Petrology, geochemistry, S, Cl and F abundances, and S oxidation state of sideromelane glass shards from Pleistocene ash layers north and south of Gran Canaria (ODP Leg 157)

Major elements, S, F, Cl concentrations and relative proportions of S⁶⁺ to total S were analyzed with electron microprobe in sideromelane glass shards from Pleistocene volcaniclastic sediments drilled during ODP Leg 157. Glasses are moderately to strongly evolved and represent a spectrum from alkali basalt, basanite and nephelinite through hawaiite, mugearite and tephrite to phonolitic tephrite. Measured S⁶⁺/ΣS (0.03–0.98) and calculated Fe²⁺/Fe³⁺ (2.5–5.8) ratios in the melt yield preeruptive redox conditions ranging from NNO−1.4 to NNO+2.1. The morphology of the glass shards, variations of S and Cl concentrations (0.010–0.127 wt% S, 0.018–0.129 wt% Cl), calculated preeruptive temperatures (1030–1200 °C) and oxygen fugacities suggest that glasses deposited even within the same ash layers have diverse origin and may have resulted from both submarine and subaerial eruptions. Most vesicle-free glasses are characterized by high concentrations of S and represent undegassed or slightly degassed submarine lavas, whereas vesiculated glasses with low concentrations of S and Cl are strongly degassed and can be ascribed to the eruptions in shallow water or on land. Sideromelane glass shards at Sites 953 are thought to have resulted from submarine eruptions northeast of Gran Canaria, glasses at Site 954 represent mostly volcaniclastic material of shallow water submarine and subaerial eruptions on Gran Canaria and Tenerife, and glasses deposited at Site 956 resulted from submarine or explosive eruptions on Tenerife. Received: 8 April 1997 / Accepted: 27 October 1997     

Lahar-Triggering Mechanisms and Hazard at Ruapehu Volcano,New Zealand

Late Holocene volcanic activity at Ruapehu has been characterizedby the generation of small (<10⁵ m³) to very large (>10⁷ m³) lahars and repeated,small to medium (VEI 1-3) tephra-producing eruptions. The Onetapu Formation groupsall lahar deposits that accumulated during the last 2,000 years on the southeastern Ruapehu ring plain. The andesitic tephras are grouped within the Tufa Trig Formation and are intercalated within the laharic sequence. By correlating these two formations with new radiocarbon ages obtained on interbedded paleosols, we reconstruct a detailed volcanic history of Ruapehu for this period.Clast assemblages identified in the laharic sequences record thelithologies of synchronous tephras and rocks within the source region. These assemblages suggest a strong genetic link between the development of Crater Lake, the variation in eruptivestyles, and the production of lahars.Lahar-triggering mechanisms include: (1) flank collapse ofhydrothermally altered and unstable portions of the cone; (2) phreatic and phreatomagmatic eruptions favoring the generation of snow-rich slurries and hyperconcentrated stream flows; (3) suddenCrater Lake rim collapse, releasing large amounts of water inducing debris flows; and (4) eruptions that generate large volumes of tephra on snow-covered slopes, later remobilized by heavy rain.Two major lahars in the Onetapu sequence had a volume 4 × 10⁷ m³, roughly 1 to 2 orders of magnitude larger than the 1953event leading to the Tangiwai disaster (151 casualties). One of these lahars crossed over a lowinterfluve currently separating the Whangaehu River from a stream feeding the Tongariro River,sometime since peat accumulated between AD 1400 and AD 1660. A repetition of such a large-scaleevent would have devastating consequences on the infrastructure, economy and environment withinthe distal areas of the two catchments. The 1995–1996 eruptions were a timely reminder ofthe hazards posed by the volcano.     

Volcaniclastic stratigraphy of the Tiscapa maar crater walls (Managua, Nicaragua): implications for volcanic and seismic hazards and Holocene climate changes

