soluble (>100
404
times) than Te in soil (Table S4). Similarly, the laboratory study10 also showed that the
405
distribution of Se to water is much higher than that of Te in the synthetic soil-water
406
system. It has been further documented that the larger affinity of Te for soil in originates
407
from the formation of the inner-sphere complexes of Te(IV) and Te(VI) on Fe(III)
408
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
410
Therefore, the difference in the speciation and solubility of Se and Te in contaminated
411
soils from abandoned mine tailings can be strongly confirmed by the distribution
412
behaviors of Se and Te observed in the laboratory study.
413 19
ACS Paragon Plus Environment
Environmental Science & Technology
414
Environmental Implications. It has been suggested that numerous ions (e.g., Zn2+, Cr3+,
415
Ge4+, As5+, and Sb5+) can be structurally incorporated into Fe(III) site of iron
416
oxides.18,41,48,49 Compared with surface adsorption, structural incorporation cannot be
417
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,
419
Te(VI) in soil can be expected to be relatively stable and difficult to mobilize if Te(VI) is
420
structurally incorporated into Fe(III) oxides in soil as demonstrated for ferromanganese
421
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
423
chemical species in addition to Te(VI) in the contaminated soil. Unlike Te(VI), Te(IV)
424
can be adsorbed by illite and Fe(III) hydroxides in soil via the formation of surface
425
complexes. Thus, the retention of Te(IV) in soil could be less stable than with that for
426
Te(VI), possibly resulting in easier release and migration for Te(IV) in soil under suboxic
427
conditions.
428
In the study area, the total Te concentrations in fern and moss species were 0.13 and
429
1.26 mg kg-1, respectively. In comparison with a recent investigation,7 these values are
430
greatly higher than Te levels in Japanese crops ranging from 0.0001 to 0.12 mg kg-1 with
431
a geometric mean of 0.0018 mg kg-1, but the soil-to-crop transfer factors (TFs) of Te in
432
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
434
documented for other trace elements like Se.50,51 It has been assumed that Te in paddy
435
soil could be reduced to highly mobile HTeO3- under flooded condition, resulting in
436
higher Te concentration in brown rice than that in upland crop.7 However, further study is 20
ACS Paragon Plus Environment
Page 20 of 35
Page 21 of 35
Environmental Science & Technology
437
necessary to clarify the bioavailability of every Te speciation in soil to different plant
438
species.
439
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
441
significant importance for better understanding the solubility, mobility, and
442
bioavailability of Te in contaminated soil environment, which also can be extended to
443
similar surface environments. As Te concentration in common sample is much lower than
444
the level required for XAFS analysis, it is needed to develop the modeling of solid-water
445
distribution of Te to extend the speciation results of Te to much lower Te level in
446
environment.
447 448 449
Supporting Information
450
Complementary materials including figures (S1-S5), tables (S1-S4), as well as
451
several supplemental texts for the materials and methods section. Figures showing the
452
location of study area, total Te concentration in soil, µ-XRD patterns of Te hotspots,
453
Eh-pH diagram for Te, and the distribution and speciation of Se in contaminated soil.
454
Tables showing the geochemical characteristics of studied samples, the best fitting results
455
for Te k-edge µ-XANES spectra of Te hotspots, structural parameters of EXAFS spectra
456
for the Te hotspot in soil and adsorbed samples, and leached results for the contaminated
457
soil using water.
458 459
21
ACS Paragon Plus Environment
Environmental Science & Technology
460
Acknowledgments
461
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,
463
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
465
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
22
ACS Paragon Plus Environment
Page 22 of 35
Page 23 of 35
Environmental Science & Technology
469
References
470
(1) Belzile, N.; Chen, Y. W. Tellurium in the environment: A critical review focused on
471
natural waters, soils, sediments and airborne particles. Appl. Geochem. 2015, 63, 83-92.
472
(2) Ba, L.A.; Doring, M.; Jamier, V.; Jacob, C. Tellurium: an element with great
473
biological potency and potential. Org. Biomol. Chem. 2010, 8, 4203-4216.
474
(3) Tang, Z. Y.; Zhang, Z. L.; Wang, Y.; Glotzre, S. C.; Kotov, N. A. Self-assembly of
475
cdte nanocrystals into free-floating sheets. Science 2006, 314, 274-278.
476
(4) Deng, Z. T.; Zhang, Y.; Yue, J. C.; Tang, F. Q.; Wei, Q. Green and orange CdTe
477
quantum dots as effective pH-sensitive fluorescent probes for dual simultaneous and
478
independent detection of viruses. J. Phys. Chem. B. 2007, 111, 12024-12031.
