粤北302铀矿床同位素地球化学研究

位于粤北诸广山岩体东南部的302铀矿床是我国规模较大、埋藏较深的花岗岩型铀矿床之一。该矿床产于印支期油洞岩体和燕山早期长江岩体的断裂蚀变带内,矿区内NWW向基性岩脉十分发育,矿体呈似脉状、扁豆状或透镜状。同位素研究表明,矿石的沥青铀矿Sm-Nd和U-Pb等时线年龄（70 Ma）与油洞岩体（232 Ma）、长江岩体（160 Ma）的年龄相差巨大;主成矿期成矿流体的δDH2O值为-65‰～-82‰（平均为-75‰）,δ18OH2O值为6.8‰～0.6‰（平均为3.9‰）,反映出成矿流体主要由地幔流体组成;方解石的δ13C值为-8.4‰～-5.3‰,表明矿化剂ΣCO2也来自地幔;矿区内辉绿岩的（87Sr/86Sr）i值为0.70861～0.70882,花岗岩的（87Sr/86Sr）i值为0.73519～0.77152,萤石的（87Sr/86Sr）i值为0.71474～0.71697,表明成矿组分Sr可能来源于基性脉岩（幔源）与赋矿花岗岩体（壳源）,并呈不同程度的混合,而主成矿组分铀主要来源于赋矿花岗岩体。     

地幔流体与铀成矿作用:以下庄矿田仙石铀矿床为例

仙石大型铀矿床位于粤北贵东复式岩体东部，矿区内NWW和NNE向基性岩脉十分发育。矿床位于NNE向硅化带和NWW向基性岩脉(辉绿岩)交接部位，矿体严格赋存于基性岩脉内部或其边缘。金属矿物以沥青铀矿和黄铁矿为主，脉石矿物以方解石和(微晶)石英为主，蚀变作用发育，主要类型包括碱交代、硅化和赤铁矿化。沥青铀矿U-Pb年龄测定结果表明，矿床中存在81Ma(主要)和125Ma(次要)两期铀矿化。H、O同位素研究表明，矿前期和成矿期成矿流体的δ^1aOH2O=1.4‰～65％，δDH2O=-65‰-34‰，反映成矿流体主要由地幔流体组成。矿脉中方解石的δ13C=-8．5‰～-3．1‰，反映矿化剂∑CO2来自地幔。上述特征表明，地幔流体在仙石铀矿床的形成中具有十分重要的意义。     

下庄矿田338矿床地幔流体与铀成矿作用

338铀矿床位于粤北贵东复式岩体东部，矿区内NWW和NNE向基性岩脉十分发育。矿床位于硅化带和基性岩脉(辉绿岩)交接部位，矿体严格赋存于基性岩脉内部或其边缘部分。金属矿物以沥青铀矿和黄铁矿为主，脉石矿物以方解石和(微晶)石英为主，蚀变作用发育，主要类型包括碱交代、硅化和赤铁矿化。沥青铀矿U-Pb年龄为125Ma，86Ma和79Ma，反映成矿作用具有多阶段性。H、O同位素研究表明，矿前期和成矿期成矿流体的δ^18OH120=1．4—6．6‰，δDH2O=-65～34‰，反映成矿流体主要由地幔流体组成。矿脉中方解石的δ^13C=-8．5～-3．1‰，反映矿化剂∑CO2来自地幔。上述特征表明，地幔流体在338铀矿床的形成中具有十分重要的意义。     

粤北仙石铀矿床的铅、碳、硫同位素研究

仙石铀矿床位于粤北贵东复式花岗岩体东部,矿体赋存于NWW向辉绿岩与NEE向硅化带交接部位。矿床中黄铁矿以富集放射成因铀铅为特征,3组比值分别为(^208Pb／^304Pb)．=18．756—23．883,(^207Pb／^304Pb)1=15．676～15．932,(^208Pb／^204Pb),=38．530—38．938,主要位于基底变质岩铅范围内;矿床中方解石δ^18C值为-8．5‰～-3．1‰,相似于地幔值((-5±2)‰);黄铁矿δ^18C值为-10．1‰～-8．3‰,它与花岗岩中黄铁矿δ^18C值(-10．9‰--7．1‰)相似,而与辉绿岩中黄铁矿δ^18C值(-0．03‰～2．1‰)区别明显。上述同位素特征表明仙石铀矿床的成矿物质具多源特征。     

