Boron isotope variations in nature: a synthesis

The large relative mass difference between the two stable isotopes of boron, ¹⁰B and ¹¹B, and the high geochemical reactivity of boron lead to significant isotope fractionation by natural processes. Published ¹¹B values (relative to the NBS SRM-951 standard) span a wide range of 90. The lowest ¹¹B values around — 30 are reported for non-marine evaporite minerals and certain tourmalines. The most ¹¹B-enriched reservoir known to date are brines from Australian salt lakes and the Dead Sea of Israel with ¹¹B values up to +59. Dissolved boron in present-day seawater has a constant world-wide ¹¹B value of + 39.5. In this paper, available ¹¹B data of a variety of natural fluid and solid samples from different geological environments are compiled and some of the most relevant aspects, including possible tracer applications of boron-isotope geochemistry, are summarized.

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Résumé La grande différence relative de masse entre les isotopes stables du bore, ¹⁰B et ¹¹B, et la grande réactivité geochimique du bore ont pour conséquence un fractionnement isotopique naturel important. Les valeurs de ¹¹B publiées (par rapport au standard NBS SRM-951) varient de 90. Les valeurs de ¹¹B les plus basses (–30) correspondent aux evaporites non-marines et à certaines tourmalines. Le réservoir le plus enrichi en ¹¹B est représenté par les saumures des lacs salés d' Australie et par la Mer Morte en Israël, qui ont des valuers de ¹¹B allent jusqu'à + 59. L'eau de mer a une valeur de ¹¹B mondialement constante de + 39.5. Des valeurs de ¹¹B des solutions naturelles ainsi que des roches et minéraux de différentes origines, publiées jusqu'à présent, sont présentées ici. En outre quelques aspects importants concernant la géochimie des isotopes du bore y compris quelques applications sont exposés.

     

Stable isotope study of carbonate-cemented rocks from the Pobitite Kamani area,north-eastern Bulgaria

The Precipitation of carbonate cements in the Pobitite Kamani area (Lower Eocene) began during early diagenesis of sediments. There is evidence, however, that calcite is still forming today.The negative ¹³C values to –29.2 suggest that the carbonate formed during degradation of ¹²C-enriched organic matter (perhaps partly from oxidation of methane). The ¹⁸O values of –0.9 to –1.6 reflect the marine origin of the early diagenetic carbonate cements. Most of the carbonates, however, formed during late diagenesis (at approximately 1300 m burial depth) and/or recently (after uplift) from percolating groundwaters. These carbonates have an isotopic composition characteristic of carbonates which precipitated from meteoric waters under normal sedimentary temperatures in isotopic equilibrium with ¹²C-enriched soil carbon dioxide.     

Geochronology and geochemistry of eclogites from the Mariánské Lázně Complex,Czech Republic: Implications for Variscan orogenesis

The Mariánské Lázn complex (MLC) is located in the Bohemian Massif along the north-western margin of the Teplá-Barrandian microplate and consists of metagabbro, amphibolite and eclogite, with subordinate amounts of serpentinite, felsic gneiss and calcsilicate rocks. The MLC is interpreted as a metaophiolite complex that marks the suture zone between the Saxothuringian rocks to the north-west and the Teplá-Barrandian microplate to the south-east. Sm-Nd geochronology of garnet-omphacite pairs from two eclogite samples yields ages of 377±7, and 367±4 Ma. Samples of eclogite and amphibolite do not define a whole rock Sm-Nd isochron, even though there is a large range in Sm/Nd ratio, implying that the suite of samples may not be cogenetic. Eclogites do not have correlated _Nd values and initial ⁸⁷Sr/⁸⁶Sr ratios. Five of the eight eclogite samples have high _Nd values (+10.2 to +7.1) consistent with derivation from a MORB-like source, but variable ⁸⁷Sr/⁸⁶Sr ratios (0.7033 to 0.7059) which probably reflect hydrothermal seawater alteration. Three other eclogite samples have lower _Nd values (+ 5.4 to –0.8) and widely variable ⁸⁷Sr/⁸⁶Sr ratios (0.7033 to 0.7096). Such low _Nd values are inconsistent with derivation from a MORB, source and may reflect a subduction or oceanic island basalt component in their source. The MLC is an important petrotectonic element in the Bohemian Massif, providing evidence for Cambro-Ordovician formation of oceanic crust and interaction with seawater, Late Devonian (Frasnian-Famennian) high- and medium-pressure metamorphism related to closure of a Saxothuringian ocean basin, Early Carboniferous (Viséan) thrusting of the Teplá terrane over Saxothuringian rocks and Late Viséan extension.     

