A review of classical hydrogen isotopes storage materials

Hydrogen storage alloys(HSAs)are attracting widespread interest in the nuclear industry because of the generation of stable metal hydrides after tritium absorption,thus effectively preventing the leakage of radioactive tritium.Commonly used HSAs in the hydrogen isotopes field are Zr2M(M=Co,Ni,Fe)alloys,metallic Pd,depleted U,and ZrCo alloy.Specifically,Zr2M(M=Co,Ni,Fe)alloys are considered promising tritium-getter materials,and metallic Pd is utilized to separate and purify hydrogen isotopes.Furthermore,depleted U and ZrCo alloy are well suited for storing and delivering hydrogen isotopes.Notably,all the aforementioned HSAs need to modulate their hydrogen storage properties for complex operating conditions.In this review,we present a comprehensive overview of the reported modification methods applied to the above alloys.Alloying is an effective amelioration method that mainly modulates the properties of HSAs by altering their local geometrical/electronic structures.Besides,microstructural modifications such as nano-sizing and nanopores have been used to increase the specific surface area and active sites of metallic Pd and ZrCo alloys for enhancing de-/hydrogenation kinetics.The combination of metallic Pd with support materials can significantly reduce the cost and enhance the pulverization resistance.Moreover,the poisoning resistance of ZrCo alloy is improved by constructing active surfaces with selective permeability.Overall,the review is constructive for better understanding the properties and mechanisms of hydrogen isotope storage alloys and provides effective guidance for future modification research.

Oxygen and Hydrogen Isotopes of Waters in the Ordos Basin,China:Implications for Recharge of Groundwater in the North of Cretaceous Groundwater Basin

Hundreds of precipitation samples collected from meteorological stations in the Ordos Basin from January 1988 to December 2005 were used to set up a local meteoric water line and to calculate weighted average isotopic compositions of modern precipitation. Oxygen and hydrogen isotopes, with averages of-7.8‰ and -53.0‰ for δ^18O and δD, respectively, are depleted in winter and rich in spring, and gradually decrease in summer and fall, illustrating that the seasonal effect is considerable. They also show that the isotopic difference between south portion and north portion of the Ordos Basin are not obvious, and the isotope in the middle portion is normally depleted. The isotope compositions of 32 samples collected from shallow groundwater （less than a depth of 150 m） in desert plateau range from -10.6‰ to -6.0‰ with an average of-8.4‰ for δ^18O and from -85‰ to -46‰ with an average of-63‰ for δD. Most of them are identical with modern precipitation. The isotope compositions of 22 middle and deep groundwaters （greater than a depth of 275 m） fall in ranges from -11.6‰ to -8.8‰ with an average of -10.2‰ for δ^18O and from -89‰ to -63‰ with an average of -76‰ for δD. The average values are significantly less than those of modern precipitation, illustrating that the middle and deep groundwaters were recharged at comparatively lower air temperatures. Primary analysis of ^14C shows that the recharge of the middle and deep groundwaters started at late Pleistocene. The isotopes of 13 lake water samples collected from eight lakes define a local evaporation trend, with a relatively flat slope of 3.77, and show that the lake waters were mainly fed by modern precipitation and shallow groundwater.

Kinetics and fractionation of hydrogen isotopes during gas formation from representative functional groups

A gold tube simulation device was used to study the cleavage of representative compounds into gas.The goal of this study is to investigate hydrogen isotope composition change of gaseous hydrocarbons during maturity.Gas chromatography and isotopic analyses were conducted to determine how the yield of natural gas components and their hydrogen isotopic composition were related to experimental temperature and heating rate.A chemical kinetic model for the generation of each component of the natural gas and for the hydrogen isotopic fractionation was established and calibrated based on the results.Results indicate that the hydrogen isotopic fractionation during the evolution of various gas-forming organic materials can be satisfactorily described by chemical kinetic models.During regular methane generation,the reactions at low-activation-energy region had a greater contribution than the high-activation-energy region.While the reactions with high-activation-energy region had greater contribution of deuterium-rich methane.Compared with carbon isotope fractionation,this results in a greater hydrogen isotopic fractionation,which is more sensitive to changes in maturity.This study lays a foundation for further investigations of genesis and maturity of natural gas provided by hydrogen isotopic fractionation.It also provides fundamental knowledge for investigating the filling history of natural gas reservoir and for identifying.