诸广岩体南部铀矿区稳定同位素组成及矿床成因分析

诸广岩体南部产出多个大中型铀矿床,笔者通过测定各主要矿床的硫、氢、氧同位素组成,探讨成矿流体和成矿物质来源。研究发现,富矿石中黄铁矿的δ34SCDT值为-17.4‰~-17.9‰,与新鲜辉绿岩中黄铁矿的δ34SCDT值(-0.5‰~-0.2‰)明显不同,表明成矿流体来自幔源的可能性很小。在δD-δ18 OH2O图中,所有氢、氧同位素组成特征值均落于地幔水、岩浆水、变质水与大气降水线之间,进一步表明成矿流体来自大气降水。δ13 CPDB值为-9.8‰~-4.3‰,显示碳很可能来自花岗岩。上述同位素特征表明,区内与花岗岩有关的脉型铀矿床可能主要由大气降水沿深大断裂循环并萃取围岩(包括花岗岩)中各种成矿元素而形成。     

江西相山矿田硫铅同位素地球化学特征

为查明江西相山矿田内铅锌矿和铀矿床的成矿物质来源,对与铅锌矿、铀矿有关的矿石矿物进行了S、Pb同位素研究,结果显示,与铅锌矿有关的金属矿物δ34S值为1.3‰~4.7‰,同铀矿伴生的黄铁矿δ34S值为7.9‰~14.9‰;赋矿围岩、基底变质岩、铀矿床黄铁矿和铅锌矿硫化物的206Pb/204Pb、207Pb/204Pb及208Pb/204Pb比值整体上有逐渐降低的趋势,均表现出放射性成因铅的特征,不同岩石或矿石的样品铅同位素组成范围基本一致。结合前人研究,说明铅锌矿和铀矿并非来自同一次成矿事件;铅锌矿的成矿期次具有阶段性,硫源具有均一性,主要以深部硫源为主,在其向上迁移的过程中有少量基底变质岩中的硫加入,按照硫化物共生矿物对计算出铅锌矿的成矿温度:早阶段为424~382℃,晚阶段为331~290℃,属中高温热液矿床;铀矿的硫源具有地层硫特征,主要来自于基底变质沉积岩。铀矿床伴生的黄铁矿铅同位素组成比铅锌矿硫化矿的铅同位素组成更具放射性成因铅,铅锌矿的铅源主要与上地壳基底变质岩有关,铀矿的铅源主要以相山火山-侵入杂岩体为主,但是可能还具有少量幔源铅参与。     

河北华尖金矿稳定同位素特征及其地质意义

华尖金矿位于冀东大型金矿带内,赋存于太古宙变质岩及中生代岩浆岩中。在详细分析华尖金矿床地质特征的基础上,研究了石英脉的氢、氧同位素和黄铁矿的硫、铅同位素组成特征。研究发现,本区载金黄铁矿δ34S值变化范围变化于1.5‰~5.8‰,具有壳源岩浆岩特征,载金黄铁矿铅同位素206Pb/204Pb值变化为16.02~16.25,207Pb/204Pb为15.161~15.213,208Pb/204Pb为35.953~36.12,均有下地壳铅源的特征。含金石英脉的δ18O水在0.49‰~5.45‰,δ18OV-SMOW为10.3‰~14.2‰,δD为-72.1‰~-63.1‰,具有岩浆热液石英的特征,部分样品偏离火成石英的区域,可能是成矿热液混有大气降水的结果。综合研究表明,该矿床成矿物质主要来源于燕山期的牛心山花岗岩体,其次为遵化群变质岩围岩。     

