Sources of in-situ 36Cl in basaltic rocks. Implications for calibration of production rates

In-situ cosmogenic ³⁶Cl production rates from spallation of Ca and K determined in several previously published calibration studies differ by up to 50%. In this study we compare whole rock ³⁶Cl exposure ages with ³⁶Cl exposure ages evaluated in Ca-rich plagioclase in the same 10 ± 3 ka lava sample taken from Mt. Etna (Sicily, 38° N). The exposure age of the sample was determined by K–Ar and corroborated by cosmogenic ³He measurements on cogenetic pyroxene phenocrysts. Sequential dissolution experiments showed that high Cl concentrations in plagioclase grains could be reduced from 450 ppm to less than 3 ppm after 16% dissolution. ³⁶Cl exposure ages calculated from the successive dissolution steps of this leached plagioclase sample are in good agreement with K–Ar and ³He age. Stepwise dissolution of whole rock grains, on the other hand, is not as effective in reducing high Cl concentrations as it is for the plagioclase. 330 ppm Cl still remains after 85% dissolution. The ³⁶Cl exposure ages derived are systematically about 30% higher than the ages calculated from the plagioclase. We could exclude contamination by atmospheric ³⁶Cl as an explanation for this overestimate. Magmatic ³⁶Cl was estimated by measuring a totally shielded sample, but was found to account for only an insignificant amount of ³⁶Cl in the case of the 10 ka whole rock sample. We suspect that the overestimate of the whole rock exposure age is due to the difficulty in accurately assessing all the factors which control production of ³⁶Cl by low-energy neutron capture on ³⁵Cl, particularly variable water content and variable snow cover. We conclude that some of the published ³⁶Cl spallation production rates might be overestimated due to high Cl concentrations in the calibration samples. The use of rigorously pretreated mineral separates reduces Cl concentrations, allowing better estimates of the spallation production rates.In the Appendix of this paper we document in detail the equations used. These equations are also incorporated into a ³⁶Cl calculation spreadsheet made available in the supplementary data.     

Cosmogenic chlorine-36 production rates in terrestrial rocks

Chlorine-36 is produced in rocks exposed to cosmic rays at the earth surface through thermal neutron activation of ³⁵Cl, spallation of ³⁹K and ⁴⁰Ca, and slow negative moun capture by ⁴⁰Ca. We have measured the ³⁶Cl content of ¹⁴C-dated glacial boulders from the White Mountains in eastern California and in a ¹⁴C-dated basalt flow from Utah. Effective, time-intergrated production parameters were calculated by simultaneous solution of the ³⁶Cl production equations. The production rates due to spallation are 4160 ± 310 and 3050 ± 210 atoms ³⁶Cl yr⁻¹ mol⁻¹³⁹K and ⁴⁰Ca, respectively. The thermal neutron capture rate was calculated to be (3.07 ± 0.24) × 10⁵ neutrons (kg of rock)⁻¹ yr⁻¹. The reported values are normalized to sea level and high geomagnetic latitudes. Production of ³⁶Cl at different altitudes and latitudes can be estimated by appropriate scaling of the sea level rates. Chlorine-36 dating was performed on carbonate ejecta from Meteor Crater, Arizona, and late Pleistocene morainal boulders from the Sierra Nevada, California. Calculated ³⁶Cl ages are in good agreement with previously reported ages obtained using independent methods.     

Surface exposure dating of the Veliki vrh rock avalanche in Slovenia associated with the 1348 earthquake

Over 30 samples from bedrock and boulders from the Veliki vrh rock avalanche have been collected for surface exposure dating. The limestone rocks have been radiochemically treated to isolate and determine long-lived ³⁶Cl by accelerator mass spectrometry. It could be shown that the Veliki vrh rock avalanche from the Košuta Mountain (Slovenia) event can be very likely linked to one of the major historical earthquakes in Europe happening on the 25^th of January 1348. Taken into account independently determined denudation rates, inherited ³⁶Cl originating from pre-exposure at shallow depths (20–55 m) could be calculated. The high amount of inherited ³⁶Cl, i.e. 17–46% of the total ³⁶Cl, makes this site not suitable for a precise determination of the ³⁶Cl production rate as it was originally anticipated. Veliki vrh is a “classic” rock avalanche of high velocity. The slope failed in the upper part with a translational slide predominantly along the bedding planes, whereas dynamic fragmentation is the cause for further crushing of the material and the long runout.     

