Name: separation of uranium and thorium for 230th-u dating of submarine hydrothermal sulfides
Uploaded: 2019-05-20T12:30:00
Description: Watch this Scientific Journal Video about Separation of Uranium and Thorium for 230Th-U Dating of Submarine Hydrothermal Sulfides at JoVE.com

This study was financially supported by Experimental Technology Innovation Foundation of Institute of Geology and Geophysics, Chinese Academy of Sciences (No. 11890940), and China Ocean Mineral Resources R &#38; D Association Project (No. DY135-S2-2-07).

1. Preparing the sample, reagents, and containers
<ol>
	<li>Clean the fume hood, hotplate and the balance room bench for the chemical experiment with sprayed alcohol or ultrapure water.</li>
	<li>Prepare sub-boiled acids (2 M HCl, 8 M HCl, 7 M HNO3, and 14 M HNO3), clean beakers and any apparatus before sample processed. 
	NOTE: Sulfide samples presented in this study were collected from newly discovered hydrothermal zones in the South Atlantic. Approximately 60 mg of powdered sample was used...

<ol>
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L., Brichet, E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Actinide-series+disequilibrium+as+a+tool+to+establish+the+chronology+of+deep-sea+hydrothermal+activity.">Actinide-series disequilibrium as a tool to establish the chronology of deep-sea hydrothermal activity.</a> Geochimica et Cosmochimica Acta. 57 (6), 1221-1231 (1993).</li><li>Lalou, C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=New+age+data+for+Mid-Atlantic+Ridge+hydrothermal+sites:+TAG+and+Snakepit+chronology+revisited.">New age data for Mid-Atlantic Ridge hydrothermal sites: TAG and Snakepit chronology revisited.</a> Journal of Geophysical Research. 98, 9705-9713 (1993).</li><li>Lalou, C., Reyss, J. L., Brichet, E., Rona, P. A., Thompson, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Hydrothermal+activity+on+a+105-year+scale+at+a+slow-spreading+ridge,+TAG+hydrothermal+field,+Mid-Atlantic+Ridge+26&#176;+N.">Hydrothermal activity on a 105-year scale at a slow-spreading ridge, TAG hydrothermal field, Mid-Atlantic Ridge 26&#176; N.</a> Journal of Geophysical Research. 100 (B9), 17855-17862 (1995).</li><li>Kadko, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Radio+isotopic+studies+of+submarine+hydrothermal+vents.">Radio isotopic studies of submarine hydrothermal vents.</a> Reviews of Geophysics. 34 (3), 349-366 (1996).</li><li>Lalou, C., Mu &#776;nch, U., Halbach, P., Reyss, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Radiochronological+investigation+of+hydrothermal+deposits+from+the+MESO+zone,+Central+Indian+Ridge.">Radiochronological investigation of hydrothermal deposits from the MESO zone, Central Indian Ridge.</a> Marine Geology. 149 (149), 243-254 (1998).</li><li>Yejian, W., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Hydrothermal+Activity+Events+at+Kairei+Field,+Central+Indian+Ridge+25&#176;S.">Hydrothermal Activity Events at Kairei Field, Central Indian Ridge 25&#176;S.</a> Resource Geology. 62 (2), 208-214 (2012).</li><li>Yejian, W., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mineralogy+and+geochemistry+of+hydrothermal+precipitates+from+Kairei+hydrothermal+field,+Central+Indian+Ridge.">Mineralogy and geochemistry of hydrothermal precipitates from Kairei hydrothermal field, Central Indian Ridge.</a> Marine Geology. 354 (3), 69-80 (2014).</li><li>Jun-ichiro, I., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Dating+of+Hydrothermal+Mineralization+in+Active+Hydrothermal+Fields+in+the+Southern+Mariana+Trough.">Dating of Hydrothermal Mineralization in Active Hydrothermal Fields in the Southern Mariana Trough.</a> Subseafloor Biosphere Linked to Hydrothermal Systems. , 289-300 (2015).</li><li>Takamasa, A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=U-Th+radioactive+disequilibrium+and+ESR+dating+of+a+barite-containing+sulfide+crust+from+South+Mariana+Trough.">U-Th radioactive disequilibrium and ESR dating of a barite-containing sulfide crust from South Mariana Trough.</a> Quaternary Geochronology. 15 (1), 38-46 (2013).