Diffusion behavior of hydrogen isotopes in tungsten revisited by molecular dynamics simulations

Molecular dynamics simulations were performed to study the diffusion behavior of hydrogen isotopes in single-crystal tungsten in the temperature range of 300-2000 K. The simulations show that the diffusion coefficient of H isotopes exhibits non-Arrhenius behavior, though this deviation from Arrhenius behavior is slight. Many-body and anharmonic effects of the potential surface may induce slight isotope-dependence by the activation energy; however, the dependence of the pre-factor of the diffusion coefficient on the isotope mass is diminished. The simulation results for H-atom migration near W surfaces suggest that no trap mutations occur for H atoms diffusing near either W{ 100} or W{ 111 } surfaces, in contrast to the findings for He diffusion near W surfaces. Based on the H behavior obtained by our MD simulations, the time evolution of the concentration distribution of interstitial H atoms in a semi-infinite W single crystal irradiated by energetic H projectiles was calculated. The effect of H concentration on H diffusion is discussed, and the applicability of the diffusion coefficients obtained for dilute H in W is assessed.

Hydrogen Isotopes Recovery from Liquid Lithium under Dynamic Conditions

In the IFMIF （International Fusion Materials Irradiation Facility）, high-intensity deuteron ion beam is targeted at flowing liquid Li to produce neutron for long-time irradiation test of fusion materials. Radioactive tritium （T） will be produced as by-product of the D-Li reaction. Y hot trap is expected as an effective system to recover T from the liquid Li target loop. In the present study, absorption behavior of hydrogen isotopes in Y plates is experimentally and analytically investigated under stirring conditions of liquid Li. Experiments clarified that H2 absorption rates of solid Y immersed in Li are independent of the rotating rate in the range of 0 to 100 rpm and are in proportion to the inlet H2 concentration. The rate-determining step is H diffusion in Y. A mass-transfer coefficient is a useful parameter to correlate the overall H transfer from the gaseous phase through liquid Li to the solid Y plate. The effect of activation temperature on the overall performance when Y absorbs H is comparatively investigated. It is considered that heating at 673 K is effective to activate Y along with HF treatment.

Plasmas Created in the Interaction of Antiprotons with Atomic and Ionized Hydrogen Isotopes. Suggested Fuels for Space Engines

The main objective of the present work is to investigate the properties of plasmas created by injecting a thermalized beam of antiprotons in two types of media. The first is hydrogen, deuterium, or tritium atoms localized in palladium crystals. The second medium is composed of protons, deuterons, or tritons localized in a magnetic cavity. Particularly, it is demonstrated that huge amounts of energy are released in both cases which could be used as fuels for space shuttle engines. A novel mathematical scheme is employed to calculate the energy yields in real space at different incident energies of the antiprotons.

Composition and Evolution of Hydrogen Isotopes of n-Akanes Generated from Anhydrous Pyrolysis of Sediments from Lake Gahai,Gannan,China

To understand the thermal evolution of lacustrine sedimentary n-alkane hydrogen isotopic composition(δD),especially bacterially derived n-alkanes,anhydrous thermal simulation experiments were performed with sediments from Lake Gahai(Gannan,China).We analyzed the original and pyrolysis-generated n-alkanes and theirδD values.The results showed that thermal maturity and n-alkane origins significantly affected the distribution of pyrolysis-generated n-alkanes.In immature to post-mature sediments,the bacterial-derived medium-chain n-alkanes generally had depletedδD values.The maximum difference in averageδD values between the bacterial-and herbaceous plant-derived medium-chain n-alkanes was 32‰,and the maximum difference in δD values among individual n-alkanes was 59‰.We found that the averageδD value of pyrolysis-generated n-alkanes from different latitude was significantly different in immature to highly mature sediments,but similar in post-mature ssediments.The hydrogen isotopes of sedimentary n-alkanes can be used as indicators for paleoclimate/paleo-environment conditions only when sediments are immature to highly mature.During thermal evolution,the δD value of generated individual n-alkanes and the averageδD value increased with thermal maturity,indicating that hydrogen isotopes of sedimentary n-alkanes can be used as an index of organic matter maturity.We established mathematical models of average δD values of generated n-alkanes from immature to post-mature sediments using n C_(21)^(-)/nC_(21)^(+)and average chain lengths.These results improve our understanding of the distribution andδD value of sedimentary n-alkanes derived from herbaceous plants in mid-latitude plateau cold regions.

