U-series evidence for crustal involvement and magma residence times in the petrogenesis of Parinacota volcano, Chile

In this study, we present Th–U disequilibria as well as radiogenic and trace element data for recent volcanic rocks from the Nevados de Payachata volcano which erupted through ∼70 km of continental crust in the Central Volcanic Zone of the Andes (18°S, 69°W). Both lavas and mineral separates were analyzed by mass spectrometry for ²³⁸U–²³⁰Th disequilibria. The lavas are characterized either by ²³⁰Th enrichment or depletion relative to its parent nuclide ²³⁸U. Mineral separates are used to derive U–Th isochron ages and these ages compare favorably with inferred stratigraphic ages or K–Ar ages, although in one case the U–Th age is significantly older than the stratigraphic age. Despite relatively constant Sr, Nd, and Pb isotope ratios, the lavas display inverse trends in ²³⁰Th/²³⁸U versus Ce/Yb or Ba/Hf diagrams. These trends cannot be interpreted by simple two-component mixing. Rather, there must be three (and perhaps four components) involved in the genesis of the Parinacota lavas. A mantle wedge, a slab fluid, and a lower crustal component can be identified. A sediment component is more difficult to detect as it is difficult to decipher its signature because of the strong crustal influence. The existence of binary arrays can be explained by variable amounts of crustal material. The process of crust–mantle interaction must have been short enough to preserve U–Th disequilibrium (<300 ka). Received: 21 April 1999 / Accepted: 11 March 2000     

Understanding melt generation beneath the slow-spreading Kolbeinsey Ridge using U, Th, and Pa excesses

To examine the petrogenesis and sources of basalts from the Kolbeinsey Ridge, one of the shallowest locations along the global ridge system, we present new measurements of Nd, Sr, Hf, and Pb isotopes and U-series disequilibria on 32 axial basalts. Young Kolbeinsey basalts (full-spreading rate = 1.8 cm/yr; 67°05′-70°26′N) display (²³⁰Th/²³⁸U) < 1 and (²³⁰Th/²³⁸U) > 1 with (²³⁰Th/²³⁸U) from 0.95 to 1.30 and have low U (11.3-65.6 ppb) and Th (33.0 ppb-2.40 ppm) concentrations. Except for characteristic isotopic enrichment near the Jan Mayen region, the otherwise depleted Kolbeinsey basalts (e.g. ⁸⁷Sr/⁸⁶Sr = 0.70272-0.70301, ε_Nd = 8.4-10.5, ε_Hf = 15.4-19.6 (La/Yb)_N = 0.28-0.84) encompass a narrow range of (²³⁰Th/²³²Th) (1.20-1.32) over a large range in (²³⁸U/²³²Th) (0.94-1.32), producing a horizontal array on a (²³⁰Th/²³²Th) vs. (²³⁸U/²³²Th) diagram and a large variation in (²³⁰Th/²³⁸U). However, the (²³⁰Th/²³⁸U) of the Kolbeinsey Ridge basalts (0.96-1.30) are inversely correlated with (²³⁴U/²³⁸U) (1.001-1.031). Samples with low (²³⁰Th/²³⁸U) and elevated (²³⁴U/²³⁸U) reflect alteration by seawater or seawater-derived materials. The unaltered Kolbeinsey lavas with equilibrium ²³⁴U/²³⁸U have high (²³⁰Th/²³⁸U) values (?1.2), which are consistent with melting in the presence of garnet. This is in keeping with the thick crust and anomalously shallow axial depth for the Kolbeinsey Ridge, which is thought to be the product of large degrees of melting in a long melt column. A time-dependent, dynamic melting scenario involving a long, slowly upwelling melting column that initiates well within the garnet peridotite stability zone can, in general, reproduce the (²³⁰Th/²³⁸U) and (²³¹Pa/²³⁵U) ratios in uncontaminated Kolbeinsey lavas, but low (²³¹Pa/²³⁵U) ratios in Eggvin Bank samples suggest eclogite involvement in the source for that ridge segment.     

A U-series study of lavas from Kamchatka and the Aleutians: constraints on source composition and melting processes

