I/I ratios in Scottish coastal surface sea water: Geographical and temporal responses to changing emissions

This work constitutes the first survey of I isotope ratios for Scottish sea water including the first data for the west of Scotland. These data are of importance because of the proximity to the world’s second largest emission source of ¹²⁹I to the sea, the Sellafield nuclear reprocessing plant, because of the increasing importance of the sea to land transfer of ¹²⁹I and also as input data for dose estimates based on this pathway of ¹²⁹I. ¹²⁹I/¹²⁷I ratios in SW Scotland reached 3 × 10⁻⁶ in 2004. No strong variation of I isotope ratios was found from 2003 to 2005 in Scottish sea waters. Iodine isotope ratios increased by about a factor of 6 from 1992 to 2003 in NE Scotland, in agreement with the increase of liquid ¹²⁹I emissions from Sellafield over that time period. It is demonstrated that ¹²⁹I/¹²⁷I ratios agree better than ¹²⁹I concentrations for samples from similar locations taken in very close temporal proximity, indicating that this ratio is more appropriate to interpret than the radionuclide concentration.     

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.     

Origin of iodine in volcanic fluids: I results from the Central American Volcanic Arc

The largest reservoir of crustal iodine is found in marine sediments, where it is closely associated with organic material. This presence, together with the existence of a long-lived, cosmogenic radioisotope ¹²⁹I (t_1/2 = 15.7 Ma), make this isotopic system well suited for the study of sediment recycling in subduction zones. Reported here are the results of ¹²⁹I/I ratios in volcanic fluids, collected during a comprehensive study of fluids and gases in the Central American Volcanic Arc. ¹²⁹I/I ratios, together with I, Br, and Cl concentrations, were determined in 79 samples from four geothermal centers and a number of crater lakes, fumaroles, hot springs, and surface waters in Costa Rica, Nicaragua, and El Salvador. Geothermal and volcanic fluids were found to have iodine concentrations substantially higher than values in seawater or meteoric waters. ¹²⁹I/I ratios in most of the geothermal fluids are below the preanthropogenic input ratio of 1500 × 10⁻¹⁵, demonstrating that recent anthropogenic additions are largely absent from the volcanic systems. The majority of the ¹²⁹I/I ratios are between 500 and 800 × 10⁻¹⁵. These ratios indicate minimum iodine ages between 25 and 15 Ma, in good agreement with the age of subducted sediments in this region. In all four geothermal systems, however, a few samples were found with iodine ages older than 40 Ma—that is, considerably below the expected age range for subducted sediments from the Cocos Plate. These samples probably reflect the presence of iodine derived from sediments in older accreted oceanic terraines. The iodine ages indicate that the magmatic end member for the volcanic fluids originates in the deeper parts of the subducted sediment column, with small additions from older iodine mobilized from the overlying crust. The high concentrations of iodine in geothermal fluids, combined with the observed iodine ages, demonstrate that remobilization in the main volcanic zone (and probably also in the forearc area) is an important part in the overall marine cycle of iodine and similar elements.     

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.     

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.     

Ra and Th adsorption coefficients in lakes—Lake Kinneret (Sea of Galilee) “natural experiment”

The adsorption rate constants of Ra and Th were estimated from empirical data from a freshwater lake and its feeding saline springs. We utilized the unique setting of Lake Kinneret (Sea of Galilee, northern Israel) in which most of the Ra and Th nuclides are introduced into the lake by saline springs with high ²²⁶Ra activities and a high ²²⁴Ra/²²⁸Ra ratio of 1.5. The mixing of the Ra enriched saline waters and freshwater in the lake causes the ²²⁴Ra/²²⁸Ra ratio to drop down to 0.1 in the Kinneret due to preferential adsorption of ²²⁸Th. These conditions constitute a “natural experiment” for estimating adsorption rates. We developed a simple mass-balance model for the radionuclides in Lake Kinneret that accurately predicted the Ra isotope ratios and the ²²⁶Ra activity in the lake. The model is comprised of simultaneous equations; one for each radionuclide. The equations have one input term: supply of radionuclides from the saline springs; and three output terms: adsorption on particles in the lake, radioactive decay and outflow from the lake. The redundancy in the analytical solutions to the mass balance equations for the relevant nuclides constrained the values of Ra and Th adsorption rate constants to a very narrow range. Our results indicate that the adsorption rate constant for Ra is between 0.005 d⁻¹ and 0.02 d⁻¹. The rate constant for Th is between 0.5 d⁻¹ and 1 d⁻¹, about fifty to a hundred times higher. The estimated desorption rate coefficient for Ra is about 50-100 times larger than its adsorption rate constant. The mass-balance equations show that the residence times of all Ra isotopes (²²⁶Ra, ²²⁸Ra,²²³Ra, ²²⁴Ra) and of ²²⁸Th in the lake are about 95, 92, 14, 6 and 1 d, respectively. These residence times are much shorter than the residence time of water in the lake (about 5.5 y). The steady state activity ratios in Lake Kinneret depend mainly on the adsorption rate constants, decay constants, the outflow rate from the lake and the activity ratios in the saline springs. The activity ratios are independent of the saline springs flow rate.     