The Tiscapa maar in the center of Managua city formed by a phreatomagmatic eruption <3 ka ago. The eruption excavated a crater deep into the basement exposing a coherent Pleistocene to Holocene volcaniclastic succession that we have divided into four formations. The lowermost, >60 ka old basaltic–andesitic formation F1 comprises mafic ignimbrites and phreatomagmatic tephras derived from the Las Sierras volcanic complex south of Managua. Formation F2 contains the ~60 ka basaltic–andesitic Fontana tephra erupted from the Las Nubes Caldera of the Las Sierras complex 15 km to the S, the 25 ka Upper Apoyo tephra from the Apoyo Caldera 35 km to the SE, and the Lower (~17 ka) and Upper (12.4 ka) Apoyeque tephras from the Chiltepe volcanic complex 15 km to the NW. These tephras are separated by weathering horizons and paleosols indicating dry climatic conditions. Fluvial deposits of a SSW-NNE running paleo-river system build formation F3. The fluvial sediments contain, from bottom to top, scoriae from the ~6 ka basaltic San Antonio tephra, pumice lapilli from the Apoyo and Apoyeque tephras and the 6.1 ka Xiloà tephra, and scoriae derived from the Fontana tephra. The fluvial sediment succession thus reflects progressively deeper carving erosion in the southern highlands (where a large-amplitude regional erosional unconformity exists at the appropriate stratigraphic level) that began after ~6 ka. This suggests that the mid-Holocene tropical high-precipitation climatic phase affected western Nicaragua about a thousand years later than other circum-Caribbean regions. The end of the wet climate phase ~3 ka ago is recorded by a deep weathering zone and paleosol atop formation F3 prior to the Tiscapa eruption. Formation F4 is the Tiscapa tuffring composed of pyroclastic surge and fallout deposits that cover a minimum area of 1.2 km². The 4 × 10⁹ kg of erupted basaltic magma is compositionally and genetically related to the low-Ti basalts of the N–S striking Nejapa-Miraflores volcanic–tectonic alignment 5 km to the West of Tiscapa. Ascent and eruption mode of the Tiscapa magma were controlled by the Tiscapa fault that has a very active seismic history as it achieved 12 m displacement in about 3000 years. Managua city is thus exposed to continued seismic and volcanic risks.     

Metal-residence sites in lavas and tuffs from Volcán Popocatépetl, Mexico: implications for metal mobility in the environment

 Volcan Popocatépetl is a Quaternary stratovolcano located 60 km southeast of Mexico City. The summit crater is the site of recent ash eruptions, excess degassing, and dacite dome growth. The modern cone comprises mainly pyroclastic flow deposits, airfall tephras, debris flows, and reworked deposits of andesitic composition; it is flanked by more mafic monogenetic vents. In least-degassed fallout tuffs and mafic scoria, transition metals are concentrated in phases formed before eruption, during eruption, and after eruption. Preeruptive minerals occur in both lavas and tephra, and include oxides and sulfides in glass and phenocrysts. The magmatic oxides consist of magnetite, ilmenite, and chromite; the sulfides consist of both (Fe,Ni)_1-xS (MSS) and Cu–Fe sulfide (ISS). Syn- and posteruptive phases occur in vesicles in both lavas and tephra, and on surfaces of ash and along fractures. The mineral assemblages in lavas include Cu–Fe sulfide and Fe–Ti oxide in vesicles, and Fe sulfide and Cu–Fe sulfide in segregation vesicles. Assemblages in vesicles in scoria include Fe–Ti oxide and rare Fe–Cu–Sn sulfide. Vesicle fillings of Fe–Ti oxide, Ni-rich chromite, Fe sulfide, Cu sulfide, and barite are common to two pumice samples. The most coarse-grained of the vesicle fillings are Cu–Fe sulfide and Cu sulfide, which are as large as 50 μ in diameter. The youngest Plinian pumice also contains Zn(Fe) sulfide, as well as rare Ag–Cu sulfide, Ag–Fe sulfide, Ag bromide, Ag chloride, and Au–Cu telluride. The assemblage is similar to those typically observed in high-sulfidation epithermal mineralization. The fine-grained nature and abundance of syn- and/or posteruptive phases in porous rocks makes metals susceptible to mobilization by percolating fluids. The abundance of metal compounds in vesicles indicates that volatile exsolution prior to and/or during eruption played an important role in releasing metals to the atmosphere. Received: March 1997 · Accepted: 27 May 1997     

Correlation of the oldest Toba Tuff to sediments in the central Indian Ocean Basin

We have identified an ash layer in association with Australasian microtektites of ∼0.77 Ma old in two sediment cores which are ∼450 km apart in the central Indian Ocean Basin (CIOB). Morphology and chemical composition of glass shards and associated microtektites have been used to trace their provenance. In ODP site 758 from Ninetyeast Ridge, ash layer-D (13 cm thick, 0.73–0.75 Ma) and layer-E (5 cm thick, 0.77–0.78 Ma) were previously correlated to the oldest Toba Tuff (OTT) eruptions of the Toba caldera, Sumatra. In this investigation, we found tephra ∼3100 km to the southwest of Toba caldera that is chemically identical to layer D of ODP site 758 and ash in the South China Sea correlated to the OTT. Layer E is not present in the CIOB or other ocean basins. The occurrence of tephra correlating to layer D suggests a widespread distribution of OTT tephra (∼3.6 × 10⁷ km²), an ash volume of at least ∼1800 km³, a total OTT volume of 2300 km³, and classification of the OTT eruption as a super-eruption.     

