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1.
Gas breakthrough experiments on fine-grained sedimentary rocks   总被引:1,自引:0,他引:1  
The capillary sealing efficiency of fine‐grained sedimentary rocks has been investigated by gas breakthrough experiments on fully water saturated claystones and siltstones (Boom Clay from Belgium, Opalinus Clay from Switzerland and Tertiary mudstone from offshore Norway) of different lithological compositions. Sand contents of the samples were consistently below 12%, major clay minerals were illite and smectite. Porosities determined by mercury injection lay between 10 and 30% while specific surface areas determined by nitrogen adsorption (BET method) ranged from 20 to 48 m2 g ? 1. Total organic carbon contents were below 2%. Prior to the gas breakthrough experiments the absolute (single phase) permeability (kabs) of the samples was determined by steady state flow tests with water or NaCl brine. The kabs values ranged between 3 and 550 nDarcy (3 × 10?21 and 5.5 × 10?19 m2). The maximum effective permeability to the gas‐phase (keff) measured after gas breakthrough on initially water‐saturated samples extended from 0.01 nDarcy (1 × 10?23 m2) up to 1100 nDarcy (1.1 × 10?18 m2). The residual differential pressures after re‐imbibition of the water phase, referred to as the ‘minimum capillary displacement pressures’ (Pd), ranged from 0.06 to 6.7 MPa. During the re‐imbibition process the effective permeability to the gas phase decreases with decreasing differential pressure. The recorded permeability/pressure data were used to derive the pore size distribution (mostly between 8 and 60 nm) and the transport porosity of the conducting pore system (10‐5–10‐2%). Correlations could be established between (i) absolute permeability coefficients and the maximum effective permeability coefficients and (ii) effective or absolute permeability coefficients and capillary sealing efficiency. No correlation was found between the capillary displacement pressures determined from gas breakthrough experiments and those derived theoretically by mercury injection.  相似文献   

2.
Analyses at the Cu–K, Fe–K and Mn–K edge were performed to study the green, marbled (green and yellow), blue and blackish (deep greyish olive green) glass slabs decorating three sectilia panels from the archaeological site of Faragola. Results indicate that all slabs were made by mixing siliceous sand with natron, sometimes probably mixed with small percentages of plant ash. Cu2+ and Pb antimonates should be responsible for the opaque green colours. The dark green and yellow portions of the marbled slabs are respectively comparable to the slabs comprising only one of these colours. Cu2+ together with Ca antimonates probably produced light blue slabs, whereas cobalt was used to produce dark blue slabs. We consider it possible that the abundance ratio of Fe2+/Fe3+ and the complex Fe3+S2? would have an effect on the blackish slabs. The contribution of Mn cannot be ascertained even if it could have played a role in darkening glass colour. The comparison between the chemical composition of Faragola samples and several glass reference groups provided no conclusive evidence of provenance; whereas, the presence of a secondary local workshop can be hypothesized.  相似文献   

3.
The state of a group of glaciers in the northern Mackenzie Mountains across the Yukon‐Northwest Territories border was investigated over a period of three decades, using Landsat TM and OLI imagery from 1987, 1994, 1999, 2004, 2013, and 2017 to examine changes in glacier extents. A thresholded red/shortwave infrared band ratio image was used to delineate glacier boundaries. The total area of 74 glaciers in the study area decreased from 52.78 ± 1.32 km2 in 1987 to 24.89 ± 0.62 km2 in 2017, a loss of 27.89 ± 1.39 km2 or 52.8 ± 2.6%, with a mean rate of reduction of 1.8% · a?1. Smaller glaciers experienced larger relative changes in area. In this study, the rates of reduction are high compared to decreases reported for other glaciers in the region in the late 20th century. Based on linear extrapolation of the trend in values of total glacier area, it is predicted—subject to uncertainties in how glaciers diminish in size and eventually disappear—that the study area could be free of visible glacier cover within three decades.  相似文献   