Iodine-129 enrichment in sediment of the Baltic Sea

Sediments are an excellent archive for evaluation of time-series environmental contamination of water systems. Measurements of ultra-trace radioactive species, such as ¹²⁹I, provide information for both chronologic calibration and anthropogenic emissions during the nuclear era. Here data are presented on ¹²⁹I and other chemical parameters from two sediment cores collected in the Baltic Sea during 1997. The sediment sections have a relatively uniform grain size (clay–mud) and cover a period of about 50 a. Distribution of ¹²⁹I in the sediment strongly relates to the liquid release records from the nuclear reprocessing facilities at Sellafield and La Hague. However, syn- and post-depositional alteration of organic matter at the sediment–water interface and within the sediment column may have contributed to slightly obliterating the anthropogenic ¹²⁹I signals. Indication of Chernobyl-derived ¹²⁹I occurs in the sediment profile, but is apparently overridden by the overwhelming flux from the nuclear reprocessing facilities. Although the record did not cover the pre-nuclear era (before 1945) sections, the ultra sensitive ¹²⁹I profile provides a potential tool for relative dating and monitoring sources of water and sediment to the region.     

The distribution of total mercury and methyl mercury in a shallow hypereutrophic lake (Lake Taihu) in two seasons

To understand the geochemical cycle of Hg in hypereutrophic freshwater lake, two sampling campaigns were conducted in Lake Taihu in China during May and September of 2009. The concentrations of unfiltered total Hg (unfTHg) were in the range of 6.8–83 ng L⁻¹ (28 ± 18 ng L⁻¹) in the lake water and total Hg in the sediment was 12–470 ng g⁻¹, both of which are higher than in other background lakes. The concentration of unfTHg in ∼11% of the lake water samples exceeded the second class of the Chinese environmental standards for surface water of 50 ng L⁻¹ (GB 3838-2002), indicating that a high ecological risk is posed by the Hg in Lake Taihu. However, the concentrations of unfiltered total MeHg (unfMeHg) were relatively low in the lake water (0.14 ± 0.05 ng L⁻¹, excluding two samples with 0.81 and 1.0 ng L⁻¹). Lake sediment MeHg varied from 0.2–0.96 ng g⁻¹, with generally low ratios of MeHg/THg of <1%. The low concentrations of TMeHg in the lake water may have resulted from a strong uptake by the high primary productivity and the demethylation of MeHg in oxic conditions. In addition, contrary to the results of previous research conducted in deep-water lakes and reservoirs, the low concentrations of MeHg and low ratio of MeHg/THg in the lake sediment indicates that the net methylation of Hg was not accelerated by the elevated organic matter load created by the eutrophication of Lake Taihu. The results also showed that sediments were a source of THg and MeHg in the water. Higher diffusion fluxes of THg and MeHg may be partly responsible for the higher concentrations of THg in the lake water in May, 2009.     

