Melting rates beneath Hawaii: Evidence from uranium series isotopes in recent lavas

²³⁸U, ²³²Th, ²³⁰Th and ²²⁶Ra abundances have been measured in six samples of recent Hawaiian basalt by high precision mass spectrometry, in an attempt to compare the melting process in plumes and at spreading ridges. The data reveal a very small range in (²³⁰Th/²³⁸U) activity ratio up to a maximum value of 1.02 ± 0.01, and (²²⁶Ra/²³⁰Th) activity ratios which lie between 1.10 ± 0.015 and 1.19 ± 0.02. UTh and RaTh abundances are linearly correlated demonstrating that the disequilibria predate crystallisation and differentiation. Using recently published estimates for the bulk partition coefficients of U and Th, the results are consistent with melting rates > 10⁻³ kg m⁻³ a⁻¹ at porosities < 10⁻³ for dynamic fractional melting in the garnet stability field.     

Uranium and thorium diffusion in diopside

This paper presents new experimental data on the tracer diffusion rates of U and Th in diopside at 1 atm and 1150–1300°C. Diffusion couples were prepared by depositing a thin layer of U–Th oxide onto the polished surface of a natural diopside single crystal, and diffusion profiles were measured by ion microprobe depth profiling. For diffusion parallel to [001] the following Arrhenius relations were obtained: log₁₀D_U=(−5.75±0.98)−(418±28 kJ/mol)/2.303RT log₁₀D_Th=(−7.77±0.92)−(356±26 kJ/mol)/2.303RT. The diffusion data are used to assess the extent to which equilibrium is obtained during near fractional melting of a high-Ca pyroxene bearing mantle peridotite. We find that the diffusion rates for both elements are slow and that disequilibrium between solid and melt will occur under certain melting conditions. For near-fractional adiabatic decompression melting at ascent rates >3 cm/yr, high-Ca pyroxene will exhibit disequilibrium effects. High-Ca pyroxene will become zoned in U and Th and the melts extracted will be depleted in these incompatible elements relative to melts produced by equilibrium fractional melting. U and Th diffusivities in high-Ca pyroxene are similar, and diffusive fractionation of these elements will be limited. Numerical solutions to a dynamic melting model with diffusion-controlled chemical equilibration indicate that the activity ratio [²³⁰Th/²³⁸U] in a partial melt of spinel peridotite will be slightly less than 1 for a broad range of melting parameters. This result reinforces the already widely accepted conclusion that melting of spinel peridotite cannot account for ²³⁰Th excesses in mid-ocean ridge and ocean island basalts, and that garnet must therefore be present over part of the melting column.     

U,U andTh in seawater

We have developed techniques to determine²³⁸U,²³⁴U and²³²Th concentrations in seawater by isotope dilution mass spectrometry. U measurements are made using a²³³U²³⁶U double spike to correct for instrumental fractionation. Measurements on uranium standards demonstrate that²³⁴U/²³⁸U ratios can be measured accurately and reproducibly.²³⁴U/²³⁸U can be measured routinely to ± 5‰ (2σ) for a sample of 5 × 10⁹ atoms of²³⁴U (3 × 10⁻⁸ g of total U, 10 ml of seawater). Data acquisition time is 1 hour. The small sample size, high precision and short data acquisition time are superior to-counting techniques.²³⁸U is measured to ± 2‰ (2σ) for a sample of 8 × 10¹² atoms of²³⁸U ( 3 × 10⁻⁹ g of U, 1 ml of seawater).²³²Th is measured to ± 20‰ with 3 × 10¹¹²³²Th atoms (10⁻¹⁰ g²³²Th, 1 1 of seawater). This small sample size will greatly facilitate investigation of the²³²Th concentration in the oceans. Using these techniques, we have measured²³⁸U,²³⁴U and²³²Th in vertical profiles of unfiltered, acidified seawater from the Atlantic and²³⁸U and²³⁴U in vertical profiles from the Pacific. Determinations of²³⁴U/²³⁸U at depths ranging from 0 to 4900 m in the Atlantic (7°44′N, 40°43′W) and the Pacific (14°41′N, 160°01′W) Oceans are the same within experimental error (± 5‰,2σ). The average of these²³⁴U/²³⁸U measurements is 144 ± 2‰ (2σ) higher than the equilibrium ratio of 5.472 × 10⁻⁵. U concentrations, normalized to 35‰ salinity, range from 3.162 to 3.281 ng/g, a range of 3.8%. The average concentration of the Pacific samples (31°4′N, 159°1′W) is 1% higher than that of the Atlantic (7°44′N, 40°43′W and 31°49′N, 64°6′W).²³²Th concentrations from an Atlantic profile range from 0.092 to 0.145 pg/g. The observed constancy of the²³⁴U/²³⁸U ratio is consistent with the predicted range of²³⁴U/²³⁸U using a simple two-☐ model and the residence time of deep water in the ocean determined from¹⁴C. The variation in salinity-normalized U concentrations suggests that U may be much more reactive in the marine environment than previously thought.     