The hydrogeochemistry of methane: Evidence from English groundwaters

The presence of methane (CH₄) in groundwater is usually only noticed when it rises to high concentrations; to date rather little is known about its production or natural ‘baseline’ conditions. Evidence from a range of non-polluted groundwater environments in England, including water supply aquifers, aquicludes and thermal waters, reveals that CH₄ is almost always detectable, even in aerobic conditions. Measurements of potable waters from Cretaceous, Jurassic and Triassic carbonate and sandstone aquifers reveal CH₄ concentrations of up to 500 μg/l, but a mean value of < 10 μg/l. However, aquiclude and thermal waters from the Carboniferous and Triassic typically contain in excess of 1500 μg/l. Such high concentrations have so far only been found at redox (Eh) potentials below 0 mV, but in general CH₄ concentration and Eh value are poorly correlated. This suggests a lack of thermodynamic equilibrium, which is confirmed by comparing pe values calculated from the redox couple C(4)/C(− 4) with those derived from Eh. Genesis of CH₄ appears to occur on two timescales: a rapid if low rate of production from labile carbon in anaerobic microsites in the soil, and a much longer, millennium scale of production from more refractory carbon. Methane is rarely measured in groundwater; there is no single ionic determinand which acts universally as a proxy, but a combination of high HCO₃ and low SO₄ concentrations, or the reverse, is an indication that high amounts of CH₄ may be present.     

Fluid sources for the La Guitarra epithermal deposit (Temascaltepec district, Mexico): Volatile and helium isotope analyses in fluid inclusions

The La Guitarra deposit (Temascaltepec district, South-Central Mexico), belongs to the low/intermediate sulfidation epithermal type, has a polymetallic character although it is currently being mined for Ag and Au. The mineralization shows a polyphasic character and formed through several stages and sub-stages (named I, IIA, IIB, IIC, IID, and III). The previous structural, mineralogical, fluid inclusion and stable isotope studies were used to constrain the selection of samples for volatile and helium isotope analyses portrayed in this study. The N₂/Ar overall range obtained from analytical runs on fluid inclusion volatiles, by means of Quadrupole Mass Spectrometry (QMS), is 0 to 2526, and it ranges 0 to 2526 for stage I, 0 to 1264 for stage IIA, 0 to 1369 for stage IIB, 11 to 2401 for stage IIC, 19 to 324 for stage IID, and 0 to 2526 for stage III. These values, combined with the CO₂/CH₄ ratios, and N₂-He-Ar and N₂-CH₄-Ar relationships, suggest the occurrence of fluids from magmatic, crustal, and shallow meteoric sources in the forming epithermal vein deposit. The helium isotope analyses, obtained by means of Noble Gas Mass Spectrometry, display R/Ra average values between 0.5 and 2, pointing to the occurrence of mantle-derived helium that was relatively diluted or “contaminated” by crustal helium. These volatile analyses, when correlated with the stable isotope data from previous works and He isotope data, show the same distribution of data concerning sources for mineralizing fluids, especially those corresponding to magmatic and crustal sources. Thus, the overall geochemical data from mineralizing fluids are revealed as intrinsically consistent when compared to each other.The three main sources for mineralizing fluids (magmatic, and both deep and shallow meteoric fluids) are accountable at any scale, from stages of mineralization down to specific mineral associations. The volatile and helium isotope data obtained in this paper suggest that the precious metal-bearing mineral associations formed after hydrothermal pulses of predominantly oxidized magmatic fluids, and thus it is likely that precious metals were carried by fluids with such origin. Minerals from base-metal sulfide associations record both crustal and magmatic sources for mineralizing fluids, thus suggesting that base metals could be derived from deep leaching of crustal rocks. At the La Guitarra epithermal deposit there is no evidence for an evolution of mineralizing fluids towards any dominant source. Rather than that, volatile analyses in fluid inclusions suggest that this deposit formed as a pulsing hydrothermal system where each pulse or set of pulses accounts for different compositions of mineralizing fluids.The positive correlation between the relative content of magmatic fluids (high N₂/Ar ratios) and H₂S suggests that the necessary sulfur to carry mostly gold as bisulfide complexes came essentially from magmatic sources. Chlorine necessary to carry silver and base metals was found to be abundant in inclusion fluids and although there is no evidence about its source, it is plausible that it may come from magmatic sources as well.     

Can stable isotopes be used to monitor landfill leachate impact on surface waters?

Bacterially mediated methanogenesis in municipal solid waste landfills has been shown to cause an enrichment of carbon stable isotope ratios of dissolved inorganic carbon and hydrogen stable isotope ratios of water in landfill leachate. In the present study, we investigate the universality of this enrichment in leachate obtained from four diverse landfill sites in New Zealand. At each site, surface water samples upstream and downstream of landfills were analysed to examine the applicability of stable isotope ratios as a tool for monitoring leachate contamination in landfill-associated streams. The design of leachate collection systems, operational history, and landfill location appeared to strongly influence leachate isotopic values and the effectiveness of isotope ratios as an environmental monitoring tool for surface water.     