How well do we understand production of 36Cl in limestone and dolomite?

We have evaluated all parameters for the calculation of cosmogenic ³⁶Cl production rates and thus surface exposure ages in dolomite and limestone. We found that we can use either of both published negative muon stopping rates until more information is available. The largest uncertainty of the age estimation in the upper meter of rock comes from the ³⁶Cl production rate from Ca spallation and, in the case of 50–100 ppm Cl content, from the production rate of epithermal neutrons, which we estimate at 760 ± 150 neutrons/g_air/yr (1σ). For a sample with representative amounts of Ca and Cl (20 wt% Ca and 50 ppm Cl, or 40 wt% Ca and 100 ppm Cl), the age can be calculated with a precision of 7–10% in the top 1.5 m of the depth profile. Further improvement of ³⁶Cl calculations depends on new calibration of ³⁶Cl production from Ca spallation, re-evaluation of ³⁶Cl production by low-energy neutron capture on ³⁵Cl, as well as of the muon flux and muon capture based on the most recent measurement data.     

Chemical equilibrium and mass balance relationships associated with the Long Valley hydrothermal system, California, U.S.A.

Recent drilling and sampling of hydrothermal fluids from Long Valley permit an accurate characterization of chemical concentrations and equilibrium conditions in the hydrothermal reservoir. Hydrothermal fluids are thermodynamically saturated with secondary quartz, calcite, and pyrite but are in disequilibrium with respect to aqueous sulfide-sulfate speciation. Hydrothermal fluids are enriched in ¹⁸O by approximately 1‰ relative to recharge waters. ¹⁸O and Cl concentrations in well cuttings and core from high-temperature zones of the reservoir are extensively depleted relative to fresh rhyolitic tuff compositions. Approximately 80% of the Li and 50% of the B are retained in the altered reservoir rock. Cl mass balance and open-system ¹⁸O fractionation models produce similar water-rock ratios of between 1.0 and 2.5 kg kg⁻¹. These water-rock ratios coupled with estimates of reservoir porosity and density produce a minimum fluid residence time of 1.3 ka. The low fluid Cl concentrations in Long Valley correlate with corresponding low rock concentrations. Mass balance calculations indicate that leaching of these reservoir rocks accounts for Cl losses during hydrothermal activity over the last 40 ka.     

Measurements of 36Cl in Antarctic meteorites and Antarctic ice using a Van de Graaff accelerator

Cosmic-ray produced ³⁶Cl(t_1/2 = 3.0 × 10⁵ years) has been measured in four Antarctic meteorites and one sample of Antarctic ice using a tandem Van de Graaff accelerator as an ultrasensitive mass spectrometer with the extremely low background level of ³⁶Cl/Cl< 2 × 10^?16. Results from this ion counting technique (applied here to extraterrestrial materals for the first time) are used to support a two-stage irradiation model for the Yamato-7301 and Allan Hills-76008 meteorites and to show a long terrestrial age (0.7 ± 0.1 m.y.) for Allan Hills-77002. Yamato-7304 has a terrestrial age of less than 0.1 m.y. The ³⁶Cl content of the Antarctic ice sample from the Yamato Mountain area implies that the age of the ice cap at this site is less than one ³⁶Cl half-life.     

Monthly record of the Cl and 36Cl fallout rates in a deciduous forest ecosystem in NE France in 2012 and 2013

This study aims at determining the chlorine and chlorine-36 fallout rates in an experimental beech forest site located in NE France (48°31′55″ N, 5°16′8″ E). A monthly record of Cl and ³⁶Cl concentrations in rainfall samples collected above the canopy was performed during two years, from March 2012 to February 2014. The results show that the Cl concentrations mainly originate from sea-spray while the ³⁶Cl concentrations originate from the stratosphere and therefore present a seasonal dependency. Abrupt and important inputs of ³⁶Cl from the stratosphere indeed yield sharp increases of the recorded concentrations during the spring-summer. We also show that a too short sampling period might bias the determined ³⁶Cl fallout rate. To smooth the seasonal and sporadic bursts of ³⁶Cl, a minimum of 6 months sampling period is required. A mean ³⁶Cl fallout rate of (77 ± 21) atoms m⁻² s⁻¹ can be deduced from our study, which is 45% higher than the modelled value. This discrepancy suggests more studies aiming at measuring the ³⁶Cl fallout rate worldwide are necessary.     