Radionuclide fluxes in the Arabian Sea: the role of particle composition

We investigated the influence of the composition of the vertical particle flux on the removal of particle reactive natural radionuclides (²³⁰Th and ²³¹Pa) from the water column to the sediments. Radionuclide concentrations determined in sediment traps moored in the western, central and eastern Arabian Sea were related to the major components (carbonate, particulate organic matter (POC), opal, lithogenic material) of the particle flux. These data were combined with sediment trap data previously published from the Southern Ocean, Equatorial Pacific and North Atlantic [Z. Chase, R.F. Anderson, M.Q. Fleisher, P.W. Kubik, The influence of particle composition and particle flux on scavenging of Th, Pa and Be in the ocean, Earth Planet. Sci. Lett. 204 (2002) 215–229; J.C. Scholten, F. Fietzke, S. Vogler, M. Rutgers van der Loeff, A. Mangini, W. Koeve, J. Waniek, P. Stoffers, A. Antia, J. Kuss, Trapping efficiencies of sediment traps from the deep eastern North Atlantic: The ²³⁰Th calibration, Deep Sea Research II 48 (2001) 2383–2408]. The correlations observed between the particle-dissolved distribution coefficients (K_d) of ²³⁰Th and ²³¹Pa and the concentrations of the particle types depend on the sediment trap data set used. This result suggests that scavenging affinities of the nuclides differ between oceanic regions. Several factors (K_d values, reactive surface areas of particles, inter-correlations in closed data set) can, however, influence the observed relationships and thus hamper the interpretation of these correlation coefficients as a measure of relative scavenging affinities of the nuclides to the particle types investigated. The mean fractionation factor (F(Pa/Th)=K_d(Pa)/K_d(Th)) from the Equatorial Pacific (F=0.11±0.03) is similar to that from the North Atlantic (F(Pa/Th)=0.077±0.026), and both are lower than the factors from the Arabian Sea (F(Pa/Th)=0.35±0.12) and from the Southern Ocean (F(Pa/Th)=0.87±0.4). For opal concentrations exceeding 60%, an increase in the fractionation factors is observed causing a higher mean fractionation factor for the Southern Ocean trap data set. For the other areas investigated, differences in the mean fractionation factors cannot be related to the particles types considered. In the Arabian Sea, seasonally variable ²³¹Pa_ex/²³⁰Th_ex ratios observed in the sediment traps as well as differences of the ratios between recently deposited phytodetritus (fluff) and normal surface sediments indicate seasonal changes in scavenging processes which the generally accepted reversible scavenging models do not envisage. We assume that variable sinking rates of particles, and/or particles not considered in this study (e.g. colloids, manganese oxides, transparent exopolymer particles) may play an important but as yet unexplored role in deep-water scavenging processes.     

Estimating the uncertainty of coral isochron U–Th ages

Recently, alternative models to estimate the age of diagenetically altered fossil reef corals have been presented based on either redistribution of U or its immediate daughters ²³⁴Th and ²³⁰Th. Here, we present three methods to estimate the uncertainty of ages derived using an amended version of our coral isochron method [Scholz et al., 2004. U-series dating of diagenetically altered fossil reef corals. Earth and Planetary Science Letters 218, 163–178], which is based on addition/loss of U. The obtained uncertainties are substantially larger than those previously published and should, in general, be more reliable. The isochron method yields larger uncertainties than alternative models based on Th redistribution due to -recoil processes. However, comparison of model open-system ages based on such redistribution of U-series daughters for different sub-samples from an individual coral specimen shows that the smaller errors derived with these models cannot account for the observed variability. We recognise that none of the available models is applicable to all corals, probably reflecting different diagenetic processes even in different sub-samples from one coral specimen. To better understand the diagenetic processes and precisely constrain the uncertainties of the ages derived from diagenetically altered corals, the application of all available models is recommended.     