New records of late Holocene tephras from Lake Futalaufquen (42.8°S), northern Patagonia

In regions with limited knowledge of the historical volcanic record, like remote areas in the Andean Southern Volcanic Zone, the definition of reliable age-depth models for lake sequences represents a valuable tool for tephra layers dating. In Lake Futalaufquen (42.8°S), Northern Patagonia, a short sedimentary sequence was extracted after the AD 2008 Chaitén eruption with the purpose to analyze the records of volcanic eruptions at these poorly studied latitudes. The sequence was dated by ²¹⁰Pb, ¹³⁷Cs, and ¹⁴C techniques. Five tephras were identified for the last 1600 years, restricted to the last 5 centuries. Sedimentology, morphology, and geochemical properties allowed the characterization of the tephras and their correlation with tephras recently identified proximal to the sources, mainly from Chaitén and Huequi volcanoes, and Michinmahuida accessory cones, representing the first distal records reported of these tephras. Furthermore, tephras modeled ages obtained by the sequence age-depth model shrink the ages for the volcanic events, like a potential cycle of activity from Michinmauida accessory cones during AD 1530 ± 55, one eruption from Huequi volcano at AD 1695 ± 50, and a possible recent eruption from Chaitén at AD 1775 ± 40. Additionally, the work contributes to improve the regional volcanic records knowledge, basic for volcanic hazard assessment.     

The significance of phenocryst diversity in tephra from recent eruptions at Popocatepetl volcano (central Mexico)

Tephra lapilli from six explosive eruptions between April 1996 and February 1998 at Popocatepetl volcano (=Popo) in central Mexico have been studied to investigate the causes of magma diversification in thick-crusted volcanic arcs. The tephra particles are sparsely porphyritic (≈5 vol%) magnesian andesites (SiO₂=58–65 wt%; MgO=2.6–5.9 wt%) that contain phenocrysts of NiO-rich (up to 0.67 wt% NiO) magnesian olivine (Fo_89–91 cores) with inclusions of Cr-spinel (cr#=59–70), orthopyroxene (mg#=63–76), clinopyroxene (mg#=68–86), intermediate to sodic plagioclase (An_33–66), and traces of amphibole. Major and trace element systematics indicate magma mixing. The liquid mg#_melt ratios inferred from the ferromagnesian phenocrysts suggest the existence of a mafic (mg#_melt ≈ 72–76) and an evolved component magma (mg#_melt ≈ 35–40). These component magmas form a hybrid magnesian andesite with an intermediate range of mg#_melt=50–72. The mafic end member (mg#_melt ≈ 72–75) is saturated with olivine and spinel and crystallizes at temperatures ≈1170–1085 °C with oxygen fugacities close to the fayalite–magnetite–quartz buffer and elevated water contents of several wt% H₂O. A likely location of crystallization is at lower crustal levels, possibly at the Moho. Olivine is followed by high-mg# clinopyroxene which could start to crystallize during magma ascent. At depths of ≈4 to 13 km, the mafic magma mixes with an evolved composition containing low-mg# clino- and orthopyroxene and plagioclase at a temperature of ≈950 °C. The repetitive ascent of batches of mafic magmas spaced days to weeks apart implies multiple episodes of crystallization and magma mixing. The tephra is similar to the Popo magnesian andesites, suggesting similar generic processes for the common lavas of the volcano. The advantage of the tephra is that it can be used to reconstruct the composition of the mafic magma. Building on the elemental systematics of the tephra and a comparison to the near-primary basalts from the surrounding monogenetic fields, we infer that the Popo mafic end member is a magnesian andesite with variable, but high SiO₂ contents of ≈55–62 wt% and near-primary characteristics, such as high-mg#_melt of 72–75, FeO*/MgO ratios <1 (if extrapolated to an mg#_melt of 72–75), and high Ni contents (=200 ppm Ni). This model implies that the typical elemental signature of the Popo andesites, such as the low CaO, Al₂O₃, FeO*, high Na₂O contents, and the depletion in high-field strength elements (e.g., P, Zr, Ti), are mantle source phenomena. Thus, determining the elemental budget of the magnesian andesite, as it is prior to the modifications by crustal differentiation, is central to quantifying the subcrustal mass fluxes beneath Popo. Received: 13 December 1999 / Accepted: 11 August 2000     