</li><li>Weifang, Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=230Th/238U+dating+of+hydrothermal+sulfides+from+Duanqiao+hydrothermal+field,+Southwest+Indian+Ridge.">230Th/238U dating of hydrothermal sulfides from Duanqiao hydrothermal field, Southwest Indian Ridge.</a> Marine Geophysical Research. 38 (1-2), 71-83 (2017).</li><li>Lisheng, W., Zhibang, M., Hai, C., Wuhui, D., Jule, X. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Determination+of+230Th+age+of+Uranium-series+standard+samples+by+multiple+collector+inductively+coupled+plasma+mass+spectromerty.">Determination of 230Th age of Uranium-series standard samples by multiple collector inductively coupled plasma mass spectromerty.</a> Journal of China Mass Spectrometry Society. 37 (3), 262-272 (2016).</li><li>Wang, L., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=U+concentration+and+234U/238U+of+seawater+from+the+Okinawa+Trough+and+Indian+Ocean+using+MC-ICPMS+with+SEM+protocols.">U concentration and 234U/238U of seawater from the Okinawa Trough and Indian Ocean using MC-ICPMS with SEM protocols.</a> Marine Chemistry. 196, 71-80 (2017).</li><li>Hai, C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Improvements+in+230Th+dating,+230Th+and+234U+half-life+values,+and+U-Th+isotopic+measurements+by+multi-collector+inductively+coupled+plasma+mass+spectrometry.">Improvements in 230Th dating, 230Th and 234U half-life values, and U-Th isotopic measurements by multi-collector inductively coupled plasma mass spectrometry.</a> Earth and Planetary Science Letters. , 82-91 (2013).</li><li>Edwards, R. L., Chen, J. H., Ku, T. -. L., Wasserburg, G. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Precise+timing+of+the+last+interglacial+period+from+mass+spectrometric+analysis+of+230Th+in+corals.">Precise timing of the last interglacial period from mass spectrometric analysis of 230Th in corals.</a> Science. 236 (4808), 1537-1553 (1987).</li><li>Edwards, R. L., Taylor, F. W., Wasserburg, G. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Dating+earthquakes+with+high+precision+thorium-230+ages+of+very+young+corals+[J].">Dating earthquakes with high precision thorium-230 ages of very young corals [J].</a> Earth and Planetary Science Letters. 90 (4), 371-381 (1988).</li><li>Hai, C., Jess, A., Edwards, R. L., Boyle, E. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=U-Th+dating+of+deep-sea+corals.">U-Th dating of deep-sea corals.</a> Geochimica et Cosmochimica Acta. 64 (14), 2401-2416 (2000).</li><li>Ishibashi, J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Dating+of+Hydrothermal+Mineralization+in+Active+Hydrothermal+Fields+in+the+Southern+Mariana+Trough.">Dating of Hydrothermal Mineralization in Active Hydrothermal Fields in the Southern Mariana Trough.</a> Subseafloor Biosphere Linked to Hydrothermal Systems. , 289-300 (2015).</li><li>Jaffey, A. H., Flynn, K. F., Glendenin, L. E., Bentley, W. C., Essling, A. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Precision+measurement+of+half-lives+and+specific+activities+of+235U+and+238U.">Precision measurement of half-lives and specific activities of 235U and 238U.</a> Physical Review C. 4, 1889-1906 (1971).</li><li>Richter, S., Goldberg, S. A., Mason, P. B., Traina, A. J., Schwieters, J. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Linearity+tests+for+secondary+electron+multipliers+used+in+isotope+ratio+mass+spectrometry.">Linearity tests for secondary electron multipliers used in isotope ratio mass spectrometry.</a> International Journal of Mass Spectrometry. 206 (1-2), 105-127 (2001).</li></ol>

Some critical steps must be followed to ensure success of this protocol. Ensure that all operations are carried out in clean chemistry room under fume hood with clean air circulation. Purify all regents in this process in advance and clean the apparatus before use. Dissolve the samples completely in the process of making the 7 M HNO3 solution which is then loaded onto the 7 M HNO3-conditioned resins. If there is any insoluble substance in the sample, it will be redissolved after drying. Additional i...