Issues in radiocarbon and U-series dating of corals from the last glacial period

Radiocarbon calibration beyond the extent of tree-ring records depends on U-series dating of fossil corals or speleothem, both of which can provide independent calendar ages. Less direct methods rely on layer counting and comparison with other well-dated records. In spite of considerable effort to provide a reliable radiocarbon calibration curve beyond 25,000 years, the majority of the data show large atmospheric radiocarbon peaks which are inconsistent both in magnitude and timing between different determinations. The results of the most recent work [Chiu, T.-C., Fairbanks, R.G., Mortlock, R.A., Bloom, A.L., 2005. Extending the radiocarbon calibration beyond 26,000 years before present using fossil corals. Quaternary Science Reviews 24 (16–17), 1797–1808], from Araki Island fossil corals, indicate a monotonic variation from about 33 to 49 ka, with no radiocarbon peaks, but with some gaps in the data. The difference between this and previous results, from fossil corals, has been attributed to selection of better-quality samples and rigorous analytical methods. However, previous results from Huon Peninsula [Yokoyama, Y., Esat, T.M., Lambeck, K., Fifield, L.K., 2000. Last ice age millennial scale climate changes recorded in Huon Peninsula corals. Radiocarbon 42 (3), 383–401; Cutler, K.B., Gray, S.C., Burr, G.S., Edwards, R.L., Taylor, F.W., Cabioch, G., Beck, J.W., Cheng, H., Moore, J., 2004. Radiocarbon calibration and comparison to 50 kyr BP with paired ¹⁴C and ²³⁰Th dating of corals from Vanuatu and Papua New Guinea. Radiocarbon 46 (3), 1127–1160] show radiocarbon peaks exclusively located within the gaps in the Araki data. The timing of the gaps are not random, but appear to be related to severe climate and sea-level variations associated with Heinrich events initiated in the North Atlantic. We propose that the Huon and Araki data sets are complementary rather than exclusive and that the absence of coral growth at Araki Island during Heinrich events presumably reflect local adverse conditions for coral growth.     

Experimental determination of U and Th partitioning between clinopyroxene and natural and synthetic basaltic liquid

Clinopyroxene-silicate liquid partition coefficients for U and Th have been determined by particle track radiography from 1 atm crystallization experiments at controlledfO₂. Two natural basaltic and one synthetic composition were studied atfO₂ values from the NiNiO oxygen buffer to 1 log unit more oxidizing than FeFeO (IW+ 1). Over the range offO₂ values and compositions studied,D_U^cpx/liq = 0.0034–0.015,D_Th^cpx/liq = 0.008–0.036, andD_ThD_U= 3.4–1.1. With decreasingfO₂,D_ThD_U can decrease by up to a factor of 3 for a given composition, primarily from an increase inD_U^cpx/liq, which we interpret as resulting from an increase in the proportion of tetravalent U in the system with decreasingfO₂. This demonstrates that crystal-liquid UTh fractionation isfO₂ dependent and that U in terrestrial magmas is not entirely tetravalent.D_Th^cpx/liq appears to decrease in the two basalts at the lowestfO₂, possibly as a result of changes in composition withfO₂.

Our data show the sense of UTh fractionation by clinopyroxene-liquid partitioning is consistent with previous experimental determinations, in thatD_Th^cpxD_U^cpx> 1 in all cases. This indicates that, during partial melting, the liquid will have aTh/U ratio less than the clinopyroxene in the source. The observed²³⁸U²³⁰Th disequilibrium in MORB requires that the partial melt should have aTh/U ratio greater than the bulk source, and, therefore, cannot result from clinopyroxene-liquid partitioning. Further, the magnitudes of the measured partition coefficients are too small to generate significant UTh fractionation in either direction. Assuming that clinopyroxene contains the bulk of the U and Th in MORB source, our results indicate that²³⁸U²³⁰Th disequilibrium in MORB may not be caused by partial melting at all.     