479
(5) Issa, Y. M.; Abdel-Fattah, H. M.; Shehab, O. R.; Abdel-Moniem, N. B. Determination
480
and speciation of tellurium hazardous species in real and environmental samples. Int. J.
481
Electrochem. Sci. 2016, 11, 7475-7498.
482
(6) Tagami, K.; Uchida, S.; Ishii, N.; Zheng, J. Estimation of Te-132 distribution in
483
Fukushima Prefecture at the early stage of the Fukushima Daiichi Nuclear Power Plant
484
reactor failures. Environ. Sci. Technol. 2013, 47, 5007-5012.
485
(7) Yang, G.; Zheng, J.; Tagami, K.; Uchida, S. Soil-to-crop transfer factors of tellurium.
486
Chemosphere 2014, 111, 554-559.
487
(8) Cohen, B. L. Anomalous behavior of tellurium abundances. Geochim. Cosmochim.
488
Acta 1984, 48, 203-205.
489
(9) Hein, J. R.; Koschinsky, A.; Halliday, A. N. Global occurrence of tellurium-rich
490
ferromanganese crusts and a model for the enrichment of tellurium. Geochim.
491
Cosmochim. Acta 2003, 67, 1117-1127. 23
ACS Paragon Plus Environment
Environmental Science & Technology
492
(10) Harada, T.; Takahashi, Y. Origin of the difference in the distribution behavior of
493
tellurium and selenium in a soil–water system. Geochim. Cosmochim. Acta 2008, 72,
494
1281-1294.
495
(11) Lee, D. S.; Edmond, J. M. Tellurium species in seawater. Nature 1985, 313,
496
782-785.
497
(12) Karlson, U.; Frankenberger, W.T. Metal ions in biological systems; Marcel Dekker:
498
New York, 1993.
499
(13) Chasteen, T. G.; Fuentes, D. E.; Tantalean, J. C.; Vasquez, C. C. Tellurite: history,
500
oxidative stress, and molecular mechanisms of resistance. FEMS Microbiol. Rev. 2009,
501
33, 820-832.
502
(14) Ramos-Ruiz, A.; Field, J. A.; Wilkening, J. V.; Sierra-Alvarez, R. Recovery of
503
elemental tellurium nanoparticles by the reduction of tellurium oxyanions in a
504
methanogenic microbial consortium. Environ. Sci. Technol. 2016, 50, 1492-1500.
505
(15) Kim, D. H.; Kim, M. G.; Jiang, S.; Lee, J. H.; Hur, H. G. Promoted reduction of
506
tellurite and formation of extracellular tellurium nanorods by concerted reaction between
507
iron and Shewanella oneidensis MR-1. Environ. Sci. Technol. 2013, 47, 8709-8715.
508
(16) Grundler, P. V.; Brugger, J.; Etschmann, B. E.; Helm, L.; Liu, W.; Spry, P. G.; Tian,
509
Y.; Testemale, D.; Pring, A. Speciation of aqueous tellurium(IV) in hydrothermal
510
solutions and vapors, and the role of oxidized tellurium species in Te transport and gold
511
deposition. Geochim. Cosmochim. Acta 2013, 120, 298-325.
512
(17) Chen, Y. W.; Alzahrani, A.; Deng, T. L.; Belzile, N. Valence properties of tellurium
513
in different chemical systems and its determination in refractory environmental samples
24
ACS Paragon Plus Environment
Page 24 of 35
Page 25 of 35
Environmental Science & Technology
514
using hydride generation-Atomic fluorescence spectroscopy. Anal. Chim. Acta. 2016,
515
905, 42-50.
516
(18) Kashiwabara, T.; Oishi, Y.; Sakaguchi, A.; Sugiyama, T.; Usui, A.; Takahashi, Y.
517
Chemical processes for the extreme enrichment of tellurium into marine ferromanganese
518
oxides. Geochim. Cosmochim. Acta 2014, 131, 150-163.
519
(19) MacLean, L. C.; Beauchemin, S.; Rasmussen, P. E. Lead speciation in house dust
520
from Canadian urban homes using EXAFS, micro-XRF, and micro-XRD. Environ. Sci.
521
Technol. 2011, 45, 5491-5497.
522
(20) Mitsunobu, S.; Takahashi, Y.; Terada, Y. µ-XANES evidence for the reduction of
523
Sb(V) to Sb(III) in soil from sb mine tailing. Environ. Sci. Technol. 2010, 44, 1281-1287.
