Inferring Heterogeneity in Aquitards Using High-Resolution δD and δ18O Profiles

Vertical depth profiles of pore water isotopes (δD and δ¹⁸O) in clay-rich aquitards have been used to show that solute transport is dominated by molecular diffusion, to define the timing of geologic events, and to estimate vertical hydraulic conductivity. The interpretation of the isotopic profiles in these studies was based on pore water samples collected from piezometers installed in nests (typically 4 to 15 piezometers) over depths of 10 to 80 m. Data from piezometer nests generally have poor vertical resolution (meters), raising questions about their capacity to reveal the impact of finer scale heterogeneities such as permeable sand bodies or fractured till zones on solute transport. Here, we used high-resolution (30-cm) depth profiles of δD and δ¹⁸O from two continuously cored boreholes in a till aquitard to provide new insights into the effects of sand bodies on solute transport. High-resolution core-derived profiles indicate that such heterogeneities can cause major deviations from one-dimensional diffusion profiles. Further, comparison of piezometer-measured values with best-fit diffusion trends shows subtle deviations, suggesting the presence of heterogeneities that should not be ignored. High-resolution profiles also more clearly defined the contact between the highly fractured oxidized zone and the underlying unoxidized zone than the piezometers.     

Stable Isotopes (δ18O, δ2H) of Pore Waters in Clay-Rich Aquitards: A Comparison and Evaluation of Measurement Techniques

Pore water collected from piezometers installed in a thick clay-rich till were used to compare and evaluate four techniques for obtaining δD and δ¹⁸O values in these media. The techniques included mechanical squeezing, centrifugation, azeotropic distillation, and a direct soil-water equilibration technique. Direct CO₂-core equilibration yielded sufficiently accurate and reproducible δ¹⁸O results of pore water in clay-rich tills. In addition, this method eliminated the need for labor-intensive complete extraction of water from the geologic media. Mechanical squeezing and centrifugation produced results similar to direct equilibration. However, both of these methods exhibited a greater degree of variability and were laborious and more time consuming. Small differences in δ¹⁸O values between piezometer water and equilibrated, squeezed, and centhfuged samples suggested that each method collected different fractions of the clay-water reservoir. Although these subtle differences were not conclusive, they did suggest the presence of weakly bound water and highlighted the difference between these three techniques for determining the stable isotopic composition of pore water in clay-rich aquitards. Azeotropic distillation produced a high level of discrepancy in δD andδ¹⁸O results compared to the other methods. Incomplete extraction was considered the most probable cause of this error. The results of this study suggested that direct equilibration is the best method for determining detailed δD and δ¹⁸O values of pore water in clay-rich aquitards.     

Correlation between the bedded chert sequence of southwest Japan and δ13C excursion of carbonate sequence, and its significance to the Permian-Triassic mass extinction

Abstract Stratigraphic productivity variations of radiolarians below the Permian-Triassic boundary are examined with Ishiga Diagrams in bedded chert sequences of southwest Japan. The diagrams of two different outcrops, drawn from the thickness variation of chert beds, show common stratigraphic variation, which indicates the diagram is a useful tool for correlation of bedded chert sequence. The common stratigraphic productivity variation is also well correlated to a compiled δ¹³C excursion of shallow carbonate sequences. Bedded chert records a dramatic extinction event in a shallow surface zone of oceans below the Permian-Triassic boundary. The Permian-Triassic mass extinction is divided into three intervals based on the Ishiga Diagrams, the stratigraphic lithological variation of bedded chert sequences, and the δ¹³C curve. The preceding extinction interval in the late Djulfian stage was not as serious an event and the biosphere soon recovered. The event of the main extinction interval commenced in the Dorashamian stage and caused a serious destruction of the biosphere. An event of the aftermath interval during the Early Triassic caused a delay in the recovery from the main extinction interval.     

Nitrate Source Identification Using δ15N in a Ground Water Plume Near an Intensive Swine Operation

Nitrate-contaminated ground water beneath and adjacent to an intensive swine ( Sus scrofa domesticus ) production facility in the Middle Coastal Plain of North Carolina was analyzed for δ¹⁵N of nitrate (δ¹⁵N-NO₃). Results show that the isotopic signal of animal waste nitrogen is readily identifiable and traceable in nitrate in this ground water. The widespread land application of animal wastes from intensive livestock operations constitutes a potential source of nitrogen contamination to natural water throughout large regions of the United States and other countries. The site of the present study has been suspected as a nitrate contamination source to nearby domestic supply wells and has been monitored for several years by government and private water quality investigators through sampling of observation wells, ditches, and streams. δ¹⁵N of nitrate allowed direct identification of animal waste-produced nitrate in 11 of 14 wells sampled in this study, as well as recognition of nitrate contributions from non-animal waste agricultural sources in remaining wells.     