Characteristics of chlorine isotope distribution and analysis on sylvinite deposit formation based on ancient salt rock in the western Tarim Basin

The Tarim Basin, located in Xinjiang (Fig. 1), is the largest deposit basin with an area of about 560000 km2 in China. From late Triassic period to early Miocene, two huge subbasins developed, named the Kuqa sub-basin at the foot of the Tianshan Mountains in the north and the Shaqa subbasin at the foot of the Kunlun Mountains in the south of the Tarim Basin. During the late Cretaceous to early Tertiary period, the Paleo-me- diterranean seawater repetitively invaded into the Shaqa subbas…     

In-situ neutron flux,Cl production and groundwater evolution in crystalline rocks at Stripa, Sweden

The meteoric input of³⁶Cl due to cosmogenic or nuclear-weapon-produced³⁶Cl cannot contribute significantly to the³⁶Cl present in the saline groundwaters (up to 700 mg l⁻¹ Cl⁻) from the Stripa granite. The extent of in-situ production of³⁶Cl has been estimated on the basis of the neutron fluxes within the granite and its surrounding leptite. The³⁶Cl present in the groundwaters is attributed to either admixture of labelled Cl⁻ from the leptite with Cl⁻ from the granite or to the total derivation of groundwater chlorinity within the leptite followed by radiochemical ingrowth of³⁶Cl during subsequent groundwater residence within the granite. The chloride derived from the leptite may be either matrix chloride or chloride from an external source which has had a long residence time within the leptite. The implications of³⁶Cl in-situ production for the estimation of groundwater residence times and for the geochemical evolution of groundwater chlorinity are discussed.     

The potential of historic rock avalanches and man-made structures as chlorine-36 production rate calibration sites

Samples from three medieval rock avalanches from the French (Le Claps, Mont Granier) and Austrian Alps (Dobratsch) and a man-made structure, i.e. the Stephansdom in Vienna, have been analysed for in-situ produced ³⁶Cl by accelerator mass spectrometry (AMS). All four sampling sites of independently known exposure duration turned out to be not appropriate as calibration sites for the determination of the ³⁶Cl-production rate from Ca. Indeed, the determination of short exposure ages for dating rock avalanches and man-made structures by ³⁶Cl is hindered dramatically by inheritance, especially for samples characterized by high ^natCl-concentrations. Generally, there are hints that the theoretical calculation of ³⁶Cl-production from epithermal and thermal neutron-capture on ³⁵Cl is highly underestimated in all existing models, thus, asking for particular precaution if working on high-Cl samples for any project. Hence, this work evidences that potential high inheritance, even for samples reasonably shielded before exhumation, has to be considered especially when dealing with recently exposed surfaces such as glacially polished rocks, alluvial terraces, fault scarps etc.     

First results on determination of cosmogenic 36Cl in limestone from the Yenicekale Complex in the Hittite capital of Hattusha (Turkey)

We have measured ³⁶Cl in three rock surfaces of the Yenicekale building complex in Hattusha (Bo?azköy, Turkey). Hattusha was the capital of Hittite Empire which lasted from about 1650/1600 to 1200 BC. At Yenicekale, Hittite masons flattened the summit of an outcropping limestone knoll to form an artificial platform as the foundation for a building. Next they built a circuit wall along the lateral precipices of the flattened bedrock platform. We took one sample from the limestone bedrock platform and two samples from limestone building blocks of the circuit wall for cosmogenic ³⁶Cl analysis. Calculated exposure ages are 20 ± 1 ka for the sample from the bedrock platform and 24 ± 1 ka and 52 ± 2 ka for the circuit wall blocks. These exposure ages are significantly older than the age expected based on the estimated time of construction between 3.2 ka and 3.7 ka. We conclude that the sampled surfaces contain significant inherited cosmogenic ³⁶Cl. We cannot directly determine exposure ages for the building complex based on these three samples. On the other hand we may use the measured concentrations to determine how much of the rock was removed from the platform during flattening. To this end we modeled the variation of ³⁶Cl production with depth at Yenicekale using the results from the bedrock sample. We conclude that the Hittite masons removed only around 3 m from top of the limestone block. This means that the volume of rock removed from the bedrock platform is significantly less than the volume in the circuit wall atop the platform. They did not gain enough rock from this flattening to make the building. In agreement with this, the first results of our detailed microfacies analysis indicate that many of the building blocks are not of the same facies as the underlying limestone and must have been quarried elsewhere. Although we were not able to exposure date the Yenicekale complex due to the presence of inherited ³⁶Cl, our data suggest that Hittite masons excavated (most of) the building stones not at Yenicekale, but in quarries outside of Hattusha and then transported them to the construction site. These quarries have not yet been identified.     