New data are presented for lavas from the Kamchatka Peninsula and the Aleutian arc. Radiogenic isotopes are strikingly homogeneous in the Kamchatka lavas and although incompatible trace element ratios exhibit much greater variability, much of this appears to result from shallow level, crystal fractionation. The data reveal little systematic across-arc change in radiogenic isotopes or trace element ratios. The Nd and Pb isotope data overlap those for Pacific MORB and limit the amount of sediment that could be incorporated in the mantle source region to <1% which is insufficient to account for the observed La/Ta ratios (50–68) in the high-MgO lavas. The lack of a positive correlation between La/Ta and depth to the slab suggests that melt–wall rock interaction was not important in controlling this ratio. Instead it is inferred that La/Ta increased during partial melting and that D_La/D_Ta = 0.11–0.06, possibly due to residual amphibole. Ba, U, Sr and Pb were added to the source by an aqueous fluid from the subducting slab and its inferred isotopic composition indicates that this fluid was derived from the altered oceanic crust. The addition of U resulted in a large range of (²³⁸U/²³²Th) from 0.79–2.48 similar to that observed in the Mariana and Lesser Antilles island arcs. However, (²³⁰Th/²³²Th) = 0.79–2.34, and the majority of samples lie close to the equiline indicating that the time since U/Th fractionation is generally ≥150 thousand years. The large width of the volcanic zone is assumed to reflect protracted fluid release from the subducting slab over the depth interval 170–380 km possibly coupled with extension across the Central Kamchatka Depression. The data from the Aleutians contrast strongly with those from Kamchatka. Radiogenic isotope data indicate that the Aleutian lavas contain a significant recycled sedimentary component, consistent with elevated ¹⁰Be/⁹Be ratios. The Aleutian lavas have (²³⁰Th/²³²Th) = 0.79–2.34 and exhibit a significant range of U/Th disequilibria [(²³⁸U/²³⁰Th) = 0.75–1.01]. However, ¹⁰Be/⁹Be is positively correlated with (²³⁸U/²³⁰Th) suggesting that the ¹⁰Be signal was carried by the aqueous fluid from the slab. The U/Th disequilibria for the Aleutian lavas lie close to a 30 thousand year reference line suggesting that this fluid was released from the slab ∼30 thousand years ago similar to recent estimates from the Lesser Antilles, Marianas, and Tonga-Kermadec island arcs from which it is inferred that fluid addition was the trigger for partial melting. Given that the rate of convergence in Kamchatka is similar to that in the Aleutians, Marianas and Tonga-Kermadec the inferred greater time since␣fluid release in Kamchatka requires further investigation. Received: 24 September 1997 / Accepted: 7 July 1998     

Extreme U-Th Disequilibrium in Rift-Related Basalts, Rhyolites and Granophyric Granite and the Timescale of Rhyolite Generation, Intrusion and Crystallization at Alid Volcanic Center, Eritrea

Rhyolite pumices and co-erupted granophyric (granite) xenolithsyield evidence for rapid magma generation and crystallizationprior to their eruption at 15·2 ± 2·9 kaat the Alid volcanic center in the Danikil Depression, Eritrea.Whole-rock U and Th isotopic analyses show ²³⁰Th excesses upto 50% in basalts <10 000 years old from the surroundingOss lava fields. The 15 ka rhyolites also have 30–40%²³⁰Th excesses. Similarity in U–Th disequilibrium, andin Sr, Nd, and Pb isotopic values, implies that the rhyolitesare mostly differentiated from the local basaltic magma. Giventhe (²³⁰Th/²³²Th) ratio of the young basalts, and presumablythe underlying mantle, the (²³⁰Th/²³²Th) ratio of the rhyolitesupon eruption could be generated by in situ decay in about 50000 years. Limited (5%) assimilation of old crust would hastenthe lowering of (²³⁰Th/²³²Th) and allow the process to takeplace in as little as 30 000 years. Final crystallization ofthe Alid granophyre occurred rapidly and at shallow depths at20–25 ka, as confirmed by analyses of mineral separatesand ion microprobe data on individual zircons. Evidently, 30000–50 000 years were required for extraction of basaltfrom its mantle source region, subsequent crystallization andmelt extraction to form silicic magmas, and final crystallizationof the shallow intrusion. The granophyre was then ejected duringeruption of the comagmatic rhyolites. KEY WORDS: U-series; zircon; ion microprobe; volcano; geochronology     

中国年轻火山岩铀钍(U-Th)非平衡研究进展

本文简述近些年中国年轻火山岩的铀钍非平衡研究进展.中国东部(五大连池,天池,镜泊湖,龙岗,大兴安岭,海南岛)的年轻火山岩都显示显著的230Th过剩,表明岩浆来源于含石榴子石的深部地幔,并且部分熔融速率低.其中五大连池主要来自深部(≥75km)的岩石圈地幔,天池、镜泊湖、龙岗和大兴安岭岩浆主要来自软流圈地幔,而海南岛火山岩则显示下地慢特征.中国东部年轻火山岩中U-Th非平衡并没有显示俯冲的太平洋板块对年轻火山岩的物质贡献.我们近来发现年轻火山岩中含有锆石.长白山天池火山岩千年喷发的碱流岩中的锆石U-Th等时线年龄为7～10ka.腾冲马鞍山的锆石表面U-Th等时线年龄为55ka,而锆石内部年龄是90ka.锆石年龄可能表明,相对于腾冲马鞍山的小喷发,大喷发的长白山天池火山岩浆滞留年龄短.长白山天池火山的很短的滞留时间表明其存在危险性.     

