Sulfur isotopic characteristics of late Cenozoic ore deposits at the arc junction of Hokkaido, Japan

Abstract Sulfide minerals of late Cenozoic vein-type deposits of southwest Hokkaido and Kuril Islands yielded δ³⁴_CDT S values of 2 to 8 permil, which are typical green-tuff values of magnetite-series igneous terrane. Sulfides of the Kitami district of northeast Hokkaido, on the other hand, are characterized by negative δ³⁴S_CDT values, ranging from 0 to - 7 permil. This unique value among ore deposits in the late Cenozoic back-arc terranes in the Japanese Islands is considered to have resulted from extraction of ³²S enriched sulfur from the basement rocks, because of well-developed N-S fracturing in the basement, which is characteristic of the axial belt and Kitami district of Hokkaido.     

Tracing coalbed natural gas-coproduced water using stable isotopes of carbon

Recovery of hydrocarbons commonly is associated with coproduction of water. This water may be put to beneficial use or may be reinjected into subsurface aquifers. In either case, it would be helpful to establish a fingerprint for that coproduced water so that it may be tracked following discharge on the surface or reintroduction to geologic reservoirs. This study explores the potential of using δ¹³C of dissolved inorganic carbon (DIC) of coalbed natural gas (CBNG)–coproduced water as a fingerprint of its origin and to trace its fate once it is disposed on the surface. Our initial results for water samples coproduced with CBNG from the Powder River Basin show that this water has strongly positive δ¹³C_DIC (12‰ to 22‰) that is readily distinguished from the negative δ¹³C of most surface and ground water (−8‰ to −11‰). Furthermore, the DIC concentrations in coproduced water samples are also high (more than 100 mg C/L) compared to the 20 to 50 mg C/L in ambient surface and ground water of the region. The distinctively high δ¹³C and DIC concentrations allow us to identify surface and ground water that have incorporated CBNG-coproduced water. Accordingly, we suggest that the δ¹³C_DIC and DIC concentrations of water can be used for long-term monitoring of infiltration of CBNG-coproduced water into ground water and streams. Our results also show that the δ¹³C_DIC of CBNG-coproduced water from two different coal zones are distinct leading to the possibility of using δ¹³C_DIC to distinguish water produced from different coal zones.     

Open-system degassing of sulfur from Krakatau 1883 magma

We present the first sulfur and oxygen isotopic data for tephra from the catastrophic 1883 eruption of Krakatau. Sulfur isotopic ratios in unaltered Krakatau tephra erupted August 26–27, 1883 are markedly enriched in ³⁴S relative to mantle sulfur. High δ³⁴S values of +6.3 to +16.4‰ can best be explained by open-system or multi-stage degassing of SO₂ from the oxidized rhyodacitic and gray dacitic magmas with ³⁴S enrichment of SO²⁻₄ remaining in the melt. Lower whole-rock δ³⁴S values of +2.6‰ and +4.0‰ in two oxidized gray dacitic samples indicate more primitive subarc mantle sulfur in the 1883 magma chamber. Initial δ³⁴S of the rhyodacitic magma was probably in the +1.5‰ to +4.0‰ range and similar to δ³⁴S values measured in arc volcanic rocks from the Mariana Arc.     

Origins of hydrocarbons in the Sagara oil field, central Japan

Abstract   We collected free-gas and in situ fluid samples up to a depth of 200.6 m from the Sagara oil field, central Japan (34°44'N, 138°15'E), during the Sagara Drilling Program (SDP) and measured the concentrations and stable carbon isotopic compositions of CH₄ and C₂H₆ in the samples. A combination of the CH₄/C₂H₆ ratios with the carbon isotope ratios of methane indicates that the hydrocarbon gases are predominantly of thermogenic origin at all depths. The isotope signature of hydrocarbon gases of δ¹³      < δ¹³     suggests that these gases in the Sagara oil field are not generated by polymerization, but by the decomposition of organic materials.     

A preliminary stable isotope study of volcanic ashes discharged by the 1979 eruption of Ontake Volcano,Nagano, Japan

Sulphur isotopic compositions of pyrite, anhydrite and native sulphur in volcanic ashes discharged by the 1979 eruption of Ontake volcano, Nagano, Japan were determined. The isotopic data indicate that sulphate in anhydrite and a part of native sulphur were produced by the disproportionation reaction of sulphite formed by dissolution of SO₂ in volcanic gases into water which filled a mud reservoir probably located just below the crater zone. Some part of H₂S in volcanic gases was fixed as pyrite and some was oxidised to form native sulphur. Hydrothermal alteration of country rocks to form pyrite, anhydrite and clay minerals had proceeded in the mud reservoir before eruption at temperatures ranging from 110° to 185°C which were estimated by oxygen isotopic fractionation between anhydrite and water.