524
(21) Grafe, M.; Donner, E.; Collins, R. N.; Lombi, E. Speciation of metal(loid)s in
525
environmental samples by X-ray absorption spectroscopy: A critical review. Anal. Chim.
526
Acta 2014, 822, 1-22.
527
(22) Hori, H.; Koyama, E.; Nagashima, K. Kinichilite, a new minera from the Kawazu
528
mine, Shimoda city, Japan. Miner. Journ. 1981, 10, 333-337.
529
(23) Shimizu, M.; Kato, A.; Matsubara, S. Hemusite and paraguanajuatite from the
530
Kawazu mine, Shizuoka Prefecture, Japan. Miner. Journ. 1988, 14, 92-100.
531
(24) Nakata, M.; Komuro, K. Chemistry and Occurrences of Native Tellurium from
532
Epithermal Gold Deposits in Japan. Resour. Geol. 2011, 61, 211-223.
533
(25) Igarashi, N.; Nitani, H.; Takeichi, Y.; Niwa, Y.; Abe, H.; Kimura, M.; Mori, T.;
534
Nagatani, Y.; Kosuge, T.; Kamijo, A.; Koyama, A.; Ohta, H.; Shimizu, N. Newly
535
designed double surface bimorph mirror for BL-15A of the photon factory. AIP
536
Conference Proceedings 2016, 1741, 040021. 25
ACS Paragon Plus Environment
Environmental Science & Technology
537
(26) Zabinsky, S. I.; Rehr, J. J.; Ankudinov, A.; Albers, R. C.; Eller, M. J.
538
Multiple-scattering calculations of X-ray-absorption spectra. Phys. Rev. B. 1995, 52,
539
2995-3009.
540
(27) Jumas, J. C.; Wintenberger, M.; Philippot, E. Etude magnetique des phases du
541
systeme Fe2O3TeO2 structure magnetique de Fe2TeO5 a 4.2 K. Mater. Resear. Bullet.
542
1977, 12, 1063-1070.
543
(28) Krishnan, K.; Singh Mudher, K. D.; Rama Rao, G. A.; Venugopal, V. Structural and
544
thermochemical studies on Cr2TeO6 and Fe2TeO6. J. Alloy. Compd. 2001, 316, 264-268.
545
(29) Salminen, R.; Plant, J. A.; Reeder, S. Geochemical atlas of Europe. Part 1,
546
background information, methodology and maps. Espoo: Geological Survey of Finland,
547
2005.
548
(30) Perkins, W. T. Extreme selenium and tellurium contamination in soils-an eighty
549
year-old industrial legacy surrounding a Ni refinery in the Swansea Valley. Sci. Total.
550
Environ. 2011, 412-413, 162-169.
551
(31) Brookins, D. G. Eh-pH diagram for geochemistry; Springer-Verlag: Berlin, 1988.
552
(32) McPhail, D. C. Thermodynamic properties of aqueous tellurium species between 25
553
and 350℃. Geochim. Cosmochim. Acta 1995, 59, 851-866.
554
(33) Dzombak, D. A.; Morel, F. M. M. Surface complexation modeling, hydrous ferric
555
oxide; John Wiley & Sons: New York, 1990.
556
(34) Dean, J. A. Lange’s Handbook of Chemistry; 15th, ed.; McGraw Hill: New York,
557
1999.
558
(35) Li, Y. H. Ultimate removal mechanisms of elements from ocean. Geochim.
559
Cosmochim. Acta 1981, 45, 1659-1664. 26
ACS Paragon Plus Environment
Page 26 of 35
Page 27 of 35
Environmental Science & Technology
560
(36) Kashiwabara, T.; Takahashi, Y.; Tanimizu, M.; Usui, A. Molecular-scale
561
mechanisms of distribution and isotopic fractionation of molybdenum between seawater
562
and ferromanganese oxides. Geochim. Cosmochim. Acta 2011, 75, 5762-5784.
563
(37) Kashiwabara, T.; Takahashi, Y.; Marcus, M. A.; Uruga, T.; Tanida, H.; Terada, Y.;
564
Usui, A. Tungsten species in natural ferromanganese oxides related to its different
565
behavior from molybdenum in oxic ocean. Geochim. Cosmochim. Acta 2013, 106,
566
364-378.
567
(38) Manceau, A.; Drits, V. A. Local structure of ferrihydrite and feroxyhite by EXAFS
568
spectroscopy. Clay. Miner. 1993, 28, 165-184.