Repeated thermal resetting of phengites in the Mulhacen Complex (Betic Zone, southeastern Spain) shown byAr/Ar step heating and single grain laser probe dating

This study reports the results of the first⁴⁰Ar/³⁹Ar combined induction furnace and laser probe dating of phengites from the Mulhacen HP/LT metamorphic complex in the Betic Cordilleras, southern Spain. Laser step heating and spot fusion analyses on different halves of a split single grain were made with a continuous laser probe. Spot fusion analysis resulted in ages of about 30–31 Ma in the core and ages as low as 25–26 Ma in the rim. Laser step heating on the other half of the grain gave a spectrum with apparent ages increasing from about 25 Ma to 29.5 Ma. The age spectrum and the decreasing ages towards the rim of the grain may imply that resetting essentially occurred by volume diffusion of radiogenic⁴⁰Ar due to late stage reheating resulting from extensional tectonics. Ages around 30 Ma in the core of the grain are interpreted as minimum estimates of the cooling age of the main tectono-metamorphic phaseD₂.

Induction furnace step heating on phengite separates from mica schists and one gneiss resulted in two types of age spectra. Type I spectra show monotonously rising apparent ages from14.5 ± 1.9 Ma to20.7 ± 0.2 Ma, and in a second sample from16.9 ± 0.7 to29.7 ± 0.2 Ma. Type II spectra are characterized by plateaus of14.4 ± 0.1 Ma (the gneiss sample),17.3 ± 0.1 Ma and17.6 ± 0.1 Ma. Type II spectra show low temperature apparent ages significantly below the plateau age, implying resetting subsequent to initial cooling. Modelling of the age spectra demonstrated that the plateau ages are possibly the result of strong resetting (75–85% of argon loss) of an older isotope system. Total fusion of a number of phengite single grains from marbles taken close to type II mica schists yielded ages of15.4 ± 1.2 Ma and17.0 ± 0.7 Ma. The observed repeated resetting is coeval with major volcanic activity in basins adjacent to the metamorphic ranges, pointing to a resetting by advective fluid transport related to volcanism.     

A record of changing redox conditions in the northern Peru Basin during the Late Quaternary deduced from Mn/Fe and growth rate variations in two diagenetic manganese nodules

Two diagenetic manganese nodules from the Peru Basin were investigated by thermal ionization mass spectrometry and high resolution alpha spectrometry for uranium and thorium. The TIMS concentrations for nodule 62KD (63KG) vary as follows: 0.12–1.01 ppb (0.06–0.59) ²³⁰Th, 0.51–1.98 ppm (0.43–1.40) ²³²Th, 0.13–0.80 ppb (0.09–0.49) ²³⁴U, and 1.95–13.47 ppm (1.66–8.24) ²³⁸U. Both nodules have average growth rates of 110 mm per million years. However, from the variations of excess ²³⁰Th with depth we estimate partial accumulation rates which range from 50 to 400 mm per million years. The δ²³⁴U dating method cannot be applied due to remobilization of U from the sediment and subsequent incorporation into the nodules' crystal lattice, reflected by decay corrected δ²³⁴U values far above the ocean water value. Sections of fast nodule growth are related to those layers having high Mn/Fe ratios (up to 200) and higher densities. As a possible explanation we develop a scenario that describes similar glacial/interglacial trends in both nodules as a record of regional changes of sediment and/or deep water chemistry.     

The effects of a spillage of diesel fuel on a rocky shore in the sub-Antarctic region (Macquarie Island)

On 3 December 1987, the supply ship Nella Dan ran aground at Macquarie Island (54°29′S, 158°58′E) releasing about 270 000 I of oil, mostly light marine diesel, into the sea. At the time of the incident, many marine invertebrates were washed up dead along 2 km of shoreline. Twelve months later, the shore community was investigated using 1. algal and invertebrate populations of the littoral and sublittoral rocky shore, and 2. the invertebrate communities living in the holdfasts of the giant kelp Durvillaea antarctica, which were collected for later examination. Investigations were undertaken at both affected and control locations. Analyses of differences in community structure involved nested ANOVA and multidimensional scaling techniques. On the rocky substrate, the effect of the spill was restricted to some biota of the lower littoral and sublittoral zones—particularly echinoderms and the patellid limpet Nacella macquariensis. There were differences in cover for some algal species between locations. Within the kelp holdfasts, communities were dominated by peracarid crustaceans at control locations and by polychaetes (particularly the opportunistic groups—capitellids, cirratulids and spionids) at oil-affected locations.