云南东川雪岭矿区浅部铜多金属矿化地质地球化学特征及成矿规律研究

雪岭矿区位于扬子板块西缘,浅部赋存的铜多金属矿化受落因断裂系南延断裂及其次级断裂和辉绿岩脉所控制产出于灯影组白云岩中。对矿区浅部铜多金属矿化的岩矿石地球化学和同位素地球化学分析显示:围岩与矿石的稀土元素特征相似,且围岩富集Cu,Ag,Pb,Zn等成矿元素,故围岩应该为成矿提供了部分成矿物质;与之共生的石英样品δD_(V-SMOW)值介于-85.7‰~-102.2‰,δ~(18) O水值介于0.9‰~2.4‰,表明成矿流体以层间封存水为主,混合了部分天水和原生岩浆水;3件来自铁矿化带中的黄铁矿δ34 SV-CDT值为+9.9‰~+27.4‰,1件来自铜银(铅锌)矿化带中裂隙脉状矿体的黄铁矿δ34 SV-CDT值为-37.5‰,暗示本区硫来源复杂,硫可能主要来源于沉积地层的海相硫酸盐,部分混染幔源硫和生物硫,或者与其成矿过程中fO2和pH值发生急剧变化有关;3件来自铁矿化带的黄铁矿~(206)Pb/~(204)Pb=18.279~18.372,~(207)Pb/~(204)Pb=15.653~15.673,208Pb/~(204)Pb=38.272~38.462,1件来自铜银(铅锌)矿化带裂隙脉状矿体的黄铁矿~(206)Pb/~(204)Pb=19.310,~(207)Pb/~(204)Pb=15.771,208Pb/~(204)Pb=38.792,显示本区铅来源复杂,具壳幔混合铅的特征;具正确铅特征的硫铁矿模式年龄为260 Ma~350 Ma,与峨眉山玄武岩的成岩时代相近。经综合分析,本区浅部铜多金属矿化应是晚二叠世时,受峨眉山玄武岩喷溢作用热动力影响导致热液萃取深部陡山沱组成矿物质,并沿途淋滤围岩中部分成矿物质,沿断裂带向上运移至浅部灯影组白云岩中沉淀富集所致。     

下庄铀矿田337矿床成矿机理及动力学背景

长期以来人们一直认为337铀矿床是下庄铀矿田成矿年龄最早、成矿温度相对较高、矿岩时差小的岩浆热液型铀矿床的代表.据作者及其他研究者近年来对该矿田及矿床开展的岩体成岩年龄、岩体蚀变年龄、岩体的主量和微量元素组成及同位素等的综合研究揭示:与337铀矿床成矿关系最为密切的帽峰岩体单颗粒锆石测试的成岩年龄为206～238.2 Ma,而岩体中次生白云母的40Ar/39Ar法坪年龄变化于131～136 Ma之间,后者与该矿床主要铀矿化年龄130.3～138 Ma相近;在贵东花岗质杂岩体中,Al2O3/TiO2含量比值表明帽峰岩体可能是源区熔融温度最低的岩体,帽峰岩体还是稀土总量最低且是唯一显示较典型"四分组效应"的岩体,同时还具有变化的δ18O值和最低的(87Sr/86Sr)i值.上述研究结果说明337铀矿床的形成过程和动力学背景可能是:印支主碰撞晚期或后碰撞阶段本区富铀地层发生部分熔融作用形成了富铀的强过铝质花岗岩帽峰岩体,燕山晚期(140 Ma以后)大陆拉张背景下多期次基性脉岩侵入,带来高热和矿化剂CO2,并驱动大规模流体运动,活化和萃取了富铀花岗岩中的铀,在不同部位(裂隙发育地段或在基性脉岩与花岗岩的接触部位)沉淀形成铀矿体(床),337铀矿床是本区第1期铀成矿作用的典型代表.     

