Cosmogenic isotope (Cl) surface exposure dating of the Norber erratics, Yorkshire Dales: Further constraints on the timing of the LGM deglaciation in Britain

Cosmogenic isotope (³⁶Cl) surface exposure dating of four of the erratic boulders at Norber in the Yorkshire Dales National Park, northwest England, yielded mean ages of ∼22.2 ± 2.0 ka BP and ∼18.0 ± 1.6 ka BP for their emplacement. These two mean values derive from different ³⁶Cl production rates used for exposure age calculation. The ages are uncorrected for temporal variations in production rates and may underestimate the true ages by 5-7%. The former age, although implying early deglaciation for this area of the British ice sheet, is not incompatible with minimum deglaciation ages from other contexts and locations in northwest England. However, the latter age is more consistent with the same minimum deglaciation ages and geochronological evidence for ice-free conditions in parts of the northern sector of the Irish Sea. Within uncertainties, the younger of the mean ages from Norber may indicate that boulder emplacement was associated with North Atlantic Heinrich event 1. The limited spatial (downvalley) extent of the Norber boulders implies that at the time of their deposition the ice margin was coincident with the distal margin of the erratic train. Loss of ice cover at Norber was followed by persistent stadial conditions until the abrupt opening of the Lateglacial Interstadial when large carnivorous mammals colonised the area. The ³⁶Cl ages are between ∼3.0 ka and ∼13.0 ka older than previous estimates based on rates of limestone dissolution derived from the heights of pedestals beneath the erratics.     

Part I. Decrepitation and degassing behaviour of quartz up to 1560 °C: Analysis of noble gases and halogens in complex fluid inclusion assemblages

Stepped heating and crushing experiments have been used to investigate the noble gas and halogen degassing behaviour of quartz in detail. Samples with diverse character were selected from the Eloise and Osborne, Iron Oxide Copper Gold (IOCG) ore deposits, and the Railway Fault, 13 km south of the Mt Isa Mine, in the Proterozoic Mt Isa Inlier of northeast Australia. Quartz has been shown to have a bimodal degassing profile. The first degassing mode at temperatures of <700 °C is caused by thermally induced mechanical decrepitation of fluid inclusions. Changes in the Br/Cl, I/Cl, Ar/Cl and ⁴⁰Ar/³⁶Ar composition of gas released at different temperatures up to 700 °C can be related to the decrepitation of different types of fluid inclusion observed by microthermometry. These variations with temperature permit deconvolution of the complex fluid inclusion assemblages associated with the IOCG samples; the ultra high salinity, multi solid (MS) and liquid-vapour-daughter (LVD) fluid inclusions, with a predominantly primary origin, decrepitate at higher temperatures than lower salinity liquid-vapour (LV) and monophase (M) fluid inclusions that have a predominantly secondary origin. Three of the IOCG samples have primary MS and LVD fluid inclusions characterized by molar Br/Cl values of between 0.25 × 10⁻³ and 0.66 × 10⁻³, I/Cl between 0.37 × 10⁻⁶ and 5.0 × 10⁻⁶, ⁴⁰Ar/³⁶Ar values of <1000 and low ³⁶Ar concentrations of 0.7-1.0 × 10⁻⁶ cm³ cm⁻³H₂O. These low values are most easily explained by the involvement of halite dissolution water in IOCG genesis. One of the IOCG samples has Br/Cl of 1.3-2.0 × 10⁻³ and I/Cl of 10 × 10⁻⁶, similar to juvenile magmatic fluids in Phanerozoic Porphyry Copper Deposits. This sample also has a higher ³⁶Ar concentration of 3.5 × 10⁻⁶ cm³ cm⁻³H₂O and a slightly elevated ⁴⁰Ar/³⁶Ar of 2236. Step heating reveals limited and non-systematic variation within the more homogenous population of LV fluid inclusions from the Railway Fault. The samples have mean values of 8.1 × 10⁻³ for Br/Cl; 9.4-12 × 10⁻⁶ for I/Cl; <2000 for ⁴⁰Ar/³⁶Ar; and 4.7-4.8 × 10⁻⁶ cm³ cm⁻³H₂O for ³⁶Ar concentration. The Br/Cl values are similar to those previously reported for basinal brines present in silicic alteration at the Mt Isa Mine and the additional data can be explained by interaction of such a bittern brine with fine grained sedimentary rocks in the sub-surface. The second mode of quartz degassing occurs between 1200 and 1450 °C and releases a greater volume of gas than the first degassing mode. Several lines of evidence, including microscope observations, indicate that the gas released at high temperature is also from the fluid inclusion reservoir. However, its release may be triggered by a metastable phase transition of quartz (∼1200 °C) and caution is required in interpretation of the fluid compositions obtained at these temperatures. The data provide an improved understanding of fluid inclusion decrepitation behaviour that is different to that obtained in lower temperatures experiments designed by other workers to investigate H-isotope fractionation.     

