九龙江河口区水体中238U、234Th地球化学行为的研究

对采自九龙江河口区盐度介于0～21.97的10个表层水样,铀、钍同位素的测定结果表明,九龙江河口区水体中溶解态的238U含量与盐度之间存在着良好的相关关系,其相关系数可达0.972,表明九龙江河口区水体中的238U呈现保守行为.当S=0时,溶解态234U/238U放射性比值为1.19和1.55(两份水样);而当S=0.90～21.97时,该比值=1.02～1.14,分别呈现河水及河口水铀同位素组成的特征.对于颗粒态铀,其238U含量则介于0.50～9.83×10-3Bq/dm3,且随盐度的增大而呈逐步降低的趋势.九龙江河口区水体中234Th的地球化学行为属于非保守行为,不可逆稳态清除模型计算的结果表明,当盐度介于9.76～17.07时,234Th相对于化学清除的停留时间为6～19d,远低于盐度为0和21.97所对应的停留时间(分别为203d及117d),反映了在该盐度范围内,胶体絮凝沉降对溶解态234Th的快速清除作用.     

悬浮泥沙在长江口铀非保守行为中的重要作用

利用高精度的电感耦合等离子体质谱仪对2014年1月长江口表层水中溶解铀浓度及其234U/238U比值、2013年3月长江口表层沉积物中各矿物组分的铀含量及其234U/238U比值进行了测定,研究了其空间分布特征和影响因素。结果表明:除了长江径流和海水之外,长江口还有其他的溶解铀来源。水体中过剩铀与悬浮颗粒物浓度呈现显著相关性（r2=0.96）。对长江口表层沉积物进行的序列提取实验进一步表明,水体中悬浮颗粒物或沉积物中可解吸态和碳酸钙结合态铀可以在河口区域释放进入水体,而铁锰氧化物和有机物结合铀比较稳定,不受河口区混合过程的影响。每千克颗粒物或沉积物能够释放约2 μmol颗粒态铀,使其转化为溶解态。然而,铁氢氧化物和细颗粒物的絮凝吸附作用也可使溶解铀同时从河口水体中清除。在低盐度区,铀的清除和添加过程速率相近,使溶解铀呈现暂时的"伪保守"现象:颗粒态释放的铀具有明显低的234U/238U比值,导致水体的234U/238U低于保守混合值。在中高盐度区域,溶解铀呈现明显的富集现象。但是由于水相和颗粒相中的铀交换,可释放颗粒态铀的234U/238U接近溶解铀的234U/238U比值,从而导致水体的234U/238U比值呈现出保守性。长江口颗粒物的铀释放通量为（3.48±0.41）×105 mol/a,约占输入的总颗粒态铀通量（1.80±0.17）×106 mol/a的19.3%。长江口输入东海的溶解铀总通量（河流溶解态铀与河口添加铀之和）为（2.68±0.13）×106 mol/a,约为世界河流入海铀通量的11.7%。     