A detailed Th,Sr and O isotope study of Hekla: differentiation processes in an Icelandic Volcano

²³⁸U–²³⁰Th disequilibria and Sr and O isotope ratios have been measured in a suite of samples from most of the known prehistoric and historic eruptions of Hekla volcano, Iceland. They cover the compositional range from basaltic andesite to rhyolite. Recent basalts erupted in the vicinity of the volcano and a few Pleistocene basalts have also been studied. Geochemical data indicate that the best tracers of magmatic processes in Hekla are the (²³⁰Th/²³²Th) and Th/U ratios. Whereas most geochemical parameters, including Sr, Nd and O isotopes, could be compatible with crystal fractionation, (²³⁰Th/²³²Th) and Th/U ratios differ in the basalts and basaltic andesites (1.05 and 3.2, respectively) and in the silicic rocks, dacites and rhyolites (0.98 and 3.4–3.7, respectively). This observation precludes fractional crystallization as the main differentiation process in Hekla. On the basis of these results, the following model is proposed: basaltic magmas rise in the Icelandic crust and cause partial melting of metabasic rocks, leading to the formation of a dacitic melt. The basaltic magma itself evolves by crystal fractionation and produces a basaltic andesite magma. The latter can mix with the dacitic liquid to form andesites. At higher levels in the magma chamber, the dacitic melt sometimes undergoes further differentiation by crystal fractionation and produces subordinate volumes of rhyolites. Together all these processes lead to a zoned magma chamber. However, complete zoning is achieved only when the repose time between eruptions is long enough to allow the production of significant volumes of dacitic magma by crustal melting. This situation corresponds to the large plinian eruptions. Between these eruptions, the so-called intra-cyclic activity is characterized by the eruption of andesites and basaltic andesites, with little crustal melting. The magmatic system beneath Hekla most probably was established during the Holocene. The shape and the size of the magma chamber may be inferred from the relationships between the composition of the lavas and the location of the eruption sites. In a cross-section perpendicular to Hekla's ridge, a bell-shaped reservoir 5 km wide and 7 km deep appears the most likely; its top could be at depth of 8 km according to geophysical data.     

中国东部全新世火山的镭-钍同位素年代学

活火山是指1万年来有过喷发历史的全新世火山。火山的高分辨年代学对火山灾害评估和火山分类具有重要意义。对于缺乏历史记载的全新世火山,直接对火山岩进行同位素定年很困难。本文利用具有高时间分辨率的镭-钍-铀非平衡确定中国东部年轻火山的年龄。根据镭-钍-铀同位素,海南岛的马鞍岭和雷虎岭是全新世火山(马鞍岭:4.3ka;雷虎岭:4.7ka);镜泊湖火山(4.9ka)也是全新世火山;龙岗火山存在晚更新世和全新世活动(7.0ka,15.0ka);大兴安岭阿尔山和诺敏河Ra/Th非平衡消失但~(230)Th/~(238)U非平衡显著,属于晚更新世喷发(阿尔山:63ka;诺敏河:71ka)。海南岛的马鞍岭火山、雷虎岭火山和东北地区的龙岗火山、镜泊湖火山,是4座活火山。至于东北地区的阿尔山和诺敏河火山是否是活火山,有待测试更多样品的Ra/Th同位素。五大连池老黑山和火烧山有历史喷发记录,这与它们都存在显著Ra/Th非平衡一致。五大连池老黑山和火烧山的岩浆滞留年龄分别小于4.2ka和3.2ka,岩浆上升速率 18～23m/y。     

Uranium-series dating of pedogenic silica and carbonate, Crater Flat, Nevada

A ²³⁰Th-²³⁴U-²³⁸U dating study on pedogenic silica-carbonate clast rinds and matrix laminae from alluvium in Crater Flat, Nevada was conducted using small-sample thermal-ionization mass spectrometry (TIMS) analyses on a large suite of samples. Though the ²³²Th content of these soils is not particularly low (mostly 0.1-9 ppm), the high U content of the silica component (mostly 4-26 ppm) makes them particularly suitable for ²³⁰Th/U dating on single, 10 to 200 mg totally-digested samples using TIMS. We observed that (1) both micro- (within-rind) and macro-stratigraphic (mappable deposit) order of the ²³⁰Th/U ages were preserved in all cases; (2) back-calculated initial ²³⁴U/²³⁸U fall in a restricted range (typically 1.67±0.19), so that ²³⁴U/²³⁸U ages with errors of about 100 kyr (2σ) could be reliably determined for the oldest, 400 to 1000 ka rinds; and (3) though 13 of the samples were >350 ka, only three showed evidence for an open-system history, even though the sensitivity of such old samples to isotopic disruption is very high. An attempt to use leach-residue techniques to separate pedogenic from detrital U and Th failed, yielding corrupt ²³⁰Th/U ages. We conclude that ²³⁰Th/U ages determined from totally dissolved, multiple sub-mm size subsamples provide more reliable estimates of soil chronology than methods employing larger samples, chemical enhancement of ²³⁸U/²³²Th, or isochrons.     

Geochemical evolution of a shallow magma plumbing system during the last 500 years, Miyakejima volcano, Japan: Constraints from U-Th-Ra systematics