Oxygenic iron clusters in ZSM-5 zeolite promote quantum sieving of gaseous hydrogen isotopes

Isotopic separation is of paramount importance for producing high-purity heavy hydrogen,yet the process remains hugely challenging.Here,we report on an Fe/ZSM-5 zeolite that was able to efficiently separate deuterium from protium via chemical quantum sieving.Structural data showed that four types of Fe species were present in Fe/ZSM-5 and oligomeric Fe-O clusters in the zeolite pores were correlated directly with gas selectivity.Gas adsorption revealed that Fe-O species served as the main adsorption sites and interacted with D_(2) more strongly than with H_(2).D_(2)/H_(2)separation was exemplified using thermal desorption spectroscopy.D_(2)/H_(2) selectivity increased with Fe loading in Fe/ZSM-5 and a selectivity of 32.1 was obtained with an optimal loading of 7 wt%.The shift of desorption temperature supports the chemical affinity-based quantum sieving of D_(2)over H_(2).This study demonstrates an effective strategy for enhancing D_(2)/H_(2) separation and the high selectivity means that Fe/ZSM-5 has strong potential in hydrogen isotope separation.

Origin of the Dashuigou independent tellurium deposit at Qinghai–Xizang Plateau: constraints from the light stable isotopes C, O, and H

By studying the light isotopic compositions of carbon,oxygen,and hydrogen,combined with previous research results on the ore-forming source of the deposit,the authors try to uncover its metallogenic origin.The δ^(18)O and δ^(13)C isotope signatures of dolomite samples vary between 10.2 and 13.0‰,and between−7.2 and−5.2‰,respectively,implying that the carbon derives from the upper mantle.δD and δ^(18) O of quartz,biotite,and muscovite from diff erent ore veins of the deposit vary between−82 and−59‰,and between 11.6 and 12.4‰,respectively,implying that the metallogenic solutions are mainly magmatic.According to the relevant research results of many isotope geologists,the fractionation degree of hydrogen isotopes increases as the depth to the Earth’s core increases,and the more diff erentiated the hydrogen isotopes are,the lower their values will be.In other words,mantle-derived solutions can have extremely low hydrogen isotope values.This means that the δD‰ value−134 of the pyrrhotite sample numbered SD-34 in this article may indicate mantle-derived oreforming fl uid of the deposit.The formation of the Dashuigou tellurium deposit occurred between 91.71 and 80.19 Ma.

Principle of Hydrogen Isotope Geochemistry Paleo-altimeter and its Potential in Reconstructing Paleo-elevation of the Southeastern Tibetan Plateau

The reconstruction of paleo-elevation serves a dual purpose to enhance our comprehension of geodynamic processes affecting terrestrial landforms and to contribute significantly to the interpretation of atmospheric circulation and biodiversity.The oxygen(δ~(18)O_w)and deuterium(δD_w)isotopes in atmospheric precipitation are systematically depleted with the increase of altitude,which are typical and widely applicated paleo-altimeters.The utilization of hydrogen isotope of hydrous silicate minerals within the shear zone system,volcanic glass,and plant leaf wax alkanes offers valuable insights for addressing evaporation and diagenesis.In this paper,we review the principle,application conditions,and influencing factors of the hydrogen isotope paleo-altimeter.In addition,we discuss the feasibility of utilizing this technique for quantitatively estimating the paleo-elevation of the southeastern Tibetan Plateau,where multiple shear zones extend over hundred kilometers parallel to the topographic gradient.

Origin of the Yueguang gold deposit in Xinhua, Hunan Province, South China: insights from fl uid inclusion and hydrogen–oxygen stable isotope analysis