4.
Br/Cl ratios of hydrothermal fluids are widely used as geochemical tracers in marine hydrothermal systems to prove fluid phase separation processes. However, previous results of the liquid–vapour fractionation of bromine are ambiguous. Here we report new experimental results of the liquid–vapour fractionation of bromine in the system H2O–NaCl–NaBr at 380–450°C and 22.9–41.7 MPa. Our data indicate that bromine is generally more enriched than chlorine in the liquid phase. Calculated exchange coefficients KD(Br‐Cl)liquid‐vapour for the reaction Brvapour + Clliquid = Brliquid + Clvapour are between 0.94 ± 0.08 and 1.66 ± 0.14 within the investigated P–T range. They correlate positively with DClliquid‐vapour and suggest increasing bromine–chlorine fractionation with increasing opening of the liquid–vapour solvus, i.e. increasing distance to the critical curve in the H2O–NaCl system. An empirical fit of the form KD(Br‐Cl)liquid‐vapour = a*ln[b*(DClliquid‐vapour?1) + e1/a] yields a = 0.349 and b = 1.697. Based on this empirical fit and the well‐constrained phase relations in the H2O–NaCl system we calculated the effect of fluid phase separation on the Br/Cl signature of a hydrothermal fluid with initial seawater composition for closed and open adiabatic ascents along the 4.5 and 4.8 J g?1 K?1 isentropes. The calculations indicate that fluid phase separation can significantly alter the Br/Cl ratio in hydrothermal fluids. The predicted Br/Cl evolutions are in accord with the Br/Cl signatures in low‐salinity vent fluids from the 9 to 10°N East Pacific Rise.  相似文献   

5.
西藏壁画表面大多刷有保护涂层。据记载,其材质主要是桐油、牛胶或清漆等。但目前,对该涂层材质科学的研究却较少,不利于后期保护修复。为配合拉卜楞寺壁画保护修复项目,本研究以衰减全反射红外光谱法(ATR-FTIR)、核磁共振氢谱法(~1H-NMR)、热裂解-气相色谱-质谱联用(Py-GC-MS)技术等分析手段,对甘肃夏河拉卜楞寺弥勒佛殿、时轮学院主殿壁画的涂层进行了分析。结果表明,两处佛殿壁画涂层可确定是一种干性油,种类与桐油较接近。但由于西藏壁画在材料和工艺上的独特性,材料老化等因素,拉卜楞寺壁画涂层在组成和结构上,与现代桐油有一定差别,表现出一定的丰富性和复杂性。后期修复,可采用性质与西藏传统涂层材料接近的干性油,例如桐油,作为新的壁画表面涂层材料。  相似文献   

6.
This paper describes a reconnaissance, high-resolution, study of stable isotopes (δ18O and δ13C) from modern shells of the estuarine bivalve Geloina erosa, and those dated to the early Holocene that were harvested by people from mangroves near the Great Cave of Niah on the north coast of Borneo. This reconnaissance study provides high-resolution palaeoclimatic-palaeohydrological information concerning early human activity in the region and the past character of the Southeast Asian Monsoon. Laser ablation continuous flow isotope ratio mass spectrometry (LA-CF-IRMS) on modern shells of Geloina erosa revealed ‘saw-tooth’ stable isotopic profiles that bear a close resemblance to peaks and troughs of trends in recent local rainfall, including the 1998 El Niño drought, highlighting the potential of Geloina erosa for reconstructing seasonality of the Southeast Asian Palaeomonsoon. LA-CF-IRMS analysis of prehistoric shells of Geloina erosa held in the Harrisson Archives of the Sarawak Museum revealed cyclical shifts in δ18O with similar amplitudes of variation as found in modern shells of Geloina erosa. As at the present day, this probably reflects the changing seasonality of the monsoon rains with shifts to negative δ18O values during periods of high runoff. Lighter mean δ18O values of the prehistoric shells, however, may indicate a greater annual surplus of rainfall and possibly consistent with the early Holocene strengthening of the summer monsoon at that time. The similarity of the last growth increment δ18O of the prehistoric shells to their mean δ18O profile values suggests that gathering took place during times of moderate runoff.  相似文献   

7.
A new genus and species of dasyurid is described on the basis of P3, M1–M3 and M2–3 collected from the middle Pliocene Chinchilla Local Fauna of south-eastern Queensland. Character analysis supports the placement of this new taxon within the dasyurid subfamily Dasyurinae. Derived dasyuromorphian features common to A. chinchillaensis and most dasyurines include: reduction of P3, reduction of stylar cusp B on M1; reduction of metaconids; approximation of stylar cusp B and the metacone on M1; alignment of the postmetacrista on M1 with the long axis of the maxilla and an oblique orientation of the hypocristids with respect to the long axis of the teeth. However in most instances, A. chinchillaensis is less specialised than other members of the subfamily for characters considered. One derived dental feature, reduction of the entoconid, may indicate a special relationship with ‘parantechinines’, Dasyuroides and/or Dasycercus. Additionally, the presence of this feature is suggestive of an open woodland/seasonal habitat. Autapomorphic P3 morphology compounds difficulties with the phylogenetic placement of this taxon.  相似文献   