In order to unravel magma processes and the geochemical evolution of shallow plumbing systems beneath active volcanoes, we investigated U-series disequilibria of rocks erupted over the past 500 years (1469-2000 AD) from Miyakejima volcano, Izu arc, Japan. Miyakejima volcanic rocks show ²³⁸U-²³⁰Th-²²⁶Ra disequilibria with excess ²³⁸U and ²²⁶Ra, due to the addition of slab-derived fluids to the mantle wedge. Basaltic bombs of the 2000 AD eruption have the lowest (²³⁰Th/²³²Th) ratio compared to older Miyakejima eruptives, yielding the youngest ²³⁸U-²³⁰Th model age of 2 kyr. This reinforces our previous model that fluid release from the slab and subsequent magma generation in the mantle wedge beneath Miyakejima occur episodically on a several-kyr timescale. In the last 500 years, Miyakejima eruptives show: (1) a vertical trend in a (²³⁰Th/²³²Th)-(²³⁸U/²³²Th) diagram and (2) a positive linear correlation in a (²²⁶Ra/²³⁰Th)₀ − 1/²³⁰Th diagram, which is also observed in lavas from some of the single eruptions (e.g., 1940, 1962, and 1983 AD). The variations cannot be produced by simple fractional crystallization in a magma chamber with radioactive decay of ²³⁰Th and ²²⁶Ra, but it is possibly produced by synchronous generation of melts in the mantle wedge with different upwelling rate or addition of multiple slab-derived fluids. A much more favorable scenario is that some basaltic magmas were intermittently supplied from deep in the mantle and injected into the crust, subsequently modifying the original magma composition and producing variations in (²³⁰Th/²³²Th) and (²²⁶Ra/²³⁰Th)₀ ratios via assimilation and fractional crystallization (AFC). The assimilant of the AFC process would be a volcanic edifice of previous Miyakejima magmatism. Due to the relatively short timescales involved, the interaction between the assimilant and recent Miyakejima magmatism has not been recorded by the Sr-Nd-Pb isotopic systems. In such cases, Th isotopes and (²²⁶Ra/²³⁰Th) ratio are excellent geochemical tracers of magmatic evolution.     

U-series disequilibria in volcanic rocks from the Canary Islands: Plume versus lithospheric melting

U-series disequilibria are presented for Holocene samples from the Canary Islands and interpreted with special emphasis on the separate roles of plume vs. lithospheric melting processes. We report Th and U concentrations and (²³⁸U)/(²³²Th), (²³⁰Th)/(²³²Th), (²³⁰Th)/(²³⁸U) and (²³⁴U)/(²³⁸U) for 43 samples, most of which are minimally differentiated, along with (²²⁶Ra)/(²³⁰Th) and (²³¹Pa)/(²³⁵U) for a subset of these samples, measured by thermal ionization mass spectrometry (TIMS). Th and U concentrations range between 2 and 20 ppm and 0.5 and 6 ppm, respectively. Initial (²³⁰Th)/(²³⁸U) ranges from 1.1 to 1.6. (²²⁶Ra)/(²³⁰Th)_o ranges between 0.9 and 1.8 while (²³¹Pa)/(²³⁵U)_o ranges between 1.0 and 2.0.Our interpretation of results is based on a three-fold division of samples as a function of incompatible element ratio, such as Nb/U. The majority of samples have Nb/U = 47 ± 10, similar to most MORB and OIB. Higher ratios are found exclusively in alkali basalts and tholeiites from the eastern Canary Islands whereas lower ratios are exclusively found in differentiated rocks from the western Canary Islands. Those with ordinary Nb/U ratios are attributed to melting within the slowly ascending HIMU-dominated Canary plume.Higher Nb/U, generally found in more silica rich basalts from the eastern islands, is attributed to lithospheric contamination. Based on their trace element characteristics, two possible contaminants are amphibole veins (± other minerals) crystallized in the mantle from previous plume-derived basanite or re-melted plume-derived intrusive rocks. The high Nb/U signature of these materials is imparted on a melt of the lithosphere created either by the diffusive infiltration of alkalis or by direct reaction between basanites and peridotite. Mixing between plume-derived basanite and lithospheric melt accounts for the U-series systematics of most eastern island magmas including the well-known Timanfaya eruption. Lower Nb/U ratios in differentiated rocks from the western islands are attributed to fractional crystallization of amphibole ± phlogopite ± sphene from basanite during its ascent through the lithosphere. Based on changes in disequilibria, phonolites and tephrites are interpreted to result from rapid differentiation of primitive parents within millennia.     

Distinguishing lower and upper crustal processes in magmas erupted during the buildup to the 7.7 ka climactic eruption of Mount Mazama, Crater Lake, Oregon, using 238U–230Th disequilibria

Uranium-series isotope ratios determined for 35 volcanic rocks and 4 glass separates erupted from ~36 to 4.8 ka at Mt. Mazama, Crater Lake, Oregon, identify both ²³⁰Th-excess and ²³⁸U-excess components. U–Th isotope compositions cover a wide range, exceeding those previously measured for the Cascade arc. Age-corrected (²³⁰Th/²³²Th) and (²³⁸U/²³²Th) activity ratios range from 1.113 to 1.464 and from 0.878 to 1.572 (44.4 % ²³⁰Th-excess to 8.8 % ²³⁸U-excess), respectively. The most distinctive aspect of the data set is the contrast in U–Th isotope ratios between low and high Sr (LSr, HSr) components that have been previously identified in products of the 7.7 ka caldera-forming climactic eruption and preclimactic rhyodacite lavas. The LSr component exclusively contains ²³⁸U-excess, but the HSr component, as well as more primitive lavas, are marked by ²³⁰Th-excess. ²³⁰Th-excesses such as those recorded at Mt. Mazama are commonly observed in the Cascades. Melting models suggest that high ²³⁰Th-excesses observed in the more primitive lavas evolved through mixing of a mantle melt with a partial melt of a mafic lower crustal composition that contained garnet in the residuum that was produced through dehydration melting of amphibolite that was initially garnet free. Dehydration melting in the lower crust offers a solution to the “hot-slab paradox” of the Cascades, where low volatile contents are predicted due to high slab temperatures, yet higher water contents than expected have been documented in erupted lavas. The ²³⁸U-excess observed at Mt. Mazama is rare in Cascade lavas, but occurs in more than half of the samples analyzed in this study. Traditionally, ²³⁸U-excess in arc magmas is interpreted to reflect slab fluid fluxing. Indeed, ²³⁸U-excess in arcs is common and likely masks ²³⁰Th-excess resulting from lower crustal interaction. Isotopic and trace element data, however, suggest a relatively minor role for slab fluid fluxing in the Cascades. We propose that ²³⁸U-excess reflects melting and assimilation of young, hydrothermally altered upper crust. The processes related to generating ²³⁸U-excess are likely important features at Mt. Mazama that accompanied development of a large-scale silicic magma chamber that led to the caldera-forming eruption.     