Analysis and speciation of selenium ions in mine environments

 Aqueous extracts of five mine soil samples and a set of selenite (SeO₃ ^2–)–selenate (SeO₄ ^2–) solutions (0.5, 1, 5, 10 and 25 mg/l) were speciated using atomic absorption spectroscopy with hydride generation (AAS-HG) and ion chromatography (IC) to compare these methods for Se speciation. In another experiment, a SeO₃ ^2––SeO₄ ^2––SO₄ ^2– solution (25 mg/l) was reacted with CaO, MgO, MnO₂, CuO, La₂O₃, and WO₃ to evaluate the relative distribution of the Se species and SO₄ ^2– in the SORB (sorbed ions that were desorbed by NaOH), SOLN (equilibrium concentrations), CMPX (irreversibly sorbed and neutral ion pair complexes) fractions. The AAS-HG method was capable of analyzing Se as low as 0.002 mg/l, which was below the detection limit of IC. High concentration of SO₄ ^2– affected the chromatographic Se speciation either by shifting or overlapping Se peaks, in which AAS-HG was more useful. However, IC was capable of speciating aqueous SeO₃ ^2––SeO₄ ^2– directly without any sample pretreatment, whereas AAS-HG measured SeO₃ ^2–+SeO₄ ^2–, and SeO₃ ^2– in separate runs and SeO₄ ^2– was calculated from the difference, i.e., spectrophotometric speciation was an indirect method. For both Se species, AAS-HG and IC data were comparable within detection standard deviations. Ratios of different Se species at measured soil pH and pe indicated that SeO₃ ^2– or SeO₄ ^2– would be the dominant Se species; the p(SeO₄ ^2–/SeO₃ ^2–) values further suggested SeO₄ ^2– would be the major solution species. Except for CaO and MgO treatments, the %SeO₃ ^2– in the SORB fraction was ≥%SeO₄ ^2–. In the SOLN fraction %SeO₄ ^2– was ≥%SeO₃ ^2– for all oxides but CaO, whereas in the CMPX fraction this order was observed for only CaO and MnO₂. The %SeO₃ ^2– was highest in the SOLN fraction for all oxides but MgO and La₂O₃ for these two oxides SeO₃ ^2– dominated in CMPX and SORB fractions, respectively. The SOLN fraction also contained the highest %SeO₄ ^2– for all oxides but MgO which retained SeO₄ ^2– primarily in the SORB fraction. The %SeO₃ ^2– and %SeO₄ ^2– in the CMPX fraction were highest for MgO, thus, suggesting a possible formation of MgSeO₃ ⁰ and MgSeO₄ ⁰. A similar trend of SORB %SO₄ ^2– and SORB %SeO₄ ^2– was attributed to the analogous adsorption mechanisms (outer-sphere complexation). For all oxides but MgO, %SO₄ ^2– was <%SeO₄ ^2– in the SOLN fraction and ≥%SeO₄ ^2– in the CMPX fraction. Comparative ionic distributions provide an overall picture of the relative abundance of different Se species in various fractions associated with different oxides present in micro- and macrolevels in soils and geological materials. Received: 27 December 1995 · Accepted: 29 April 1997     

Assessment of natural attenuation of aromatic hydrocarbons in groundwater near a former manufactured-gas plant, South Carolina, USA

 Shallow, anaerobic groundwater near a former manufactured-gas plant (MGP) in Charleston, South Carolina, USA, contains mono- and polycyclic aromatic hydrocarbons (MAHs and PAHs, respectively). Between 1994 and 1997, a combination of field, laboratory, and numerical-flow and transport-model investigations were made to assess natural attenuation processes affecting MAH and PAH distributions. This assessment included determination of adsorption coefficients (K _ad ) and first-order biodegradation rate constants (K _bio ) using aquifer material from the MGP site and adjacent properties. Naphthalene adsorption (K _ad =1.35×10^–7 m³/mg) to aquifer sediments was higher than toluene adsorption (K _ad =9.34×10^–10 m³/mg), suggesting preferential toluene transport relative to naphthalene. However, toluene and benzene distributions measured in January 1994 were smaller than the naphthalene distribution. This scenario can be explained, in part, by the differences between biodegradation rates of the compounds. Aerobic first-order rate constants of ¹⁴C-toluene, ¹⁴C-benzene, and ¹⁴C-naphthalene degradation were similar (–0.84, –0.03, and 0.88 day^–1, respectively), but anaerobic rate constants were higher for toluene and benzene (–0.002 and –0.00014 day^–1, respectively) than for naphthalene (–0.000046 day^–1). Both areal and cross-sectional numerical simulations were used to test the hypothesis suggested by these rate differences that MAH compounds will be contained relative to PAHs. Predictive simulations indicated that the distributions of toluene and benzene reach steady-state conditions before groundwater flow lines discharge to an adjacent surface-water body, but do discharge low concentrations of naphthalene. Numerical predictions were "audited" by measuring concentrations of naphthalene, toluene, and benzene at the site in early 1997. Measured naphthalene and toluene concentrations were substantially reduced and the areal extent of contamination smaller than was both observed in January 1994 and predicted for 1997. Measured 1997 benzene concentrations and distribution were shown to be relatively unchanged from those measured in 1994, and similar to predictions for 1997. Received: 26 June 1997 · Accepted: 25 August 1997     

