A tetrad effect in the liquid-liquid extraction ordering of lanthanides(III)

Peppard, D.F.; Mason, G.W.; Lewey, S.

doi:10.1016/0022-1902(69)90044-x

Cited by 275 publications

(138 citation statements)

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“…It is of great significance that these two tetrads are in com plete agreement with the third and fourth tetrads pointed out by PEPPARD et al (1969). However, it is hard to recognize tetrad effect on REE lighter than Gd.…”

Section: Introductionsupporting

confidence: 76%

“…

We have found that lanthanide tetrad effect (PEPPARD et al, 1969) is operative for heavy rare-earth elements (REE) in a phosphorite sample (GOLDBERG et al, 1963). Also it has been evinced that the similar effect is observed for REE in sea waters.

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mentioning

confidence: 76%

“…In studies of liquid-liquid (aqueous-benzene) extraction involving H[DOP], di n-octyl phos phinic acid, (n-C8H17)2PO(OH) and DEH[C1MP], di 2-ethyl hexyl chloromethyl phosphonate, (C1CH2)PO(OC6H12 C2H5)2, PEPPARD et al (1969) recognized tetrad effect on lanthanides (III). According to their observation, when the concentration ratios between the aqueous phase and the organic phase is plotted on semi-loga rithmic diagram against the atomic number of the lanthanide, the plot consists of four separate curves, encompassing four points, La-Ce-Pr-Nd, Pm-Sm-Eu-Gd, Gd-Tb-Dy-Ho and Er-Tm-Yb-Lu, with Gd being an element common to the second and the third tetrad.…”

Section: Introductionmentioning

confidence: 99%

“…1. Example of the tetrad effect (PEPPARD et al, 1969). Variation of log K with atomic number Z where K is the equilibrium distribution constant between an aqueous solution of 1.1 F LiBr + 0.…”

Section: Introductionmentioning

confidence: 99%

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Lanthanide tetrad effect observed in marine environment.

1979

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We have found that lanthanide tetrad effect (PEPPARD et al., 1969) is operative for heavy rare-earth elements (REE) in a phosphorite sample (GOLDBERG et al., 1963). Also it has been evinced that the similar effect is observed for REE in sea waters. However, in the case where the plot (Masuda-Coryell plot) is void of the points for Tb, Ho and Tm, the resultant joint-line pattern is to have the common characteristics that the zigzag pattern is pointed downward at Dy and Yb and upward at Er. That is, the zigzag pattern with phase coincidence in breaking and its direction is a partially cut-off reflection of lanthanide tetrad effect.Employing the stable isotope dilution technique, we could determine REE in one-liter sample of sea water, with errors less than 2-3%.

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Section: Introductionsupporting

confidence: 76%

“…

…”

mentioning

confidence: 76%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Lanthanide tetrad effect observed in marine environment.

1979

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“…The (Pr/ Yb) cn ratio gives a measure of the overall slope of the normalized plot if this can be approximated as a straight line, and thereby the extent of fractionation of the LREEs from the HREEs. The (La/Yb) cn ratio is more frequently used as an index of REE fractionation, but lanthanum is often depleted relative to other trivalent REEs because of tetrad effect (Peppard et al, 1969;Masuda and Ikeuchi, 1979). Therefore the (Pr/Yb) cn ratio is mostly discussed in the present paper.…”

Section: Analytical Methods and Ree Terminologymentioning

confidence: 99%

Rare Earth Elements as an Indicator to Origins of Skarn Deposits: Examples of the Kamioka Zn‐Pb and Yoshiwara‐Sannotake Cu(–Fe) Deposits in Japan