569
(39) Waychunas, G. A.; Rea, B. A.; Fuller, C. C.; Davis, J. A. Surface-chemistry of
570
ferrihydrite: part 1. EXAFS studies of the geometry of coprecipitated and adsorbed
571
arsenate. Geochim. Cosmochim. Acta 1993, 57, 2251-2269.
572
(40) Langmuir, D. Aqueous environmental geochemistry; Prentice Hall: Upple Saddle
573
River, 1997.
574
(41) Mitsunobu, S.; Takahashi, Y.; Terada, Y.; Sakata, M. Antimony(V) incorporation
575
into synthetic ferrihydrite, goethite, and natural iron oxyhydroxides. Environ. Sci.
576
Technol. 2010, 44, 3712-3718.
577
(42) Qin, H. B.; Yokoyama, Y.; Fan, Q. H.; Iwatani, H.; Tanaka, K.; Sakaguchi, A.;
578
Kanai, Y.; Zhu, J.; Onda, Y.; Takahashi, Y. Investigation of cesium adsorption on soil
579
and sediment samples from Fukushima Prefecture by sequential extraction and EXAFS
580
technique. Geochem. J. 2012, 46, 355-360.
581
(43) Fan, Q. H.; Tanaka, M.; Tanaka, K.; Sakaguchi, A.; Takahashi, Y. An EXAFS study
582
on the effects of natural organic matter and the expandability of clay minerals on cesium 27
ACS Paragon Plus Environment
Environmental Science & Technology
583
adsorption and mobility. Geochim. Cosmochim. Acta 2014, 135, 49-65.
584
(44) Goldberg, S. Modeling selenite adsorption envelopes on oxides, clay minerals, and
585
soils using the triple layer model. Soil. Sci. Soc. Am. J. 2013, 77, 64-71.
586
(45) Missana, T.; Alonso, U.; García-Gutiérrez, M. Experimental study and modelling of
587
selenite sorption onto illite and smectite clays. J. Colloid. Interf. Sci. 2009, 334, 132-138.
588
(46) Ryser, A. L.; Strawn, D. G.; Marcus, M. A.; Fakra, S.; Johnson-Maynard, J. L.;
589
Möller, G. Microscopically focused synchrotron X-ray investigation of selenium
590
speciation in soils developing on reclaimed mine lands. Environ. Sci. Technol. 2006, 40,
591
462-467.
592
(47) Hayes, K. F.; Roe, A. L.; Brown, G. E.; Hodgson, K. O.; Leckie, J. O.; Parks, G. A.
593
In situ x-ray absorption study of surface complexes: selenium oxyanions on a-FeOOH.
594
Science 1987, 238, 783-786.
595
(48) Manceau, A.; Schlegel, M. L.; Musso, M.; Sole, V. A.; Gauthier, C.; Petit, P. E.;
596
Trolard, F. Crystal chemistry of trace elements in natural and synthetic goethite. Geochim.
597
Cosmochim. Acta 2000, 64, 3643-3661.
598
(49) Martinez, C. E.; McBride, M. B. Cd, Cu, Pb, and Zn coprecipitates in Fe oxides
599
formed at different pH: aging effects on metal solubility and extractability by citrate.
600
Environ. Chem. 2001, 20, 122-126.
601
(50) Qin, H. B.; Zhu, J. M.; Su, H. Selenium fractions in organic matter from Se-rich
602
soils and weathered stone coal in selenosis areas of China. Chemosphere 2012, 86,
603
626-633.
604
(51) Qin, H. B.; Zhu, J. M.; Liang, L.; Wang, M. S.; Su, H. The bioavailability of
605
selenium and risk assessment for human selenium poisoning in high-Se areas, China. 28
ACS Paragon Plus Environment
Page 28 of 35
Page 29 of 35
606
Environmental Science & Technology
Environ. Int. 2013, 52, 66-74.
607
29
ACS Paragon Plus Environment
Environmental Science & Technology
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
ACS Paragon Plus Environment
Page 30 of 35
Page 31 of 35
Environmental Science & Technology
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
ACS Paragon Plus Environment
Environmental Science & Technology
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
ACS Paragon Plus Environment
Page 32 of 35
Page 33 of 35
Environmental Science & Technology
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
ACS Paragon Plus Environment
Environmental Science & Technology
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
ACS Paragon Plus Environment
Page 34 of 35
Page 35 of 35
Environmental Science & Technology
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
ACS Paragon Plus Environment