A Late Glacial–Holocene Tephrochronology for Glacial Lakes in Southern Ecuador

Despite the presence of numerous active volcanoes in the northern half of Ecuador, few, if any, distal tephras have been previously recognized in the southern one third of the country. In this article, we document the presence of thin (0.1–1.0-cm-thick) distal tephras comprising glass and/or phenocrysts of hornblende and feldspar in sediment cores from five glacial lakes and one bog in Las Cajas National Park (2°40′–3°00′S, 79°00′–79°25′W). The lake cores contain from 5 to 7 tephras, and each has a diagnostic major element geochemistry as determined from electron microprobe analysis of 710 glass shards and 440 phenocrysts of feldspar and hornblende. The loss of sodium with exposure to the electron microbeam causes a 10±7 wt.% (±1σ) reduction in Na content, which we empirically determined and corrected for before correlating tephras among the sediment cores. We use a similarity coefficient to correlate among the sediment cores; pair-wise comparison of all tephras generally yields an unambiguous correlation among the cores. Six tephras can be traced among all or most of the cores, and several tephras are present in only one or two of the cores. Twenty-six accelerator mass spectrometry ¹⁴C dates on macrofossils preserved in the sediment cores provide the basis for establishing a regional tephrochronology. The widespread tephras were deposited 9900, 8800, 7300, 5300, 2500, and 2200 cal yr B.P. The oldest tephras were deposited 15,500 and 15,100 cal yr B.P., but these are not found in all cores. Two of the tephras appear correlative with volcaniclastic strata on the flanks of Volcán Cotopaxi and one tephra may correlate with strata on the flanks of Volcán Ninahuilca; both volcanoes are in central Ecuador. The absence of tephras in sediment cores correlative with the numerous eruptions of active volcanoes of the past two millennia implies that the earlier eruptions, which did deposit tephras in the lakes, must have been either especially voluminous, or southerly winds must have prevailed at the time of the eruption, or both.     

Effects of quarry mining and of other environmental impacts in the mountainous Chicam-Toctina drainage basin (Córdoba, Argentina)

 The environmental conditions prevailing in the Chicam-Toctina drainage system (approx. 138 km² in Córdoba, Argentina) are considered representative of a number of catchments in Argentina's Sierras Pampeanas Range. Two groups of ions reflect the sources of dissolved species in the catchment: a) a group (Cl^–, SO^2– ₄, and Na⁺) which recognizes natural and anthropogenic sources, and which exhibits significant correlations with N^– ₃ and NO^– ₂, and b) another group of components (Ca²⁺, Mg²⁺, and HCO^– ₃) which is clearly controlled by carbonate rocks and their waste rock products. In the headwaters, stockpiled marble quarry mining wastes provide a more open system to CO₂ gaseous exchange than the outcropping rocks, thus promoting the increase of carbonate dissolution (up to 4.88 g km^–2 s^–1 during the rainy season). This specific yield was 20% higher than the amount estimated for an area with fewer extended mining activities. The dissolved load delivered by the upper reaches is subjected in the lower drainage area to various processes, mainly controlled by the presence of the city of Alta Gracia (approx. 40,000 inhabitants). In the dry season, due to nutrient inputs supplied by the city, photosynthetic activity plays a major role controlling stream pH. Hence, the high values of calcite saturation indexes and the increase of CaCO₃ concentration in bed sediments can be explained by calcite precipitation. Such a process could be accompanied by the coprecipitation on calcium carbonate of low solubility heavy metal carbonates. Received : 17 January 1997 · Accepted : 31 March 1997     

A shift in eruption mode of Hekla volcano,Iceland, 3000 years ago: two-coloured Hekla tephra series,characteristics, dispersal and age