8.
S. SAKATA  T. MAEKAWA  S. IGARI  Y. SANO 《Geofluids》2012,12(4):327-335
Previous geochemical studies indicated that most natural gases dissolved in brines in Japan are of microbial origin, consisting of methane produced via carbonate reduction. However, some of those from gas fields in southwest Japan contain methane relatively enriched in 13C, whose origin remains to be clarified. To address this issue, chemical and isotopic analyses were performed on natural gases and brines from the gas fields in Miyazaki and Shizuoka prefectures, southwest Japan. Methane isotopic signatures (δ13C ≈ ?68‰ to ?34‰ VPDB; δ2H ≈ ?183‰ to ?149‰ VSMOW) suggest that these gases are of microbial (formed via carbonate reduction) or of mixed microbial and thermogenic origin. The relatively high δ2H‐CH4 values and their relationship with the δ2H‐H2O values argue against the possibility of their formation via acetate fermentation. The δ13C‐CO2 values (≈?5‰), together with the slope of the correlation between δ2H‐CH4 and δ13C‐CH4δ2H‐CH4δ13C‐CH4 ≈ 1), contradict the possibility of their formation via carbonate reduction followed by partial oxidation by methanotrophs. The 3He/4He ratios of the gases from Miyazaki (≈0.11–1.3 Ra) and their low correlation with δ13C‐CH4 values do not support an abiogenic origin. It is inferred therefore that the high δ13C‐CH4 values of natural gases dissolved in brines from gas fields in southwest Japan are indications of the contribution of thermogenic hydrocarbons, although whether abiogenic hydrocarbons contribute significantly to the gases from Shizuoka requires further investigation. This study has clarified that, for the future exploration of natural gases in southwest Japan, we should adopt the strategies for conventional thermogenic gas accumulations, such as checking the content, type and maturity of organic matter in the underlying sedimentary rocks.  相似文献   

9.
Seasonal δ13C and δ18O data are presented from 14 Unio sub-fossil shells unearthed at the archaeological site of Çatalhöyük in central Turkey, spanning the occupation period ca. 9150–8000 cal years BP. The shells likely lived in the small lakes/wetlands around the site before being gathered and taken to Çatalhöyük. Wet-dry seasonal cycles are clearly apparent in the δ18Oshell profiles with low winter values reflecting winter precipitation and high δ18O in the summer resulting from evaporation. The most striking trend in the δ18O data is the drop in maximum summer δ18O ca. 8300 years BP, which we infer as indicating lower summer evaporation and hence a reduction in seasonality. Previous palaeoclimate records from the area have suggested cooler and more arid conditions, with reduced precipitation, around this time. While the drop in summer δ18O values could be due to reduced summer temperatures reducing summer evaporation, but there was little change in winter δ18O, perhaps suggesting winter growth cessation or reduced influence of winter climate change on δ18O. This shift in seasonal climate could be linked to solar-forced climate change beginning ca. 8600 years BP, and enhanced by the regional expression of the 8·2k event. Changing water balance over the occupation period is likely an important contributory factor behind observed cultural changes at Çatalhöyük in the Late Neolithic/Early Chalcolithic period. Our results might be considered to support the fission-fusion farming hypothesis as we provide additional evidence for wet winter/early spring conditions during the Early Holocene which likely caused flooding of the Çar?amba Fan. The changing water balance after ca. 8300 years BP (i.e. reduced seasonality and potentially reduced local summer evaporation) is also coincidental with the proposed end of this farming system due to multi-decadal drought.  相似文献   

