海水中钚的分析方法

一、引言自原子能时代开始以来,超铀元素得到广泛地应用,它们通过各种途径,以不同的速度进入海洋。由于核试验的大气散落,已经有12.0±1.3PBq的钚进入生物圈,其中大部分进入海洋。钚的半衰期很长,在海洋中的物理化学状态也比较复杂,将来它还可能成为增殖反应堆的燃料,所以人们对它在海洋中的浓度分布、迁移变化和最后的归宿愈来愈感兴趣。     

海带雌性配子体克隆细胞的超低温保存实验

生物种质资源保存的超低温冷冻保存技术在国内外已进行了广泛的研究[1],在藻类种质保存工作方面,绿藻、硅藻、蓝藻[2~6]以及紫菜[7~9]的超低温保存工作也取得了良好的进展.海带配子体(克隆)是一种以有丝分裂方式进行细胞增殖的微小藻体,并可通过两性生殖或单性生殖发育成大型叶状体.     

大亚湾海洋沉积物的人工放射性核素

对大亚湾核电站邻近海的海洋沉积物中人工放射性核素~(144)Ce,~(103)Ru,~88Rn,~(85)Sr,~(90)Sr,~(134)Cs,~(137)Cs,~(124)Sb,~(54)Mn,~(60)Co进行了调查研究;得到核素的区域变化规律和与沉积物性质的相互关系,以及获得各核素的分配系数(K_d)。     

热带不稳定波的年际变化及其与ENSO的关系

使用最优插值的1/4?逐日海温再分析资料(NOAA OISST V2.0)逐日海温资料研究了热带不稳定波(TIWs)的年际变化特征及其与厄尔尼诺与南方涛动(ENSO)的关系。结果表明:TIWs一般在每年的5~7月开始出现,在11~12月末或次年1月末消亡。TIWs和ENSO存在负相关关系,即在ENSO暖位相年(厄尔尼诺年),TIWs强度减弱;在ENSO的冷位相年(拉尼娜年),TIWs强度增强。进一步分析表明,在TIWs活跃的6~12月,其与ENSO存在很好的负相关,且相关性在12月最好。对TIWs和尼诺3.4区指数(NINO 3.4)海表面温度距平(SSTA)进行超前滞后相关分析,发现在TIWs超前ENSO 2~3个月时两者的相关性最显著,这意味着TIWs可能对ENSO循环具有调控作用。     

壳聚糖硫酸酯金属配合物的抗氧化活性

以吩嗪硫酸甲酯-NADH为超氧阴离子自由基(O_2~(·-))产生、检测体系和EDTANa_2-Fe(Ⅱ)-H_2O_2为羟自由基(~·OH)产生、检测体系,对壳聚糖硫酸酯铜、锌配合物和不同分子质量壳聚糖进行了抗O_2~(·-)和~·OH自由基的活性研究.结果表明,壳聚糖硫酸酯金属配合物对于O_2~(·-)自由基的清除能力明显高于壳聚糖,在质量浓度为0.025 g/L时,壳聚糖硫酸酯铜配合物对O_2~(·-)自由基的清除能力达到94.18%,壳聚糖硫酸酯锌配合物达到93.19%;壳聚糖硫酸酯铜、锌配合物对~·OH自由基的清除能力(67.39%、60.46%)低于相同分子质量的壳聚糖(88.06%),而高于高分子质量壳聚糖761 ku(18.71%);壳聚糖分子质量大小对O_2~(·-)和~·OH自由基的清除能力有较大影响,质量浓度为1.6 g/L壳聚糖分子质量为20 ku时,对O_2~(·-)清除率达54.69%,而分子质量在761 ku时,对O_2~(·-)清除率仅为35.50%;各样品对O_2~(·-)和~·OH自由基的清除能力均随着质量浓度的增加而上升,壳聚糖硫酸酯铜、锌配合物在相当低的浓度下(0.025 g/L)就可以达到明显清除O_2~(·-)自由基的效果(≥90%).     

青岛近海悬浮物含量及吸附性能研究

海洋中的大量微细悬浮物,由于其表面积很大,所以有很强的吸附效应,它们对于微量元素(包括放射性核素)在海洋中的转移过程起着非常重要的作用。悬浮物中的无机组份对海水中各种微量元素的吸附,国内外曾进行了一些研究,但对放射性核素的吸附性能研究得比较少。为了进一步探讨青岛近海的自净能力,我们对该海区的悬浮物含量、组成及吸附性能进行了调查、研究。本次着重调查研究了长寿命裂变产物~(90)Sr,~(137)Cs,~(106)Ru及感生同位素~(60)Co在海水和天然悬浮物之间的分配情况,并用~(137)Cs,~(60)Co两种示踪剂对悬浮物的吸附性能进行了研究。     

加速器质谱计在地球科学中的应用^＊

加速器质谱计是近十年来迅速发展起来的超高灵敏同位素分析技术,灵敏度可达10~(-15),它所需要的样品量极少,仅毫克量级.它已成功地测量了~(14)C、~(10)Be、~(36)Cl、~(26)Al、~(129)l~(41)Ca等宇宙成因核素,而这些核素作为示迹剂或测年计在地质、海洋、环境和考古等多学科的研究中得到广泛的应用.本文是综合评述该方法应用于地球科学所取得的成果、前景和目前尚存在的困难.     