Noble gas and oxygen isotope studies of aubrites: A clue to origin and histories

Noble gas measurements were performed for nine aubrites: Bishopville, Cumberland Falls, Mayo Belwa, Mount Egerton, Norton County, Peña Blanca Spring, Shallowater, ALHA 78113 and LAP 02233. These data clarify the origins and histories, particularly cosmic-ray exposure and regolith histories, of the aubrites and their parent body(ies). Accurate cosmic-ray exposure ages were obtained using the ⁸¹Kr-Kr method for three meteorites: 52 ± 3, 49 ± 10 and 117 ± 14 Ma for Bishopville, Cumberland Falls and Mayo Belwa, respectively. Mayo Belwa shows the longest cosmic-ray exposure age determined by the ⁸¹Kr-Kr method so far, close to the age of 121 Ma for Norton County. These are the longest ages among stony meteorites. Distribution of cosmic-ray exposure ages of aubrites implies 4-9 break-up events (except anomalous aubrites) on the parent body. Six aubrites show “exposure at the surface” on their parent body(ies): (i) neutron capture ³⁶Ar, ⁸⁰Kr, ⁸²Kr and/or ¹²⁸Xe probably produced on the respective parent body (Bishopville, Cumberland Falls, Mayo Belwa, Peña Blanca Spring, Shallowater and ALHA 78113); and/or (ii) chondritic trapped noble gases, which were likely released from chondritic inclusions preserved in the aubrite hosts (Cumberland Falls, Peña Blanca Spring and ALHA 78113). The concentrations of ¹²⁸Xe from neutron capture on ¹²⁷I vary among four measured specimens of Cumberland Falls (0.5-76 × 10⁻¹⁴ cm³STP/g), but are correlated with those of radiogenic ¹²⁹Xe, implying that the concentrations of (¹²⁸Xe)_n and (¹²⁹Xe)_rad reflect variable abundances of iodine among specimens. The ratios of (¹²⁸Xe)_n/(¹²⁹Xe)_rad obtained in this work are different for Mayo Belwa (0.045), Cumberland Falls (0.015) and Shallowater (0.001), meaning that neutron fluences, radiogenic ¹²⁹Xe retention ages, or both, are different among these aubrites. Shallowater contains abundant trapped Ar, Kr and Xe (2.2 × 10⁻⁷, 9.4 × 10⁻¹⁰ and 2.8 × 10⁻¹⁰ cm³STP/g, respectively) as reported previously (Busemann and Eugster, 2002). Isotopic compositions of Kr and Xe in Shallowater are consistent with those of Q (a primordial noble gas component trapped in chondrites). The Ar/Kr/Xe compositions are somewhat fractionated from Q, favoring lighter elements. Because of the unbrecciated nature of Shallowater, Q-like noble gases are considered to be primordial in origin. Fission Xe is found in Cumberland Falls, Mayo Belwa, Peña Blanca Spring, ALHA 78113 and LAP 02233. The majority of fission Xe is most likely ²⁴⁴Pu-derived, and about 10-20% seems to be ²³⁸U-derived at ¹³⁶Xe. The observed (¹³⁶Xe)_Pu corresponds to 0.019-0.16 ppb of ²⁴⁴Pu, from which the ²⁴⁴Pu/U ratios are calculated as 0.002-0.009. These ratios resemble those of chondrites and other achondrites like eucrites, suggesting that no thermal resetting of the Pu-Xe system occurred after ∼4.5 Ga ago. We also determined oxygen isotopic compositions for four aubrites with chondritic noble gases and a new aubrite LAP 02233. In spite of their chondritic noble gas signatures, oxygen with chondritic isotopic compositions was found only in a specimen of Cumberland Falls (Δ¹⁷O of ∼0.3‰). The other four aubrites and the other two measured specimens of Cumberland Falls are concurrent with the typical range for aubrites.     

Diffusion of HTO,Cl and I in Upper Toarcian argillite samples from Tournemire: Effects of initial iodide concentration and ionic strength