The communities have recently been re-surveyed (in the summer of 1994–1995) to assist in the interpretation of the results and to gauge the extent of recovery of the affected biota.     

Sulfate reduction using methane in sediments beneath a bathyal “cold seep” giant clam community off Hatsushima Island, Sagami Bay, Japan

Two sandy sediment cores (Cores D227-120 and D380) were collected from inside a deep-sea giant clam (Calyptogena soyoae) community off Hatsushima Island, western Sagami Bay, central Japan (35°59.9′N, 139°13.6′E; 1160 m deep) and a muddy sediment core (Core D227-202) was obtained from outside the community by the submersibleShinkai 2000. The chloride concentration of the pore waters is constant vertically and sulfate reduction using sedimentary organic matter occurs in Core D227-202 (21 cm long). The chloride concentrations are lower by 7% at the 7.5–9 cm depth in Core D227-120 (9 cm long) and by 3% at the 11–12 cm depth in Core D380 (16 cm long) than those of the overlying bottom waters in the cores from inside of the community. Sulfate concentration decreases remarkably and dissolved inorganic carbon, alkalinity, ammonium-N, and hydrogen sulfide concentrations increase significantly with increasing depth in Core D380.δ³⁴S values of sulfate ions increase from +20.5 to +35.3‰ andδ¹³C values of dissolved inorganic carbon decrease drastically from −7.0 to −45‰ with increasing depth from the top to the bottom of the core, although theδ¹³C values of the organic carbon of the sediments are−23.7 ± 0.9‰ in Core D380. These results indicate that sulfate reduction using methane is active within the sediments just beneath the living clams and that the hydrogen sulfide produced can be used by endosymbiotic sulfur oxidizing bacteria living in the gills ofC. soyoae in the community.     

The influence of particle composition on thorium scavenging in the NE Atlantic ocean (POMME experiment)

²³⁰Th, ²³²Th and ²³⁴Th were analyzed in sinking particles collected by moored and drifting sediment traps in the NE Atlantic Ocean (POMME experiment) in order to constrain the phase(s) carrying Th isotopes in the water column. It reveals a contrasted behaviour between ²³⁴Th and ²³⁰Th. ²³⁴Th is correlated to the particulate organic carbon suggesting that it is primarily scavenged by organic compounds in the surface waters. ²³⁰Th_xs is correlated with Mn, Ba and the lithogenic fraction that are enriched in small suspended particles and incorporated in the sinking particulate flux throughout the water column. The lack of correlation between ²³⁰Th_xs and CaCO₃ or biogenic silica (bSi) indicates that CaCO₃ and bSi are not responsible for ²³⁰Th scavenging in the deep waters of this oceanic region. ²³⁰Th is generally correlated with the lithogenic content of the trapped material but this correlation disappears in winter during strong atmospheric dust inputs suggesting that lithogenic matter is not directly responsible for ²³⁰Th scavenging in the deep waters or that sufficient time is required to achieve particle–solution equilibration. MnO₂ could be the prevalent ²³⁰Th_xs-bearing phase. The narrow range of K_{d_MnO2}^Th obtained for very contrasted oceanic environments supports a global control of ²³⁰Th_xs scavenging by MnO₂ and raises the possibility that the ²³⁰Th–²³¹Pa fractionation is controlled by the amount of colloidal MnO₂ in seawater.     

Precise Th/U-dating of small and heavily coated samples of deep sea corals

Marine carbonate skeletons like deep-sea corals are frequently coated with iron and manganese oxides/hydroxides which adsorb additional thorium and uranium out of the sea water. A new cleaning procedure has been developed to reduce this contamination. In this further cleaning step a solution of Na₂EDTA (Na₂H₂T_B) and ascorbic acid is used which composition is optimised especially for samples of 20 mg of weight. It was first tested on aliquots of a reef-building coral which had been artificially contaminated with powdered ferromanganese nodule. Applied on heavily contaminated deep-sea corals (scleractinia), it reduced excess ²³⁰Th by another order of magnitude in addition to usual cleaning procedures. The measurement of at least three fractions of different contamination, together with an additional standard correction for contaminated carbonates results in Th/U-ages corrected for the authigenic component. A good agreement between Th/U- and ¹⁴C-ages can be achieved even for extremely coated corals.     