Hydrochemical and isotopical tracers in the lacustrine aquifer of the Cerro Prieto area, Baja California, México

A series of patterns in the chemical and isotopic composition of the groundwater of the Cerro Prieto area have been recognized. These patterns were used to define four hydrochemical and isotopical zones in the area. One of these areas located at the east side was found to be the source of recharge, while another in the central part is where an older aquifer exist in lacustrine deposits. The low permeability of the area causes the aquifer to act as an aquitard, which at least is partly surrounded by an interface zone where mixing of waters occurs. Tritium and radiocarbon method revealed that the aquitard is an isolate system whose residence time is of 32 ka.     

High-resolution sedimentary record of lead in the coastal mud of the East China Sea in the past one hundred and fifty years

In the East China Sea （ECS）, there are some mud areas, including the south coastal mud area, the north coastal mud area, and the mud area to the southwest of Cheju Island. X-ray fluorescence （XRF） techniques and Thermal Ionization Mass Spectrometry （TIMS） were used to study the high-resolution sedimentary record of Pb concentrations and Pb stable isotopic compositions in the past one hundred and fifty years in the coastal mud of the ECS. Pb concentrations of a ^210Pb dating S5 core in the study area have increased rapidly since 1980, and reached the maximal value with 65.08 μg/g in 2000, corresponding to the fast economic development of China since the implementation of the ＂Reform and Open Policy＂ in 1978; ^206Pb/^207Pb ratios generally had stabilized at 1.195 from 1860 to 1966, and decreased gradually from 1966 to 2000, indicating that the anthropogenic source Pb contribution to the ECS has increased gradually since 1966, especially since 1980. Pb concentrations decreased distinctly from 2000 to 2003 and ^206Pb/^207Pb ratios increased from 2001 to 2003, corresponding closely to the ban of lead gasoline from 2000 in China. From 1950 to 2003, there occurred four distinct decrease events of ^206Pb/^207Pb, possibly responding to the Changjiang River （Yangtze River） catastrophic floods in 1998, 1991, 1981 and 1954; from 1860 to 1966, there were two decrease periods of ^206Pb/^207Pb, which may respond to the catastrophic floods of Changjiang River in 1931 and 1935, and 1870. As a result of the erosion and drowning by the catastrophic floods, the anthropogenic lead accumulated in soil and water environments over a long period of time was brought into the Changjiang River, then part of them was finally transported into the ECS, which leads to changes in Pb stable isotopic composition.     

Distribution and mode of occurrences of radionuclides in phosphogypsum from the Aqaba and Eshidiya fertilizer plants, Jordan

Phosphogypsum is a waste by-product of the phosphate fertilizer industry that has relatively high concentrations of some U decay-series radionuclides such as ^226Ra and ^210Pb. The distribution and environmental mobility of radionuclides in phosphogypsum are an important concern because this gypsum by-product is used for wallboard, in agriculture and as a soil amendment. This study determined the distribution of ^226Ra, ^210Pb, within phosphogypsum stacks of varying age and among three size fractions （coarse： 〈0.212 mm; medium： 0.212-0.053 mm; fine： 〈0.053 mm）, in phosphogypsum derived from Aqaba and Eshidiya fertilizer plants. The results indicated that ^226Ra and ^210Pb were generally uniformly distributed in phosphogypsum stacks and showed no significant difference in the concentration of these elements with the age of stack. In the Aqaba phosphogypsum ^226Ra was slightly 10% enriched in the coarse fraction, while ^210Pb was 10% enriched in the free size fraction. In the Eshidiya phosphogypsum ^226Ra and ^210Pb contents were both relatively enriched （10%） in the fine size fraction.     

Lower Eocene carbonate-cemented “chimney” structures (Varna, Bulgaria) — Control of seepage rates on their formation and stable isotopic signature

The genesis of Lower Eocene calcite-cemented columns, “pisoid”-covered structures and horizontal interbeds, clustered in dispersed outcrops in the Pobiti Kamani area (Varna, Bulgaria) is related to fossil processes of hydrocarbon migration. Field observations, petrography and stable isotope geochemistry of the cemented structures and associated early-diagenetic veins, revealed that varying seepage rates of a single, warm hydrocarbon-bearing fluid, probably ascending along active faults, controlled the type of structure formed and its geochemical signature. Slow seepage allowed methane to oxidize within the sediment under ambient seafloor conditions (δ¹⁸O = − 1 ± 0.5‰ V-PDB), explaining columns' depleted δ¹³C ratios of − 43‰. Increasing seepage rates caused methane to emanate into the water column (δ¹³C = − 8‰) and raised precipitation temperatures (δ¹⁸O = − 8‰). Calcite-cemented conduits formed and upward migrating fluids also affected interbed cementation. Even higher-energy fluid flow and temperatures likely controlled the formation of “pisoids”, whereby sediment was whirled up and cemented.