Neutron capture effects in lunar gadolinium and the irradiation histories of some lunar rocks

The Gd isotopic composition in 19 lunar rock and soil samples from three Apollo sites is reported. The analytical techniques and the high precision mass spectrometric measurements are discussed. Enrichments in¹⁵⁸GdO/¹⁵⁷GdO due to neutron capture range up to 0.75%. Integrated ‘thermal’ neutron fluxes derived from the isotopic anomalies of Gd are compared with spallation Kr data from aliquot samples to construct a model which gives both average cosmic-ray irradiation depths and effective neutron exposure ages (T_n) for some rocks. In the case of rock 12053, this yields an average sample location of ∼300 g/cm² below the lunar surface and an effective irradiation age of ∼230 my, compared to 99 my obtained by the⁸¹Kr-Kr method. Rock 14310 is the first lunar sample where Kr anomalies due to resonance neutron capture in Br are observed. A⁸¹Kr-Kr exposure age of 262 ± 7 my is calculated for this rock.     

Sr–Nd isotope ratios of gabbroic and dioritic rocks in a Cretaceous-Paleogene granite terrain, Southwest Japan

Abstract Whole‐rock chemical and Sr and Nd isotope data are presented for gabbroic and dioritic rocks from a Cretaceous‐Paleogene granitic terrain in Southwest Japan. Age data indicate that they were emplaced in the late Cretaceous during the early stages of a voluminous intermediate‐felsic magmatic episode in Southwest Japan. Although these gabbroic and dioritic rocks have similar major and trace element chemistry, they show regional variations in terms of initial Sr and Nd isotope ratios. Samples from the South Zone have high initial ⁸⁷Sr/⁸⁶Sr (0.7063–0.7076) and low initial Nd isotope ratios (?_Nd, ?2.5 to ?5.3); whereas those from the North Zone have lower initial ⁸⁷Sr/⁸⁶Sr (usually less than 0.7060) and higher Nd isotope ratios (?_Nd, ?0.8 to + 3.3). Regional variations in Sr and Nd isotope ratios are similar to those observed in granitic rocks, although gabbroic and dioritic rocks tend to have slightly lower Sr and higher Nd isotope ratios than granitic rocks in the respective zones. Limited variations in Sr and Nd isotope ratios among samples from individual zones may be attributed partly to a combination of upper crustal contamination and heterogeneity of the magma source. Contamination of magmas by upper crustal material cannot, however, explain the observed Sr and Nd isotope variations between samples from the North and South Zones. Between‐zone variations would reflect geochemical difference in magma sources. The gabbroic and dioritic rocks are enriched in large ion lithophile elements (LILE) and depleted in high field strength elements (HFSE), showing similar normal‐type mid‐ocean ridge basalt (N‐MORB) normalized patterns to arc magmas. Geochronological and isotopic data may suggest that some gabbroic and dioritic rocks are genetically related to high magnesian andesite. Alternatively, mantle‐derived mafic or intermediate rocks which were underplated beneath the crust may be also plausible sources for gabbroic and dioritic rocks. The magma sources (the mantle wedge and lower crust) were isotopically more enriched beneath the South Zone than the North Zone during the Cretaceous‐Paleogene. Sr and Nd isotope ratios of the lower crustal source of the granitic rocks was isotopically affected by mantle‐derived magmas, resulting in similar initial Sr and Nd isotope ratios for gabbroic, dioritic and granitic rocks in each zone.     

36Cl and53Mn in Antarctic meteorites and10Be-36Cl dating of Antarctic ice

Cosmic-ray-produced⁵³Mn (t_1/2 = 3.7 × 10⁶years) has been measured in twenty Antarctic meteorites by neutron activation analysis.³⁶Cl (t_1/2 = 3.0 × 10⁵years) has been measured in fourteen of these objects by tandem accelerator mass spectrometry. Cosmic ray exposure ages and terrestrial ages of the meteorites are calculated from these results and from rare gases.¹⁴C (t_1/2 = 5740years) and²⁶Al (t_1/2 = 7.2 × 10⁵years) data. The terrestrial ages range from 3 × 10⁴ to 5 × 10⁵ years. Many of the L3 Allan Hills chrondrites seem to be a single fall based on these results. In addition,¹⁰Be (t_1/2 = 1.6 × 10⁶years) and³⁶Cl have been measured in six Antarctic ice samples. The first measurements of¹⁰Be/³⁶Cl ratios in the ice core samples demonstrate a new dating method for ice.     