Diffusion parameters for HTO, ³⁶Cl⁻_, and ¹²⁵I⁻ were determined on Upper Toarcian argillite samples from the Tournemire Underground Research Laboratory (Aveyron, France) using the through diffusion technique. The direction of diffusion was parallel to the bedding plane. The purpose of the present study was 3-fold; it was intended (i) to confirm the I⁻ interaction with Upper Toarcian argillite and to verify the effects of initial I⁻ concentration on this affinity, as previously observed by means of radial diffusion experiments, (ii) to highlight any discrepancy between Cl⁻ and I⁻ diffusivity, and (iii) to investigate the effect of an increase of the ionic strength of the solution on the anionic tracers’ diffusive behaviour. The results show that the effective diffusion coefficient (D_e) and diffusion accessible porosity (ε_a) values obtained with an ionic strength (I.S.) synthetic pore water of 0.01 eq L⁻¹ are: D_e = 2.35–2.50 × 10⁻¹¹ m² s⁻¹ and ε_a = 12.0–15.0% for HTO, and D_e = 14.5–15.5 × 10⁻¹³ m² s⁻¹ and ε_a = 2.5–2.9% for ³⁶Cl⁻. Because of anionic exclusion effects, anions diffuse slower and exhibit smaller diffusion accessible porosities than HTO, taken as a water tracer. The associated effective diffusion coefficient (D_e) and rock capacity factor (α) obtained for ¹²⁵I are: D_e = 7.00–8.60 × 10⁻¹³ m² s⁻¹ and α = 4.3–7.2%. Such values make it possible to calculate low ¹²⁵I distribution ratios (0.0057 < R_D < 0.0192 mL g⁻¹) which confirm the trend indicating that the ¹²⁵I rock capacity factor increases with the decrease of the initial I⁻ concentration. Additional through-diffusion experiments were carried out with a higher ionic strength synthetic pore water (I.S. = 0.11 eq L⁻¹). No evolution of HTO diffusion parameters was observed. The anionic tracers’ effective diffusion coefficient increased by a factor of two but no clear evolution of their accessible porosity was observed. Such a paradox could be related to the particularly small mean pore size of the Upper Toarcian argillite of Tournemire. The most significant finding of this study is the large discrepancy (factor of two) between the values of the effective diffusion coefficient for ¹²⁵I and ³⁶Cl. Whatever the ionic strength of the synthetic solution used, ¹²⁵I exhibited D_e values two times lower than those of ³⁶Cl. A detailed explanation for this difference cannot be given at present even if a hypothesis based on ion-pairing or on steric-exclusion cannot be excluded. This makes questionable the assumption usually made for quantifying ¹²⁵I sorption and postulating that ³⁶Cl and ¹²⁵I would diffuse in the same porosity. In other terms, at Tournemire, ¹²⁵I sorption could be more pronounced than previously indicated.     

Mn-Cr systematics of carbonates in CM chondrites: Implications for the timing and duration of aqueous alteration

CM chondrites contain carbonates and other secondary minerals such as phyllosilicates, sulfides, sulfates, oxides and hydroxides that are believed to have formed by aqueous alteration reactions on their parent asteroid. We report in situ Mn-Cr isotope measurements in the highly aqueously altered CM2.1 chondrites QUE 93005 and ALH 83100 using secondary ion mass spectrometry (Cameca ims-1270 ion microprobe). The ⁵³Cr excesses are correlated with the ⁵³Mn/⁵⁵Mn ratio and result from the in situ decay of ⁵³Mn, a short-lived radioisotope with a half-life of 3.7 Ma. If we assume that carbonate grains in samples QUE 93005 and ALH 83100 are cogenetic, then the excesses define initial ⁵³Mn/⁵⁵Mn ratios ((⁵³Mn/⁵⁵Mn)₀) of (4.1 ± 1.2) × 10⁻⁶ and (5.1 ± 1.7) × 10⁻⁶, respectively. These values are comparable to those in carbonates from other CM chondrites as reported in the literature. Initial ⁵³Mn/⁵⁵Mn ratios for calculated model isochrones for individual carbonate grains range from (3.8 ± 1.4) × 10⁻⁶ to (4.8 ± 2.1) × 10⁻⁶ for QUE 93005 and from (3.1 ± 1.6) × 10⁻⁶ to (1.3 ± 0.5) × 10⁻⁵ for ALH 83100. A possible interpretation for the ranges in (⁵³Mn/⁵⁵Mn)₀ could be that alteration in individual CM chondrites was episodic and occurred over an extended period of time. However, isochrones based on the entire set of carbonate grains in each of the CM chondrites imply that the degree of aqueous alteration is roughly correlated with the age of carbonate formation in CM chondrites of different subtypes and that alteration on the CM parent asteroid started contemporaneously with or shortly after CAI formation and lasted at least 4 Ma.     