Note on the isotopic geochemistry of fossil-lacustrine tufas in carbonate plateau—A study from Dungul region (SW Egypt)

Lithological, chemical, and stable isotope data are used to characterize lacustrine tufas dating back to pre-late Miocene and later unknown times, capping different surfaces of a Tertiary carbonate (Sinn el-Kedab) plateau in Dungul region in the currently hyperarid south-western Egypt. These deposits are composed mostly of calcium carbonate, some magnesium carbonate and clastic particles plus minor amounts of organic matter. They have a wide range of (Mg/Ca)_molar ratios, from 0.03 to 0.3. The bulk-tufa carbonate has characteristic isotope compositions: (δ¹³C_mean = −2.49 ± 0.99‰; δ¹⁸O_mean = −9.43 ± 1.40‰). The δ¹³C values are consistent with a small input from C4 vegetation or thinner soils in the recharge area of the tufa-depositing systems. The δ¹⁸O values are typical of fresh water carbonates. Covariation between δ¹³C and δ¹⁸O values probably is a reflection of climatic conditions such as aridity. The tufas studied are isotopically similar to the underlying diagenetic marine chalks, marls and limestones (δ¹³C_mean = −2.06 ± 0.84‰; δ¹⁸O_mean = −10.06 ± 1.39‰). The similarity has been attributed to common meteoric water signatures. This raises large uncertainties in using tufas (Mg/Ca)_molar, δ¹³C and δ¹⁸O records as proxies of paleoclimatic change and suggests that intrinsic compositional differences in material sources within the plateau may mask climatic changes in the records.     

Atmospheric sources and sinks of volcanogenic elements in a basaltic volcano (Etna, Italy)

This study reports on the first quantitative assessment of the geochemical cycling of volcanogenic elements, from their atmospheric release to their deposition back to the ground. Etna’s emissions and atmospheric depositions were characterised for more than 2 years, providing data on major and trace element abundance in both volcanic aerosols and bulk depositions. Volcanic aerosols were collected from 2004 to 2007, at the summit vents by conventional filtration techniques. Precipitation was collected, from 2006 to 2007, in five rain gauges, at various altitudes around the summit craters. Analytical results for volcanic aerosols showed that the dominant anions were S, Cl, and F, and that the most abundant metals were K, Ca, Mg, Al, Fe, and Ti (1.5-50 μg m⁻³). Minor and trace element concentrations ranged from about 0.001 to 1 μg m⁻³. From such analysis, we derived an aerosol mass flux ranging from 3000 to 8000 t a⁻¹. Most analysed elements had higher concentrations close to the emission vent, confirming the prevailing volcanic contribution to bulk deposition. Calculated deposition rates were integrated over the whole Etna area, to provide a first estimate of the total deposition fluxes for several major and trace elements. These calculated deposition fluxes ranged from 20 to 80 t a⁻¹ (Al, Fe, Si) to 0.01-0.1 t a⁻¹ (Bi, Cs, Sc, Th, Tl, and U). Comparison between volcanic emissions and atmospheric deposition showed that the amount of trace elements scavenged from the plume in the surrounding of the volcano ranged from 0.1% to 1% for volatile elements such as As, Bi, Cd, Cs, Cu, Tl, and from 1% to 5% for refractory elements such as Al, Ba, Co, Fe, Ti, Th, U, and V. Consequently, more than 90% of volcanogenic trace elements were dispersed further away, and may cause a regional scale impact. Such a large difference between deposition and emission fluxes at Mt. Etna pointed to relatively high stability and long residence time of aerosols in the plume.     

Comparison of stable isotopes,ratios of Cl/Cl and I/I in brine and deep groundwater from the Pacific coastal region and the eastern margin of the Japan Sea

Fifty-three samples, including brines associated with oil and natural gas reservoirs and groundwater samples from deep boreholes, were collected from the Pacific and Japan Sea coastal regions in Japan. The ¹²⁹I/¹²⁷I and ³⁶Cl/Cl ratios, and stable isotopes (δD and δ¹⁸O) are compared to investigate differences related to the geotectonic settings of the two regions. The δD and δ¹⁸O data indicate that brine and groundwater from the Pacific coastal region reflect mixing of meteoric water with connate seawater in the pores of sedimentary rocks. On the other hand, brine and groundwater from the Japan Sea coastal region have been hydrothermally altered. In particular, brines associated with petroleum accumulations at Niigata and Akita showed the same isotopic characteristics as fluids found in the Kuroko deposits of the Green Tuff region in northeastern Japan. There is little difference in the ³⁶Cl/Cl ratios in brine and groundwater from the Pacific and Japan Sea coasts. Most brine and some deep groundwater, except those from the Pleistocene Kazusa Group, have already reached the average secular equilibrium ratio of 9.9 ± 2.7 × 10⁻¹⁵ for their mudstone and sandstone reservoirs. There was no correlation between the ³⁶Cl/Cl ratios and differences in geotectonic setting between the Pacific and the Japan Sea coast. The molar I/Br ratio suggests that the I in all of water samples was of biogenic origin. The average ¹²⁹I/¹²⁷I ratio was 290 ± 130 × 10⁻¹⁵ to 294 ± 105 × 10⁻¹⁵ in both regions, showing no relationship to the different geotectonic settings. The uncontaminated brine and groundwater samples are likely to have retained the original ¹²⁹I/¹²⁷I ratios of marine I released from the old organic matter stored in sedimentary rock.     