Hekla volcano is a major producer of large, widespread silicic tephras. About 3000 years ago, the dominant eruption mode shifted from infrequent large (>1 km³) to more frequent moderate (<1 km³) eruptions. In the following two millennia ≥20 explosive silicic-to-intermediate eruptions occurred, and six or more basaltic. Three categories can be identified with dacite/andesite to basaltic andesite in the oldest eruptions through basaltic andesite to basalt in the youngest eruptions. Ten tephra layers of the first category have distinct field characteristics: a pale lower unit and a dark upper unit (two coloured or TC-layers). Colour separation is sharp indicating a stratified magma chamber origin. The lower unit is dominantly andesitic (61–63% SiO₂), while the upper unit is basaltic andesite (53–57% SiO₂). Volumes of the eight largest TC-layers range from 0.2 to 0.7 km³ as freshly fallen. Radiocarbon and soil accumulation rate dates constrain the TC-layers to between 3000 and 2200 years ago. Two of these (~2890 and ~2920 b2k) are likely to occur overseas. Low SiO₂ in the last erupted tephra of the TC-layers is comparable to that of historical Hekla lavas, implying a final effusive phase. The Hekla edifice may, consequently, be younger than 3000 years.     

Water quality of two streams near Yellowstone Park, Wyoming, following the 1988 Clover-Mist wildfire

 In 1988, wildfire burned over 50% of the Jones Creek watershed near Yellowstone Park, Wyoming. Crow Creek, an adjacent watershed, was unburned. Water quality data collected from 1989–1993 may show the fire's effect on weathering and nutrient transport. Jones Creek had 25–75% larger concentrations of dissolved solids than Crow Creek during the sampling period. Both streams revealed molar ratios consistent with the stoichiometry of andesine and pyroxene hydrolysis in the trachyandesites that underlie the basins. During 1989, nitrate transported from the unburned Crow Creek basin peaked at 2 mmol ha^–1 s^–1. This was twice as much as Jones Creek, possibly indicating a source from ash fallout. By 1992 these rates diminished to 0.1 mmol ha^–1 s^–1 in Crow Creek and increased to 1.8 mmol ha^–1 s^–1 in Jones Creek, suggesting later nitrate mobilization in the burned watershed. Phosphorus transported from Jones Creek basin averaged 0.011 mmol ha^–1 s^–1 during summer 1989, but fell to 0.004 mg ha^–1 s^–1 in subsequent years. Received: 28 May 1997 · Accepted: 18 November 1997     

Hydrogeologic and hydrochemical framework of the shallow groundwater system in the southern Voltaian Sedimentary Basin, Ghana

 The southern Voltaian Sedimentary Basin underlies an area of about 5000 km² in east-central Ghana. Groundwater in the basin occurs in fractures in highly consolidated siliciclastic aquifers overlain by a thin unsaturated zone. Aquifer parameters were evaluated from available aquifer-test data on 28 shallow wells in the basin. Hydraulic-conductivity values range from 0.04–3.6 m/d and are about two orders of magnitude greater than the hydraulic conductivity calculated using Darcy's Law and the average groundwater velocity estimated from carbon-14 dating. Linear-regression analysis of the transmissivity and specific-capacity data allowed the establishment of an empirical relationship between log transmissivity and log specific capacity for the underlying aquifers. Groundwater chemistry in the basin is controlled by the weathering of albitic plagioclase feldspar. The weathering rates of various minerals were estimated using ¹⁴C-derived average velocity in the basin. The weathering rate of albite was calculated to be 2.16 μmol L^–1 yr^–1 with the resulting formation of 3.3 μmol L^–1 yr^–1 of kaolinite and 0.047 μmol L^–1 yr^–1 of calcite. The low porosity and permeability of the aquifers in the basin are attributed to the precipitation of secondary minerals on fracture surfaces and interlayer pore spaces. Received, September 1997 Revised, July 1998, August 1998 Accepted, August 1998     

Diffusion of dissolved SiO2 in H2O at 1 GPa, with implications for mass transport in the crust and upper mantle

Cation diffusion rates at 690 ± 30 °C have been calculated by inverse modelling of observed manganese (Mn) zonation profiles in 40 garnets from two kyanite-bearing metapelite samples from the High Himalayan Crystalline Series, Zanskar, northwest India. Knowledge of the initial growth profile of Mn in garnet is a pre-requisite for this technique. Following previous workers we model Mn partitioning into growing garnet in terms of a Rayleigh fractionation process, and demonstrate that the Mn_{garnet:whole rock} partition coefficient is 60–100. Three-dimensional zonation profiles were obtained by successively grinding and polishing ∼1 cm slabs of each sample at 0.1–0.2 mm intervals and analysing the garnets at each stage, thus ensuring that core sections were measured. The diffusion model assumes that garnet has a spherical geometry and behaves as a closed system, and simulates diffusive modification of the hypothetical Mn Rayleigh growth profile for each garnet. The derived measure of the time-integrated diffusion history for each garnet is then combined with radiometric and field-relation constraints for the duration of the Himalayan metamorphic event to calculate cation diffusion rates. The average cation interdiffusion rate calculated for garnets in the two samples examined is (6 ± 3.2) × 10⁻²³ m²s⁻¹. This interdiffusion rate pertains to a temperature of 690 ± 30 °C, which is 0.97 × T _PEAK, the peak temperature conditions experienced by the samples estimated using standard thermobarometric techniques. Garnet compositions are P_y2–17Alm_65–77Gro_6–16Sp_1–17. These new diffusion data are consistent with, and more precise than, existing high-temperature (>1000 °C) experimentally determined diffusion data, although some uncertainties remain difficult to constrain. Qualitative comparison between diffusively modified Mn growth profiles in garnets from the Scottish Dalradian and the Himalayan garnets suggests that the duration of metamorphism affecting the Dalradian garnets was 10–20 times longer than that endured by the Himalayan garnets. Received: 5 June 1996 / Accepted: 29 January 1997     