230Th/234U and 14C dating of a lowstand coral reef beneath the insular shelf off Irabu Island, Ryukyus, southwestern Japan

Abstract   High-resolution seismic reflection profiles delineated the distribution of mound-shaped reflections, which were interpreted as reefs, beneath the insular shelf western off Irabu Island, Ryukyus, southwestern Japan. A sediment core through one of the mounded structures was recovered from the sea floor at a depth of −118.2 m by offshore drilling and was dated by radiometric methods. The lithology and coral fauna of the core indicate that the mounded structure was composed of coral–algal boundstone suggesting a small-scaled coral reef. High-precision α-spectrometric ²³⁰Th/²³⁴U dating coupled with calibrated accelerator mass spectrometric ¹⁴C ages of corals obtained reliable ages of this reef ranging from 22.18 ± 0.63 to 30.47 ± 0.98 ka. This proves that such a submerged reef was formed during the lowstand stage of marine oxygen isotope stages 3–2. The existence of low-Mg calcite in the aragonitic coral skeleton of 22.18 ± 0.63 ka provides evidence that the reef had once been exposed by lowering of the relative sealevel to at least −126 m during the last glacial maximum in the study area. There is no room for doubt that a coral reef grew during the last glacial period on the shelf off Irabu Island of Ryukyus in the subtropical region of western Pacific.     

40Ar/ 39Ar and K–Ar geochronological age constraints for the inception and early evolution of the Izu–Bonin – Mariana arc system

K–Ar and ⁴⁰Ar/³⁹Ar dates are presented for locations in the Izu–Bonin – Mariana (IBM) forearc (Ocean Drilling Program (ODP) sites 786 & 782, Chichijima, Deep Sea Drilling Program (DSDP) sites 458 & 459, Saipan), and Palau on the remnant arc of the Kyushu–Palau Ridge. For a number of these locations, the ⁴⁰Ar/³⁹Ar plateau and ³⁶Ar/⁴⁰Ar versus ³⁹Ar/⁴⁰Ar isochrons give older ages than the K–Ar results. The most important results are: (i) at site 786, initial construction of the proto-IBM (now forearc) basement occurred at least by ca 47–45 Ma, consistent with the age of the immediately overlying sediments (middle Eocene nannofossil Zone CP13c); the younger pulse of construction dated at ca 35 Ma by K–Ar could not be confirmed by ⁴⁰Ar/³⁹Ar analysis; (ii) ⁴⁰Ar/³⁹Ar ages for the initial construction of the Mariana portion of the IBM system are as old as those of the Izu–Bonin portion, for example at site 458, initial construction commenced at least by ca 49 Ma and at ca 47 Ma at Saipan (Sankakayuma Formation); and (iii) a combination of K–Ar and ⁴⁰Ar/³⁹Ar ages indicate continued boninite magmatism in the Izu–Bonin forearc (and remnant arc at Palau) until ca 35 Ma. Subduction inception including boninite series rocks along most of the exposed length of the IBM system, clearly preceded by some 5 million years the Middle Eocene (ca 43.5 Ma) change in Pacific plate motion. Boninitic series magmatism persisted at locations now exposed in the forearc for ～ 15 million years after arc inception concurrently with low-K tholeiitic series eruptions from a subaerial arc system, established at ≥ 40 Ma, on the Kyushu–Palau Ridge. For the Mariana portion of the IBM system, reconstruction of the proto-arc places this activity adjacent to the concurrent but orthogonally spreading Central Basin Ridge of the West Philippine Basin. It is possible that a combination of subduction of a young North New Guinea Plate beneath newly created back-arc basin crust may account for some of the features of the Mariana system. It is clear, however, that the understanding of the processes of subduction initiation and early IBM arc development is incomplete.     

40Ar–39Ar analysis of phlogopite in the Horoman Peridotite Complex, Hokkaido, Japan and implications for its origin

Abstract ⁴⁰Ar–³⁹Ar analysis of phlogopite separated from a plagioclase lherzolite of the Horoman Peridotite Complex, Hokkaido, Japan, has yielded a plateau age of 20.6 ± 0.5 Ma in an environment where the metamorphic fluid was characterized by an almost atmospheric Ar isotopic ratio. The age spectrum is slightly saddle-shaped, implying some incorporation of excess ⁴⁰Ar during the formation of the phlogopite at a depth. As the phlogopite has been inferred to have formed in veins and/or interstitials during exhumation of the peridotite body, metasomatic fluids, to which ground- and sea water might have contributed, were probably involved in the formation of phlogopite in the crustal environment. A total ⁴⁰Ar–³⁹Ar age of 129 Ma of a whole rock sample of the plagioclase lherzolite, from which the phlogopite was separated and is representative of the main lithology of the Horoman Peridotite Complex, indicates the occurrence of excess ⁴⁰Ar. Hence, the age has no geological meaning.     