粤北下庄矿田帽峰岩体的岩石地球化学特征

从主元素、微量元素、稀土元素的四分组效应及结合已有的锶同位素比值等方面研究了帽峰岩体的岩石地球化学特征,研究结果表明:(1)帽峰岩体具有富铝、硅和碱,A/CNK平均值为1.2,A′为正值等主量元素特征,富含石榴石、白云母等过铝矿物,强烈的铕亏损(δEu=0.01～0.25)及基本上无轻重稀土分异的稀土元素配分特征等,表明帽峰岩体是强过铝花岗岩,其物质来源主要是壳源;与同区域其它岩体相比较低的锶同位素比值((87Sr/86Sr)i=0.7185)是伴随着区域伸展构造所带来的幔源流体成分叠加所导致的。(2)帽峰岩体具有较为典型的稀土元素四分组效应,较低的Y/Ho比值(<28)及Zr/Hf比值(7.52～24.75),岩体的锆石年龄老(207.6±3.2Ma),而白云母KAr年龄(141.2Ma)与区域地壳伸展年龄(140Ma)及铀矿体的形成时代(138Ma)相接近,且岩体中常见碳酸盐团块,因此帽峰岩体较为典型的稀土元素的四分组效应是伴随着区域伸展和铀成矿过程与重碳酸络合物有关的流体之间的相互作用形成的。     

Wavelength-dispersive X-ray fluorescence spectrometric determination of Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites

Komatiites are mantle-derived ultramafic volcanic rocks. Komatiites have been discovered in several States of India, notably in Karnataka. Studies on the distribution of trace-elements in the komatiites of India are very few. This paper proposes a simple, accurate, precise, rapid, and non-destructive wavelength-dispersive x-ray fluorescence (WDXRF) spectrometric technique for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites, and discusses the accuracy, precision, limits of detection, x-ray spectral-line interferences, inter-element effects, speed, advantages, and limitations of the technique. The accuracy of the technique is excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Zr, Nb, Ba, Pb, and Th and very good (within 4%) for Y. The precision is also excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th. The limits of detection are: 1 ppm for Sc and V; 2 ppm for Cr, Co, and Ni; 3 ppm for Cu, Zn, Rb, and Sr; 4 ppm for Y and Zr; 6 ppm for Nb; 10 ppm for Ba; 13 ppm for Pb; and 14 ppm for Th. The time taken for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in a batch of 24 samples of komatiites, for a replication of four analyses per sample, by one operator, using a manual WDXRF spectrometer, is only 60 hours.     

硅酸盐类样品中硅、铁、铝、钛、锰、钙、镁、钾、钠和磷的x射线荧光光谱测定

本文拟定了一种以熔融法制备样片,用X射线荧光光谱测定硅酸盐类样品中Si、Fe、Al、Tj、Mn、Ca、Mg、K、Na、P等元素的分析方法。在对不同靶材X光管和分光晶体实验对比的基础上,选择了最佳的测量条件。该法具有快速、准确,测量范围广,检测限低,价格便宜等优点。经过近百个各种类型标样或管理样品的分析对比表明,本法不仅适用于硅酸盐类岩石样品的分析,还适用于铁矿、铝土矿、碳酸盐类岩矿样品以及水泥、耐火材料等样品的分析。     

高压微波消解法测定醋酸纤维过滤器采集的微尘粒子中的砷镉钴铬铜铁锰镍铅钒锌

最新的流行病学研究表明,空气中较高浓度的悬浮细颗粒可能对人类的健康有不利的影响。根据该项研究显示,由于心脏病、慢性呼吸问题和肺功能指标恶化而导致死亡率的升高与细尘粒子有关。这些研究结果已经促使欧盟于1999年4月出台了限制空气中二氧化硫、二氧化氮、氧化氮、铅和颗粒物含量的法案(1999/30/EC),对各项指标包括对可吸入PM10颗粒的浓度提出了新的限制性指标。PM10颗粒是指可以通过预分级器分离采集的气体动力学直径小于10μm的细颗粒。目前研究的兴趣重点逐步偏向PM2.5这些更细微颗粒物,PM2.5这种颗粒物对健康有明显的不利影响。在欧盟指令2008/50/EC中,对PM10和PM2.5都提     

Isotopic systematics of He,Ar, S,Cu, Ni,Re, Os,Pb, U,Sm, Nd,Rb, Sr,Lu, and Hf in the rocks and ores of the Norilsk deposits

