Isotope Dilution MC-ICP-MS Rare Earth Element Analysis of Geochemical Reference Materials NIST SRM 610, NIST SRM 612, NIST SRM 614, BHVO-2G, BHVO-2, BCR-2G, JB-2, WS-E, W-2, AGV-1 and AGV-2

We present data for the concentrations of eleven rare earth elements (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Lu) in eleven international geochemical reference materials obtained by isotope dilution multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). We have analysed both rock powders and synthetic silicate glasses, and the latter provide precise data to support the use of these as reference materials for in situ trace element determination techniques. Our data also provide precise measurements of the abundance of mono-isotopic Pr in both glasses and powders, which allows more accurate constraints on the anomalous redox-related behaviour of Ce during geochemical processes. All materials were analysed in replicate providing data that typically reproduce to better than one percent. Sm/Nd ratios in all these materials also reproduce to better than 0.2% and are accurate to < 0.2% and can thus be used as calibrants for Sm-Nd geochronology. Our analyses agree well with existing data on these reference materials. In particular, for NIST SRM 610, USGS BHVO-2, AGV-1 and AGV-2, our measured REE abundances are typically within < 2% (and mostly 1%) of REE concentrations previously determined by isotope dilution analysis and thermal ionisation mass spectrometry, consistent with the higher degree of precision and accuracy obtained from isotope dilution techniques. Close agreement of results between basaltic glass reference materials USGS BHVO-2G and BCR-2G and the BHVO-2 and BCR-2 powders from which they were created suggests that little fractionation, concentration or dilution of REE contents occurred during glass manufacture.     

The influence of groundwater chemistry on arsenic concentrations and speciation in a quartz sand and gravel aquifera)

We examined the chemical reactions influencing dissolved concentrations, speciation, and transport of naturally occurring arsenic (As) in a shallow, sand and gravel aquifer with distinct geochemical zones resulting from land disposal of dilute sewage effluent. The principal geochemical zones were: (1) the uncontaminated zone above the sewage plume [350 μM dissolved oxygen (DO), pH 5.9]; (2) the suboxic zone (5 μM DO, pH 6.2, elevated concentrations of sewage-derived phosphate and nitrate); and (3) the anoxic zone [dissolved iron(II) 100–300 μM, pH 6.5–6.9, elevated concentrations of sewage-derived phosphate]. Sediments are comprised of greater than 90% quartz but the surfaces of quartz and other mineral grains are coated with nanometer-size iron (Fe) and aluminum (Al) oxides and/or silicates, which control the adsorption properties of the sediments. Uncontaminated groundwater with added phosphate (620 μM) was pumped into the uncontaminated zone while samples were collected 0.3 m above the injection point. Concentrations of As(V) increased from below detection (0.005 μM) to a maximum of 0.07 μM during breakthrough of phosphate at the sampling port; As(III) concentrations remained below detection. These results are consistent with the hypothesis that naturally occurring As(V) adsorbed to constituents of the coatings on grain surfaces was desorbed by phosphate in the injected groundwater. Also consistent with this hypothesis, vertical profiles of groundwater chemistry measured prior to the tracer test showed that dissolved As(V) concentrations increased along with dissolved phosphate from below detection in the uncontaminated zone to approximately 0.07 and 70 μM, respectively, in the suboxic zone. Concentrations of As(III) were below detection in both zones. The anoxic zone had approximately 0.07 μM As(V) but also had As(III) concentrations of 0.07–0.14 μM, suggesting that release of As bound to sediment grains occurred by desorption by phosphate, reductive dissolution of Fe oxides, and reduction of As(V) to As(III), which adsorbs only weakly to the Fe-oxide-depleted material in the coatings. Results of reductive extractions of the sediments suggest that As associated with the coatings was relatively uniformly distributed at approximately 1 nmol/g of sediment (equivalent to 0.075 ppm As) and comprised 20%-50% of the total As in the sediments, determined from oxidative extractions. Quartz sand aquifers provide high-quality drinking water but can become contaminated when naturally occurring arsenic bound to Fe and Al oxides or silicates on sediment surfaces is released by desorption and dissolution of Fe oxides in response to changing chemical conditions.