Characteristics of deep groundwater flow in a basin marginal setting at Sellafield,Northwest England: Cl and halide evidence

A number of chemical and physical processes inside and outside a sedimentary basin (e.g. evaporite dissolution and topographic drive, respectively) affect groundwater flow near the basin’s margin. Contrasting formations at the margin, typically basinal sedimentary rocks and basement, are host to the interplay between these processes so that groundwater flows and compositions change within a relatively small volume. To interpret how groundwater flow and geochemistry have evolved, interactions between these processes must be understood. Such interactions were investigated near the margin of the East Irish Sea Basin in NW England, by sampling deep groundwaters (to 1500 m below sea level) from Ordovician volcanic basement rocks and Carboniferous to Triassic sedimentary cover rocks. Variable Br/Cl ratios and Cl concentrations in deep saline waters and brines indicate mixing patterns. Variations in ³⁶Cl/Cl constrain the timing of mixing. Relatively low Br/Cl ratios (ca. 1 × 10⁻³ by mass) characterise brine from the western sedimentary cover and reflect halite dissolution further west. Saline water with relatively high Br/Cl ratios (ca. 2 × 10⁻³ by mass) of uncertain origin occupies the eastern basement. These two waters mix across the area. However, mixing alone cannot explain variable ³⁶Cl/Cl ratios, which partly reflect differing in situ³⁶Cl production rates in different rock formations. Most ³⁶Cl/Cl ratios in groundwater sampled from the eastern metavolcanic basement (mean = 25 × 10⁻¹⁵) and western sedimentary cover (mean = 10 × 10⁻¹⁵) are at or close to equilibrium with in situ³⁶Cl production. These variations in ³⁶Cl/Cl across the site possibly took >1.5 Ma to be attained, implying that deep groundwater flow responded only slowly to the Quaternary glaciation of the site. Interplay between varied processes in basin marginal settings does not necessarily imply flow instability.     

Volatile composition of microinclusions in diamonds from the Panda kimberlite, Canada: Implications for chemical and isotopic heterogeneity in the mantle

In order to better investigate the compositions and the origins of fluids associated with diamond growth, we have carried-out combined noble gas (He and Ar), C and N isotope, K, Ca and halogen (Cl, Br, I) determinations on fragments of individual microinclusion-bearing diamonds from the Panda kimberlite, North West Territories, Canada. The fluid concentrations of halogens and noble gases in Panda diamonds are enriched by several orders of magnitude over typical upper mantle abundances. However, noble gas, C and N isotopic ratios (³He/⁴He = 4-6 Ra, ⁴⁰Ar/³⁶Ar = 20,000-30,000, δ¹³C = −4.5‰ to −6.9‰ and δ¹⁵N = −1.2‰ to −8.8‰) are within the worldwide range determined for fibrous diamonds and similar to the mid ocean ridge basalt (MORB) source value. The high ³⁶Ar content of the diamonds (>1 × 10⁻⁹ cm³/g) is at least an order of magnitude higher than any previously reported mantle sample and enables the ³⁶Ar content of the subcontinental lithospheric mantle to be estimated at ∼0.6 × 10⁻¹² cm³/g, again similar to estimates for the MORB source. Three fluid types distinguished on the basis of Ca-K-Cl compositions are consistent with carbonatitic, silicic and saline end-members identified in previous studies of diamonds from worldwide sources. These fluid end-members also have distinct halogen ratios (Br/Cl and I/Cl). The role of subducted seawater-derived halogens, originally invoked to explain some of the halogen ratio variations in diamonds, is not considered an essential component in the formation of the fluids. In contrast, it is considered that large halogen fractionation of a primitive mantle ratio occurs during fluid-melt partitioning in forming silicic fluids, and during separation of an immiscible saline fluid.     

Does reactive surface area depend on grain size? Results from pH 3, 25 °C far-from-equilibrium flow-through dissolution experiments on anorthite and biotite