Submarine hydrothermal sulfides have been a steady source of metals like iron, copper, zinc and lead. They are also seen as economically viable resources of silver and gold. The location and size of the deposits are a record of the history of hydrothermal venting on the seafloor. Dating of a hydrothermal sulfide can provide important information regarding the formation and alteration mechanism of the sulfide ore deposit, seafloor hydrothermal activity history, and growth rate of large sulfide deposits1,2,3. 238U-234U-230Th disequilibrium dating is an effective isotopic method of age estimation for hydrothermal sulfides4,5,6,7,8,9,10,11,12, where the purification and separation of U and Th isotopes is necessary. This text describes a protocol for U and Th isotopes separation and 230Th-U dating of sulfides sample by MC-ICPMS.
Geological materials which contain U and Th remain undisturbed for several million years, and a state of secular equilibrium between all the nuclides in the radioactive series is established. However, a combination of chemical solubility and nuclear recoil factors often create disequilibrium, in which the members of the decay series are separated from each other through processes such as deposition, transport and weathering. For example, when a sulfide deposit is formed, the state of 238U, 234U and 230Th is of disequilibrium, and the long-lived 238U can decay gradually towards short-lived 234U and 230Th subsequently. Assuming (i) the system remains closed with respect to U and Th isotopes, and (ii) initial amount of 230Th and 232Th incorporated into sulfide samples is zero, it is possible to determine the time of deposition by measuring the present-day activity ratios of 230Th/238U and 234U/238U. However, the initial amount of Th is not zero in the sample, and we assume the initial 230Th/232Th atomic ratio is 4.4 &#177; 2.2 x 10-6. The applicable dating range of this method is approximately ~10-6 x 105 years13,14. However, the large difference between the abundance of uranium and thorium makes measurement challenging. Hence, it is very important to establish a chemical procedure for U-Th dating by MC-ICPMS.
In the past 30 years, most studies focused more measurements of carbonate materials14,15,16,17 and less on sulfide deposits11,12,18,19. Alpha-particle counting methods have traditionally been used for the study of 230Th/238U disequilibrium of submarine hydrothermal sulfides1. However, analytical uncertainty of 5-17% is a limiting factor that affects the precision of age determination of sulfides1,8,9. These techniques generally suffer from the use of relatively large columns and reagent volumes and the need for multiple column passes for purification and separation U-Th from a sample. Recent developments in MC-ICPMS have greatly improved the precision of U-Th isotopic measurements (&#60;5&#8240; for ages)14 and have significantly reduced the sample size (&#60;0.2 g) required for analysis. In these works, many chemical separation procedures have been developed, and have achieved excellent chemical yields with low chemical background12,13.
Here we present a chemical-based protocol to obtain samples that are sufficiently clean for MC-ICPMS analysis. It is suitable for the dating of hydrothermal sulfide samples of age &#60;6 x 105 years14. With this technique, the separated U and Th isotopic fractions can meet measuring requirements by MC-ICPMS. The age of the hydrothermal sulfide sample can be calculated from the extent of disequilibria between 230Th and 234U and between 234U and 238U by using the described activity decay equation.