The Yueguang gold deposit is located in Fengjia,Xinhua County,Hunan Province,South China.It represents a recently discovered small-scale gold deposit situated in the southwestern region of the Jiangnan Orogenic Belt,west of the Baimashan granitic batholith.In order to discern the characteristics of the ore-formingfluids,the underlying mineralization processes,and establish a foundation for the origin of the Yueguang gold depositfluid inclusion micro-thermometry,as well as quartz hydrogen and oxygen isotope analysis,have been carried out on samples obtained from various stages of mineralization.The hydrothermal miner-alization stages within the Yueguang gold deposit can be categorized into three stages:(i)the barren,pre-ore quartz-pyrite stage(Stage Ⅰ),the quartz-pyrite-gold stage(Stage Ⅱ),and the post-ore quartz-carbonate stage(Stage Ⅲ),with the second stage being the main mineralization stage.Thefluid inclusions identified in samples from the main min-eralization stage can predominantly be described with the NaCl–H_(2)O and CO_(2)–NaCl–H_(2)O systems.These inclusions display homogenization temperatures ranging from 158.8 to 334.9℃,and thefluid salinity ranges from 0.3%to 4.0%(wt.%NaCl equiv.).Laser Raman spectroscopy analysis of individual inclusions further reveals the presence of gas-phases such as CO_(2),CH_(4),and N_(2).Isotopic analysis indicatesδ^(18)Ofluid values ranging from 3.95 to 6.7‰ and δDH_(2)O values ranging from-71.9 to-55.7‰.These results indi-cate that the ore-formingfluid of the Yueguang gold deposit belongs to metamorphic hydrothermalfluids of middle-low temperature and low salinity.In the process of ore formation,gold is transported in the form of Au(HS)2-complexes,with gold deposition being driven byfluid immiscibility.Therefore,the Yueguang gold deposit is categorized as an orogenic gold deposit dominated by metamorphic hydrother-malfluid.It may become a new target for gold exploration in the Baimashan region,central Hunan Province.

Diffusion behaviors of hydrogen isotopes in niobium from first-principles

We investigate diffusion behaviors of hydrogen(H),deuterium(D),and tritium(T) in bulk niobium(Nb) using first-principles method.The diffusion energy barrier with quantum-correction has been calculated to be 0.12 eV,which is in good agreement with the experimental value of ～0.106 eV.According to diffusion theory presented by Wert and Zener,the diffusion pre-exponential factors of H,D,and T are shown to be 7.74×10-8m 2 s-1,5.47×10-8 m 2 s-1 and 4.48×10-8 m 2 s-1,respectively.These results are also in quantitative agreement with the corresponding experimental values.

Stable carbon and hydrogen isotopes of gases from the large tight gas fields in China

By the end of the year 2010, a total of 15 large tight gas fields have been found in China, located in the Ordos, Sichuan, and Tarim basins. The annual production and total reserves of these fields in 2010 were 222.5× 108 and 28657× 108 m3, respectively, accounting for 23.5% and 37.3%, respectively, of the total annual production and reserves of natural gases in China. They took a major part of all natural gas production and reserves in China. According to the analyses of 81 gas samples, the stable carbon and hydrogen isotopic compositions of tight gases in China have following characteristics： （1） Plots of δ13CI-δ13C2-δ13C3, δ13C1-C1/C2＋3 and δ13C1-δ 13C2 demonstrate the coal-derived origin of tight gases in China; （2） For the primary alkane gases, both carbon and hydrogen isotopic values increase with increasing molecular mass, i.e., δ13C1〈δ13C2〈δ13C3〈δ13C4 and δ2HI〈δ2Hz〈δ2H3; （3） The isotopic differences of δ13C2-δ13C1, δ13C3-δ13C1, δ2H2-δ22Hl and cTZH3-62H1 decrease with in- creasing Ro （%） and C1/C1-4; （4） There are seven causes for the carbon and hydrogen isotopic reversal, however, the carbon and hydrogen isotopic reversal of tight gases in China is caused mainly by multiple stages of gas charge and accumulation.

Compound-specific hydrogen isotopes of long-chain n-alkanes extracted from topsoil under a grassland ecosystem in northern China