天然气水合物赋存区甲烷渗漏活动的地球化学响应特征

综述了天然气水合物赋存区甲烷渗漏活动的地球化学响应指标的研究进展,分析了应用单一指标识别甲烷渗漏活动各自所存在的问题,包括浅表层沉积物孔隙水中CH_4、SO_4~(2–)、Cl~–等离子浓度随深度的变化;浅层沉积物全岩W_(TOC)(W表示质量分数,TOC表示总有机碳)和W_(TS)(TS表示总硫)之间的相关性及比值;自生碳酸盐岩δ~(13)C和δ~(18)O;自生矿物重晶石、黄铁矿、自生石膏的δ~(34)S;有孔虫壳体和生物标志化合物的δ~(13)C等。结果表明孔隙水中的CH_4、SO4_~(2–)浓度及溶解无机碳的碳同位素组成可以用来识别目前正在发生的甲烷渗漏活动;而沉积物中的WTS、自生矿物的δ~(34)S、钡含量及其异常峰值和生物标志化合物的δ~(13)C等指标的联合使用可以更真实准确地反映地质历史时期天然气水合物赋存区的甲烷渗漏活动。因此,在实际研究过程中,可将孔隙水和沉积物两种介质的多种指标相结合。随着非传统稳定同位素(Fe、Ca、Mg等)和沉积物氧化还原敏感元素(Mo、V、U等)等研究的发展,甲烷渗漏活动地球化学响应指标的研究也将得到拓展,而多种地球化学指标的联合使用将为天然气水合物勘探及其形成分解过程识别研究提供重要的科学依据。     

海水对近岸沉积物中放射性同位素~(90)Sr(~(85)Sr)、~(137)Cs、~(60)Co及~(106)Ru的解吸性能研究

本文应用同位素示踪和γ能谱测定方法,就海水对近岸沉积物中放射性同位素~(90)Sr(~(85)Sr)、~(137)Cs、~(60)Co及~(106)Ru的解吸性能进行了初步研究。海水对沉积物中四种同位素解吸性能的变化顺序为~(90)Sr(~(85)Sr)>~(106)Ru>~(60)Co>~(137)Cs,沉积物吸附的~(90)Sr(~(85)Sr)易被海水解吸,而~(137)Cs和~(60)Co则易被沉积物吸附固定。     

中国东海及邻近大洋表层海水中的~(90)Sr含量

在海洋放射性污染研究中,~(90)Sr的调查占有重要的位置。尤其在七十年代之前,许多从事海洋研究的国家都开展了这项工作。其主要原因:(1)~(90)Sr是核爆炸的裂变物质;(2)它是亲骨性核素,毒性很大;(3)存在时间和人的寿命相近;(4)在研究水体运动中是良好的示踪剂。七十年代之后,美、苏等国在大气层中的核武器试验大大减少,海洋中~(90)Sr分布的研究工作也有所削弱。但是,许多国家仍然保留了这个核素的调查,其原因一方面是因为~(90)Sr仍然存在于海洋中,大气沉降还在继续。另一方面,还有一些国家仍在进行新的核装置试验     

Plutonium in intertidal coastal and estuarine sediments in the Northern Irish Sea

Surface intertidal sediments from 35 sites in the Irish Sea have been analysed for their ²³⁸Pu and ^239,240Pu activities, together with an intensive study of plutonium in sediments of the Esk Estuary (NW England). The range of plutonium activities for the whole survey were 0·14–4118 and 1·3–16 026 Bq kg⁻¹ for ²³⁸Pu and ^239,240Pu, respectively. The levels of Pu activity, derived from the Sellafield nuclear fuel reprocessing effluents, in sediments are controlled by lithological factors and the influence of transport and post-depositional processes. Grain size distribution is particularly important, the major part of plutonium activity being in the mud fraction of all sediments.The data suggest that over the Irish Sea coastline, dynamic mixing of sediment grains by reworking and resuspension and/or by dispersion in tidal currents are important in determining plutonium distributions. The exponential decrease in sediment plutonium activities away from the Sellafield source is attributed to the progressive mixing with older contaminated and uncontaminated sediments.     

239+240Pu and 238Pu in seawater,marine organisms and sediments of Taranto Gulf (Ionian Sea)

Results of the radiochemical determination of ^239+240Pu and ²³⁸Pu in seawater, plankton, marine organisms and sediment are reported. The samples were collected in the Taranto Gulf, and the data are compared with those obtained from other stations in the Mediterranean Sea. The vertical distribution of plutonium isotopes in sediments is also presented and discussed.     