This paper reports the first results of a study of 11 isotope systems (³He/⁴He, ⁴⁰Ar/³⁶Ar, ³⁴S/³²S, ⁶⁵Cu/⁶³Cu, ⁶²Ni/⁶⁰Ni, ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, ^206–208Pb/²⁰⁴Pb, Hf–Nd, U–Pb, and Re–Os) in the rocks and ores of the Cu–Ni–PGE deposits of the Norilsk ore district. Almost all the results were obtained at the Center of Isotopic Research of the Karpinskii All-Russia Research Institute of Geology. The use of a number of independent genetic isotopic signatures and comprehensive isotopic knowledge provided a methodic basis for the interpretation of approximately 5000 isotopic analyses of various elements. The presence of materials from two sources, crust and mantle, was detected in the composition of the rocks and ores. The contribution of the crustal source is especially significant in the paleofluids (gas–liquid microinclusions) of the ore-forming medium. Crustal solutions were probably a transport medium during ore formation. Air argon is dominant in the ores, which indicates a connection between the paleofluids and the atmosphere. This suggests intense groundwater circulation during the crystallization of ore minerals. The age of the rocks and ores of the Norilsk deposits was determined. The stage of orebody formation is restricted to a narrow age interval of 250 ± 10 Ma. An isotopic criterion was proposed for the ore-bearing potential of mafic intrusions in the Norilsk–Taimyr region. It includes several interrelated isotopic ratios of various elements: He, Ar, S, and others.     

Viscous, cohesive, non-Newtonian, depositing, radial slurry flow

Mining induced subsidence can significantly affect mining costs where major surface facilities and natural environment need to be protected. Overburden grout injection is a technology used to control coal mine subsidence by injecting the mine waste material extracted from the coal back into the inter-burden rock during longwall mining. The flowing slurry is here categorised as a nonlinear viscous cohesive (Bingham plastic) fluid. During longwall mining the grout slurry is pumped into the separated beds of the rock mass through a central vertical borehole, which is drilled deep into the inter-burden rock strata above the coal seam. However, a blockage can occur in the injection system when the slurry velocity falls below a certain critical threshold velocity, indicating a material phase change from cohesive-viscous to cohesive-frictional. In situ field injection tests through boreholes have been simulated at a smaller scale at the CSIRO laboratory in Brisbane by pumping the slurry through a radial disk (gap = 4 mm) from its centre. Laboratory experiments indicate a general, nonlinear, cohesive, viscous, frictional model for shear behaviour of the slurry, in which the material shear parameters are functions of the disk radial distance. Complete dimensional and dimensionless analytical solutions have been developed based on an approach related to Bingham–Herschel–Bulkley fluid mechanics. The derived formulae include relations for minimum pump pressure, local pressure and pressure gradient, wall shear stress, volume rate, velocity and velocity gradient. The theoretical results match the experimental measurements. The experiments covered slurries with maximum particle sizes of 0.5 to 2 mm with about 50% being larger than 100 µm. The viscosities at the various solids concentrations were measured with a standard torsion viscometer. This study differs from the previous research in several distinct aspects, namely, consideration of the variable shear parameters rather than fixed values, inclusion of total nonlinear behaviour, and implementation of a friction function to mimic behaviour of the deposited and consolidating stiff slurry, which can cause a significant pressure rise as a result of the increased shear resistance.     

硅酸盐中铁、锰、钛、钙、钾、磷、硅、铝、镁、钠、锶、铷、钡的X-射线荧光光谱定量测定

本文介绍样品经四硼酸锂熔融制成玻璃小饼。采用Lachance模式和理论a系数来校正元素间的效应,由3080E型X-射线荧光谱仪和DF-350B数据处理系统完成硅酸盐中十三个项目的测定。     

Mercury,arsenic, antimony,and selenium contents of sediment from the Kuskokwim River,Bethel, Alaska,USA

The Kuskokwim River at Bethel, Alaska, drains a major mercury-antimony metallogenic province in its upper reaches and tributaries. Bethel (population 4000) is situated on the Kuskokwim floodplain and also draws its water supply from wells located in river-deposited sediment. A boring through overbank and floodplain sediment has provided material to establish a baseline datum for sediment-hosted heavy metals. Mercury (total), arsenic, antimony, and selenium contents were determined; aluminum was also determined and used as normalizing factor. The contents of the heavy metals were relatively constant with depth and do not reflect any potential enrichment from upstream contaminant sources.     