Kato

1999

Resource Geology

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: Systematic data of rare earth elements (REEs) are presented in order to put some constraints on the origin of hydrothermal fluids responsible for two contrastive skarn deposits in Japan; the Kamioka Zn‐Pb and Yoshiwara‐Sannotake Cu(‐Fe) deposits. Carbon and oxygen isotopic studies have demonstrated that the hydrothermal fluids responsible for the Kamioka Zn‐Pb deposits are of meteoric water origin whereas those for the Yoshiwara‐Sannotake Cu(‐Fe) deposits are of magmatic water origin. The REE abundances of epidote skarn derived from aluminous rocks, garnet and clinopyroxene in calcic exoskarn derived from limestone, and interstitial calcite associated with sulfide minerals were determined for these contrastive skarn deposits by inductively‐coupled plasma mass spectrometry (ICP‐MS). A significant difference in the REE concentrations is not found between epidote skarn and aluminous original rock (plagioclase‐clinopyroxene rock, called Inishi rock) from the Kamioka Zn‐Pb deposits, indicating that the REEs are generally immobile during the formation of epidote skarn, and that the REE concentrations of the hydrothermal fluid are considerably low relative to the aluminous original rock. In contrast, the epidote skarn exhibits enrichment of Eu with increasing total REE concentrations relative to the aluminous original rock (quartz diorite) in the Yoshiwara‐Sannotake Cu(‐Fe) deposits, implying a contribution of magmatic fluid derived from granitoids during the skarn formation. Limestone generally has much lower REE concentrations related to surrounding aluminous rocks, and thus the REE concentrations of garnet and clinopyroxene in calcic exoskarn, originated from limestone, are variable due to the interaction with the hydrothermal fluids. The chondrite‐normalized REE patterns of garnet, clinopyroxene, and interstitial calcite exactly provide useful information on origins of hydrothermal fluids. The REE patterns of these minerals from the Kamioka Zn‐Pb deposits show lower (Pr/Yb)cn ratios, and negative Ce and Eu anomalies inherited from limestone with the decrease of This suggests that the hydrothermal fluids responsible for the Kamioka Zn‐Pb deposits were depleted in REEs, and were not magmatic water in origin, but presumably meteoric one. In striking contrast, the REE patterns of exoskarn minerals and calcite from the Yoshiwara‐Sannotake Cu(‐Fe) deposits exhibit a positive Eu anomaly, and high (Pr/Yb)cn ratios with the considerable increase of σREE and the disappearance of negative Ce anomaly, implying that the fluids were dominantly of magmatic origin. The REE indices are very likely to be an excellent indicator to origins of the skarn deposits.

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Zusammenhang zwischen chemischer Bindung und Struktur; ¹H‐NMR‐ und IR‐spektroskopische Studie an Triscyclopentadienylcyclohexylisonitril‐Lanthanoid‐Komplexen)

Ammon

Kanellakopulos

1972

Ber Bunsenges Phys Chem

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Die metallorganischen Komplexe des Typs (C5H5)3LnCNC6H11 (Ln = Y, La ‐Lu) wurden IR‐ und 1H‐NMR‐spektroskopisch unter‐sucht. Bei einem Vergleich der Wellenzahlen der v(CN)‐Valenzschwingung der koordinierten Isonitril‐Liganden aller Komplexe wird ein Tetradeneffekt beobachtet. Dieser Effekt wird mit einem kovalenten Anteil an der Ln ‐C‐Bindung gedeutet. Die Analyse der paramagnetischen Verschiebungen der C6H11‐Protonen in den Tieftemperatur‐NMR‐Spektren der Komplexe mit Ln = Ce+3, Pr+3. Nd+3 und Eu+3 ergibt Anzeichen für eine schwache Abwinkelung der Isonitrilgruppe. Die Möglichkeit eines Zusammenhangs dieses sterischen Effekts mit einer elektronischen Ursache (f ⇒π‐Rückbindung) wird diskutiert.

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A tetrad effect in the liquid-liquid extraction ordering of lanthanides(III)

Cited by 275 publications

References 6 publications

Lanthanide tetrad effect observed in marine environment.

Lanthanide tetrad effect observed in marine environment.

Rare Earth Elements as an Indicator to Origins of Skarn Deposits: Examples of the Kamioka Zn‐Pb and Yoshiwara‐Sannotake Cu(–Fe) Deposits in Japan

Zusammenhang zwischen chemischer Bindung und Struktur; ¹H‐NMR‐ und IR‐spektroskopische Studie an Triscyclopentadienylcyclohexylisonitril‐Lanthanoid‐Komplexen)

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A tetrad effect in the liquid-liquid extraction ordering of lanthanides(III)

Cited by 275 publications

References 6 publications

Lanthanide tetrad effect observed in marine environment.

Lanthanide tetrad effect observed in marine environment.

Rare Earth Elements as an Indicator to Origins of Skarn Deposits: Examples of the Kamioka Zn‐Pb and Yoshiwara‐Sannotake Cu(–Fe) Deposits in Japan

Zusammenhang zwischen chemischer Bindung und Struktur; 1H‐NMR‐ und IR‐spektroskopische Studie an Triscyclopentadienylcyclohexylisonitril‐Lanthanoid‐Komplexen)

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Zusammenhang zwischen chemischer Bindung und Struktur; ¹H‐NMR‐ und IR‐spektroskopische Studie an Triscyclopentadienylcyclohexylisonitril‐Lanthanoid‐Komplexen)