Oxygen diffusion in anhydrous sanidine feldspar

Oxygen exchange experiments have been performed between single crystals of sanidine feldspar and oxygen gas enriched in ¹⁸O, at temperatures in the range 869–1053 °C, total pressure 1 atmosphere, for times up to 28 days. Oxygen isotope diffusion profiles in a direction perpendicular to (001) were determined with an ion microprobe. The experimental data obey a single Arrhenius relationship of the form D = 8.4 × 10⁻¹¹ exp. (−245 ± 15 kJ mol⁻¹/RT) m²s⁻¹. The results indicate that oxygen diffusion in anhydrous sanidine feldspar is marginally slower than oxygen diffusion in anhydrous anorthite. Comparison with published atomistic simulation studies suggests that oxygen transport in feldspar is by an interstitial mechanism. Received: 17 October 1997 / Accepted: 6 July 1998     

The groundwater resources and sustainable yield of Cheju volcanic island, Korea

 Hydrogeologic data of 455 water wells comprising geologic logs, water qualities, and aquifer test results are analyzed to determine hydrogeological characteristics, water quality, and sustainable yield of the groundwater resources of Cheju volcanic island. The groundwater of the island occurs in unconsolidated pyroclastic deposits and clinkers interbedded in highly jointed basaltic and andesitic rocks as high-level, basal, and parabasal groundwater under unconfined conditions. The total storage of groundwater is estimated at about 44 billion m³. The average transmissivity and specific yield of the aquifer are at about 0.34 m² s^–1(29300 m² day^–1) and 0.12, respectively. The average annual precipitation is about 3.39 billion m³, of which 1.49 billion m³– equivalent to 44.0% of the total annual precipitation – is recharged into aquifers, with 0.638 billion m³ year^–1 of runoff and 1.26 billion m³ year^–1 of evapotranspiration. Based on a groundwater budget analysis, the sustainable yield is estimated at about 0.62 billion m³ year^–1, equivalent to 41.6% of annual recharge. A low-permeability marine sedimentary formation (Sehwari formation), composed of loosely cemented sandy silt, was recently found to be situated at 120±68 m below mean sea level. If the said marine sediment is distributed as a basal formation of the freshwater zone of the island, most of its groundwater will be of parabasal type. So the marine sediment is one of the most important hydrogeological boundaries and groundwater occurrences in the area. Received: 16 January 1997 / Accepted: 16 June 1997     

Fluid flow in marbles at Jervois, central Australia: oxygen isotope disequilibrium and zoning produced by decoupling of mineralogical and isotopic resetting

The Jervois region of the Arunta Inlier, central Australia, contains para- and orthogneisses that underwent low-pressure amphibolite facies metamorphism (P = 200–300 MPa, T = 520–600 °C). Marble layers cut by metre-wide quartz + garnet ± epidote veins comprise calcite, quartz, epidote, clinopyroxene, grandite garnet, and locally wollastonite. The marbles also contain locally discordant decimetre-thick garnet and epidote skarn layers. The mineral assemblages imply that the rocks were infiltrated by water-rich fluids (XCO₂ = 0.1–0.3) at ∼600 °C. The fluids were probably derived from the quartz-garnet vein systems that represent conduits for fluids exsolved from crystallizing pegmatites emplaced close to the metamorphic peak. At one locality, the marble has calcite (Cc) δ¹⁸O values of 9–18‰ and garnet (Gnt) δ¹⁸O values of 10–14‰. The δ¹⁸O(Gnt) values are only poorly correlated with δ¹⁸O(Cc), and the δ¹⁸O values of some garnet cores are higher than the rims. The isotopic disequilibrium indicates that garnet grew before the δ¹⁸O values of the rock were reset. The marbles contain  ≤15% garnet and, for water-rich fluids, garnet-forming reactions are predicted to propagate faster than O-isotopes are reset. The Sm-Nd and Pb-Pb ages of garnets imply that fluid flow occurred at 1750–1720 Ma. There are no significant age differences between garnet cores and rims, suggesting that fluid flow was relatively rapid. Texturally late epidote has δ¹⁸O values of 1.5–6.2‰ implying δ¹⁸O(H₂O) values of 2–7‰. Waters with such low-δ¹⁸O values are probably at least partly meteoric in origin, and the epidote may be recording the late influx of meteoric water into a cooling hydrothermal system. Received: 29 April 1996 / Accepted: 12 March 1997     