Laboratory determined mineral weathering rates need to be normalised to allow their extrapolation to natural systems. The principle normalisation terms used in the literature are mass, and geometric- and BET specific surface area (SSA). The purpose of this study was to determine how dissolution rates normalised to these terms vary with grain size. Different size fractions of anorthite and biotite ranging from 180-150 to 20-10 μm were dissolved in pH 3, HCl at 25 °C in flow through reactors under far from equilibrium conditions. Steady state dissolution rates after 5376 h (anorthite) and 4992 h (biotite) were calculated from Si concentrations and were normalised to initial- and final- mass and geometric-, geometric edge- (biotite), and BET SSA. For anorthite, rates normalised to initial- and final-BET SSA ranged from 0.33 to 2.77 × 10⁻¹⁰ mol_feldspar m⁻² s⁻¹, rates normalised to initial- and final-geometric SSA ranged from 5.74 to 8.88 × 10⁻¹⁰ mol_feldspar m⁻² s⁻¹ and rates normalised to initial- and final-mass ranged from 0.11 to 1.65 mol_feldspar g⁻¹ s⁻¹. For biotite, rates normalised to initial- and final-BET SSA ranged from 1.02 to 2.03 × 10⁻¹² mol_biotite m⁻² s⁻¹, rates normalised to initial- and final-geometric SSA ranged from 3.26 to 16.21 × 10⁻¹² mol_biotite m⁻² s⁻¹, rates normalised to initial- and final-geometric edge SSA ranged from 59.46 to 111.32 × 10⁻¹² mol_biotite m⁻² s⁻¹ and rates normalised to initial- and final-mass ranged from 0.81 to 6.93 × 10⁻¹² mol_biotite g⁻¹ s⁻¹. For all normalising terms rates varied significantly (p ? 0.05) with grain size. The normalising terms which gave least variation in dissolution rate between grain sizes for anorthite were initial BET SSA and initial- and final-geometric SSA. This is consistent with: (1) dissolution being dominated by the slower dissolving but area dominant non-etched surfaces of the grains and, (2) the walls of etch pits and other dissolution features being relatively unreactive. These steady state normalised dissolution rates are likely to be constant with time. Normalisation to final BET SSA did not give constant ratios across grain size due to a non-uniform distribution of dissolution features. After dissolution coarser grains had a greater density of dissolution features with BET-measurable but unreactive wall surface area than the finer grains. The normalising term which gave the least variation in dissolution rates between grain sizes for biotite was initial BET SSA. Initial- and final-geometric edge SSA and final BET SSA gave the next least varied rates. The basal surfaces dissolved sufficiently rapidly to influence bulk dissolution rate and prevent geometric edge SSA normalised dissolution rates showing the least variation. Simple modelling indicated that biotite grain edges dissolved 71-132 times faster than basal surfaces. In this experiment, initial BET SSA best integrated the different areas and reactivities of the edge and basal surfaces of biotite. Steady state dissolution rates are likely to vary with time as dissolution alters the ratio of edge to basal surface area. Therefore they would be more properly termed pseudo-steady state rates, only appearing constant because the time period over which they were measured (1512 h) was less than the time period over which they would change significantly.     

Surface heat flow and CO2 emissions within the Ohaaki hydrothermal field,Taupo Volcanic Zone,New Zealand

Carbon dioxide emissions and heat flow have been determined from the Ohaaki hydrothermal field, Taupo Volcanic Zone (TVZ), New Zealand following 20 a of production (116 MW_e). Soil CO₂ degassing was quantified with 2663 CO₂ flux measurements using the accumulation chamber method, and 2563 soil temperatures were measured and converted to equivalent heat flow (W m⁻²) using published soil temperature heat flow functions. Both CO₂ flux and heat flow were analysed statistically and then modelled using 500 sequential Gaussian simulations. Forty subsoil CO₂ gas samples were also analysed for stable C isotopes. Following 20 a of production, current CO₂ emissions equated to 111 ± 6.7 T/d. Observed heat flow was 70 ± 6.4 MW, compared with a pre-production value of 122 MW. This 52 MW reduction in surface heat flow is due to production-induced drying up of all alkali–Cl outflows (61.5 MW) and steam-heated pools (8.6 MW) within the Ohaaki West thermal area (OHW). The drying up of all alkali–Cl outflows at Ohaaki means that the soil zone is now the major natural pathway of heat release from the high-temperature reservoir. On the other hand, a net gain in thermal ground heat flow of 18 MW (from 25 MW to 43.3 ± 5 MW) at OHW is associated with permeability increases resulting from surface unit fracturing by production-induced ground subsidence. The Ohaaki East (OHE) thermal area showed no change in distribution of shallow and deep soil temperature contours despite 20 a of production, with an observed heat flow of 26.7 ± 3 MW and a CO₂ emission rate of 39 ± 3 T/d. The negligible change in the thermal status of the OHE thermal area is attributed to the low permeability of the reservoir beneath this area, which has limited production (mass extraction) and sheltered the area from the pressure decline within the main reservoir. Chemistry suggests that although alkali–Cl outflows once contributed significantly to the natural surface heat flow (∼50%) they contributed little (<1%) to pre-production CO₂ emissions due to the loss of >99% of the original CO₂ content due to depressurisation and boiling as the fluids ascended to the surface. Consequently, the soil has persisted as the major (99%) pathway of CO₂ release to the atmosphere from the high temperature reservoir at Ohaaki. The CO₂ flux and heat flow surveys indicate that despite 20 a of production the variability in location, spatial extent and magnitude of CO₂ flux remains consistent with established geochemical and geophysical models of the Ohaaki Field. At both OHW and OHE carbon isotopic analyses of soil gas indicate a two-stage fractionation process for moderate-flux (>60 g m⁻² d⁻¹) sites; boiling during fluid ascent within the underlying reservoir and isotopic enrichment as CO₂ diffuses through porous media of the soil zone. For high-flux sites (>300 g m⁻² d⁻¹), the δ¹³CO₂ signature (−7.4 ± 0.3‰ OHW and −6.5 ± 0.6‰ OHE) is unaffected by near-surface (soil zone) fractionation processes and reflects the composition of the boiled magmatic CO₂ source for each respective upflow. Flux thresholds of <30 g m⁻² d⁻¹ for purely diffusive gas transport, between 30 and 300 g m⁻² d⁻¹ for combined diffusive–advective transport, and ?300 g m⁻² d⁻¹ for purely advective gas transport at Ohaaki were assigned. δ¹³CO₂ values and cumulative probability plots of CO₂ flux data both identified a threshold of ∼15 g m⁻² d⁻¹ by which background (atmospheric and soil respired) CO₂ may be differentiated from hydrothermal CO₂.     