Variation of initial Th/Th and limits of high precision U-Th dating of shallow-water corals

One hundred eighty U-Th data, including 23 isochrons on 24 pristine modern and Holocene corals and 33 seawater samples, were analyzed using sector-field mass spectrometry to understand the variability of initial ²³⁰Th/²³²Th (²³⁰Th/²³²Th₀). This dataset allows us to further assess the accuracy and precision of coral ²³⁰Th dating method. By applying quality control, including careful sampling and subsampling protocols and the use of contamination-free storage and workbench spaces, the resulting low procedural blanks give an equivalent uncertainty in age of only ±0.2-0.3 yr for 1-2 g of coral sample. Using site-specific ²³⁰Th/²³²Th₀ values or isochron techniques, our study demonstrates that corals with an age less than 100 yrs can be ²³⁰Th-dated with precisions of ±1 yr. Six living subtidal coral samples were collected from two continental shelf sites, Nanwan off southern Taiwan in the western Pacific and Son Tra off central Vietnam in the South China Sea; one coral core was drilled from an open-ocean site, Santo Island, Vanuatu, in the western tropical Pacific; and modern and fossil intertidal coral slabs, 17 in total, were cut from six sites around the islands of Simeulue, Lago, North Pagai and South Pagai of Sumatra in the eastern Indian Ocean. The results indicate that the main source of thorium is the dissolved phase of seawater, with variation of ²³⁰Th/²³²Th₀ depending on local hydrology. With intense input of terrestrial material, low ²³⁰Th/²³²Th₀ atomic ratios of 4.9 × 10⁻⁶ and 3.2 × 10⁻⁶ with a 10% variation are observed in Nanwan and Son Tra, respectively. At the Santo site, we find a value of 5.6 × 10⁻⁶ at 4 horizons and one high value of 24 × 10⁻⁶ in a sample from AD 1974.6 ± 0.5, likely due to the upwelling of cold water during a La Niña event between AD 1973 and 1976. The natural dynamics of ²³⁰Th/²³²Th₀ recorded in the intertidal corals at sites in the Sumatran islands are complicated so that this value varies significantly from 3.0 to 9.4 × 10⁻⁶. Three of the 141 modern coral ²³⁰Th ages differ from their true ages by −23 to +4, indicating the presence of detrital material with anomalous ²³⁰Th/²³²Th values. Duplicate measurement of coeval subsamples is therefore recommended to verify the age accuracy. This improved high precision coral ²³⁰Th dating method raises the prospects of refining the age models for band-counted and tracer-tuned chronologies and of advancing coral paleoclimate research.     

An iodine mass-balance for Lake Constance, Germany: Insights into iodine speciation changes and fluxes

Lake Constance is one of Europe’s largest oligotrophic lakes and provides a water source for more than 4.5 million people in Germany and Switzerland. We present here a 12 month study on iodine concentrations, speciation and fluxes to and from the lake to gain a quantitative understanding of the limnic iodine cycle. Monthly water samples were obtained from all major tributaries (14) and the outflow to construct a mass-balance model. Sediment traps were also deployed in the lake for two years at two different stations. Total soluble iodine (TSI) in aqueous samples were analysed by ICP-MS and speciation (iodide, iodate and soluble organically bound iodine, SOI) by ion chromatography-ICP-MS. Iodine concentrations in the Alpine tributaries (1-2 μg l⁻¹) decreased over the summer months due to increasing proportions of snow and glacial melt water from the Alps, while iodine levels in the lowland rivers (∼2-10 μg l⁻¹) increased over the summer. Deposition of TSI to the catchment (16,340 kg I yr⁻¹) was similar to the TSI out-flux by rivers (16,000 kg I yr⁻¹). By also including the particulate riverine iodine flux out of the catchment (∼12,350 kg I yr⁻¹) it is shown that the catchment is a net source of iodine, with the highest particulate fluxes coming from the Alpine rivers. The total TSI flux to the lake was 16,770 kg I yr⁻¹, the largest proportion coming from the Alpenrhein (43%), followed by the Schussen (8%) and Bregenzer Ach (7.7%). Overall the mass-balance for TSI in the lake was negative, with more iodine flowing out of the lake than in (−2050 kg I yr⁻¹; 12% of TSI in-flux). To maintain mass-balance, 8.8 μg I m⁻² d⁻¹ from the Obersee and 23 μg I m⁻² d⁻¹ from the Untersee must be released from the sediments into the water column. Thus, in comparison with the total iodine flux to the sediments measured by the sediment traps (4762-8075 kg I yr⁻¹), up to 39% of the deposited iodine may be mobilised back into the lake. SOI was the dominant iodine fraction entering the lake, with a total flux of 10,290 kg I yr⁻¹ (64% of TSI input), followed by iodate (3120 kg I yr⁻¹) and iodide (2760 kg I yr⁻¹). Net formation of SOI from iodide and iodate was also noted within the lake, with an estimated production of 6560 kg I yr⁻¹, suggesting a strong role for biology in iodine cycling. In conclusion, organically bound iodine was the dominant iodine species in aqueous and solid phases in Lake Constance, despite low DOC concentrations (<2 mg l⁻¹), and thus is expected to play an important role in iodine cycling in most freshwater environments.     