Silicic magmas from the continental Cameroon Volcanic Line (Oku, Bambouto and Ngaoundere): 40Ar-39Ar dates, petrology, Sr-Nd-O isotopes and their petrogenetic significance

The intraplate Cameroon Volcanic Line (CVL) straddles the African-South Atlantic continent-ocean boundary and is composed mainly of alkaline basic volcanic rocks. Voluminous silicic volcanics characterize the continental sector of the CVL. We present here new geochemical, isotopic (Sr-Nd-O) and ⁴⁰Ar/³⁹Ar geochronological data on the main silicic volcanic centres of the Western (Mt. Oku, Sabga and Mt. Bambouto) and Eastern (Ngaoundere plateau) Cameroon Highlands. The silicic volcanism of Mt. Oku, Sabga and Mt. Bambouto occurred between 25 and 15 Ma and is represented by voluminous quartz-normative trachytes and minor rhyolitic ignimbrites. At Mt. Bambouto central volcano about 700 m of silicic volcanics erupted in less than 2.7 million years. These silicic volcanics are associated with slightly to moderately alkaline basalts and minor basanites. In general, onset of the silicic volcanism migrated from NE (Oku: 25 Ma) to SW (Sabga: 23 Ma; Bambouto: 18 Ma; and Mt. Manengouba: 12 Ma). The silicic volcanism of the Ngaoundere plateau (eastern branch of the CVL) is instead dominated by nepheline-normative trachytes which are associated with strongly alkaline basalts and basanitic rocks. These Ne-trachytes are younger (11-9 Ma) than the Q-trachytes of the Western Highlands. The least differentiated silicic volcanics are isotopically similar (⁸⁷Sr/⁸⁶Sr < 0.70380; ¹⁴³Nd/¹⁴⁴Nd > 0.51278) to the associated alkaline basalts suggesting differentiation processes without appreciable interaction with crustal materials. Such interactions may, however, have played some role in the genesis of the most evolved silicic volcanics which have ⁸⁷Sr/⁸⁶Sr as high as 0.705–0.714. Fractional crystallization is the preferred mechanism for genesis of the silicic melts of both Western and Eastern Highlands, as shown by modeling major and trace element variations. The genesis of the least evolved Q-trachytes from the Western Highlands, starting from slightly to moderately alkaline basalts, is compatible with fractionation of dominantly plagioclase, clinopyroxene and magnetite. Crystal fractionation may have occurred at low pressure and at QFM buffer f _O2conditions. Parental magmas of the Ngaoundere Ne-trachytes are likely instead to have been strongly alkaline basalts which evolved through crystal fractionation at higher P (6-2 kbar) and f _O2 (QFM + 2). The migration (25 to 12 Ma) of the silicic volcanism from NE to SW in the continental sector of the CVL is reminiscent of that (31-5 Ma) of the onset of the basic volcanism in the oceanic sector (Principe to Pagalu islands) of the CVL. These ages, and that (11-9 Ma) of the silicic volcanism of the Ngaoundere plateau, indicate that the Cameroon Volcanic Line as a whole may not be easily interpreted as the surface expression of hot-spot magmatism. Received: 24 February 1998 / Accepted: 22 September 1998     

U-Th chronology and paleoceanographic record in a Fe-Mn crust from the NE Atlantic over the last 700 ka