Kinetics of Fe(III) precipitation in aqueous solutions at pH 6.0-9.5 and 25 °C

The kinetics of Fe(III) precipitation in synthetic buffered waters have been investigated over the pH range 6.0-9.5 using a combination of visible spectrophotometry, ⁵⁵Fe radiometry combined with ion-pair solvent extraction of chelated iron and numerical modeling. The rate of precipitation, which is first order with respect to both dissolved and total inorganic ferric species, varies by nearly two orders of magnitude with a maximum rate constant of 16 ± 1.5 × 10⁶ M⁻¹ s⁻¹ at a pH of around 8.0. Our results support the existence of the dissolved neutral species, Fe(OH)₃⁰, and suggest that it is the dominant precursor in Fe(III) polymerization and subsequent precipitation at circumneutral pH. The intrinsic rate constant of precipitation of Fe(OH)₃⁰ was calculated to be allowing us to predict rates of Fe(III) precipitation in the pH range 6.0-9.5. The value of this rate constant, and the variation in the precipitation rate constant over the pH range considered, are consistent with a mechanism in which the kinetics of iron precipitation are controlled by rates of water exchange in dissolved iron hydrolysis species.     

Joint determination of K decay constants and Ar∗/K for the Fish Canyon sanidine standard, and improved accuracy for Ar/Ar geochronology

⁴⁰Ar/³⁹Ar and K-Ar geochronology have long suffered from large systematic errors arising from imprecise K and Ar isotopic data for standards and imprecisely determined decay constants for the branched decay of ⁴⁰K by electron capture and β⁻ emission. This study presents a statistical optimization approach allowing constraints from ⁴⁰K activity data, K-Ar isotopic data, and pairs of ²³⁸U-²⁰⁶Pb and ⁴⁰Ar/³⁹Ar data for rigorously selected rocks to be used as inputs for estimating the partial decay constants (λ_ε and λ_β) of ⁴⁰K and the ⁴⁰Ar∗/⁴⁰K ratio (κ_FCs) of the widely used Fish Canyon sanidine (FCs) standard. This yields values of κ_FCs = (1.6418 ± 0.0045) × 10⁻³, λ_ε = (0.5755 ± 0.0016) × 10⁻¹⁰ a⁻¹ and λ_β = (4.9737 ± 0.0093) × 10⁻¹⁰ a⁻¹. These results improve uncertainties in the decay constants by a factor of >4 relative to values derived from activity data alone. Uncertainties in these variables determined by our approach are moderately to highly correlated (cov(κ_FCs, λ_ε) = 7.1889 × 10⁻¹⁹, cov(κ_FCs, λ_β) = −7.1390 × 10⁻¹⁹, cov(λ_ε, λ_β) = −3.4497 × 10⁻²⁶) and one must take account of the covariances in error propagation by either linear or Monte Carlo methods. ⁴⁰Ar/³⁹Ar age errors estimated from these results are significantly reduced relative to previous calibrations. Also, age errors are smaller for a comparable level of isotopic measurement precision than those produced by the ²³⁸U/²⁰⁶Pb system, because the ⁴⁰Ar/³⁹Ar system is now jointly calibrated by both the ⁴⁰K and ²³⁸U decay constants, and because λ_ε(⁴⁰K) < λ(²³⁸U). Based on this new calibration, the age of the widely used Fish Canyon sanidine standard is 28.305 ± 0.036 Ma. The increased accuracy of ⁴⁰Ar/³⁹Ar ages is now adequate to provide meaningful validation of high-precision U/Pb or astronomical tuning ages in cases where closed system behavior of K and Ar can be established.     

Predicting the impact of land use on the major element and nutrient fluxes in coastal Mediterranean rivers: The case of the Têt River (Southern France)

This study presents a detailed discrimination between the natural and anthropogenic sources of dissolved major elements in the Têt River, a typical small coastal river in the south of France. The main objectives were to quantify the materials that were released by human activities in the basin, and to determine the specific element inputs for the major land use forms. The dissolved material fluxes were estimated by weekly monitoring over a hydrological year (2000–2001) along the major water gauging stations, and the flux relationships were examined in the context of anthropogenic and natural basin characteristics as determined by a Geographical Information System (GIS). Intensive agricultural land use in the form of fruit tree cultures and vineyards has a strong control on the dissolved element fluxes in the river. Area specific element releases for these cultures are greatest for SO₄, with an estimated average of about 430 ± 18 keq km⁻² a⁻¹. This is ?11 times the natural SO₄ release by rock weathering. Also for K, NO₃, PO₄ and Mg, the specific releases were ?6 times the natural weathering rates (respectively about 44, 60, 4 and 265 keq km⁻² a⁻¹). Waste-waters are the other major source of anthropogenic elements in the river. They have an important role for the fluxes of inorganic P and N, but they are also a considerable source of Cl and Na to the river. For example, the average annual release of Cl is around 150 moles/inhabitant in the rural basin parts. Further downstream, however, where population density strongly increases, industrial effluents can enhance this value (>300 moles/inhabitant). The waste-waters contribute more than 70% of the dissolved inorganic N export to the sea, although their contribution to the average DOC export is almost negligible (3%).     

