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.     

Radiocarbon and δ13C Values Related to Ground-Water Recharge and Mixing

Ground-water levels in the Upper Floridan aquifer beneath the southeastern coast of South Carolina have undergone pumpage-induced declines approaching 20 ft below sea level at the southern end of Hilton Head Island. This scenario suggests the potential exists for the inducement of recharge to the Upper Floridan aquifer across the island, which could affect the quality of water being pumped by wells. However, low radiocarbon concentrations in ground-water samples (0.5 to 1.4 ± 0.1 PMC) indicate that most of the water is relict ground water reflecting prepumpage ground-water flow conditions in the Upper Floridan aquifer. The isotopic data indicate long residence times and water-chemistry evolution more characteristic of ground-water recharge occurring farther inland prior to the commencement of pumpage in the late 1800s. Radiocarbon concentrations (as Percent Modern Carbon) and stable carbon isotope ratios (as δ¹³C in dissolved inorganic carbon) determined during this study and reported in other studies on and around Hilton Head Island varied in a systematic manner. Heavier δ¹³C values (–2.8 to –1.6 per mil) in ground water beneath southern Hilton Head Island reflect ground-water discharge from prepumpage flowpaths originating over 100 miles away, hence a depletion in radiocarbon concentration with corrected ground-water ages no younger than 16,000 yrs BP. In contrast, lighter δ¹³C values (–13.9 to –8.67 per mil) beneath the northern part of the island indicate recent recharge as a result of water-level declines, and recharge in areas off the island that have not changed as a result of pumpage (evidenced by enrichment in radiocarbon with corrected ground-water ages no older than 4,000 yrs BP). This suggests that the δ¹³C composition of ground water in the Upper Floridan aquifer is a useful indicator of mixing between ground waters from different sources, and can be used to delineate recharge-discharge patterns. This approach may be applicable to other aquifers of highly evolved ground-water chemistry in regional carbonate aquifer systems that may be receiving recent recharge. Moreover, this approach could prove useful in delineating the contribution of recent water being captured by pumped wells as part of wellhead protection programs designed to assess aquifer vulnerability from surficial contaminant sources.     

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.     

18O/16O ratios in lunar fines and rocks

¹⁸O/¹⁶O ratios have been measured for Luna 20 and Apollo 15 fines and Apollo 15 rocks.Isotopic composition and fractionation between minerals are compared with previous results.Partial fluorination experiments on Luna 20 soil and Apollo 15021 extreme fines show large¹⁸O enrichments in grain surfaces. These results are discussed.     

18O/16O ratios in sulfate from fossil shells

The measurement of the oxygen isotopic composition of the sulfate separated from fossil shells supplies no reliable information on the isotopic values of dissolved ocean water sulfate in the past. The results obtained suggest that fossils behave as open systems from the point of view of the possible influence of post-depostional processes on the isotopic composition of shell sulfate.     

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.     

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 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.     

18O/16O ratios in cherts associated with the saline lake deposits of East Africa

The cherts formed from sodium silicate precursors in East African saline, alkaline lakes have δ¹⁸O values ranging from 31.1 to 44.1. The δ¹⁸O values correlate in general with lake salinities as inferred from geologic evidence, indicating that most chert was formed from its precursor in contact with lake water trapped at the time of deposition. A few of the analyzed cherts probably formed in contact with dilute meteoric water. From the widely varying δ¹⁸O values we conclude that precursors were transformed to chert in fluids of widely varying salinity and a_Na⁺/a_H⁺ ratio.     

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.     

Correlation of magnetitic susceptibility with18O/16O data in late orogenic granites of the southern Appalachian Piedmont

Initial magnetic susceptibility (generally indicative of magnetite content) has been determined for 445 samples from 17 granites located in the southern Appalachian Piedmont of Georgia and South Carolina. These values have been correlated with whole rock δ¹⁸O data from the same plutons, yielding a pronounced inverse relationship. It has previously been shown for the southern Piedmont that low oxygen isotopic (¹⁸O-enriched) values usually occur in S-type granites (Wenner [1], this issue). It follows, then, that I-type granites are characterized by high susceptibilities (χ > 1 × 10^?4 G/Oe), and S-type granites by low susceptibilities (χ < 1 × 10^?4 G/Oe). An interesting result of this work has been the observation that some S-type granites exhibit good within-site clusters of remanent magnetic directions while I-type granites generally do not.     

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.     

Variation of precipitation δ18O in Langtang Valley Himalayas

The variation of the δ¹⁸O in precipitation and the relationship with precipitation amount at Kyangjin Base House and Yala Glacier Camp in Langtang Valley, Nepal Himalayas were analyzed. The variations of the δ¹⁸O with precipitation had great scatter, and the correlations between the δ¹⁸O and precipitation changed with time on the synoptic scale. On the seasonal scale, there was marked amount effect at Kyangjin Base House. However, the δ¹⁸O-precipitation gradient was smaller than that on the synoptic scale. Because of the maintenance of the basic equilibrium between stable isotopic compositions in atmospheric vapor and precipitation, the evaporation enrichment was light during the rainy season. Therefore, the variation of stable isotopic compositions in precipitation was independent on the sampling intervals. Simulations show that the rainfall in Langtang Valley was not the outcome of the initial condensation of ocean vapor that originated from low latitudes. The stable isotopic compositions in precipitation were greatly depleted due to the strong rainout of the vapor from oceans as the vapor was raised over the Himalayas.     

40Ar/39Ar ages of blueschist facies pelitic schists from Qingshuigou in the Northern Qilian Mountains, western China

Abstract   Pelitic schists from Qingshuigou in the Northern Qilian Mountains of China contain mainly glaucophane, garnet, white mica, clinozoisite, chlorite and piemontite. Isotopic age dating of these schists provides new constraints on the formation of the high-grade blueschists at Qingshuigou. White mica ⁴⁰Ar/³⁹Ar ages range from 442.1 to 447.5 Ma (total fusion age of single grain) and from 445.7 to 453.9 Ma (integrated age of white mica concentrates). These ages (442.1–453.9 Ma) represent the peak metamorphic ages or cooling ages of the blueschists during exhumation shortly after peak metamorphism. The ⁴⁰Ar/³⁹Ar dates in the present study are similar to ages previously reported for eclogites and blueschists in the area; this suggests that both the eclogites and pelitic sediments underwent high-grade metamorphism during the same subduction event. From this chronological evidence and the presence of well-developed Silurian remnant-sea flysch and Devonian molasse, it is concluded that the Northern Qilian Ocean had closed by the end of the Ordovician, and rapid orogenic uplift followed in the Devonian.