Tin and organotin in water, sediments, and benthic organisms of Poole Harbour

Tributyltin (TBT) concentrations in waters of Poole Harbour ranged between 2–139 ng l⁻¹ (as Sn) and increased to 234–646 ng l⁻¹ within marinas. Seasonal trends in contamination coincided with boat usage patterns and peaked during summer months. A combination of poor tidal flushing and removal of TBT to particulates restricts high levels of contamination to areas closest to marinas and moorings; TBT concentrations in benthic sediments decreased from 0.52 μg g⁻¹ near such sites to 0.02 μg g⁻¹ at the harbour mouth. Organotin accumulations in several benthic invertebrates including polychaetes (Nereis diversicolor), snails (Littorina littorea) and clams (Scrobicularia plana, Mya arenaria) reflect the distribution of contamination in the environment, though concentration factors (relative to water) vary considerably between species and were highest in sediment dwelling clams, notably Mya (1.3×10⁵). Compared to organotins, biological availability of inorganic tin is low.

Levels of TBT in parts of Poole Harbour exceed Environmental Quality Targets designed to protect marine life and may be responsible for poor recruitment, particularly in bivalves, at heavily contaminated sites.     

Shape analysis of Pacific seamounts

Shape statistics have been compiled from 85 profiles of well-surveyed Pacific seamounts in the height range 140–3800 m. A flat-topped cone was fit to each seamount's cross-sectional profile maintaining the slopes of the sides as closely as possible. On each profile a basal widthd_b, a summit widthd_t, and a maximum heighth, were measured. The height-to-basal-radius ratio isξ_h is estimated by the ratio2hd_b and flatnessf by the ratiod_td_b. Slope angleφ = arctan(ε) is estimated fromε =2h(d_b − d_t). Summit height and basal radius are found to be highly correlated (r = 0.93). The 85-point sample mean of the height-to-basal-radius ratio isξ_h = 0.21 ± 0.08 implying that a seamount's summit height is typically one fifth its basal radius. Despite the high correlation, individual points show some scatter, and there may be groupings into different morphological types. For example, all but one of the seamounts with summit heights above 1000 m have values ofξ_h that are larger than the sample mean. The 85-point sample mean of flatness isf = 0.31 ± 0.18. Data points show a large scatter with values off varying between 0 (a pointy cone) and 0.69 (a flat-topped cone). A histogram representation of flatness, however, indicates that certain values off may be more common than others: the histogram shows a bimodal distribution with maxima occurring at values off in the ranges 0.10–0.20 and 0.35–0.50. Moreover, there is some evidence that the mean flatness decreases with summit height so that the preferred shape of a large-sized seamount may be a pointy cone. Slope angle has an 85-point sample mean ofφ = 18 ± 6°; individual values ofφ vary between 5° and 36°. In addition to having a lower than average mean flatness seamounts with heights above 2600 m also have a lower than average mean slope angle (15°). To determine which variables account for most of the observed variation in the seamount shapes, a multivariate principal component analysis was performed on the data using five shape variables (summit height, basal radius, summit radius, flatness, and slope). The analysis indicates that most of the variation is described by two variables: flatness and summit height.     