Search for extinct Cl: Vigarano CAIs, the Pink Angel from Allende, and a Ningqiang chondrule

We have searched for excesses of ³⁶S derived from the decay of extinct ³⁶Cl in sodalite, a secondary Cl-rich mineral, in Ca-Al-rich inclusions (CAIs) from the Vigarano and Allende CV3 chondrites and in a chondrule from the Ningqiang carbonaceous chondrite. The presence of sodalite in two CAIs from Vigarano and its absence from surrounding CAI fragments suggests sodalite formation after CAI fragmentation. As for sodalite in the Allende Pink Angel CAI, oxygen isotopic compositions have been interpreted as indicative of high temperature interactions, thus suggesting formation prior to accretion to the parent body, probably in a nebular setting. Sodalite in the Ningqiang chondrule is considered to have formed via alkali-Ca exchange, which is believed to have occurred before accretion to the parent body.Sodalites in the Vigarano CAIs and in the Ningqiang chondrule show no clear evidence for the presence of radiogenic ³⁶S. The inferred 2σ upper limits for ³⁶Cl/³⁵Cl at the time of sodalite formation are 1.6 × 10⁻⁶ (Vigarano CAIs) and 3.3 × 10⁻⁶ (Ningqiang chondrule), respectively. In the Pink Angel CAI sodalite exhibits small ³⁶S excesses which weakly correlate with ³⁵Cl/³⁴S ratios. The inferred ³⁶Cl/³⁵Cl ratio of (1.8 ± 2.2) × 10⁻⁶ (2σ error) is lower than that found by Hsu et al. [Hsu, W., Guan, Y., Leshin, L. A., Ushikubo, T. and Wasserburg, G. J. (2006) A late episode of irradiation in the early solar system: Evidence from extinct ³⁶Cl and ²⁶Al in meteorites. Astrophys. J. 640, 525-529], thus indicative of heterogeneous distribution of ³⁶Cl in this CAI. Spallation reactions induced by energetic particles from the young Sun are suggested for the origin of ³⁶Cl, similar to the case of ¹⁰Be. While ¹⁰Be appears to be present in roughly equal abundance in all studied CAIs, our study indicates the level of ³⁶Cl abundances to be variable so that there seems to be no simple relationship between ¹⁰Be and ³⁶Cl. This would be expected if trapped cosmic rays rather than Early Solar System spallation were the dominant source of ¹⁰Be in the Early Solar System, since their contribution to ³⁶Cl would have been tiny.If the variability of ³⁶Cl abundances is caused by temporal differences in the alteration that formed sodalite, sodalite in the Vigarano CAIs and in the Ningqiang chondrule may have formed ?0.5 and ?0.2 Ma after formation of the sodalite in the Ningqiang CAI analyzed by Lin et al. [Lin, Y., Guan, Y., Leshin, L. A., Ouyang, Z. and Wang, D. (2005) Short-lived chlorine-36 in a Ca- and Al-rich inclusion from the Ningqiang carbonaceous chondrite. Proc. Natl. Acad. Sci. USA 102, 1306-1311]. The Pink Angel sodalite that we analyzed may have formed ∼0.3 Ma after formation of the sodalite in the Pink Angel analyzed by Hsu et al. [Hsu, W., Guan, Y., Leshin, L. A., Ushikubo, T. and Wasserburg G. J. (2006) A late episode of irradiation in the early solar system: Evidence from extinct ³⁶Cl and ²⁶Al in meteorites. Astrophys. J. 640, 525-529]. The estimated temporal differences suggest that alteration extended over at least 0.5 Ma. If previous works showing very low initial ³⁶Cl/³⁵Cl in the Allende CAIs and a H3 chondrite CAI are also considered, then alteration processes may have been more than 1.7 Ma.     

A hot spring in granite of the Western Tianshan,China

The western Tianshan range is a major Cenozoic orogenic belt in central Asia exposing predominantly Paleozoic rocks including granite. Ongoing deformation is reflected by very rugged topography with peaks over 7000 m high. Active tectonic deformation is tied to an E–W trending fracture and fault system that sections the mountain chain into geologically diverse blocks that extend parallel to the orogen. In the Muzhaerte valley upwelling hot water follows such a fault system in the Muza granite. About 20 L min⁻¹ Na–SO₄–Cl water with a temperature of 55 °C having a total mineralization of about 1 g L⁻¹ discharge from the hot spring. The water is used in a local spa that is frequented by the people of the upper Ili river area. Its waters are used for balneological purposes and the spa serves as a therapeutic institution. The major element composition of the hot water is dominated by Na and by SO₄ and Cl, Ca is a minor component. Dissolved silica (1.04 mmol L⁻¹) corresponds to a quartz-saturation temperature of 116 °C and a corresponding depth of the source of the water of about 4600 m. This temperature is consistent with Na/K and Na/Li geothermometry. The water is saturated with respect to fluorite and contains 7.5 mg L⁻¹ F⁻ as a consequence of the low Ca-concentration. The water is undersaturated with respect to the primary minerals of the reservoir granite at reservoir temperature causing continued irreversible dissolution of granite. The waters are oversaturated with respect to Ca–zeolite minerals (such as stilbite and mesolite), and it is expected that zeolites precipitate in the fracture pore space and in alteration zones replacing primary granite.     