The fate of B, Cl and Li in the subducted oceanic mantle and in the antigorite breakdown fluids

We present an inventory of B, Cl and Li concentrations in (a) key minerals from a set of ultramafic samples featuring the main evolutionary stages encountered by the subducted oceanic mantle, and in (b) fluid inclusions produced during high-pressure breakdown of antigorite serpentinite. Samples correspond to (i) nonsubducted serpentinites (Northern Apennine and Alpine ophiolites), (ii) high-pressure olivine-bearing antigorite serpentinites (Western Alps and Betic Cordillera), (iii) high-pressure olivine-orthopyroxene rocks recording the subduction breakdown of antigorite serpentinites (Betic Cordillera). Two main dehydration episodes are recorded by the sample suite: partial serpentinite dewatering during formation of metamorphic olivine, followed by full breakdown of antigorite serpentine to olivine+orthopyroxene+fluid. Ion probe and laser ablation ICP-MS (LA ICP-MS) analyses of Cl, B and Li in the rock-forming minerals indicate that the hydrous mantle is an important carrier of light elements. The estimated bulk-rock B and Cl concentrations progressively decrease from oceanic serpentinites (46.7 ppm B and 729 ppm Cl) to antigorite serpentinites (20 ppm B and 221 ppm Cl) to olivine-orthopyroxene rocks (9.4 ppm B and 45 ppm Cl). This suggests release of oceanic Cl and B in subduction fluids, apparently without inputs from external sources. Lithium is less abundant in oceanic serpentinites (1.3 ppm) and the initial concentrations are still preserved in high-pressure antigorite serpentinites. Higher Li contents in olivine, Ti-clinohumite of the olivine-orthopyroxene rocks (4.9 ppm bulk rock Li), as well as in the coexisting fluid inclusions, suggest that their budget may not be uniquely related to recycling of oceanic Li, but may require input from external sources.Laser ablation ICP-MS analyses of fluid inclusions in the olivine-orthopyroxene rocks enabled an estimate of the Li and B concentrations in the antigorite breakdown fluid. The inclusion compositions were quantified using a range of salinity values (0.4-2 wt.% NaCl_equiv) as internal standards, yielding maximum average ^fluid/rockD_B∼5 and ^fluid/rockD_Li∼3.5. We also performed model calculations to estimate the B and Cl loss during the two dehydration episodes of serpentinite subduction. The first event is characterized by high fluid/rock partition coefficients for Cl (∼100) and B (∼60) and by formation of a fluid with salinity of 4-8 wt.% NaCl_equiv. The antigorite breakdown produces less saline fluids (0.4-2 wt.% NaCl_equiv) and is characterized by lower partition coefficients for Cl (25-60) and B (12-30). Our calculations indicate that the salinity of the subduction fluids decreases with increasing depths. ^fluid/rockD_B/^fluid/rockD_Cl<1 (∼0.5) indicates that Cl preferentially partitions into the evolved fluids relative to B and that the B/Cl of fluids progressively increases with increasing depths and temperatures.Despite light element release in fluids, appreciable B, Cl and Li are still retained in chlorite, olivine and Ti-clinohumite beyond the antigorite stability field. This permits a bulk storage of about 10 ppm B, 45 ppm Cl and 5 ppm Li, i.e., concentrations much higher than in mantle reservoirs. Chlorite is the Cl repository and its stability controls the Cl and H₂O budget beyond the antigorite stability; B and Li are bound in olivine and clinohumite. The subducted oceanic mantle thus retains light elements beyond the depths of arc magma sources, potentially introducing anomalies in the upper mantle.     