To investigate characteristics of H isotope variation in long-chain n-alkanes （δDn-alkanes） from higher plants in surface soils under a single ecosystem, 12 samples from a basalt regolith were randomly collected from Damaping in Wanquan County of Zhangjiakou in North China. Molecular distribution and C （δ^13Cn-alkanes） and H isotopes of long-chain n-alkanes, as well as C isotopes of TOC （δ^13CTOC）, were analyzed. Both δ^13CTOC and δ^13Cn-alkanes values from four representative dominant long-chain n-alkanes （n-C27, n-C29, n-C31, n-C33） derived from terrestrial higher plants show minor variations among the 12 samples, indicating the major contributor is from local grasses with a uniform C3 photosynthetic pathway. In contrast, variations in δ^13Cn-alkanes values of the four long-chain n-alkanes are relatively large, with the more abundant homologs generally showing more negative δDn-alkanes values and less variation. However, variation of 〈30‰ among weighted averaged δDn-alkanes values of the four long-chain n-alkanes is not only less than that among δDn-alkanes values for different modern terrestrial C3 grasses from the specific locations, but also less than the literature values of δDn-alkanes of long-chain n-alkanes for single species over different seasons. Thus, because the sources of long-chain n-alkanes in surface soils and sediments are similarly from multiple individual plants, our results are significant in confirming that paleoclimatic, paleoenvironmental and paleohydrological information can be interpreted more accurately from δDn-alkanes values of long-chain n-alkanes from sediments, particularly terrestrial sediments with organic matter derived from in-situ plants.

Estimating distribution of water uptake with depth of winter wheat by hydrogen and oxygen stable isotopes under different irrigation depths

Crop root system plays an important role in the water cycle of the soil-plant-atmosphere continuum. In this study, com- bined isotope techniques, root length density and root cell activity analysis were used to investigate the root water uptake mechanisms of winter wheat （Triticum aesfivum L.） under different irrigation depths in the North China Plain. Both direct inference approach and multisource linear mixing model were applied to estimate the distribution of water uptake with depth in six growing stages. Results showed that winter wheat under land surface irrigation treatment （Ts） mainly absorbed water from 10-20 cm soil layers in the wintering and green stages （66.9 and 72.0%, respectively）; 0-20 cm （57.0%） in the jointing stage; 0-40 （15.3%） and 80-180 cm （58.1%） in the heading stage; 60-80 （13.2%） and 180-220 cm （35.5%） in the filling stage; and 0-40 （46.8%） and 80-100 cm （31.0%） in the ripening stage. Winter wheat under whole soil layers irrigation treatment （Tw） absorbed more water from deep soil layer than Ts in heading, filling and ripening stages. Moreover, root cell activity and root length density of winter wheat under TW were significantly greater than that of Ts in the three stages. We concluded that distribution of water uptake with depth was affected by the availability of water sources, the root length density and root cell activity. Implementation of the whole soil layers irrigation method can affect root system distribution and thereby increase water use from deeper soil and enhance water use efficiency.

Hydrogen isotopes in palmitic and stearic acids in suspended particles from the Changjiang River Estuary

Hydrogen isotopes in lipid biomarkers can trace past changes in the hydrologic cycle. Recent studies have revealed the potential of hydrogen isotopes in microalgal lipids for quantitatively reconstructing water δ~2H（δD） values and salinity. In this study we collected suspended particles along a salinity gradient from the Changjiang River Estuary（CRE）, and measured δD values in fatty acids in these particles. The results indicated that δD values of water were correlated highly with salinity from the CRE, in agreement with the results from other estuaries. δD values in palmitic acid and stearic acid had a positive correlation with δD values of water from the CRE. Nevertheless, in the CRE, hydrogen isotope fractionation in fatty acids relative to water increased as salinity increased, opposite the trend in hydrogen isotope fractionation with salinity found in microalgal culture and field studies. We attribute the increase in hydrogen isotope fractionation as salinity increased to light availability, which was likely lower in the particle rich mixing zone at the end of the estuary, and potentially as well to multiple sources of fatty acids in the CRE.

Characteristics of Hydrogen and Oxygen Isotopes and Noble Gas Isotopes in the Groundwater of Weishan, Wudalianchi, Northeast China

According to the hydrochemical characteristics, hydrogen and oxygen isotope characteristics and the ratio of noble gas isotopes of the sandstone aquifer and basalt aquifer, this study calculated the recharge temperature and residence time of groundwater in the Weishan area of Wudalianchi, also calculating the contribution of noble gas components from different sources to the samples. Based on the characteristics of hydrogen and oxygen isotopes and noble gases Xe and Ne, the recharge altitude and recharge temperature of the two aquifers were estimated, and the recharge temperature fitting with the NGT model as verified, the results showing that the main recharge altitude of groundwater in the region was 500–600 m, the recharge temperature being 2–7°C. He_(eq) and He_(ea) of the samples have been simulated using the OD model, the content of radioactive ~4He in the crust being obtained, the groundwater ages under the two conditions(closed condition and open condition) both being simulated. The results show that groundwater from the sandstone layer water is older than groundwater from the basalt layer. Hydrochemical characteristics and noble gas isotope ratios indicate that in the basalt aquifer and sandstone aquifer in the Weishan area, in addition to atmospheric and crustal helium, there is also an input of mantle-derived helium. The fault constitutes the uplift channel for groundwater containings mantle components, which results in the mantle source composition in water samples near the fault being much higher than those form non-fault areas.