Chlorine isotopic composition in seafloor serpentinites and high-pressure metaperidotites. Insights into oceanic serpentinization and subduction processes

Bulk-rock chlorine content and isotopic composition (δ³⁷Cl) were determined in oceanic serpentinites, high-pressure metaperidotites and metasediments in order to gain constraints on the global chlorine cycle associated with hydrothermal alteration and subduction of oceanic lithosphere. The distribution of insoluble chlorine in oceanic serpentinites was also investigated by electron microprobe. The hydrothermally-altered ultramafic samples were dredged along the South West Indian Ridge and the Mid-Atlantic Ridge. The high-pressure metamorphic samples were collected in the Western Alps: metaperidotites in the Erro-Tobbio unit and metasediments in the Schistes Lustrés nappe.Oceanic serpentinites show relatively large variations of bulk-rock Cl contents and δ³⁷Cl values with mean values of 1105 ± 596 ppm and −0.7 ± 0.4‰, respectively (n = 8; 1σ). Serpentines formed after olivine (meshes) show lower Cl content than those formed after orthopyroxene (bastites). In bastites of two different samples, Cl is positively correlated with Al₂O₃ and negatively correlated with SiO₂. These relationships are interpreted as reflecting preferential Cl-incorporation into the bastite structure distorted by Al (substituted for Si) rather than different alteration conditions between olivine and orthopyroxene minerals. High-pressure metaperidotites display relatively homogeneous Cl contents and δ³⁷Cl values with mean values of 467 ± 88 ppm and −1.4 ± 0.1‰, respectively (n = 7; 1σ). A macroscopic high-pressure olivine-bearing vein, formed from partial devolatilization of serpentinites at ∼2.5 GPa and 500-600 °C, shows a Cl content and a δ³⁷Cl value of 603 ppm and −1.6‰, respectively. Metasediments (n = 2) show low whole-rock Cl contents (<15 ppm Cl) that did not allow Cl isotope analyses to be obtained.The range of negative δ³⁷Cl values observed in oceanic serpentinites is likely to result from water-rock interaction with fluids that have negative δ³⁷Cl values. The homogeneity of δ³⁷Cl values from the high-pressure olivine-bearing vein and the metaperidotite samples implies that progressive loss of Cl inherited from oceanic alteration throughout subduction did not significantly fractionate Cl isotopes. Chlorine recycled in subduction zones via metaperidotites should thus show a range of δ³⁷Cl values similar to the range found in oceanic serpentinized peridotites.     

Determination of Cl Production Rates Derived from the Well-Dated Deglaciation Surfaces of Whidbey and Fidalgo Islands, Washington

The ³⁶Cl dating method is increasingly being used to determine the surface-exposure history of Quaternary landforms. Production rates for the ³⁶Cl isotopic system, a critical component of the dating method, have now been refined using the well-constrained radiocarbon-based deglaciation history of Whidbey and Fidalgo Islands, Washington. The calculated total production rates due to calcium and potassium are 91±5 atoms ³⁶Cl (g Ca)⁻¹ yr⁻¹ and are 228±18 atoms ³⁶Cl (g K)⁻¹ yr⁻¹, respectively. The calculated ground-level secondary neutron production rate in air, P_f(0), inferred from thermal neutron absorption by ³⁵Cl is 762±28 neutrons (g air)⁻¹ yr⁻¹ for samples with low water content (1–2 wt.%). Neutron absorption by serpentinized harzburgite samples of the same exposure age, having higher water content (8–12 wt.%), is 40% greater relative to that for dry samples. These data suggest that existing models do not adequately describe thermalization and capture of neutrons for hydrous rock samples. Calculated ³⁶Cl ages of samples collected from the surfaces of a well-dated dacite flow (10,600–12,800 cal yr B.P.) and three disparate deglaciated localities are consistent with close limiting calibrated ¹⁴C ages, thereby supporting the validity of our ³⁶Cl production rates integrated over the last 15,500 cal yr between latitudes of 46.5° and 51°N. Although our production rates are internally consistent and yield reasonable exposure ages for other localities, there nevertheless are significant differences between these production rates and those of other investigators.     