Late cretaceous to early paleogene paleomagnetic results from Sikhote Alin, far eastern Russia: implications for deformation of East Asia

Welded tuffs in the Bogopol and Sijanov groups were sampled at 27 sites from 12 caldera formations in the Sikhote Alin mountain range around Kavalerovo (44.3°N, 135.0°E) for chronological and paleomagnetic studies. KAr age dates show that the welded tuffs erupted between 66 Ma and 46 Ma. All sites yield reliable paleomagnetic directions, with unblocking temperatures higher than 560°C. The high-temperature component at 12 sites and the medium-temperature component at 3 sites in the Bogopol Group show reversed polarity (D = 193.7°, I = −57.6°,₉₅ = 8.1°). The high-temperature component at 11 sites in the Sijanov Group showed both reversed and normal polarities and its mean direction reveals no detectable deflection from north (D = −2.9°, I = 59.6°,₉₅ = 11.2°). The combined paleomagnetic direction of the two groups yields a paleomagnetic pole of 250.5°E, 84.1°N (A₉₅ = 8.8°), which falls near Cretaceous paleomagnetic poles from Outer Mongolia, Inner Mongolia, the North China Block and the South China Block. The Sikhote Alin area appears not to have been subjected to detectable motion with respect to East Asia since about 50 Ma. This implies that the Sikhote Alin area behaved as an integral part of East Asia during the opening of the Japan Sea at about 15 Ma. However, significant separation between the paleomagnetic poles of East Asia and Europe during the Jurassic-Paleogene implies a major relative movement between these two blocks since the Paleogene.     

Brine history indicated by argon, krypton, chlorine, bromine, and iodine analyses of fluid inclusions from the Mississippi Valley type lead-fluorite-barite deposits at Hansonburg, New Mexico

Argon, krypton, chlorine, bromine, and iodine were measured in a homogeneous population of high-salinity hydrothermal fluid inclusions from the Tertiary-age Mississippi Valley-type (MVT) lead-fluorite-barite deposits at Hansonburg, New Mexico to establish new types of evidence for the history of both the fluid and the major dissolved salts. Noble gases and halogens in fluid inclusions containing 10⁻¹⁰–10⁻⁹ L of brine (Cl= 3 molal) were analyzed by laser microprobe noble-gas mass spectrometry (lmngms) on neutron-irradiated samples.

The concentrations of³⁶Ar (4.7 × 10⁻⁸ molal) and⁸⁴Kr1.8 × 10⁻⁹ molal) in the fluid inclusions are equal to those of fresh surface waters in equilibrium with air at approximately20 ± 5°. The mole ratios ofBr/Cl (1.2 × 10⁻⁴) andI/Cl (1–2 × 10⁻⁶) are among the lowest measured in any natural waters, similar to those of modern brines formed by dissolution of Permian NaCl-bearing evaporites in southeast New Mexico.⁴⁰Ar/³⁶Ar ratios (600) are twice that of air, and indicate that the fluid inclusions had excess radiogenic⁴⁰Ar (1.4 × 10⁻⁵ molal) when trapped. The amount of excess⁴⁰Ar appears to be too large to have been acquired with Cl by congruent dissolution of halite-bearing evaporites, and possibly too small to have been acquired with Pb by congruent dissolution of granitic basement rocks with Proterozoic KAr ages.

From thelmngms data, combined with published Pb and S isotope data, we infer the following sequence of events in the history of the Hansonburg MVT hydrothermal brine: (1) the brine originated as relatively dilute meteoric water, and it did not gain or lose atmospheric Ar or Kr after recharge; (2) the originally dilute fluid acquired the bulk of its Cl and sulfate in the subsurface after recharge by dissolving halite-bearing Permian? marine evaporites; (3) the high salinity brine then acquired most of its Pb and excess radiogenic⁴⁰Ar from interactions with aquifer rocks other than evaporites, possibly clastic sedimentary rocks or basement rocks with Phanerozoic KAr “ages”; and (4) the brine deposited fluorite without having boiled or degassed.     

REE diffusion in calcite

Chemical diffusion of four rare-earth elements (La, Nd, Dy and Yb) has been measured in natural calcite under anhydrous conditions, using rare-earth carbonate powders as the source of diffusants. Experiments were run in sealed silica capsules along with finely ground calcite to ensure stability of the single-crystal samples during diffusion anneals. Rutherford backscattering spectroscopy (RBS) was used to measure diffusion profiles. The following Arrhenius relations were obtained over the temperature range 600–850°C: D_La =2.6×10⁻¹⁴ exp(−147±14 kJ mol⁻¹/RT) m² s⁻¹, D_Nd =2.4×10⁻¹⁴ exp(−150±13 kJ mol⁻¹/RT) m² s⁻¹, D_Dy =2.9×10⁻¹⁴ exp(−145±25 kJ mol⁻¹/RT) m² s⁻¹, D_Yb =3.9×10⁻¹² exp(−186±23 kJ mol⁻¹/RT) m² s⁻¹. In contrast to previous findings for refractory silicates (e.g. zircon), differences in transport rates among the REE are not pronounced over the range of temperature conditions investigated in this study. Diffusion of the REE is significantly slower than diffusion of the divalent cations Sr and Pb and slower than transport of Ca and C at temperatures above 650°C. Fine-scale zoning and isotopic and REE chemical signatures may be retained in calcites under many conditions if diffusion is the dominant process affecting alteration.     