Hydrogenetic ferromanganese crusts (Fe-Mn crusts) provide a secular record of the variations of seawater composition responding to changes in ocean circulation and erosion processes. In this respect, the acquisition of an absolute and reliable chronology in Fe-Mn crusts is a prerequisite. Here we combine four different and complementary chronometers (¹⁰Be, ²³⁰Th_ex, ²³⁰Th_ex/²³²Th, ²³⁴U/²³⁸U) in a Fe-Mn crust dredged at ∼2000 m depth in the east Atlantic to first establish a reliable chronology over the Quaternary period. Then, we use EDS chemical analysis to look for correlation between major element chemistry and climate changes. (²³⁰Th_ex), (²³⁰Th_ex/²³²Th), and Be data give very consistent growth rates. In particular, the good match between (²³⁰Th_ex) and (²³⁰Th_ex/²³²Th) data indicates that at the location of crust 121DK, ²³⁰Th and ²³²Th fluxes in the water column change simultaneously and suggests that the normalization of ²³⁰Th_ex to ²³²Th makes (²³⁰Th_ex/²³²Th) a better chronometer. Our best-fit model suggests that crust 121DK experienced changes in growth rates at ∼122 and 312 ka and a growth with a constant ²³⁰Th initial flux. This chronology returns an age of 680 ka for the uppermost 1.5 mm. The (²³⁴U/²³⁸U) depth profile, however, was clearly affected by diffusion of ²³⁴U in the porous crust and can therefore not be used to derive a reliable chronology. One part of the crust seems isolated from pore water diffusion and can be physically recognized as a zone of very small porosity. On the basis of the (²³⁰Th_ex/²³²Th) chronology, major element chemistry is shown to be linked to climate change. Mn/Fe variations compare well with those in a Fe-Mn crust from the Pacific, showing systematic maxima during glacial stages 2 and 4. High Mn/Fe are tentatively interpreted to reflect expansion of the oxygen minimum zone during glacial periods, resulting from higher bioproductivity. In addition we note that the surface (²³⁰Th/²³²Th) activity ratio of crust 121DK is entirely consistent with advection of deep water from the western toward the eastern Atlantic basin.     

Timescales of magma differentiation from basalt to andesite beneath Hekla Volcano, Iceland: Constraints from U-series disequilibria in lavas from the last quarter-millennium flows

Measurements of ²³⁸U-²³⁰Th-²²⁶Ra disequilibria, Sr-Nd-Pb-Hf isotopes and major-trace elements have been conducted for lavas erupted in the last quarter-millennium at Hekla volcano, Iceland. The volcanic rocks range from basalt to dacite. Most of the lavas (excluding dacitic samples) display limited compositional variations in radiogenic Sr-Nd-Pb-Hf isotopes (⁸⁷Sr/⁸⁶Sr = 0.70319-0.70322; ¹⁴³Nd/¹⁴⁴Nd = 0.51302-0.51305; ²⁰⁶Pb/²⁰⁴Pb = 19.04-19.06; ²⁰⁷Pb/²⁰⁴Pb = 15.53-15.54; ²⁰⁸Pb/²⁰⁴Pb = 38.61-38.65; ¹⁷⁶Hf/¹⁷⁷Hf = 0.28311-0.28312). All the samples possess (²³⁰Th/²³⁸U) disequilibrium with ²³⁰Th excesses, and they show systematic variations in (²³⁰Th/²³²Th) and (²³⁸U/²³²Th) ratios. The highest ²²⁶Ra excesses occur in the basalt and most differentiated andesite lavas, while some basaltic-andesite lavas have (²²⁶Ra/²³⁰Th) ratio that are close to equilibrium. The ²³⁸U-²³⁰Th-²²⁶Ra disequilibria variations cannot be produced by simple closed-system fractional crystallization with radioactive decay of ²³⁰Th and ²²⁶Ra in a magma chamber. A closed-system fractional crystallization model and assimilation and fractional crystallization (AFC) model indicate that the least differentiated basaltic andesites were derived from basalt by fractional crystallization with a differentiation age of ∼24 ± 11 kyr, whereas the andesites were formed by assimilation of crustal material and fractionation of the basaltic-andesites within 2 kyr. Apatite is inferred to play a key role in fractionating the parent-daughter nuclides in ²³⁰Th-²³⁸U and ²²⁶Ra-²³⁰Th to make the observed variations. Our proposed model is that several batches of basaltic-andesite magmas that formed by fractional crystallization of a basaltic melt from a deeper reservoir, were periodically injected into the shallow crust to form individual magma pockets, and subsequently modifying the original magma compositions via simultaneous assimilation and fractional crystallization. The assimilant is the dacitic melt, which formed by partial melting of the crust.     

Pleistocene climatic change in Southern Australia and its effect on speleothem deposition in some Nullarbor caves

Activity ratios of ²³⁴U/²³⁸U, ²³⁰Th/²³⁴U, and ²³⁰Th/²³²Th have been determined for calcite, gypsum and halite speleothems from caves of the Nullarbor Plain, mostly in the area N and NW of Mundrabilla Station, for the purpose of U-series dating. All calcite speleothems contain adequate amounts of uranium for dating, but some show an excess of ²³⁰Th. Stratigraphic relationships indicate that there were at least three phases of calcium carbonate deposition in the Nullarbor caves. The calcite samples, with one possible exception, have ages in excess of ca. 400000 yrs BP. This suggests that no significant amounts of calcium carbonate deposition have taken place during the last 400ka. At present, active deposition of speleothems is restricted almost entirely to gypsum and halite. The only gypsum speleothem dated was found to have a finite age of ca. 185 ka. Six dates on a small halite speleothem containing insect and arachnid remains indicate that it formed rapidly during Holocene time.     