Origin and history of waters associated with coalbed methane: I, Cl, and stable isotope results from the Fruitland Formation, CO and NM

The Fruitland Formation of the San Juan Basin was deposited during the late Cretaceous and is associated with significant reservoirs of coalbed methane (CBM). The purpose of this study is to determine the origin and history of waters associated with the formation, using long-lived cosmogenic and stable isotope systems. Ratios of ¹²⁹I/I and stable isotope values (δD and δ¹⁸O) were determined in waters from close to 100 wells, ³⁶Cl/Cl ratios for a subset of these samples. A significant group of samples has ¹²⁹I/I ratios between 100 × 10⁻¹⁵ and 200 × 10⁻¹⁵, indicating minimum iodine ages close to 60 Ma. If these ages are corrected for the addition of fissiogenic ¹²⁹I, they are compatible with the depositional age of the Fruitland Formation (Late Cretaceous).Several sets of waters are clearly present within the data. A group dominated by infiltration of recent surface waters is restricted to the uplifted basin margins, with a lateral extent of less than 5 km from outcrop, and is characterized by ¹²⁹I/I ratios in excess of 1500 × 10⁻¹⁵ and meteoric δD, δ¹⁸O, and ³⁶Cl/Cl signatures. The rest of the basin is characterized by several subsets of formation waters which have undergone variable degrees of iodine enrichment through diagenesis as well as variable degrees of dilution. The first subgroup is found in coals of relatively low vitrinite reflectance and moderate enrichment of iodine. This subgroup predominantly consists of entrapped pore fluids, although it may also contain waters which infiltrated the coals at the time of the Laramide uplift, between 25 and 30 Ma. A second subgroup consists of formation waters associated with coals of high vitrinite reflectance. Despite subsequent uplift, the high iodine concentrations and low ¹²⁹I/I ratios of this subgroup, as well as a moderate depletion of deuterium relative to ¹⁸O, suggest that these waters were not significantly altered since the time when diagenetic reactions occurred in the deepest portion of the basin. A third subgroup, with higher δD and δ¹⁸O values as well as higher ¹²⁹I/I ratios, extends roughly west to east at the New Mexico-Colorado state line and corresponds to a region of extensive fracturing of the coalbeds. In this case, the higher ¹²⁹I/I ratios are probably due to contributions of fissiogenic ¹²⁹I through fracture flow, perhaps from deeper formation waters. Our results do not support models of subsequent basin-wide groundwater migration in the Fruitland Formation. The combined use of ¹²⁹I and ³⁶Cl with stable isotope studies provides valuable information as to the hydrologic history of coalbed methane deposits, as well as their potential for commercial exploitation.     