厦门湾海水中不同粒级铀同位素的深度分布

于2003年3月在厦门湾一个时间系列研究站(24°25.88’N,118°04.72’E)采集了高潮时不同深度的海水,用聚碳酸酯膜分离不同粒级悬浮颗粒物(SPM),用α能谱法测定各粒级悬浮颗粒物的铀同位素,研究了海水中238U和234U的体积比活度(AV)、质量比活度(Am)、活度比值[AR(234U/238U)]及238U、234U条件分配系数的粒级与深度分布特征.研究结果揭示了以下海洋学信息:(1)各粒级悬浮颗粒物中238U、234U的体积比活度和质量比活度的深度分布均表明,这两核素的深度分布趋势一致,反映出它们地球化学行为的一致性.(2)在所研究的不同水深处,在0.2～0.4、0.4～2.0、2.0～10.0、>10.0μm等4个粒级的SPM中,238U体积比活度AV(238U)的变化范围分别为0.04±0.00～0.15±0.01、0.04±0.00～0.13±0.01、0.29±0.02～0.43±0.02、1.06±0.06～4.11±0.24 Bq/m3;AV(234U)的相应值分别为0.08±0.00～0.08±0.00、0.05±0.00～0.13±0.01、0.27±0.01～0.37±0.02、0.84±0.05～3.95±0.24 Bq/m3.(3)在所研究的4个水深处的0.2～0.4、0.4～2.0、2.0～10.0、>10.0μm等4个粒级的SPM中,238U质量比活度Am(238U)的变化范围分别为0.100±0.000～0.319±0.021、0.022±0.000～0.167±0.013、0.049±0.003～0.113±0.005、0.024±0.002～0.081±0.005 Bq/g,而Am(234U)的相应值分别为0.114±0.014～0.364±0.045、0.027±0.005～0.168±0.013、0.052±0.003～0.098±0.008、0.029±0.002～0.064±0.005 Bq/g.(4)与238U、234U体积比活度的粒级变化顺序[也就是AV(>10.0μm)AV(2.0～10.0μm)>AV(0.4～2.0μm)=AV(0.2～0.4μm)]相反,这两核素质量比活度的粒级变化顺序为Am(0.2～0.4μm)≥Am(0.4～2.0μm)>Am(2.0～10.0μm)>Am(>10.0μm)≈Am(>0.2μm).(5)溶解态铀控制着总铀的地球化学行为,而颗粒态铀的地球化学行为则受控于大粒级颗粒物.(6)表层各粒级颗粒态AR(234U/238U)值均<1.0,而溶解态铀和总铀的AR(234U/238U)值均介于1.10～1.17之间.(7)不同粒级238U的条件分配系数(Kd)介于802～11 406 dm3/kg之间,Kd值随粒径减小而增大,意味着铀更有效地与小颗粒物相结合.     

南沙海域基于234Th-238U不平衡的颗粒态有机碳输出通量研究

利用234Th-238U不平衡方法研究南沙群岛海域春季真光层颗粒动力学性质,测定了4个站位水柱中颗粒态有机碳(POC)、溶解态及颗粒态234Th和238U的含量,讨论了各站位水柱中234Th/238U)A.R.的垂直分布.运用稳态箱式模型计算各站位不同水层中溶解态234Th相对于清除至颗粒物的平均停留时间和颗粒态234Th相对于迁出作用的平均停留时间.结合POC/234ThP比值,用两种方法估算出各站位的颗粒态有机碳输出通量分别为8.51-34.94和13.28-50.06mmol·(m2·d)-1.两种方法结果一致,说明234Th是表征POC循环的良好示踪剂.     

234 Th示踪法测定北太平洋西北海域冬季真光层中颗粒态有机碳输出通量

讨论了1997年冬季在北太平洋西北海域7个站位的表层至200m水深水柱中溶解及颗粒态234Th,颗粒态有机碳(POC)、氮(PON)及叶绿素a浓度的垂直分布剖面.溶解态、颗粒态及总的234Th的放射性在真光层中显著低于母体238U的放射性,总的234Th放射性在水深大于100m时趋于平衡.利用234Th-238U在海洋表层海水中的放射性不平衡推导出了北太平洋西北海域冬季真光层海水中234Th的平均停留时间和输出通量以及颗粒态有机碳和有机氮的输出通量.在亚北极环流区溶解态234Th的停留时间为40~50d,而在黑潮-亲潮共同影响区为20d左右.颗粒态有机碳和有机氮从真光层的输出通量范围分别为3.8~8.2和0.50~0.98mmol/(m2·d),西部海区高于东部海区,南部海区高于北部海区.在黑潮-亲潮共同影响区较高的颗粒态有机碳输出通量表明光照量及陆源营养盐物质的提供是两个决定生产力的主要因素.叶绿素a的水深分布和POC/PON的值同Redfield的比值的一致性表明这个海区的冬季颗粒物主要由浮游植物构成.北太平洋西北海域在冬季的颗粒有机碳输出通量可高于世界大洋一些海区春、夏季的颗粒有机碳输出通量.     