U‐Th Zircon Dating by Laser Ablation Single Collector Inductively Coupled Plasma‐Mass Spectrometry (LA‐ICP‐MS)

Zircon crystals in the age range of ca. 10–300 ka can be dated by ²³⁰Th/²³⁸U (U‐Th) disequilibrium methods because of the strong fractionation between Th and U during crystallisation of zircon from melts. Laser ablation inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) analysis of nine commonly used reference zircons (at secular equilibrium) and a synthetic zircon indicates that corrections for abundance sensitivity and dizirconium trioxide molecular ions (Zr₂O₃⁺) are critical for reliable determination of ²³⁰Th abundances in zircon. When corrected for abundance sensitivity and interferences, mean activity ratios of (²³⁰Th)/(²³⁸U) for nine reference zircons analysed on five different days averaged 0.995 ± 0.023 (95% confidence weighted by data‐point uncertainty only, MSWD = 1.6; n = 9), consistent with their U‐Pb ages > 4 Ma that imply equilibrium for all intermediate daughter isotopes (including ²³⁰Th) within the ²³⁸U decay chain. U‐Th zircon ages generated by LA‐ICP‐MS without mitigating (e.g., by high mass resolution) or correcting for abundance sensitivity and molecular interferences on ²³⁰Th are potentially unreliable. To validate the applicability of LA‐ICP‐MS to this dating method, we acquired data from three late Quaternary volcanic units: the 41 ka Campanian Ignimbrite (plutonic clasts), the 161 ka Kos Plateau Tuff (juvenile clasts) and the 12 ka Puy de Dôme trachyte lava (all eruption ages by Ar/Ar, with zircon U‐Th ages being of equal or slightly older). A comparison of the corrected LA‐ICP‐MS results with previously published secondary ion mass spectrometry (SIMS) data for these rocks shows comparable ages with equivalent precision for LA‐ICP‐MS and SIMS, but much shorter analysis durations (~ 2 min vs. ~ 15 min) per spot with LA‐ICP‐MS and much simpler sample preparation. Previously undated zircons from the Yali eruption (Kos‐Nisyros volcanic centre, Greece) were analysed using this method. This yielded a large age spread (~ 45 to > 300 ka), suggesting significant antecryst recycling. The youngest zircon age (~ 45 ± 10 ka) provides a reasonable maximum estimate for the eruption age, in agreement with the previously published age using oxygen isotope stratigraphy (~ 31 ka).     

Transport of radionuclides in an unconfined chalk aquifer inferred from U-series disequilibria

U-series disequilibria measured in waters and rocks from a chalk aquifer in France have been used as an analog for long-term radionuclide migration. Drill core samples from a range of depths in the vadose zone and in the saturated zone, as well as groundwater samples were analyzed for ²³⁸U, ²³⁴U, ²³²Th and ²³⁰Th to determine transport mechanisms at the water/rock interface and to quantify parameters controlling the migration of radionuclides. Isotope measurements in rocks were done by TIMS, whereas (²³⁴U/²³⁸U) and (²³⁰Th/²³²Th) activity ratios in water samples were measured by multi-collector-ICP-MS. Both depletion and enrichment in ²³⁴U relative to ²³⁸U were observed in carbonate rock samples resulting from chemical weathering in the unsaturated zone and calcite precipitation in the zone of water-table oscillation, respectively. The correlation between (²³⁰Th/²³²Th) activity ratios and ⁸⁷Sr/⁸⁶Sr ratios found in the chalk samples indicates that thorium is mainly contained in a minor silicate phase whose abundance is variable in chalk samples. Water samples are all characterized by (²³⁴U/²³⁸U) > 1 resulting from α-recoil effect of ²³⁴Th. Groundwaters are characterized by a more radiogenic signature in ⁸⁷Sr/⁸⁶Sr than the rocks. Moreover, (²³⁰Th/²³²Th) activity ratios in the waters are lower than in the rocks, and increase with distance from the water divide, which suggests that Th transport is controlled by colloids formed during water infiltration in the soil. A 1-D transport model has been developed in order to constrain the U-series nuclide transport considering a transient behavior of radionuclides in the aquifer and a time-dependent composition for the solid phase. This model permits a prediction of the time scale of equilibration of the system, and an estimation of parameters such as weathering rate, distribution coefficients and α-recoil fractions. Retardation factors of 10-35 and from 1 × 10⁴ to 2 × 10⁵ were predicted for U and Th, respectively, and can be used to predict the migration of radionuclides released as contaminants in the environment. At the scale of our watershed (∼32 km²), a characteristic migration time from recharge to riverine discharge of 200-600 yr for U and 0.2-3.7 Myr for Th was obtained.     