A chlorine isotope study of DSDP/ODP serpentinized ultramafic rocks: Insights into the serpentinization process

Eight DSDP/ODP cores were analyzed for major ion concentrations and δ³⁷Cl values of water-soluble chloride (δ³⁷Cl_WSC) and structurally bound chloride (δ³⁷Cl_SBC) in serpentinized ultramafic rocks. This diverse set of cores spans a wide range in age, temperature of serpentinization, tectonic setting, and geographic location of drilled serpentinized oceanic crust. Three of the cores were sampled at closely spaced intervals to investigate downhole variation in Cl concentration and chlorine isotope composition.The average total Cl content of all 86 samples is 0.26 ± 0.16 wt.% (0.19 ± 0.10 wt.% as water-soluble Cl (X_WSC) and 0.09 ± 0.09 wt.% as structurally bound Cl (X_SBC)). Structurally bound Cl concentration nearly doubles with depth in all cores; there is no consistent trend in water-soluble Cl content among the cores. Chlorine isotope fractionation between the structurally bound Cl⁻ site and the water-soluble Cl⁻ site varies from − 1.08‰ to + 1.16‰, averaging to + 0.21‰. Samples with negative fractionations may be related to reequilibration of the water-soluble chloride with seawater post-serpentinite formation. Six of the cores have positive bulk δ³⁷Cl values (+ 0.05‰ to + 0.36‰); the other two cores (173-1068A (Leg-Hole) and 84-570) have negative bulk δ³⁷Cl values (− 1.26‰ and − 0.54‰). The cores with negative δ³⁷Cl values also have variable Cl⁻ / SO₄² ratios, in contrast to all other cores. The isotopically positive cores (153-920D and 147-895E) show no isotopic variation with depth; the isotopically negative core (173-1068A) decreases by ∼1‰ with depth for both the water-soluble and structurally bound Cl fractions.Non-zero bulk δ³⁷Cl values indicate Cl in serpentinites was incorporated during original hydration and is not an artifact of seawater infiltration during drilling. Cores with positive δ³⁷Cl values are most likely explained by open system fractionation during hydrothermal alteration, with preferential incorporation of ³⁷Cl from seawater into the serpentinite and loss of residual light Cl back to the ocean. Fluid / rock ratios were probably low as evidenced by the presence of water-soluble salts. The two isotopically negative cores are characterized by a thick overlying sedimentary package that was in place prior to serpentinization. We believe the low δ³⁷Cl values of these cores are a result of hydration of ultramafic rock by infiltrating aqueous pore fluids from the overlying sediments. The resulting serpentinites inherit the characteristic negative δ³⁷Cl values of the pore waters. Chlorine stable isotopes can be used to identify the source of the serpentinizing fluid and ultimately discern chemical and tectonic processes involved in serpentinization.     

Radium uptake during barite recrystallization at 23 ± 2 °C as a function of solution composition: An experimental Ba and Ra tracer study

High-purity synthetic barite powder was added to pure water or aqueous solutions of soluble salts (BaCl₂, Na₂SO₄, NaCl and NaHCO₃) at 23 ± 2 °C and atmospheric pressure. After a short pre-equilibration time (4 h) the suspensions were spiked either with ¹³³Ba or ²²⁶Ra and reacted under constant agitation during 120-406 days. The pH values ranged from 4 to 8 and solid to liquid (S/L) ratios varied from 0.01 to 5 g/l. The uptake of the radiotracers by barite was monitored through repeated sampling of the aqueous solutions and radiometric analysis. For both ¹³³Ba and ²²⁶Ra, our data consistently showed a continuous, slow decrease of radioactivity in the aqueous phase.Mass balance calculations indicated that the removal of ¹³³Ba activity from aqueous solution cannot be explained by surface adsorption only, as it largely exceeded the 100% monolayer coverage limit. This result was a strong argument in favor of recrystallization (driven by a dissolution-precipitation mechanism) as the main uptake mechanism. Because complete isotopic equilibration between aqueous solution and barite was approached or even reached in some experiments, we concluded that during the reaction all or substantial fractions of the initial solid had been replaced by newly formed barite.The ¹³³Ba data could be successfully fitted assuming constant recrystallization rates and homogeneous distribution of the tracer into the newly formed barite. An alternative model based on partial equilibrium of ¹³³Ba with the mineral surface (without internal isotopic equilibration of the solid) could not reproduce the measured activity data, unless multistage recrystallization kinetics was assumed. Calculated recrystallization rates in the salt solutions ranged from 2.8 × 10⁻¹¹ to 1.9 × 10⁻¹⁰ mol m⁻² s⁻¹ (2.4-16 μmol m⁻² d⁻¹), with no specific trend related to solution composition. For the suspensions prepared in pure water, significantly higher rates (∼5.7 × 10⁻¹⁰ mol m⁻² s⁻¹ or ∼49 μmol m⁻² d⁻¹) were determined.Radium uptake by barite was determined by monitoring the decrease of ²²⁶Ra activity in the aqueous solution with alpha spectrometry, after filtration of the suspensions and sintering. The evaluation of the Ra uptake experiments, in conjunction with the recrystallization data, consistently indicated formation of non-ideal solid solutions, with moderately high Margules parameters (W_AB = 3720-6200 J/mol, a₀ = 1.5-2.5). These parameters are significantly larger than an estimated value from the literature (W_AB = 1240 J/mol, a₀ = 0.5).In conclusion, our results confirm that radium forms solid solutions with barite at fast kinetic rates and in complete thermodynamic equilibrium with the aqueous solutions. Moreover, this study provides quantitative thermodynamic data that can be used for the calculation of radium concentration limits in environmentally relevant systems, such as radioactive waste repositories and uranium mill tailings.