Preliminary stratigraphic and structural architecture of Bhutan: Implications for the along strike architecture of the Himalayan system

High-precision in-situ ion microprobe (SIMS) oxygen isotope analysis of zircons from two diorite intrusions associated with the late Caledonian Lochnagar pluton in Scotland has revealed large differences in the degree of heterogeneity in zircon δ¹⁸O between the diorites. Zircon crystals from the Cul nan Gad diorite (CnG) show a unimodal distribution of oxygen isotope values (δ¹⁸O = 6.0 ± 0.6‰ (2σ)) and no or only minor grain-scale variation. Those from the Allt Darrarie diorite (AD1) show a large range in δ¹⁸O and an apparent bimodal distribution with modes of 6.6 ± 0.4‰ and 7.3 ± 0.4‰. Variations of up to 1.2‰ occur between and within grains; both an increase and decrease in δ¹⁸O with zircon growth has been observed. The δ¹⁸O composition of growing zircon can only change if open-system processes affect the magma composition, i.e. if material of contrasting δ¹⁸O composition is added to the magma. The variability in AD1 is interpreted to represent a cryptic record of magma mixing. A ‘deep crustal hot zone’ is a likely site for generation of the dioritic magmas which developed by mixing of residual melts and crustal partial melts or by melting of mafic lower crustal rocks. The overall small number of zircons with mantle-like δ¹⁸O values (5.3 ± 0.6‰ (2σ)) in the Lochnagar diorites is largely the product of crustal differentiation rather than crustal growth.

The δ¹⁸O of quartz from the CnG and AD1 diorites shows only minor variation (CnG: 10.9 ± 0.5‰ (2σ), AD1: 11.7 ± 0.6‰ (2σ)) within single populations, with no evidence of mixing. Quartz–zircon isotopic disequilibrium is consistent with later crystallisation of quartz from late magmatic fluids, and in case of the AD1 diorite after the inferred magma mixing from a homogenised, higher δ¹⁸O melt.

High-precision SIMS oxygen isotope analysis of zircon provides a new approach to identifying and resolving previously undetected early-stage magma mixing and constraining the compositions and origins of the component magmas. A combination of zircon, quartz and whole-rock data has proven to be a powerful tool in reconstructing the petrogenetic evolution of diorite from early crystallisation to late alteration.     

Sublethal effects of cupric ion activity on the grazing behaviour of three calanoid copepods

This research (1) characterized the effects of sublethal cupric ion activities on the grazing behavior of two estuarine copepods (Acartia tonsa, Acartia hudsonica) and one nearshore, neritic copepod (Temora longicornis) and (2) compared the sensitivity of short-term sublethal behavioral assays with that of longer-term acute toxicity tests. A nitrilotriacetate-trace-metal-ion buffer system at 27‰. S was used to quantify and control the free cupric ion activity. Acute toxicity tests were used to determine the mortality of A. tonsa and T. longicornis over 72 h within the approximate cupric ion activity range of 10⁻¹³ to 10^−9.5 M. 24 h survival was not affected within the approximate cupric ion activity range of 10⁻¹³ to 10^−9.7 M, the range used for subsequent grazing activity experiments after 24 h exposure to Cu. Grazing activity was significantly diminished at cupric ion activities of ≈ 10⁻¹⁰ M for A. tonsa and T. longicornis, and at ≈ 10⁻¹¹ M for A. hudsonica. A hormetic pattern of response in feeding activity was observed with A. tonsa and T. longicornis. Grazing activity was found to be a sensitive measure of sublethal Cu stress compared with the acute toxicity tests. Grazing activity was affected at environmentally relevant cupric ion activities.