Cosmic-ray-produced36Cl and53Mn in Allan Hills-77 meteorites

Cosmic-ray-produced⁵³Mn (t_1/2 = 3.7 × 10⁶years) has been determined by neutron activation in nine Allan Hills-77 meteorites. Additionally,³⁶Cl (_1/2 = 3.0 × 10⁵years) has been measured in seven of these objects using tandem accelerator mass spectrometry. These results, along with¹⁴C (t_1/2 = 5740years) and²⁶Al (7.2 × 10⁵ years) concentrations determined elsewhere, yield terrestrial ages ranging from 0.1 × 10⁵ to 7 × 10⁵ years. Weathering was not found to result in⁵³Mn loss.     

Testing less-conventional methods to date a late-pleistocene to Holocene eruption: Radiocarbon dating of paleosols and 36Cl exposure ages at Pelado volcano,Sierra Chichinautzin,Central Mexico

Despite their significance for estimating hazards and forecasting future activity, dating young volcanic deposits and landforms (<50,000 yrs old) remains a challenge due to the limitations inherent to the different isotopic chronometers used. The Trans-Mexican Volcanic Belt is one of the most active and populated continental arcs worldwide, yet its temporal pattern of activity is poorly constrained. Such deficiency is particularly problematic for the Sierra Chichinautzin Volcanic Field (SCVF) that is located at the doorstep of Mexico City and Cuernavaca and is hence a major source of risk for these cities. Existing ages for this area derive mostly from either radiocarbon on charcoal, which is rare and may be contaminated, or ⁴⁰Ar/³⁹Ar on rock matrix, which is poorly precise for this time period and rock type. Here, we focus on the Pelado monogenetic volcano, which is located in the central part of the SCVF and erupted both explosively and effusively, producing a large lava shield and a widespread tephra blanket. This unique eruptive event was previously dated at ∼12 calibrated (cal) kyrs BP, using radiocarbon dating on charcoal from deposits related to the eruption. To test alternative dating approaches and confirm the age of this significant eruption, we applied two less conventional techniques, radiocarbon dating of bulk paleosol samples collected below the complete tephra sequence at nine sites around the shield, and in-situ ³⁶Cl exposure dating of two samples of an aphyric lava from the base of the shield. Radiocarbon paleosol ages span a continuous time interval from 13.2 to 20.2 cal kyrs BP (2σ), except for one anomalously young sample. This wide age spread, along with the low organic contents of the paleosols, may be due to erosive conditions, related to the sloping topography of the sampling sites and the cool and relatively dry climate of the Younger Dryas (11.7–12.9 ka), during which the Pelado eruption probably occurred. The two ³⁶Cl-dated lava samples have consistent ages at 1σ analytical errors of 15.5 ± 1.4 ka and 13.2 ± 1.2 ka, respectively, yielding an average age of 14.3 ± 1.6 ka for this lava flow. The high full uncertainty in ³⁶Cl ages (24%) is due to high rock Cl content. We conclude that paleosol radiocarbon dating is useful if numerous samples are analyzed and climatic and relief conditions at the time of the eruption and at the sites of tephra deposition are considered. The ³⁶Cl dating technique is an alternative method to date volcanic eruptions, as it gave consistent results, but in the specific case of Pelado volcano, the high Cl content in the analyzed rocks increases the age uncertainties.     

A Geochemical Approach to Determine Sources and Movement of Saline Groundwater in a Coastal Aquifer

Geochemical evaluation of the sources and movement of saline groundwater in coastal aquifers can aid in the initial mapping of the subsurface when geological information is unavailable. Chloride concentrations of groundwater in a coastal aquifer near San Diego, California, range from about 57 to 39,400 mg/L. On the basis of relative proportions of major‐ions, the chemical composition is classified as Na‐Ca‐Cl‐SO₄, Na‐Cl, or Na‐Ca‐Cl type water. δ²H and δ¹⁸O values range from ?47.7‰ to ?12.8‰ and from ?7.0‰ to ?1.2‰, respectively. The isotopically depleted groundwater occurs in the deeper part of the coastal aquifer, and the isotopically enriched groundwater occurs in zones of sea water intrusion. ⁸⁷Sr/⁸⁶Sr ratios range from about 0.7050 to 0.7090, and differ between shallower and deeper flow paths in the coastal aquifer. ³H and ¹⁴C analyses indicate that most of the groundwater was recharged many thousands of years ago. The analysis of multiple chemical and isotopic tracers indicates that the sources and movement of saline groundwater in the San Diego coastal aquifer are dominated by: (1) recharge of local precipitation in relatively shallow parts of the flow system; (2) regional flow of recharge of higher‐elevation precipitation along deep flow paths that freshen a previously saline aquifer; and (3) intrusion of sea water that entered the aquifer primarily during premodern times. Two northwest‐to‐southeast trending sections show the spatial distribution of the different geochemical groups and suggest the subsurface in the coastal aquifer can be separated into two predominant hydrostratigraphic layers.     