     

Delayed impact of new volcanic ejecta on ground water quality

We observed long-term changes in the concentrations of dissolved ions in ground water caused by leachate from new volcanic ejecta deposited on the ground surface of the volcanic Miyakejima Island, Japan. Water samples were collected from nine wells and two rain collectors over a period of more than 10 years, and samples of runoff water were collected periodically. The samples were analyzed for temperature, pH, alkalinity, Cl⁻, and SO₄²⁻; some of the samples were also analyzed for δ¹³C. Because the leachate from the volcanic ejecta contained sulfate, we recorded an increase in SO₄²⁻ concentrations in the (unconfined) well water. The increase in SO₄²⁻ was initially detected between less than 1.4 and 5.2 years after the eruption, showing peak concentrations from 2.4 to 6.4 years after the eruption. This delayed response reflects the transit time of downward-moving SO₄²⁻ in the vadose zone, corresponding to an apparent movement rate of 0.4 to 7.2 cm/d. The rate relates to the mean recharge, represented as a fraction of local mean rainfall, and is calculated using the Cl⁻ balance method. The magnitude of the recorded increases reflects the volume of volcanic mudflow on the ground surface within the basin. For the management of ground water after an eruption, it is therefore important to know the chemical properties of the volcanic ejecta and the spatial distribution of mudflow to estimate the magnitude of the effect of ejecta on ground water quality.     

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.     

Geochemistry of geopressured hydrothermal waters in the Niigata Sedimentary Basin, Japan

Abstract   Geothermal waters in the Niigata Sedimentary Basin, central Japan, are divided into four groups based on their chemical composition (i.e. Na-SO₄-type, Na-SO₄-Cl-type, Na-Cl-type and Na-Cl-HCO₃-type). The Na-SO₄-type geothermal water forms as a consequence of water–rock interaction and generally occurs in the outer part of the basin. The Na-Cl-type geothermal water is further subdivided into the original Na-Cl-type geopressured thermal water and the mixed Na-Cl-type geothermal water, in terms of its geochemical and isotopic composition. The original Na-Cl-type geopressured thermal water originates from a geopressured hydrothermal system containing the altered fossil formation waters that are sealed at depth. It moves up to the upper part of the depositional succession or the ground, and generally does not mix with groundwater that is of meteoric origin. This type of water is cooled by heat conduction. The concentration of Cl^– in this type of thermal water is very similar to that in seawater. The δD and δ¹⁸O values are approximately constant and independent of temperature. The original Na-Cl-type geopressured thermal water is distributed mainly along anticlinal axes in folded Neogene formations. The mixed Na-Cl-type geothermal water is related to the expulsion activity of the geopressured hydrothermal system and occurs mostly along active faults. It is formed by shallow groundwater of meteoric origin being mixed with geopressured hydrothermal water when the geopressured hydrothermal system was expulsed along active faults by paroxysmal tectonic events.     

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.     

MIS11–19 pollen stratigraphy from the 250-m Choshi core, northeast Boso Peninsula, central Japan: Implications for the early/mid-Brunhes (400–780 ka) climate signals

Abstract   The 250-m Choshi core (CHOSHI-1), drilled from hemipelagic muds of the Inubo Group, has been physically, geochemically and tephrochronologically analyzed back to 1 Ma. We provide pollen results for the 19–169 m section of the core (400–780 ka) bracketed by the marker tephra Ty1 (equivalent to J4) and the Brunhes–Matuyama paleomagnetic boundary. The results show good agreement with the corresponding oxygen isotope (δ¹⁸O) profile, with high δ¹⁸O intervals dominated by boreal conifers Picea , Abies , Pinus (subgen. Haploxylon ) and Tsuga ( diversifolia ), whereas low δ¹⁸O intervals are dominated by temperate conifers Cryptomeria , Taxaceae-Cephalotaxaceae-Cupressaceae and Sciadopitys . In order to confirm pollen-climate relations for the relevant taxa, a modern surface pollen dataset for the Japanese archipelago was consulted. In this analysis, the ratios of Cryptomeria / Picea and temperate/boreal conifers serve as proxies for the 100-kyr glacial/interglacial cycle during the Middle Pleistocene. Distinct signals for marine isotope stages (MIS) 11, 12, 13–15, 16, 17 and 18–19 are recognized in accordance with the tephrochronology and δ¹⁸O of the same core. Application of the criteria to an independent pollen record from Lake Biwa provides an integrated pollen stratigraphy for mid-latitude Japan during the past 800 ky. Some degree of uncertainty remains in the chronology of the MIS13–15 interval, relating to the uncertainty in the eruption age of widespread tephra Ks11.     