南大洋普里兹湾基于234Th/238U不平衡法的POC输出通量研究

中国第22次南极科学考察(2005年11月至2006年3月)期间,测定了南极普里兹湾海域5个站位的从表层至150 m水深的不同层位水样中溶解态和颗粒态234Th,238U的放射性比活度以及颗粒有机碳.利用234Th/238U在上层水体中的不平衡,计算了南极普里兹湾上层水体中234Th的平均停留时间和输出通量.结果显示,随着纬度的增加,上层水体中颗粒态和溶解态234Th的平均停留时间总体趋向减小,并在中纬度站位出现了最低值,分别为1~8和29~48 d,而颗粒态和溶解态234Th的输出通量则在中纬度站位出现了最大值,分别为21~38和26~39 dpm/(m3·d).运用箱型清除模式,利用两种不同的方法估算了各水柱中从真光层底部输出的POC通量,平均值分别达到104.7 mmol/(m2·d)(E法)和120.6 mmol/(m2·d)(B法),表明南极普里兹湾夏季存在很高的新生产力,它将会对该海域碳的生物泵过程产生重要作用.     

九龙江河口区溶解态、颗粒态铀同位素的地球化学行为

对九龙江河口区枯、丰水期水体中溶解态、颗粒态铀同位素地球化学行为的研究表明,溶解态铀与盐度存在良好的正相关关系,证实枯、丰水期该河口区水体中的铀均是保守行为。在低盐度区域（Ｓ＜１０）,~２３８Ｕ主要以颗粒态形式存在,颗粒态~２３８Ｕ所占份额随盐度增加而降低。~（２３８）Ｕ之条件分配系数介于 １． ２ × １０~３～１． ５ ×１０~５ｄｍ~３／ｋｇ之间,它与盐度呈负相关关系,但与悬浮颗粒物浓度无相关关系存在。枯水期悬浮颗粒物上~２３４Ｕ／~２３８Ｕ_Ａ．Ｒ．与盐度的负相关关系为河口区悬浮颗粒物中~２３４Ｕ的优先沥取理论提供了有力的证据。     

真光层的颗粒动力学──Ⅵ.南海东北部海域上层水体颗粒动力学的示踪研究

利用234Th－238U不平衡研究南海东北部海域3个站位上层水体中的颗粒动力学性质，测定了水往中溶解态及颗粒态234Th的比活度，具体讨论各相中234Th／238U）AR（放射性活度比）比值的垂直分布情况及其与水化学要素间的关系。运用稿态箱式模型计算出各站位不同水层中溶解态234Th相对于清除至颗粒物的平均停留时间和颗粒态234Th相对于迁出作用的停留时间。由模型得出的参数表明3个站位的真光层具有两种不同的层化图像，这一情形与我们在南沙群岛海域得到的结果相一致。结合POC／PTh比值，估算出3个站位从真光层输出的颗粒有机碳（POC）通量分别为4.025.0和5．4mmolC·m－3－d-1。文中进一步讨论了234Th与POC两者停留时间的关系。     

不同潮时对厦门湾水体中234Th/238U不平衡的影响

厦门海水体中^234Th/^238U不平衡的时间序列数据表明，无论是溶解态、颗粒态^234Th还是总^234Th,相对于母体^238U均严重亏损，呈现出与开阔大洋水明显不同的特征。溶解态、颗粒态^234Th的停留时间介于0．5－41d之间，其中低潮时停留时间比高潮时小2－4倍，证实近岸海域具有强烈的清除、迁出作用，且潮汐变化对海域颗粒动力学特征有重要影响。^234Th停留时间与总悬浮颗粒物浓度（TSM）、Ch1.α的关系则表明，近岸海域元素的清除、迁出作用主要受陆源颗粒物输送的影响，与生物活动关系并不密切。此外，非稳态与稳态清除模型结果的对比证明，稳态模型对于具有强烈清除、迁出作用的近岸海域是适用的。     

中国近海沉积物中钍同位素的分布

本文对采自中国7个近岸海域的沉积物中钍(铀)同位素的分布进行了研究。发现表层沉积物中,~(230)Th/~(232)Th)_(A.R.)均小于1.0且呈均匀分布的态势。但~(230)Th/~(232)Th)_(A.R.)的数值及其深度分布特征与深海沉积物截然不同。~(230)Th/~(232)Th)_(A.R.)与水深呈良好的正相关。钍系不平衡普遍存在,其特征是~(228)Th/~(232)Th)_(A.R.)<1.0,据此推测了沉积物中可溶化学物质与上覆海水发生交换的深度。研究了沉积物中~(232)Th的含量、比度和~(232)Th/~(238)U)_(C.R.)的分布特征。从~(234)Th_(ex.)的深度分布求出秀屿站的表层混合系数(0.49×10~(-6)cm~2/s)和沉积柱中~(234)Th_(ex.)的总量。     