The case for a martian origin of the shergottites: nitrogen and noble gases in EETA 79001

Nitrogen and noble gases were measured in samples of a glass inclusion and the surrounding basaltic matrix from the antarctic shergottite EETA 79001. A nitrogen component trapped in the glass, but not present in the matrix, has a δ¹⁵N value at least as high as +190‰. Ratios of⁴⁰Ar/¹⁴N and¹⁵N/¹⁴N in the glass are consistent with dilution of a martian atmospheric component (δ¹⁵N = 620 ± 160‰,⁴⁰Ar/¹⁴N= 0.33 ± 0.03) by either terrestrial atmosphere adsorbed on the samples or by indigenous nitrogen from the minerals of the rock. Trapped noble gases in the glass reproduce, within error, the elemental and isotopic compositions measured in Mars' atmosphere by Viking, and are in general agreement with previous measurements except for much lower abundances of neutron-generated krypton and xenon isotopes. The most reasonable explanation at the present time for the noble gas pattern and the isotopically heavy nitrogen is that a sample of martian atmosphere has been trapped in the EETA 79001 glass, and that this meteorite, and thus the shergottites and probably the nakhlites and chassignites as well, originated on Mars.Nitrogen in the non-glassy matrix of EETA 79001 amounts to less than 0.5 ppm and has a spallation-corrected δ¹⁵N value in the range 0 to ?20‰; it may reflect indigenous nitrogen in the basalt or a mixture of indigenous and adsorbed terrestrial nitrogen. Spallogenic noble gases yield single-stage exposure ages between 400,000 and 900,000 years, depending on irradiation geometry. Trapped argon may have an unusually low³⁶Ar/³⁸Ar ratio. Trapped krypton, except for a small excess at⁸⁰Kr, is smoothly mass-fractionated with respect to either terrestrial or chondritic Kr. The trapped xenon composition is consistent with addition of neutron-capture, radiogenic and fissiogenic isotopes to a base composition resembling terrestrial atmospheric Xe. The elemental⁸⁴Kr/¹³²Xe ratio of 25 is close to the terrestrial value and very different from the chondritic ratio.     

Neutron capture logging calibration and data analysis for environmental contaminant assessment

This paper describes a method to calibrate a neutron capture sonde equipped with a high resolution γ-ray detector, and analyze log data. The method utilizes the 1460.8-keV passive γ-ray of ⁴⁰K, the 770.3-keV capture γ-ray of ³⁹K, and a capture γ-ray from a target element. An equation containing the spectral line intensities for the two capture γ-rays, nuclear capture data, and the detector efficiency function expresses the concentration of the target element as a multiple of the ³⁹K concentration. The concentration of ³⁹K is easily deduced from the ⁴⁰K concentration, which is calculated directly from the line intensity for the 1460.8-keV γ-ray in a passive γ-ray spectrum.The calibration automatically adjusts to changes in the neutron transport properties of the logged medium that may result, for example, from variations in the H density and the concentrations of neutron poisons. Fluctuations in the neutron source output are similarly accommodated. The calibration utilizes U.S. Department of Energy (DOE) passive γ-ray calibration standards that contain well established concentrations of K, U, and Th. The passive γ-rays from K, U, and Th (and the U and Th decay progenies) provide data for the detector efficiency function determination.Data for proof-of-principle demonstrations of the method were acquired by logging boreholes penetrating the shallow subsurface at a DOE waste site with a simple, reliable neutron capture logging system. The system had a ²⁵²Cf source and a high purity germanium (HPGe) detector. Time gating could not be used to sort signals originating from capture and activation, but the excellent energy resolution permitted capture γ-ray identifications based solely on the γ-ray energies. Cl, H, and other elements were detected and assessed.A conventional calibration and data analysis method was also employed. The method was specific to Cl and was based on measurements in two Cl-impregnated concrete blocks. Cl concentrations inferred with this method were often consistent with the concentrations determined with the new method. When the two methods produced different Cl concentrations, the discrepancies could be explained by variations in formation parameters.