<table border="1" fo:keep-together.within-page="1" fo:keep-with-next.within-page="always">
	<tbody>
		<tr>
			<td>AG 1-X8 anion-exchange resin</td>
			<td>BIO-RAD</td>
			<td>140-1441</td>
			<td>Separating rare elements</td>
		</tr>
		<tr>
			<td>Ammonia solution</td>
			<td>Kanto Chemical CO., INC.</td>
			<td>1336-21-6</td>
			<td>Reagent</td>
		</tr>
		<tr>
			<td>Glass vials</td>
			<td>BOTEX</td>
			<td>None</td>
			<td>Sample collection</td>
		</tr>
		<tr>
			<td>Hydrochloric acid</td>
			<td>Sinopharem chemical reagent Co. Ltd</td>
			<td>7647-01-0</td>
			<td>Reagent</td>
		</tr>
		<tr>
			<td>Hydrofluoric acid</td>
			<td>EMD Millipore CO.</td>
			<td>7664-39-5</td>
			<td>Reagent</td>
		</tr>
		<tr>
			<td>Neptune Plus</td>
			<td>Thermo Fisher Scientific CO.</td>
			<td>None</td>
			<td>Apparatus</td>
		</tr>
		<tr>
			<td>Nitric acid</td>
			<td>Sinopharem chemical reagent Co. Ltd</td>
			<td>7697-37-2</td>
			<td>Reagent</td>
		</tr>
		<tr>
			<td>Perchloric acid</td>
			<td>Kanto Chemical CO., INC.</td>
			<td>32059-1B</td>
			<td>Reagent</td>
		</tr>
		<tr>
			<td>Ultrapure water</td>
			<td>Merck Millipore</td>
			<td>None</td>
			<td>Producted by Mill-Q Advantage systerm</td>
		</tr>
		<tr>
			<td>Wipe paper</td>
			<td>Kimberley-Clark</td>
			<td>0123-12</td>
			<td>Wipe and clean</td>
		</tr>
		<tr>
			<td>2 ml vial</td>
			<td>Nelgene</td>
			<td>5000-0020</td>
			<td>Sample collection</td>
		</tr>
		<tr>
			<td>229Th-233U-236U spike</td>
			<td>None</td>
			<td>None</td>
			<td>Reagent</td>
		</tr>
		<tr>
			<td>7 ml PFA beaker</td>
			<td>Savillex</td>
			<td>200-007-20</td>
			<td>Sample treatment</td>
		</tr>
		<tr>
			<td>10 ml centrifuge</td>
			<td>Nelgene</td>
			<td>3110-1000</td>
			<td>Sample treatment</td>
		</tr>
		<tr>
			<td>30 ml PFA beaker</td>
			<td>Savillex</td>
			<td>200-007-20</td>
			<td>Sample treatment</td>
		</tr>
	</tbody>
</table>

separation of uranium and thorium for 230th-u dating of submarine hydrothermal sulfides

The age of a submarine hydrothermal sulfide is a significant index for estimating the size of hydrothermal ore deposits. Uranium and thorium isotopes in the samples can be separated for 230Th-U dating. This article presents a method to purify and separate U and Th isotopes in submarine hydrothermal sulfide samples. Following this technique, the separated U and Th fractions can meet measuring requirements by multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS). The age of the hydrothermal sulfide sample can be calculated by measuring the present-day activity ratios of 230Th/238U and 234U/238U. A super clean room is necessary for this experiment. Cleaned regents and supplies are used to reduce the contamination during the sample processes. Balance, hotplate, and centrifuge are also used. The sulfide sample is powdered for analysis and less than 0.2 g sample is used. Briefly, the sample is weighed, dissolved, added to 229Th-233U-236U double spike solution, Fe co-precipitated, and separated on an anion-exchange resin extraction column. Approximately 50 ng U is consumed for 230Th-U dating of sulfides sample by MC-ICPMS.

Using this procure, a submarine hydrothermal sulfide sample can be completely dissolved. Following this protocol, the Th fraction was eluted from the hydrothermal sulfide sample using 8 M HCl. Meanwhile, the U fraction of the hydrothermal sulfide sample was eluted with 0.1 M HNO3. U and Th fractions were dissolved in the 2% HNO3 (+0.1% HF) solution (see Figure 2) and stored in 2 mL capacity vials. The mixture was then analyzed by MC-ICPMS.
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Watch this Scientific Journal Video about Separation of Uranium and Thorium for 230Th-U Dating of Submarine Hydrothermal Sulfides at JoVE.com

Separation of Uranium and Thorium for 230Th-U Dating of Submarine Hydrothermal Sulfides

The protocol describes a method to purify and separate the U and Th nuclide in submarine hydrothermal sulfide sample with Fe co-precipitation and extraction chromatography for 230Th-U disequilibrium dating.

Separation of Uranium and Thorium for 230Th-U Dating of Submarine Hydrothermal Sulfides

The age of a submarine hydrothermal sulfide is a significant index for estimating the size of hydrothermal ore deposits. Uranium and thorium isotopes in ...

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