滇东南花岗岩与锡、银、铜、铅、锌多金属矿床的成因关系

滇东南锡、银、铅、锌多金属矿床主要分布在个旧、白牛厂、都龙3个矿区,而滇东南较大的3个花岗岩体又分别出露在3个矿区或附近.花岗岩体均形成于燕山晚期,岩石化学、矿物成分相似,富含锡、银、铅、锌、钨、铜等成矿元素.矿床主金属元素组合与岩体之间的距离由远而近出现由锡、钨、(铍、铌、钽)→锡、钨、(铁)、铜、铟→锡、铅、锌、银、铟、(锑)有规律的变化.花岗岩浆是成矿物质来源和成矿热源.岩浆侵入初期使上覆地层隆起产生背斜(凹陷部位成向斜);同时使地层产生一系列裂隙、压性断层或层间断裂;岩浆侵入晚期,这些断层再次活动,表现为张性,岩浆产生的含矿热液沿由其活动所造成的断裂迁移、充填、交代、沉淀而形成矿床.     

岩石密度和超高压岩石折返速率

在常温常压条件下对中国大陆科学钻CCSD主孔100-3000米岩心样品进行了密度测量,建立了密度连续剖面,并界定了不同超高压岩石的密度值。通过对比高温高压物性实验资料,岩石密度随着退变程度增强而降低,榴辉岩密度变化序列为3.52g/cm3→3.49g/cm3→3.07g/cm3→2.93g/cm3。超高压长英质岩石密度变化序列为3.00g/cm→2.80g/cm3→2.65g/cm3。上述实验资料是讨论不同折返阶段岩石所受浮力的基础,为研究折返速率大小提供了基本参数。本文通过折返板块运动平衡时,上浮力与粘滞力平衡这一关系式,定量研究了大陆俯冲板块的折返速率,认为密度差产生上浮力从而引起折返,温度对板块折返速率的影响最为显著;密度差大小、折返角度、折返板块大小对折返速率也有直接的影响。定量模拟分析表明,在温度高于850℃时,板块的折返速率可以超过100mm/a;当温度降至700℃时,折返速率则低于1.5mm/a。作者认为在折返早期,温度较高,板块快速折返至60-70km榴辉岩相深度;随着传导散热,温度降低,板块以较慢的速率折返至中下地壳。折返速率的估算表明,浮力是板块折返第一阶段(从>100km深部折返至<40km的中下地壳)的主要驱动力。     

Bellechester,Minnesota, USA,lagoon collapses

Bellechester, Minnesota, is a small community of approximately 155 residents located on the county line between Goodhue and Wabasha counties in southeast Minnesota's karst region. Bellechester is served by a 21-year-old wastewater treatment facility (WWTF) consisting of three waste-stabilization ponds. On 28 April 1992 six sinkholes were discovered to have drained cell 2 of the WWTF resulting in the loss of approximately 8.7×10⁶ 1 of partially treated effluent and about 600 m³ of soil into previously undetected subsurface voids of unknown dimensions. In the week following the collapse, approximately 200 water wells located within a 5-km radius of the WWTF were sampled in an after-the-fact, emergency sampling program. Twelve samples with elevated fecal coliform levels, 18 samples with nitrate-nitrogen greater than the 10 mg/1 standard, and no samples with elevated chlorides were found. However, the elevated levels could not be unambiguously attributed to the WWTF collapse. This is the third WWTF to fail by sinkhole collapse in southeast Minnesota since 1974. All three collapsed lagoons have been located in similar geomorphic and stratigraphic settings. However, at least two lagoons have collapsed in the adjacent area in northeast Iowa, and these lagoons are located at different stratigraphic positions. Twenty-two WWTFs constructed in southeast Minnesota's karst region in the last 25 years have been identified as subject to potential sinkhole collapse. An unknown but significant number of manure storage lagoons, flood control structures, etc., have also been constructed in the karst region and are at risk. Public agencies are beginning to develop plans to deal with the risk associated with existing and future waste lagoons in this environment. The critical hydrogeologic parameters that can be used to prioritize the risk of collapse at existing facilities include: (1) the lithology of the first bedrock beneath each lagoon, (2) the thickness of surficial materials between the lagoon and the bedrock surface, (3) the presence and construction of liners (seepage rate), and (4) the proximity to existing sinkholes.