Geochemistry of bedded barite of the Mesoproterozoic Aggeneys-Gamsberg Broken Hill-type district,South Africa

Stratiform and stratabound barite ± magnetite beds are intimately associated with the polymetallic Broken Hill-type (BHT) massive sulfide deposits of the Aggeneys-Gamsberg Pb–Zn–Cu ± Ag–Ba district in the Northern Cape Province, South Africa. Barite samples were collected and studied from four localities in the district. Although metamorphic water–rock interaction processes have partially altered the chemical and to a lesser degree the isotopic composition of barite, samples identified as being the least altered display distinctly different isotopic compositions that are thought to reflect different modes of origin. All barite samples are marked by low concentrations of SrO (0.5 ± 0.2 wt%), highly radiogenic ⁸⁷Sr/⁸⁶Sr ratios, elevated δ ³⁴S and δ ¹⁸O values compared to contemporaneous Mesoproterozoic seawater. Radiogenic ⁸⁷Sr/⁸⁶Sr signatures (0.7164 ± 0.0028) point to an evolved continental crustal source for Sr and Ba, while elevated δ ³⁴S values (27.3 ± 4.9‰) indicate that contemporaneous seawater sulfate, modified by bacterial sulfate reduction, was the single most important sulfur reservoir for barite deposition. Most importantly, δ ¹⁸O values suggest a lower temperature of formation for the Gamsberg deposit compared with the occurrences in the Aggeneys area, i.e. Swartberg-Tank Hill and Big Syncline. The obvious differences in temperature of formation are in good agreement with the Cu-rich, Ba-poor nature of the sulfide mineralization of the Aggeneys deposits vs the Cu-poor, Ba-rich character of the Gamsberg deposit. In conjunction with this, isotopic and petrographic arguments favor a sub-seafloor replacement model for the stratabound barite occurrences of the Aggeneys deposits, while at Gamsberg, deposition at the sediment–water interface as a true sedimentary exhalite appears more likely.     

Comparison of soil erosion and deposition rates using radiocesium, RUSLE, and buried soils in dolines in East Tennessee

 Three dolines (sinkholes), each representing different land uses (crop, grass, and forest) in a karst area in East Tennesse, were selected to determine soil erosional and depositional rates. Three methods were used to estimate the rates: fallout radiocesium (¹³⁷Cs) redistribution, buried surface soil horizons (Ab horizon), and the revised universal soil loss equation (RUSLE). When ¹³⁷Cs redistribution was examined, the average soil erosion rates were calculated to be 27 t ha^–1 yr^–1 at the cropland, 3 t ha^–1 yr^–1 at the grassland, and 2 t ha^–1 yr^–1 at the forest. By comparison, cropland erosion rate of 2.6 t ha^–1 yr^–1, a grassland rate of 0.6 t ha^–1 yr^–1, and a forest rate of 0.2 t ha^–1 yr^–1 were estimated by RUSLE. The ¹³⁷Cs method expressed higher rates than RUSLE because RUSLE tends to overestimate low erosion rates and does not account for deposition. The buried surface horizons method resulted in deposition rates that were 8 t ha^–1 yr^–1 (during 480 yr) at the cropland, 12 t ha^–1 yr^–1 (during 980 yr) at the grassland, and 4 t ha^–1 yr^–1 (during 101 yr) at the forest site. By examining ¹³⁷Cs redistribution, soil deposition rates were found to be 23 t ha^–1 yr^–1 at the cropland, 20 t ha^–1 yr^–1 at the grassland, and 16 t ha^–1 yr^–1 at the forest site. The variability in deposition rates was accounted for by temporal differences;¹³⁷Cs expressed deposition during the last 38 yr, whereas Ab horizons represented deposition during hundreds of years. In most cases, land use affected both erosion and deposition rates – the highest rates of soil redistribution usually representing the cropland and the lowest, the forest. When this was not true, differences in the rates were attributed to differences in the size, shape, and closure of the dolines. Received: 10 October 1995 · Accepted: 13 October 1995