Size-fractionated uranium isotopes in surface waters in the Jiulong Estuary in China

Surface water was collected from the Jiulong Estuary for determination of activity concentrations of uranium isotopes in different size fractions, namely, greater than 53, 10 -53, 2 - 10, 0.4 -2 μm, 10 000 u -0.4 μm and less than 10 000 u fractions by microfihration and cross-flow uhrafiltration technologies. Results indicated that most of the dissolved uranium （ 〈 0.4 μm） exis- ted in the low molecular mass fraction （ 〈 10 000 u）, and the colloidal uranium-238 （10 000 u -0.4 μm） only contributed less than 1% of the dissolved uranium-238. The fractions of colloidal uranium in the dissolved phases decreased with the increasing sa- linity. A positive linear relationship between uranium-238 activities and salinities was observed for the dissolved, colloidal and low molecular mass fractions, indicating a conservative behavior of uranium in the Jiulong Estuary. In the particulate phases （ 〉 0.4 μm）, the partitioning of uranium isotopes among different size fractions was controlled by the partitioning of particle concentrations. In the regions with salinities below 20, the partitioning of uranium-238 among different size fractions was as follows： 10 - 53 μm 〉 2 - 10 μm 〉 0.4 - 2 μm greater than above 53 μm. However, the order at the offshore station with salinities above 30 changed as follows ： 0.4 - 2 μm 〉 10 - 53 μm 〉 2 - 10 μm greater than above 53 μm. The fraction of the 0.4 - 2 μm particles increased at the offshore station, suggesting the increased contribution of the authigenic uranium. The activity ratio of uranium-234 to uranium-238 in the dissolved phases, including the low molecular mass fraction and the colloidal fraction, was larger than unity, showing the occurrence of excess uranium-234. In contrast, the activity ratio of uranium-234 to uranium-238 in all size fractions of the particulate phase was close to the equilibrium value （1.0）. The observed different values of the activity ratio of uranium-234 to uranium-238 in the dissolved phase and the partic     

Role of colloidal material in the removal of 234Th in the Canada basin of the Arctic Ocean

The phase partitioning of ²³⁴Th between dissolved (<10-kiloDalton, kD), colloidal (10 kD—0.4 μm), and particulate (⩾0.5 μm) matter across a horizontal transect, from a coastal station to the deep Canada Basin, and a vertical profile in the deep Canada Basin of the western Arctic Ocean was investigated. Concentrations of suspended particulate matter (SPM), dissolved, colloidal and particulate organic carbon, particulate organic nitrogen and nutrients (silicate, phosphate and nitrate) were also measured to assess transport and scavenging processes.Total ²³⁴Th (colloidal+particulate+dissolved) indicated deficiencies relative to secular equilibrium with its parent, ²³⁸U in the upper 100 m, which suggests active scavenging of ²³⁴Th onto particle surfaces. In contrast, at depths >200 m, general equilibrium existed between total ²³⁴Th and ²³⁸U. The inventory of SPM and the specific activity of particulate ²³⁴Th in the Canada Basin was about an order of magnitude higher than the profile reported for the Alpha Ridge ice camp station. This higher concentration of SPM in the southwestern Canada Basin is likely derived from ice-rafted sedimentary particles. Inventories of nutrients, and dissolved organic carbon and nitrogen in the upper 100 m of the Canada Basin are comparable to the other estimates for the central Arctic Ocean. Comparison of the mass concentrations of colloidal and filter-retained particulate matter as well as the activity of ²³⁴Th in these phases indicates that only a very small component of the colloidal material is actively involved in Th scavenging. Lower values of the conditional partition coefficient between the colloidal and dissolved phase indicate that the Arctic colloids are less reactive than colloidal material from other regions. The conditional partition coefficient between the filter-retained and dissolved phases (K_f) is generally higher than that for other regions, which is attributed to the higher complexation capacity of glacio-marine sedimentary particles in these waters. The ²³⁴Th-derived export of POC for the shelf and deep Canada Basin ranges between 5.6 and 6.5 mmol m⁻² d⁻¹, and is in agreement with other estimates reported for the central Arctic Ocean and Beaufort Sea.     