K–Ar and 40Ar/39Ar phengite ages of Sanbagawa schist clasts from the Kuma Group, central Shikoku, southwest Japan

Conglomerates of the Kuma Group, central Shikoku, southwest Japan contain Sanbagawa schist clasts with a variety of metamorphic grades and lithologies. K–Ar and ⁴⁰Ar/³⁹Ar dating of phengite show all the pelitic schist clasts from low- to high-grade zones have similar phengite ages (82–84 Ma) that are significantly older than those from the in situ Sanbagawa sequence of central Shikoku. This is because the Kuma–Sanbagawa sequence was exhumed earlier than the in situ Asemi sequence with an exhumation process intermediate between those for the Kanto Mountains and the in situ Asemi sequences. ⁴⁰A/³⁹Ar plateau ages (103 and 117 Ma) of phengite in amphibolites indicate the timing of the early stage of the exhumation of the metamorphic pile, probably close to the peak metamorphic age.     

Correlations between13C and ΣCO2 in surface waters and atmospheric CO2

¹³C and ΣCO₂ data from the North and South Atlantic, the Antarctic, and the North and South Pacific are given. The δ¹³C of the ΣCO₂ in the deep water (～3000m) decreases from 1.7‰ in the North Atlantic to ?0.10‰ in the North Pacific. This change is attributed to the addition of about 158 μmoles of CO₂ per kg of seawater. The in-situ oxidation of organic matter accounts for 83% of this increase in ΣCO₂, while the remainder is attributed to dissolution of calcium carbonate.The δ¹³C of the dissolved CO₂ in mid-latitude surface water samples is controlled by a quasi-steady-state equilibrium with atmospheric CO₂ at a mean temperature of 16°C. The δ¹³C and ΣCO₂ values of Antarctic surface water samples suggest that these waters are derived from a mixture of North Atlantic deep water and equilibrated surface water.     

18O and 13C in the shells of freshwater molluscs and their environments

Carbon and oxygen isotope analyses on shells of freshwater molluscs and their habitat are presented. The data obtained reconfirm the usefulness of such ¹⁸O analyses for paleoenvironmental and paleohydrological studies.The ¹³C analyses on freshwater molluscs from lakes in southwestern Ontario, specimens grown under laboratory conditions and a comparison with the ¹³C contents of the dissolved inorganic carbon in their habitat show that the ¹³C contents in mollusc shells are primarily controlled by the aqueous carbonate species. Vital effects and food control appear to have only minor importance. The significance of this observation on the usufulness of mollusc shells for ¹⁴C dating is discussed.     

Evolution of West Rota Volcano, an extinct submarine volcano in the southern Mariana Arc: Evidence from sea floor morphology, remotely operated vehicle observations and 40Ar–39Ar geochronological studies

Abstract West Rota Volcano (WRV) is a recently discovered extinct submarine volcano in the southern Mariana Arc. It is large (25 km diameter base), shallow (up to 300 m below sealevel), and contains a large caldera (6 × 10 km, with up to 1 km relief). The WRV lies near the northern termination of a major NNE‐trending normal fault. This and a second, parallel fault just west of the volcano separate uplifted, thick frontal arc crust to the east from subsiding, thin back‐arc basin crust to the west. The WRV is distinct from other Mariana Arc volcanoes: (i) it consists of a lower, predominantly andesite section overlain by a bimodal rhyolite‐basalt layered sequence; (ii) andesitic rocks are locally intensely altered and mineralized; (iii) it has a large caldera; and (iv) WRV is built on a major fault. Submarine felsic calderas are common in the Izu and Kermadec Arcs but are otherwise unknown from the Marianas and other primitive, intraoceanic arcs. ⁴⁰Ar–³⁹Ar dating indicates that andesitic volcanism comprising the lower volcanic section occurred 0.33–0.55 my ago, whereas eruption of the upper rhyolites and basalts occurred 37–51 thousand years ago. Four sequences of rhyolite pyroclastics each are 20–75 m thick, unwelded and show reverse grading, indicating submarine eruption. The youngest unit consists of 1–2 m diameter spheroids of rhyolite pumice, interpreted as magmatic balloons, formed by relatively quiet effusion and inflation of rhyolite into the overlying seawater. Geochemical studies indicate that felsic magmas were generated by anatexis of amphibolite‐facies meta‐andesites, perhaps in the middle arc crust. The presence of a large felsic volcano and caldera in the southern Marianas might indicate interaction of large normal faults with a mid‐crustal magma body at depth, providing a way for viscous felsic melts to reach the surface.     

13C/12C ratios of rocks and inclusions in popping rocks of the Mid-Atlantic Ridge and their bearing on the problem of isotopic composition of deep-seated carbon

CO₂-rich inclusions recovered from “popping” and related tholeiitic rocks from the Mid-Atlantic Ridge have δ¹³C values of ?7.6 ± 0.5%. relative to PDB. δ¹³C values of total carbon in the same rocks range from ?12 to ?13.7‰. These values are discussed in the light of the known δ¹³C variations in rocks of deep-seated origin. The ?7.6‰ value is interpreted as a reasonable estimate of the primary value of δ¹³C of deep-seated carbon in the ridge area.