Fukutoku-oka-no-ba Volcano: A new perspective on the Alkalic Volcano Province in the Izu–Bonin – Mariana arc

Pumice samples from Fukutoku-oka-no-ba in the Izu–Bonin – Mariana (IBM) arc were analysed for 40 trace elements and Sr, Nd, and Pb isotopic compositions. These samples are shoshonites (59.4–61.8 wt% SiO₂), characterized by high contents of K₂O (3.74–4.64 wt%), Ba (1274–1540 p.p.m.), Rb (91–105 p.p.m.), and light rare earth elements. The characteristics of alkali-element enrichment are similar to those of other parts of the Alkalic Volcano Province (AVP) in the northern Mariana and southernmost Volcano arcs. Sr (⁸⁷Sr/⁸⁶Sr = 0.7036–0.7038) and Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 19.08–19.11, ²⁰⁷Pb/²⁰⁴Pb = 15.62–15.63, ²⁰⁸Pb/²⁰⁴Pb = 38.85–38.91) of Fukutoku-oka-no-ba pumice are relatively radiogenic, whereas Nd is unradiogenic (¹⁴³Nd/¹⁴⁴Nd = 0.51283–0.51286). Fukutoku-oka-no-ba is isotopically distinct from Iwo Jima and is similar to the Hiyoshi Volcanic Complex, suggesting that Fukutoku-oka-no-ba might have a magma source similar to that of the Hiyoshi volcanic complex. Plots of Pb and Nd isotopes for AVP lavas trend toward the fields of ocean island basalt (OIB) source and pelagic sediments, which are possible sources of AVP enrichments.     

The Matsue Formation: Evidence for gross mantle heterogeneity beneath Southwest Japan at 11 Ma

Abstract Middle Miocene basalts and basaltic andesites of the Matsue Formation outcrop within a 5 km radius of Matsue city in eastern Shimane Prefecture. Despite their limited outcrop and age (11.0 ± 1.5 Ma), they show a wide range in ⁸⁷Sr-⁸⁶Sr(0.70370–0.70593), ¹⁴³Nd-¹⁴⁴Nd(0.512904–0.512471) and large ion lithophile element (LILE) contents, but a relatively narrow range for some high field strength elements (HFSE) such as Nb and Ti. These basalts and andesites can be divided into three groups based on petrography, major element, trace element and isotope chemistry. Although one group has undergone some fractional crystallization, isotope chemistry precludes linkage of the groups by a closed-system process. Crustal contamination can explain isotope chemistry, but is not consistent with trace element variations. The most satisfactory model is eruption of two compositionally distinct magmas, with limited magma mixing and fractional crystallization. Published experimental work shows that one end-member resulted from shallow melting of upwelling mantle at ∼25 km. The simultaneous eruption of the other end member magma in the same area points towards a heterogeneous mantle. The isotopic composition of Matsue Formation basalts and andesites covers the entire range of Late Miocene mafic volcanic rocks of southwest Japan. Such gross heterogeneity developed on a local scale has implications for models that deal with regional chemical variations of mafic volcanic rocks in southwest Honshu.     

Environmental hazards of fluoride in volcanic ash: a case study from Ruapehu volcano, New Zealand