Oxygen isotope fractionation of dissolved oxygen during reduction by ferrous iron

The oxygen isotope fractionation factor of dissolved oxygen gas has been measured during inorganic reduction by aqueous FeSO₄ at 10−54 °C under neutral (pH 7) and acidic (pH 2) conditions, with Fe(II) concentrations ranging up to 0.67 mol L⁻¹, in order to better understand the geochemical behavior of oxygen in ferrous iron-rich groundwater and acidic mine pit lakes. The rate of oxygen reduction increased with increasing temperature and increasing Fe(II) concentration, with the pseudo-first-order rate constant k ranging from 2.3 to 82.9 × 10⁻⁶ s⁻¹ under neutral conditions and 2.1 to 37.4 × 10⁻⁷ s⁻¹ under acidic conditions. The activation energy of oxygen reduction was 30.9 ± 6.6 kJ mol⁻¹ and 49.7 ± 13.0 kJ mol⁻¹ under neutral and acidic conditions, respectively. Oxygen isotope enrichment factors (ε) become smaller with increasing temperature, increasing ferrous iron concentration, and increasing reaction rate under acidic conditions, with ε values ranging from −4.5‰ to −11.6‰. Under neutral conditions, ε does not show any systematic trends vs. temperature or ferrous iron concentration, with ε values ranging from −7.3 to −10.3‰. Characterization of the oxygen isotope fractionation factor associated with O₂ reduction by Fe(II) will have application to elucidating the process or processes responsible for oxygen consumption in environments such as groundwater and acidic mine pit lakes, where a number of possible processes (e.g. biological respiration, reduction by reduced species) may have taken place.     

Timing of glaciation and last glacial maximum paleoclimate estimates from the Fish Lake Plateau, Utah

The High Plateaus of Utah include seven separate mountain ranges that supported glaciers during the Pleistocene. The Fish Lake Plateau, located on the eastern edge of the High Plateaus, preserves evidence of at least two glacial advances. Four cosmogenic ³He exposure ages of boulders in an older moraine range from 79 to 159 ka with a mean age of 129 ± 39 ka and oldest ages of 152 ± 3 and 159 ± 5 ka. These ages suggest deposition during the type Bull Lake glaciation and Marine Oxygen Isotope Stage (MIS) 6. Twenty boulder exposure ages from four different younger moraines indicate a local last glacial maximum (LGM) of ~ 21.1 ka, coincident with the type Pinedale glaciation and MIS 2. Reconstructed Pinedale-age glaciers from the Fish Lake Plateau have equilibrium-line altitudes ranging from 2950 to 3190 m. LGM summer temperature depressions for the Fish Lake Plateau range from −10.7 to −8.2°C, assuming no change in precipitation. Comparison of the Fish Lake summer temperature depressions to a regional dataset suggests that the Fish Lake Plateau may have had a slight increase (~ 1.5× modern) in precipitation during the LGM. A series of submerged ridges in Fish Lake were identified during a bathymetric survey and are likely Bull Lake age moraines.     

Arsenic, iron and sulfur co-diagenesis in lake sediments

Profiles of porewater pH and dissolved As, Fe, Mn, sulfate, total sulfide (ΣS^−II), total zero-valent sulfur (ΣS⁰), organic carbon and major ion concentrations, as well as those of solid As, acid-volatile sulfide (AVS), total S, Fe, Mn, Al, organic C, ²¹⁰Pb and ¹³⁷Cs were determined in the sediment of four lakes spanning a range of redox and geochemical conditions. An inverse modeling approach, based on a one-dimensional transport-reaction equation assuming steady-state, was applied to the porewater As profiles and used to constrain the net rates of reactions involving As (). The model defines depth intervals where As is either released to (positive ) or removed from (negative ) the porewaters.At two of the sites, whose bottom water were oxygenated at sampling time, a production zone ( = 12 × 10⁻¹⁸ mol cm⁻³ s⁻¹-71 × 10⁻¹⁸ mol cm⁻³ s⁻¹) is inferred a few cm below the sediment-water interface, coincident with sharp porewater As and Fe peaks that indicate an intense coupled recycling of As and Fe. This process is confirmed by solid As and Fe maxima just below the sediment surface. In these two lakes a zone of As consumption ( = −5 × 10⁻¹⁸ mol cm⁻³ s⁻¹ to −53 × 10⁻¹⁸ mol cm⁻³ s⁻¹), attributed to the slow adsorption of As to authigenic Fe oxyhydroxides, occurs just above the production zone. A second-order rate constant of 0.12 ± 0.03 cm³ mol⁻¹ s⁻¹ is estimated for this adsorption reaction.Such features in the porewater and solid profiles were absent from the two other lakes that develop a seasonally anoxic hypolimnion. Thermodynamic calculations indicate that the porewaters of the four lakes, when sulfidic (i.e., ΣS^−II ? 0.1 μM), were undersaturated with respect to all known solid As sulfides; the calculation also predicts the presence of As^V oxythioanions in the sulfidic waters, as suggested by a recent study. In the sulfidic waters, the removal of As ( = −1 × 10⁻¹⁸ mol cm⁻³ s⁻¹ to −23 × 10⁻¹⁸ mol cm⁻³ s⁻¹) consistently occurred when saturation, with respect to FeS_(s), was reached and when As^V oxythioanions were predicted to be significant components of total dissolved As. This finding has potential implications for As transport in other anoxic waters and should be tested in a wider variety of natural environments.     