The uranium content and the activity ratio234U/238U in marine organisms and sea water in the western North Pacific

The uranium content and activity ratio A²³⁴U/A²³⁸U were determined in open ocean water, marine plankton, marine algae and sea water in the environment in which plankton and algae live. The average uranium content of 3.34±0.28×10⁻⁶ g/l and the average activity ratio of 1.13±0.04 were obtained in open ocean water. The uranium contents in plankton and algae were respectively from 1.7 to 7.8×10⁻⁷ g/g and 0.4 to 23.5×10⁻⁷ g/g on dry basis with the respective concentration factors of 48 to 260 and 10 to 733. The activity ratio in plankton and algae ranged from 1.07 to 1.18 which coincided well with those in the environmental sea water.     

Precipitation of authigenic uranium in suboxic continental margin sediments from the Okinawa Trough

Concentrations of U and Th isotopes in Okinawa Trough and East China Sea sediment cores were determined by isotope dilution inductively coupled plasma-mass spectrometry (ID-ICP-MS) to investigate the behavior of redox sensitive uranium in suboxic hemipelagic sediments and determine their significance in oceanic uranium balance. ²³⁸U concentrations and ²³⁸U/²³²Th activity ratios in the East China Sea sediments showed no remarkable variation with depth. However, ²³⁸U and ²³⁸U/²³²Th ratios in the Okinawa Trough sediments were low in the surface oxidizing layer but increased where the suboxic condition was encountered. The distribution profiles of ²³⁰Th and ²³²Th concentrations were relatively constant with depth in both the Okinawa Trough and East China Sea sediment cores. These results suggested that there has been post-depositional precipitation of authigenic uranium within the suboxic Okinawa Trough sediment column. The post-depositional precipitation rates of authigenic uranium were estimated to be 47 ± 5 to >62 ± 8 ng cm⁻² yr⁻¹; these rates were comparable to those previously reported for several anoxic sediments. A mechanism controlling precipitation of uranium may be the downward diffusion of uranium U(VI), reduction to U(IV) and finally precipitation onto the solid phase. The accumulation rate of uranium for the Okinawa Trough sediments was approximately eight times higher than the world average rate reported for suboxic sediments. This removal of uranium in the oceanic budget increases the importance of the suboxic sediment sink.     

Accumulation of uranium in sediments and phosphorites on the South West African shelf

Organic-rich sediments and coexisting phosphorites from the continental shelf off South West Africa have been analysed for uranium and thiorum by alpha-spectrometry. The uranium concentrations in the sediments range from 10 to 55 ppm, with an isotopic composition close to that of sea-water, indicating that uranium is passing into the sediments at the present time. The phosphorites occur in the sediments as thin unconsolidated laminae and as lithified nodules and pellets, with uranium contents ranging from 79 to 158 ppm. Based on the uranium isotopic composition, only the unconsolidated phosphorite laminae are recent, while the lithified nodules and pellets, with ²³⁴U/²³⁸U and ²³⁰Th/²³⁴U ratios close to radio-active equilibrium, appear to be inherited from a previous period of phosphorite deposition. Deposition of uranium appears to take place predominantly by incorporation into carbonate fluorapatite growing authigenically within the sediment. Uranium accumulation rates, computed from ¹⁴C-dated sections of the sediment cores, and using only uranium values with modern isotopic composition, range from 232 to 765 μg/cm² per 1,000 years. These results stress the importance of organic-rich sediments containing authigenic phosphorite beneath areas of high organic productivity as a major sink for uranium in the ocean.     