Ore genesis of Badi copper deposit, northwest Yunnan Province, China： evidence from geology, fluid inclusions, and sulfur, hydrogen and oxygen isotopes

The Badi copper deposit is located in Shangjiang town, Shangri-La County, Yunnan Province. Tectonically, it belongs to the Sanjiang Block. Vapor-liquid two-phase fluid inclusions, CO2-bearing fluid inclusions, and daugh- ter-beating inclusions were identified in sulfide-rich quartz veins. Microthermometric and Raman spectroscopy studies revealed their types of ore-forming fluids： （1） low-tem- perature, low-salinity fluid; （2） medium-temperature, low salinity CO2-bearing; and （3） high-temperature, Fe-rich, high sulfur fugacity. The δ^18O values of chalcopyrite- bearing quartz ranged from 4.96‰ to 5.86%0, with an average of 5.40%0. The δD values of ore-forming fluid in equilibrium with the sulfide-bearing quartz were from - 87‰ to - 107‰, with an average of - 97.86%0. These isotopic features indicate that the ore-forming fluid is a mixing fluid between magmatic fluid and meteoric water. The δ^34S values of chalcopyrite ranged from 13.3‰ to 15.5‰, with an average of 14.3‰. Sulfur isotope values suggest that the sulfur in the deposit most likely derived from seawater. Various fluid inclusions coexisted in the samples; similar homogenization temperature to different phases suggests that the Badi fluid inclusions might have been captured under a boiling system. Fluid boiling caused by fault activity could be the main reason for the mineral precipitation in the Badi deposit.

Hydrogen and Oxygen Isotopes of Fluid Inclusion in Halite,Northern Shaanxi Salt Basin China

The Ordovician was an important transitional period for global climate and organic evolution,the global was in the flood and glacial,Onganism was extinction(Zhan,2007;Trotter et al.,2008;Axel et al.,2010).Under the influence

Genesis of the Ciemas Gold Deposit and Relationship with Epithermal Deposits in West Java,Indonesia:Constraints from Fluid Inclusions and Stable Isotopes

The Ciemas gold deposit is located in West Java of Indonesia, which is a Cenozoic magmatism belt resulting from the Indo-Australian plate subducting under the Eurasian plate. Two different volcanic rock belts and associated epithermal deposits are distributed in West Java： the younger late Miocene-Pliocene magmatic belt generated the Pliocene-Pleistocene epithermal deposits, while the older late Eocene-early Miocene magmatic belt generated the Miocene epithermal deposits. To constrain the physico-chemical conditions and the origin of the ore fluid in Ciemas, a detailed study of ore petrography, fluid inclusions, laser Raman spectroscopy, oxygen-hydrogen isotopes for quartz was conducted. The results show that hydrothermal pyrite and quartz are widespread, hydrothermal alteration is well developed, and that leaching structures such as vuggy rocks and extension structures such as comb quartz are common. Fluid inclusions in quartz are mainly liquid-rich two phase inclusions, with fluid compositions in the NaCI-H2O fluid system, and contain no or little CO2. Their homogenization temperatures cluster around 240℃-320℃, the salinities lie in the range of 14-17 wt.% NaCI equiv, and the calculated fluid densities are 0.65-1.00 g/cm^3. The values of δ18OH2O-VSMOW for quartz range from ＋5.5%0 to ＋7.7‰, the δDVSMOW of fluid inclusions in quartz ranges from -70‰ to -115‰. All of these data indicate that mixing of magmatic fluid with meteoric water resulted in the formation of the Ciemas deposit. A comparison among gold deposits of West Java suggests that Miocene epithermal ore deposits in the southernmost part of West Java were more affected by magmatic fluids and exhibit a higher degree of sulfidation than those of Pliocene-Pleistocene.