Diffusion of HTO,Br, I,Cs, Sr and Co in a clay formation: Results and modelling from an in situ experiment in Opalinus Clay

The migration of radioactive and chemical contaminants in clay materials and argillaceous host rocks is characterised by diffusion and retention processes. Valuable information on such processes can be gained by combining diffusion studies at laboratory scale with field migration tests. In this work, the outcome of a multi-tracer in situ migration test performed in the Opalinus Clay formation in the Mont Terri underground rock laboratory (Switzerland) is presented. Thus, 1.16 × 10⁵ Bq/L of HTO, 3.96 × 10³ Bq/L of ⁸⁵Sr, 6.29 × 10² Bq/L of ⁶⁰Co, 2.01 × 10⁻³ mol/L Cs, 9.10 × 10⁻⁴ mol/L I and 1.04 × 10⁻³ mol/L Br were injected into the borehole. The decrease of the radioisotope concentrations in the borehole was monitored using in situ γ-spectrometry. The other tracers were analyzed with state-of-the-art laboratory procedures after sampling of small water aliquots from the reservoir. The diffusion experiment was carried out over a period of one year after which the interval section was overcored and analyzed. Based on the experimental data from the tracer evolution in the borehole and the tracer profiles in the rock, the diffusion of tracers was modelled with the numerical code CRUNCH.     

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.     

Stable isotope geochemistry of ground and surface waters associated with undisturbed massive sulfide deposits; constraints on origin of waters and water-rock reactions

Stable isotopes (H, O, C) were determined for ground and surface waters collected from two relatively undisturbed massive sulfide deposits (Halfmile Lake and Restigouche) in the Bathurst Mining Camp (BMC), New Brunswick, Canada. Additional waters from active and inactive mines in the BMC were also collected. Oxygen and hydrogen isotopes of surface and shallow groundwaters from both the Halfmile Lake and Restigouche deposits are remarkably uniform (− 13 to − 14‰ and − 85 to − 95‰ for δ¹⁸O_VSMOW and δ²H_VSMOW, respectively). These values are lighter than predicted for northern New Brunswick and, combined with elevated deuterium excess values, suggest that recharge waters are dominated by winter precipitation, recharged during spring melting. Deeper groundwaters from the Restigouche deposit, and from active and inactive mines have heavier δ¹⁸O_VSMOW ratios (up to − 10.8‰) than shallow groundwaters suggesting recharge under warmer climate or mixing with Shield-type brines. Some of the co-variation in Cl concentrations and δ¹⁸O_VSMOW ratios can be explained by mixing between saline and shallow recharge water end-members. Carbon isotopic compositions of dissolved inorganic carbon (DIC) are variable, ranging from − 15 to − 5‰ δ¹³C_VPDB for most ground and surface waters. Much of the variation in the carbon isotopes is consistent with closed system groundwater evolution involving soil zone CO₂ and fracture zone carbonate minerals (calcite, dolomite and siderite; average = − 6.5‰ δ¹³C_VPDB). The DIC of saline Restigouche deposit groundwater is isotopically heavy (∼+ 12‰ δ¹³C_VPDB), indicating carbon isotopic fractionation from methanogenesis via CO₂ reduction, consistent with the lack of dissolved sulfate in these waters and the observation of CH₄-degassing during sampling.