The distributions of uranium, radium and thorium isotopes in two anoxic fjords: Framvaren Fjord (Norway) and Saanich Inlet (British Columbia)

Depth profiles of the naturally-occurring radionuclides ²³⁸U, ²³⁴U, ²²⁶Ra, ²²⁸Ra and ²²⁸Th were obtained in two diverse anoxic marine environments; the permanently anoxic Framvaren Fjord in southern Norway and the intermittently anoxic Saanich Inlet in British Columbia. Concentrations of total H₂S were over three orders of magnitude greater in the anoxic bottom waters of Framvaren Fjord compared to those in Saanich Inlet.In Framvaren Fjord, the O₂/H₂S interface was located at 17 m. While dissolved ²³⁸U behaved conservatively throughout the oxic and anoxic water columns, concentrations based on the ²³⁸U/salinity ratio in oxic oceanic waters were almost 30% lower. Dissolved ²²⁶Ra displayed a sharp maximum just below the O₂/H₂S interface, coinciding with dissolved Mn (II) and Fe (II) maxima in this zone. It is suggested that reductive dissolution of Fe-Mn oxyhydroxides remobilizes ²²⁶Ra in this region.In Saanich Inlet, the O₂/H₂S interface was located at 175 m. Dissolved ²³⁸U displayed a strongly nonconservative distribution. The depth profiles of dissolved ²²⁶Ra and ²²⁸Th correlated well with the distribution of dissolved Mn (II) in the suboxic waters above the O₂/H₂S interface, suggesting that reduction of particulate Mn regulates the behavior of ²²⁶Ra and ²²⁸Th in this region.Removal residence times for dissolved ²²⁸Th in the surface oxic waters of both systems are longer than those generally reported for particle-reactive radionuclides in coastal marine environments. In the anoxic waters of Framvaren Fjord and Saanich Inlet, however, the dissolved ²²⁸Th removal residence times are quite similar to values reported for dissolved ²¹⁰Pb in the anoxic waters of the Cariaco Trench and the Orca Basin. This implies that the geochemistries of Th and Pb may be similar in anoxic marine waters.     

Behavior of uranium in two estuaries of the southeastern United States

Soluble uranium concentrations in the Ogeechee and Savannah Rivers are 0.046 ± 0.005 and 0.026 ± 0.01 μg/l, respectively. Particulate concentrations are approximately similar in the Ogeechee River but are about four times the soluble concentration in the Savannah River. River end-member ²³⁴U/²³⁸U ratios range from 1.04 ± 0.04 to 1.08 ± 0.12. Observations suggest that uranium is removed from estuarine waters at low salinities during low discharge.     

台湾海峡铀的来源及保守性混合

Seawater samples are collected in the spring of 2013 from the Taiwan Strait for the analysis of uranium(U)concentrations and isotopic compositions using MC-ICP-MS, and the geochemical behavior patterns of U in the Taiwan Strait are then investigated. Average concentrations of individual U isotopes are(3.23±0.14) μg/kg for 238 U,(2.34±0.09)×10~(–2) μg/kg for ~(235)U and(2.05±0.07)×10~(–4) μg/kg for 234 U. Correspondingly, the U isotopic compositions are 155±18 for δ234U and 138±2 for 238U:235U. The U concentrations and isotopic ratios in the Taiwan Strait are similar to those of open ocean seawater, suggesting the dominance of the open ocean input to the strait's U pool.However, river input, as suggested by the slightly lower salinity than that of the open ocean, also affected the U concentrations and isotopic compositions in the strait. From a compilation of U concentrations in the Taiwan Strait and adjacent areas, including the Jiulong Estuary and Zhujiang Estuary, the Xiamen Bay and the northern South China Sea, a strong and significant relationship between U concentration and salinity [U:S; U=(0.093 4±0.002 4)S+(0.092 0±0.061 5)] is revealed, suggesting conservative mixing of U in the Taiwan Strait. To better understand the U geochemistry in the Taiwan Strait, a multiple endmembers mixing model is applied to estimate the contributions of potential sources. The open ocean seawater contributed 69%–95% of U in the Taiwan Strait, with river water approximately 2%, and dust deposition only around 0.13%. Therefore, the model results supported the open ocean input source and the conservative mixing behavior of U derived from the observation of U concentrations and isotopic ratios and U:S ratios. The sediment interstitial water may be an important source of U to the Taiwan Strait with a possible contribution of 3%–29%, consistent with previous investigations based on radium isotopes.However, further investigations are warranted to examine the U concentration in the sediment interstitial water and its input to the overlying seawater in the Taiwan Strait.