Factors controlling the groundwater transport of U, Th, Ra, and Rn

A model for the groundwater transport of naturally occurring U, Th, Ra, and Rn nuclides in the²³⁸U and²³²Th decay series is discussed. The model developed here takes into account transport by advection and the physico-chemical processes of weathering, decay, α-recoil, and sorption at the water-rock interface. It describes the evolution along a flowline of the activities of the²³⁸U and²³²Th decay series nuclides in groundwater. Simple sets of relationships governing the activities of the various species in solution are derived, and these can be used both to calculate effective retardation factors and to interpret groundwater data. For the activities of each nuclide, a general solution to the transport equation has been obtained, which shows that the activities reach a constant value after a distance ϰ_i, characteristic of each nuclide. Where ϰ_i is much longer than the aquifer length, (for²³⁸U,²³⁴U, and²³²Th), the activities grow linearly with distance. Where gKⁱ is short compared to the aquifer length, (for²³⁴Th,²³⁰Th,²²⁸Th,²²⁸Ra, and²²⁴Ra), the activities rapidly reach a constant or quasi-constant activity value. For²²⁶Ra and²²²Rn, the limiting activity is reached after 1 km. High δ²³⁴U values (proportional to the ratio^ɛ234Th/^W238U) can be obtained through high recoil fraction and/or low weathering rates. The activity ratios²³⁰Th/²³²Th,²²⁸Ra/²²⁶Ra and²²⁴Ra/²²⁶Ra have been considered in the cases where either weathering or recoil is the predominant process of input from the mineral grain. Typical values for weathering rates and recoil fractions for a sandy aquifer indicate that recoil is the dominant process for Th isotopic ratios in the water. Measured data for Ra isotope activity ratios indicate that recoil is the process generally controlling the Ra isotopic composition in water. Higher isotopic ratios can be explained by different desorption kinetics of Ra. However, the model does not provide an explanation for²²⁸Ra/²²⁶Ra and²²⁴Ra/²²⁶Ra activity ratios less than unity. From the model, the highest²²²Rn emanation equals 2ɛ. This is in agreement with the hypothesis that²²²Rn activity can be used as a first approximation for input by recoil (Krishnaswamiet al 1982). However, high²²²Rn emanation cannot be explained by production from the surface layer as formulated in the model. Other possibilities involve models including surface precipitation, where the surface layer is not in steady-state.     

Plume-lithosphere interaction beneath Mt. Cameroon volcano, West Africa: Constraints from U-Th-Ra and Sr-Nd-Pb isotope systematics

Precise measurements of ²³⁸U-²³⁰Th-²²⁶Ra disequilibria in lavas erupted within the last 100 yr on Mt. Cameroon are presented, together with major and trace elements, and Sr-Nd-Pb isotope ratios, to unravel the source and processes of basaltic magmatism at intraplate tectonic settings. All samples possess ²³⁸U-²³⁰Th-²²⁶Ra disequilibria with ²³⁰Th (18-24%) and ²²⁶Ra (9-21%) excesses, and there exists a positive correlation in a (²²⁶Ra/²³⁰Th)-(²³⁰Th/²³⁸U) diagram. The extent of ²³⁸U-²³⁰Th-²²⁶Ra disequilibria is markedly different in lavas of individual eruption ages, although the (²³⁰Th/²³²Th) ratio is constant irrespective of eruption age. When U-series results are combined with Pb isotope ratios, negative correlations are observed in the (²³⁰Th/²³⁸U)-(²⁰⁶Pb/²⁰⁴Pb) and (²²⁶Ra/²³⁰Th)-(²⁰⁶Pb/²⁰⁴Pb) diagrams. Shallow magma chamber processes like magma mixing, fractional crystallization and wall rock assimilation do not account for the correlations. Crustal contamination is not the cause of the observed isotopic variations because continental crust is considered to have extremely different Pb isotope compositions and U/Th ratios. Melting of a chemically heterogeneous mantle might explain the Mt. Cameroon data, but dynamic melting under conditions of high D_U and D_U/D_Th, long magma ascent time, or disequilibrium mineral/melt partitioning, is required. The most plausible scenario to produce the geochemical characteristics of Mt. Cameroon samples is the interaction of melt derived from the asthenospheric mantle with overlying sub-continental lithospheric mantle which has elevated U/Pb (>0.75) and Pb isotope ratios (²⁰⁶Pb/²⁰⁴Pb > 20.47) due to late Mesozoic metasomatism.     

Uranium-series chronology for sediments of Lake Hovsgol, Mongolia, and the 1-Ma records of uranium and thorium isotopes from the HDP-04 drill core

Uranium and thorium isotopes in an 81-m long sediment core (HDP-04) of Lake Hovsgol, Mongolia, were measured to investigate their downcore distributions and to explore potential linkage to paleoenvironmental changes. Three-dimensional isochron techniques using isotope-ratio diagrams in ²³⁸U–²³⁴U–²³⁰Th–²³²Th system presented by Ludwig and Titterington were applied to age date the lake sediments at the depths of 11.42, 14.71 and 14.83 m in the HDP-04 section, the estimated ages of these horizons are 66 ± 8, 122 ± 11 and 128 ± 22 ka, respectively. The ²³⁸U concentration throughout the entire section fluctuated by a factor of 12, ranging from 19.9 to 232.1 mBq/g with anomalously high ²³⁸U peak at 23.8 m in depth, while the ²³²Th concentration varied only by a factor of about two between 24.3 and 54.0 mBq/g. The discrimination of the bulk ²³⁸U into authigenic and terrigenous ²³⁸U fractions was attempted, based on the measured ²³²Th as a correction index for terrigenous materials. In the upper 24 m corresponding to the last 250 ka, the authigenic ²³⁸U was higher in interglacials and lower in glacials. This depth profile of authigenic ²³⁸U contents was almost identical pattern with that found in a sediment core (VER98-1-6) from the Academician Ridge, Lake Baikal. Further, this profile can be correlated well with that of photosynthetic pigment contents, one of proxies of paleoproductivity, suggesting that the variation of authigenic ²³⁸U contents were associated with the environmental change around Lake Hovsgol.