10.
In order to interpret strontium and oxygen isotope values in Neolithic human skeletons analysed previously, we begin to map the biologically available strontium, carbon and oxygen isotopic signatures of prehistoric southern Germany by analysing tooth enamel of pigs from archaeological sites distributed around the region. The mapping shows a marked upland–lowland difference in biologically available 87 Sr/ 86 Sr values, ranging between 0.7086 and 0.7103 in the sedimentary lowlands, and from 0.710 to as high as 0.722 in the crystalline uplands of the Odenwald, the Black Forest and the Bavarian Forest. In addition, carbon isotopes in the carbonate fraction of pig enamel were generally about 1–2 more enriched in 13 C in the uplands. Despite the expected depletion of 18 O with altitude, oxygen isotopes in pig enamel showed little correlation with site altitude, although for pig samples not older than the Iron Age there was some geographical correlation withδ18O patterns in modern precipitation.  相似文献   

11.
The paper deals with the major chemistry and stable isotopes (hydrogen, oxygen, carbon, sulfur, strontium) of waters and solutes from the Salar de Atacama basin (Rio Pedro, Honar Creek and Laguna Chaxa) and Andean Altiplano (Laguna Miñique and Laguna Miscanti). The water inflows of the Salar are chemically quite different, the Rio San Pedro being of Na‐Cl type and the Honar Creek of Na‐HCO3 type, in keeping with the sedimentary‐evaporitic and volcanic nature of the catchment rocks respectively. The δ34S and δ18O values of sulfate and the 87Sr/86Sr ratio of strontium in the streams match those of drained rocks, whereas the δ13C values of dissolved carbonate are largely controlled by vegetation. The lagoons are evaporated meteoric water bodies, and the relative air humidity estimated from the slope of the isotopic evaporation line is in accordance with historical data on air humidity in the area. The Laguna Chaxa is Na‐Cl rich, and its isotopic composition are consistent with a mixed sedimentary‐volcanic provenance of sulfur and strontium solutes. The Laguna Miñique is Na‐SO4 rich, and its sulfate δ34S is nearly identical to that of Laguna Chaxa. The δ13C(HCO3) values are quite different in the Laguna Chaxa and Laguna Miñique, with the former being notably enriched in 13C probably because of preferential uptake of 12C by the high biological productivity occurring in the lagoon. The limited set of new data is interpreted in the context of a much larger literature database. In particular, previous chemical data on inflows and brines in the Salar de Atacama were revisited, and compared with evaporation path models and mineral stability diagrams (boron, lithium and Mg‐minerals) computed using updated software and thermodynamic databases. The modeling shows that the removal of boron and lithium from sulfate‐rich brines possibly occurs, respectively, as ulexite and sulfate salts, and carnallite should be the final magnesium phase of the brine evolution.  相似文献   

12.
A landmark, Webster's New Collegiate Dictionary tells us, is “an event or development that marks a turning point or a stage.” In my life, the case of Dennis v. United States 1 is a landmark, or perhaps more accurately, a series of landmarks. My 1973 doctoral dissertation was on Dennis. 2 Four years later that thesis became my first book. 3 My second book, a collection of articles on American political trials that appeared in 1981, contained an essay by me on Dennis. 4 By then, I assumed, I had said about everything I had to say on the case. In 1993, though, Mel Urofsky brought me back to it, asking me to write a retrospective article on Dennis for the Journal of Supreme Court History, of which he had just become the editor. 5 Now, fifteen years later, here we are together again. I am beginning to think that the “grave and probable danger” test that Dennis introduced into constitutional law will be inscribed on my tombstone.  相似文献   

13.
Geochemical and isotopic studies have been undertaken to assess the origin of CO2‐rich waters issuing in the northern part of Portugal. These solutions are hot (76°C) to cold (17°C) Na–HCO3 mineral waters. The δ2H and δ18O signatures of the mineral waters reflect the influence of altitude on meteoric recharge. The lack of an 18O‐shift indicates there has been no high temperature water–rock interaction at depth, corroborating the results of several chemical geothermometers (reservoir temperature of about 120°C). The low 14C activity (up to 9.9 pmC) measured in some of the cold CO2‐rich mineral waters (total dissolved inorganic carbon) is incompatible with the presence of 3H (from 1.7 to 4.1 TU) in those waters, which indicates relatively short subsurface circulation times. The δ13C values of CO2 gas and dissolved inorganic carbon range between ?6‰ and ?1‰ versus Vienna‐Peedee Belemnite, indicating that the total carbon in the recharge waters is being diluted by larger quantities of CO2 (14C‐free) introduced from deep‐seated (upper mantle) sources, masking the 14C‐dating values. The differences in the 87Sr/86Sr ratios of the studied thermal and mineral waters seem to be caused by water–rock interaction with different granitic rocks. Chlorine isotope signatures (?0.4‰ < δ37Cl < +0.4‰ versus standard mean ocean chloride) indicate that Cl in these waters could be derived from mixing of a small amount of igneous Cl from leaching of granitic rocks.  相似文献   