The vent-hosted hydrothermal system of Ruapehu volcano is normally covered by a c. 10 million m³ acidic crater lake where volcanic gases accumulate. Through analysis of eruption observations, granulometry, mineralogy and chemistry of volcanic ash from the 1995–1996 Ruapehu eruptions we report on the varying influences on environmental hazards associated with the deposits. All measured parameters are more dependent on the eruptive style than on distance from the vent. Early phreatic and phreatomagmatic eruption phases from crater lakes similar to that on Ruapehu are likely to contain the greatest concentrations of environmentally significant elements, especially sulphur and fluoride. These elements are contained within altered xenolithic material extracted from the hydrothermal system by steam explosions, as well as in residue hydrothermal fluids adsorbed on to particle surfaces. In particular, total F in the ash may be enriched by a factor of 6 relative to original magmatic contents, although immediately soluble F does not show such dramatic increases. Highly soluble NaF and CaSiF₆ phases, demonstrated to be the carriers of ‘available’ F in purely magmatic eruptive systems, are probably not dominant in the products of phreatomagmatic eruptions through hydrothermal systems. Instead, slowly soluble compounds such as CaF₂, AlF₃ and Ca₅(PO₄)₃F dominate. Fluoride in these phases is released over longer periods, where only one third is leached in a single 24-h water extraction. This implies that estimation of soluble F in such ashes based on a single leach leads to underestimation of the F impact, especially of a potential longer-term environmental hazard. In addition, a large proportion of the total F in the ash is apparently soluble in the digestive system of grazing animals. In the Ruapehu case this led to several thousand sheep deaths from fluorosis.     

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.     

Noble gas isotopic composition of deep underground water in Osaka plain, central Japan: Evidence for mantle He and model for new volcanism

Abstract Elemental and isotopic compositions of noble gases extracted from the bore hole water in Osaka plain, central Japan were examined. The water samples were collected from four shallow bore holes (180-450 m) and seven deep bore holes (600-1370 m) which have been used for an urban resort hot spring zone. The water temperatures of the deep bore holes were 22-50°C and that of the shallow bore holes, 13-23°C. The elemental abundance patterns show the progressive enrichment of the heavier noble gases compared with the atmospheric noble gas composition except for He, which is heavily enriched in deep bore hole water samples. ³He/⁴He ratios from the bore holes reaching the Ryoke granitic basement were higher than the atmospheric value (1.4 × 10⁻⁶), indicating a release of mantle He through the basement. The highest value of 8.2 × 10⁻⁶ is in the range of arc volcanism. On the other hand, the bore holes in sedimentary rocks overlying the basement release He enriched in radiogenic ⁴He, resulted in a low ³He/⁴He ratio of 0.5 × 10⁻⁶. ⁴He/²⁰Ne and ⁴⁰Ar/³⁶Ar ratios indicate that the air contamination is generally larger in shallow bore holes than in deep ones from each site. The helium enriched in mantle He is compatible with the previous work which suggested up-rising magma in 'Kinki Spot', the area of Osaka and western Wakayama, in spite of no volcanic activity in the area. A model to explain an initiation of magma generation beneath this area is presented.     

Scoria cone formation through a violent Strombolian eruption: Irao Volcano, SW Japan

Scoria cones are common volcanic features and are thought to most commonly develop through the deposition of ballistics produced by gentle Strombolian eruptions and the outward sliding of talus. However, some historic scoria cones have been observed to form with phases of more energetic violent Strombolian eruptions (e.g., the 1943–1952 eruption of Parícutin, central Mexico; the 1975 eruption of Tolbachik, Kamchatka), maintaining volcanic plumes several kilometers in height, sometimes simultaneous with active effusive lava flows. Geologic evidence shows that violent Strombolian eruptions during cone formation may be more common than is generally perceived, and therefore it is important to obtain additional insights about such eruptions to better assess volcanic hazards. We studied Irao Volcano, the largest basaltic monogenetic volcano in the Abu Monogenetic Volcano Group, SW Japan. The geologic features of this volcano are consistent with a violent Strombolian eruption, including voluminous ash and fine lapilli beds (on order of 10^?1 km³ DRE) with simultaneous scoria cone formation and lava effusion from the base of the cone. The characteristics of the volcanic products suggest that the rate of magma ascent decreased gradually throughout the eruption and that less explosive Strombolian eruptions increased in frequency during the later stages of activity. During the eruption sequence, the chemical composition of the magma became more differentiated. A new K–Ar age determination for phlogopite crystallized within basalt dates the formation of Irao Volcano at 0.4?±?0.05 Ma.     