     

The Muralla Pircada—an ancient Andean debris flow retention dam, Santa Rita B archaeological site, Chao Valley, Northern Perú

Debris flows caused by El Niño events, earthquakes, and glacial releases have affected northern Perú for centuries. The Muralla Pircada, a northeast-trending, 2.5 km long stone wall east of the Santa Rita B archaeological site (Moche-Chimú) in the Chao Valley, is field evidence that ancient Andeans recognized and, more importantly, attempted to mitigate the effects of debris flows. The Muralla is upstream from the site and is perpendicular to local drainages. It is 1–2 m high, up to 5 m wide, and is comprised of intentionally-placed, well-sorted, well-rounded, 20–30 cm cobbles and boulders from nearby streams. Long axes of the stones are gently inclined and parallel local drainage. Case-and-fill construction was used with smaller cobbles and pebbles used as fill. Pre-Muralla debris flows are indicated by meter-sized, angular boulders that were incorporated in-place into construction of the dam and are now exposed in breeches in the dam. Post-Muralla debris flows in the Chao Valley are indicated by meter-sized, angular boulders that now abut the retention dam.     

Seasonal Variability of Adsorption and Exchange Equilibria in Soil Waters

Chemical analyses for major ions have been conducted on waters,collected on an approximately weekly basis over the period April, 1993 toNovember, 1996, that drain three small experimental ecosystems(sandboxes) at Hubbard Brook, New Hampshire. One sandbox is planted withpine trees, another with grass, and the third is left bare (actually itis covered sporadically by bryophytes and lichens). Results show linearcorrelations, independent of discharge, between the concentrations ofdissolved Na⁺ and K⁺ on the one hand andCa⁺⁺ and Mg⁺⁺ on the other for all threesandboxes. No correlations between singly charged and doubly chargedcations were found. These correlations are interpreted to represent cationexchange equilibria between soil waters and clay minerals plus soil organicmatter. The correlation slope, representing the exchange constant, for Na vsK is different for the pine-covered sandbox than for the other two whereasfor Ca vs Mg the correlation is independent of the presence or absence oftrees. We interpret this as representing a shift of cation exchangeequilibria in the pine sandbox by the activities of growing trees.Concentrations of Na, K, Ca, Mg, and H₄SiO₄from the barren and grass-lined sandboxes were found to vary seasonally witha marked sinusoidal pattern which was independent of the discharge from eachsandbox. (The discernment of a similar pattern in the tree lined sandbox wasdifficult due to a lack of discharge over much of the year.) Concentrationmaxima occurred in August and minima in February, and there is a closeparallelism with soil temperature. We interpret this as representingtemperature induced variations in cation exchange equilibria and silicaadsorption. Independence from highly varying water discharge, e.g.,. thataccompanying severe rainstorms, indicates rapidly re-attained equilibrium.Variations in the concentrations of cations are likely due to exchange withunmeasured cations, probably H⁺ or dissolved Al species, as aresult of possible seasonal changes in internal acid production and externalinput of acid rain to the sandboxes. Internal production may represent aresponse to seasonal changes in respiration rate as it responds toseasonally varying temperature. Added to this is the effect of temperatureon exchange equilibrium. Seasonal variations in dissolved silica are mostlikely due to the dependence of adsorption/desorption equilibria ontemperature. The temperature dependence of a number of silica-consumingreactions are consistent with the measured values.     

The relative stabilities of the reverse and normal polarity states of the earth's magnetic field

Recent analyses of the geomagnetic reversal sequence have led to different conclusions regarding the important question of whether there is a discernible difference between the properties of the two polarity states. The main differences between the two most recent studies are the statistical analyses and the possibility of an additional 57 reversal events in the Cenozoic. These additional events occur predominantly during reverse polarity time, but it is unlikely that all of them represent true reversal events. Nevertheless the question of the relative stabilities of the polarity states is examined in detail, both for the case when all 57 “events” are included in the reversal chronology and when they are all excluded. It is found that there is not a discernible difference between the stabilities of the two polarity states in either case. Inclusion of these short events does, however, change the structure of the non-stationarity in reversal rate, but still allows a smooth non-stationarity. Only 7 of the 57 short events are pre-38 Ma, but the evidence suggests that this is a real geomagnetic phenomenon rather than degradation of the magnetic recording or a bias in observation. This could be tested by detailed magnetostratigraphic and oceanic magnetic surveys of the Paleogene and Late Cretaceous. Overall it would appear that the present geomagnetic polarity timescale for 0–160 Ma is probably a very good representation of the actual history, and that different timescales and additional events now represent only changes in detail.     