14.
Caesium-137 from fallout from nuclear weapons tests is adsorbed on fine sediments and becomes an effective tracer. It is hypothesised that within a drainage basin, sites undergoing little or no erosion accumulate 137 Cs in their upper layers; cultivated soils will have 137 Cs uniformly distributed within the cultivated layer; eroded soils, cultivated or not, will have relatively less l37 Cs, depending on the severity of erosion. Accumulated sediments will have characteristic 137 Cs profiles reflecting temporal fallout variations and sedimentation history. This hypothetical model is largely confirmed by results from Maluna Creek basin, where erosion and accumulation of sediments has taken place. Soils under viticulture have about one third the 137 Cs content of soils with grass cover, indicating more severe erosion under cultivation. Caesium-137 profiles in alluvial fan and flood plain deposits correlate with sediment layers and known cultivation history.  相似文献   

15.
Nitrogen isotope analysis is now commonly used to investigate the diets, and to a lesser extent, the environments of ancient populations. These studies assume that mammals are predictably enriched in 15N over their food, and concomitantly, that 15N becomes increasingly concentrated as one moves up the food chain. The literature commonly states that this 15N-enrichment of mammalian tissues is due to preferential excretion of light nitrogen (14N), but there are few data to support this assertion. To address the gap, we conducted two nitrogen flux trials in which four llamas (Lama glama) were fed high- and low-protein diets. The ratios of fecal nitrogen loss to urinary nitrogen loss were 0.30 and 0.88 on the high- and low-protein diets respectively. Feces were enriched in 15N by approximately +3‰ on both diets, whereas urinary nitrogen was depleted in 15N (−2.1‰) on the low-protein diet, but not significantly different from intake δ15N on the high-protein diet. Most importantly, there was no statistically significant difference between dietary and total excreta δ15N on either diet. Given these data and theoretical considerations, we argue that the nitrogen influx and efflux of adult mammals at steady state should be isotopically commensurate. However, during growth, diet change, thermal or nutritional stress, animals may not be at steady state and fractionation between intake and excreta δ15N may occur.  相似文献   

16.
Stable nitrogen isotopes have been used to reconstruct infant feeding practices as nursing infants have elevated δ15N ratios compared with their mothers. However, infancy is also a time of rapid growth, which may alter nitrogen isotope diet‐to‐tissue spacing. Several studies have documented a decrease in δ15N during growth in tissues with relatively fast accretion rates. This study investigates the effect that the growth of long bones, via collagen accretion, has on δ15N ratios. Long bones from individuals aged seven to nineteen years were obtained from a protohistoric ossuary in Ontario, Canada. Analysis of juveniles and adolescents permitted the examination of growth in a group who were not also nursing. It is concluded that a nitrogen isotope growth effect is not detectable in bone collagen from juveniles and adolescents, because: (1) δ15N ratios are not significantly different among the epiphyses, metaphyses and diaphysis of a growing long bone; (2) δ15N ratios are not significantly different between faster‐growing versus slower‐growing metaphyses; and (3) δ15N ratios are not significantly different between bones (or areas of a bone) that are still undergoing growth, versus bones that have ceased growing. The relatively slow speed of collagen accretion may explain why a growth effect is not manifested. Ultimately this research lends support to the use of nitrogen isotopes from bone collagen for infant feeding reconstructions. Copyright © 2009 John Wiley & Sons, Ltd.  相似文献   