Hydrothermal alteration of green tuff belt, Japan: Implications for the influence of seawater/volcanic rock interaction on the seawater chemistry at a back-arc basin

Abstract Chemical data on hydrothermally altered volcanic rocks from a green tuff belt in Japan indicate that the average rate of Mg removal from seawater due to seawater cycling through back-arc basins in the circum-Pacific region during the early to middle Miocene (25–15 Ma) is estimated to be 2.6±1 × 10¹³ g/year. This is similar to that through present-day mid-ocean ridges (2.4 × 10¹³ g/year). Hydrothermal fluxes of K, Ca and Si are calculated to be 4.2±1.6 × 10¹³ g/year, 4.3±1.7×10¹³ g/year and 1.0±0.4 × 10¹⁴ g/year, respectively. These calculated results indicate that the seawater/volcanic rocks interaction at subduction-related tectonic settings have to be taken into account in considering the geochemical mass balance of seawater over geologic time.     

Primordial helium isotope signature from Plio–Quaternary alkaline basalts in Yemen

Abstract Isotopic compositions of He, Ne and Ar were measured on Plio–Quaternary alkaline basalts of Marib–Sirwah and Shuqra volcanic fields in Yemen, south-western Arabian Peninsula. Very high ³He/⁴He isotope ratios were found in olivine phenocrysts of some Quaternary alkaline basalts in both volcanic fields, located on the margin of the dispersed Afar mantle plume, compared with the Afar–Ethiopian province in the center of the mantle plume. This suggests that the Afar mantle plume source may consist of common component (C or focal zone (FOZO)) with variable primordial ³He/⁴He ratio rather than high μ mantle (HIMU) component. The three component mixing C as the Afar mantle plume, depleted mantle (DM) as upper mantle and lithospheric mantle with a hybrid enriched mantle I–II (EM I–EM II) characteristics may be adequate to explain He–Sr–Nd–Pb isotope variation for the Afar–Arabian Cenozoic volcanics. The occurrence of high ³He/⁴He ratios in the Marib–Sirwah volcanic field appears to show that the primitive basaltic magma, derived from the margin of the dispersed trous-like Afar mantle plume during 15–0 Ma, was not by contamination of lithospheric and upper mantle materials in comparison with that from the center of the Afar mantle plume as a result of relatively low thermal anomaly.     

Noble gases in pillow basalt glasses from the northern Mariana Trough back-arc basin

Noble gas concentrations and isotopic compositions have been measured in eight samples of pillow basalt glasses collected from seven different localities along 250 km of the Mariana Trough spreading and rifting axis. The samples have uniform and mid-ocean ridge basalt (MORB)-like ³He/⁴He values of 9–12 × 10^–6 (6.4–8.6 times atmospheric) despite large variations in ⁴He. Concentrations of the noble gases Ne, Ar, Kr, and Xe show much smaller variations between samples, but larger variations in isotopic compositions of Ne, Ar, and Xe. Excess radiogenic ²¹Ne is observed in some samples. ⁴⁰Ar/³⁶Ar varies widely (atmospheric to 1880). Kr is atmospheric in composition for all samples. Some samples show a clear excess ¹²⁹Xe, which is a well-known MORB signature. Isotopic compositions of the heavier noble gases (Ar, Kr, and Xe) in some samples, however, show more atmospheric components. These data reflect the interaction of a MORB-like magma with an atmospheric component such as seawater or of a depleted mantle source with a water-rich component that was probably derived from the subducting slab.     

Geographical distribution of helium isotope ratios in northeastern Japan

In order to study the precise geographical distribution of helium isotope ratios in northeastern Japan and compare it with geophysical data, we collected 43 gas and water samples from hot and mineral springs in the region where the ratio had never been reported, and measured the ³He/⁴He and ⁴He/²⁰Ne ratios of these samples. It was found that the ³He/⁴He ratios show clear contrasts between the forearc and the back-arc regions in the Tohoku district in northeastern Japan. In the forearc region, the ratios are smaller than 1 R_A (1 R_A = 1.4 × 10⁻⁶; R_A means the ³He/⁴He ratio of the atmosphere). On the other hand, those along the volcanic front and in the back-arc region are apparently higher. Moreover, we found a variation in the ³He/⁴He ratios along the volcanic front. In Miyagi Prefecture (38–39°N), the ratios range from 2 to 5 R_A. On the other hand, the ratios are less than 1 R_A in and around the southern border between Iwate and Akita Prefectures (39–39.5°N). Comparing the distribution of helium isotope ratios to results of recent geophysical studies, we found that the features in geographical distribution of helium isotope ratios are similar to those of seismic low-velocity zone distributions and high Qp⁻¹ distributions in the uppermost mantle. These observations strongly suggest that the helium isotope ratios reflect the distribution of melts in the uppermost mantle and are a useful tool for investigating the origin, behavior, and distribution of deep fluids and melts.