Archean geotherms and supracrustal assemblages

Metamorphic mineral assemblages suggest the existence of variable geotherms and lithospheric thicknesses beneath late Archean continental crust. Archean granite-greenstone terranes reflect steep geotherms (50–70°C/km) while high-grade terranes reflect moderate geotherms similar to present continental crust with high heat flow (25–40°C/km). Corresponding lithosphere thicknesses for each terrane during the late Archean are 35–50 km and 50–75 km, respectively.Early Archean ( 3.0 b.y.) greenstones differ from late Archean ( 2.7 b.y.) greenstones by the rarity or absence of andesite and graywacke and the relative abundance of pelite, quartzite, and komatiite. Mature clastic sediments in early greenstones reflect shallow-water, stable-basin deposition. Such rocks, together with granite-bearing conglomerate and felsic volcanics imply the existence of still older granitic source terranes. The absence or rarity of andesite in early greenstones reflects the absence of tectonic conditions in which basaltic and tonalitic magmas are modified to produce andesite.A model is presented in which early Archean greenstones form at the interface between tonalite islands and oceanic lithosphere, over convective downcurrents; high-grade supracrustals form on stable continental edges or interiors; and late Archean greenstones form in intracontinental rifts over mantle plumes.     

SAMPLING METHODS AND APPROACHES USING RADIONUCLIDE TRACERS IN THE STUDY OF SEDIMENT RESUSPENSION AND CROSS MARGIN TRANSPORT IN NEARSHORE OF THE LAURENTIAN GREAT LAKES

1 INTRODUCTION Sediment resuspension, particularly in response to episodic storm events, is a common characteristic of coastal and nearshore environments. The resulting 揵enthic storms?may play a significant role in the dynamics of benthic systems, including structuring the physical characteristics of the bottom, providing a mechanism for the recycling of biogeochemically important materials to the water column, and driving horizontal and cross margin transport of suspended particulates …     

The behaviour of platinum-group elements in basalts from the East Greenland rifted margin

. The continental flood basalts of the East Greenland volcanic rifted margin were extruded during continental breakup above the ancestral Iceland mantle plume at 55 Ma. Three distinct magma types, the low-Ti, high-Ti and very high-Ti series (LTS, HTS and VHTS respectively), are found intercalated in the ~6-km-thick Plateau Lava sequence. Incompatible trace elements indicate that the LTS are derived from a more depleted mantle source compared to HTS and VHTS. The LTS is characterised by increasing Cu (105 to 248 ppm) and Pd (7 to 24 ppb), constant Cu/Pd ratio (~10,000), and decreasing Ir (1.1 to <0.05 ppb) and Ru (1.8 to <0.3 ppb) concentrations during magmatic differentiation (16 to 7 wt% MgO). The constant Cu/Pd ratio reflects silicate- and chromite-dominated fractionation without concurrent segregation of sulphide. S-undersaturated differentiation is also indicated in the HTS, which also displays increasing Pd (6-16 ppb) and decreasing Ir concentrations (1 to <0.05 ppb) during differentiation, and the Cu/Pd ratios for the entire series average 21,000. However, some HTS samples have elevated Cu/Pd ratios (up to 33,000). Cu/Pd ratios in the HTS do not correlate with MgO, and this is interpreted to reflect varying Cu/Pd ratios of HTS parental magmas rather than S-saturated differentiation. During S-undersaturated differentiation of the LTS and HTS, Pt/Pd ratios decrease from 1.3 to 0.11 and 1.1 to 0.2 respectively, which indicates that Pd is much more incompatible than Pt during S-undersaturated differentiation. The VHTS consists exclusively of highly evolved samples with low MgO (6.6-6.1 wt%) and Pd/Ir ratios 98-228. Here, Cu/Pd ratios increase from 17,500 to 35,000 with decreasing Cr concentrations which indicate that these magmas experienced silicate fractionation with concurrent segregation of sulphide. The LTS represent melting of a depleted source and show high PGE concentrations and constant Cu/Pd ratios during S-undersaturated differentiation. Melting of a normal depleted upper mantle source generates S-saturated melts (MORB), and the depleted LTS source is therefore considered an extraordinary S-poor component within the ancestral Iceland plume. Of the three series, the VHTS contain the largest contribution from enriched mantle portions. The VHTS have similar PGE but much higher Nb concentrations for instance compared to the most evolved LTS and HTS samples, indicating that the enriched source contributes Nb but not PGE.