17.
The purpose of this study is to compare the site effect section of building codes (EC8 and UBC97) with the set of data provided by the Kyoshin network. In order to obtain a set of site coefficients and spectral shapes, we have first deduced an attenuation law for both horizontal and vertical motion. Site conditions are represented by the shear velocity averaged over the upper 30 m (V s 30). Our site classification (4 categories similar to those proposed in the new ECS and the UBC97) is based on borehole investigations at every station. This classification has permitted to distinguish clearly four response spectra which demonstrates the efficiency of V s 30 as characterising site conditions. Our law is then used to test site coefficients and spectral shapes of building codes ECS and UBC97. Concerning spectral shapes and site coefficients, our results are found to be in good agreement with EC8 and UBC97 only if category B (400<V s 30<800 m/s) is taken as reference. We also conclude that a site which is characterised as “rock” on geological criteria can not generally be classified in category A (V s 30>800 m/s). This suggests that classification in category A should be based only on field measurements. Concerning vertical motion, our analysis of the K-NET data shows that the ratio av/ah (vertical peak ground acceleration over horizontal peak ground acceleration) is between 0.50 and 0.68.  相似文献   

18.
Twenty‐six tesserae (red, orange, yellow, light amber, green, blue and white) from the balneum of the villa at Faragola (Ascoli Satriano, Foggia) have been examined by colorimetry, ICP–MS, ICP–OES and SEM–EDS. Different types of calcareous sands have been used as the source of silica (network former), also providing the stabilizing agent. A natron‐type soda source served as the network modifier; however, the use of a sodium‐rich plant ash and the recycling process have been hypothesized for the production of two tesserae (FT 1 red and FT 3 orange). The colouring and opacifying agents were Cu oxide (cuprite, orange), metallic copper (red), Pb antimonates (yellow), Ca antimonates (white), a mixture of copper (Cu2+) and Pb antimonates (green), a mixture of cobalt (Co2+) or copper (Cu2+) and Ca antimonates (blue). The light amber tesserae should owe their colour to iron (Fe3+) alone or associated with sulphide (S2?) and Ca antimonates. It is likely that the Faragola tesserae were locally produced in a secondary glass workshop.  相似文献   

19.
This paper reports the δ13C and δ15N values of bone collagen, muscle and skin from several late prehistoric–early colonial (AD 1490–1640) mummies from Perú's Ayacucho Valley. The mean of the δ13C and δ15N values of bone collagen are −11.5 ± 1.4 and 11.1 ± 0.7‰, respectively. The mean of the δ13C values for Vinchos skin is −11.8 ± 1.2‰ and the mean of δ15N values is 13.2 ± 0.5‰. The samples of muscle tissue have a δ13C mean of −11.9 ± 0.9‰ and a δ15N mean of 12.7 ± 0.3‰. The data from bone collagen indicate maize was the basis of the region's subsistence economy. A significant correlation between δ13C and δ15N values of bone collagen (R2 = 0.75) is consistent with the preferential fertilization of maize with composted manure. Both skin and muscle samples are consistently enriched in δ15N relative to paired samples of bone (2.1 ± 0.5 and 1.6 ± 0.7‰, respectively), possibly as a result of short term physiological stress or differential decomposition.  相似文献   

20.
Absolute intensity determinations using the Coe variant of the Thellier method have been carried out on some selected pottery fragments collected in the wetlands of the lower Paraná (Pampean region, Argentina) in order to construct the first archaeointensity master curve for South America. Associated radiometric ages range between 1640 ± 70 and 730 ± 70 bp . Twenty‐one samples (five fragments) out of 46 studied (eight fragments) provided successful absolute intensity determinations. The fragment‐mean archaeointensity values obtained in this study range from 21.9 ± 2.3 to 42.6 ± 5.4 μT, with corresponding virtual axial dipole moments (VADMs) ranging from 4.0 ± 0.5 to 8.1 ± 1.0 x 1022Am2. This corresponds to a mean VADM of (6.4 ± 1.8) × 1022 Am2. The synthetic record retrieved from southern Argentina and Brazil consists of 17 mean archaeointensities distributed between approximately ad 700 and ad 1700. The data set shows several distinct periods of fluctuations of quite large intensity. However, most data are concentrated into a relatively narrow time period from ad 950 to ad 1300. Three general features may be detected: the time intervals from about ad 950 to 1130 and 1350 to 1480 are characterized by quite monotonic increases of geomagnetic intensity, while some decrease is observed from ad 1150 to 1280. These variations may be speculatively correlated to climate changes over multi‐decadal time scales. Important differences are observed between the data and the geomagnetic field predictions derived from recently reported global models, which reinforces the importance of regional reference curves for dating purposes.  相似文献   

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