Plutonium and cesium radionuclides in sediments of the Savannah River estuary

A study was made of the ²³⁹Pu, ²⁴⁰Pu, ²³⁸Pu and ¹³⁷Cs concentrations in tidal marsh sediments of the Savannah River estuary. Tidal marshes are identified as special locations for plutonium deposition because of the high biological productivity and relative stability of sediments as compared to channel sediments. The ^239,240Pu deposition averaged 3·2 mCi km⁻², which is higher than land-based fallout values of about 2 mCi km⁻². The ^239,240Pu to ¹³⁷Cs ratio was about three times higher than fallout deposition estimates, indicating a more rapid desorption of ¹³⁷Cs from sediment in the saline waters of the area.     

Content of plutonium,thorium and protactinium in sea water and recent coral in the North Pacific

The contents of plutonium isotopes (²³⁹Pu and²³⁸Pu), thorium isotopes (²³²Th,²³⁰Th and²²⁸Th) and protactinium-231 in sea water collected in the North Pacific, the East China Sea and the Japan Sea were determined. These nuclides were sequentially analyzed byα-ray spectrometry after separating them mainly with solvent extraction technique. The contents of²³⁹Pu in surface sea water ranged from 0.6 to 1.6 pCi/10001,²³⁸Pu/²³⁹Pu activity ratios being 0.2～0.7. The²²⁸Th/²³²Th activity ratios for the North Pacific waters varied between 7.6 and 30, whereas the sample from the East China Sea showed the very high value, 65. The contents of²³¹Pa are less than 6 percent of that in equilibrium with its parent²³⁵U. Furthermore, the analysis of plutonium isotopes in recent coral from Yoron Island was carried out and it was confirmed that plutonium isotopes have concentrated in recent coral with the concentration factor of about 1～2×10³.     

Evaluation of the chemical forms of plutonium in seawater

Thermodynamic considerations based on existing data from various laboratory studies of plutonium species in aqueous solution are used to predict the speciation of this radioactive pollutant in seawater. Oxidation-reduction data for plutonium suggest that Pu(VI) should be very dominant in seawater solution compared to Pu(IV), and that Pu(III) and Pu(V) should be absent. The disproportionation reactions and the alpha reduction mechanism are probably of no consequence to the oxidation state in seawater. However, the irreversible hydrolysis of Pu⁴⁺ and the associated formation of polymeric Pu(OH)₄ colloids are important mechanisms of speciation control and plutonium removal to sediments, by adsorption onto suspended matter. Stability constants for plutonium complexation with inorganic ligands in seawater suggest that Pu(VI) dissolved in seawater will be dominantly PuO₂CO₃OH⁻.The theoretical predictions of plutonium speciation and behaviour in seawater are compared to the only available data on plutonium speciation in seawater (Nelson and Lovett, 1978). Good agreement between the predictions and field observations was obtained, within the limitations imposed by the scarcity of data on this subject.     

Distribution and inventories of 90Sr, 137Cs, 241Am and Pu isotopes in sediments of the Northwest Pacific Ocean

Bottom sediments collected in the Northwest (NW) Pacific Ocean in 1997 were analysed for ⁹⁰Sr, ¹³⁷Cs, ^239,240Pu and ²⁴¹Am contents to determine their distribution patterns, inventories and sources. Enhanced inventories of ^239,240Pu and ²⁴¹Am were observed in the latitudinal belts of 10–20°N and 30–40°N, which correspond to major areas of local (tropospheric) and global (stratospheric) fallout (with a contribution from local fallout), respectively. The sediment inventory of ^239,240Pu near the Bikini Atoll exceeded its overlying water inventory, however, in the mid-latitudes, more than 70% of ^239,240Pu still remains in the water column. ²⁴¹Am inventories in sediments exceeded that of the water column for the entire NW Pacific Ocean. Higher ¹³⁷Cs and ⁹⁰Sr sediment inventories in the latitudinal belt of 30–40°N are due to global fallout, and they account for about 10% and less than 5% of the water column inventories, respectively. The observed activity ratios of ¹³⁷Cs/⁹⁰Sr, ²³⁸Pu/^239,240Pu and ²⁴¹Am/^239,240Pu in sediment were at some stations higher than the global fallout ratios due to contributions from local fallout and due to specific processes in the water column. Two end-member mixing model based on the ²⁴⁰Pu/²³⁹Pu atom ratios observed in global and local fallout yielded ∼60% contribution of the local fallout in the bottom sediments near the Bikini Atoll. The upward decrease in the ²⁴⁰Pu/²³⁹Pu atom ratios in the sediment column indicates a decrease in the contribution of local fallout to the Pu inventory with time. ²⁴¹Am and ²⁴¹Pu dating of sediment layers was utilized to explain a hiatus in sediment accumulation in the deep seafloor.     

Sedimentation and mixing rates of radionuclides in Barents Sea sediments off Novaya Zemlya

Radionuclide measurements have been conducted on sediment cores collected in 1992 in the south-eastern region of the Barents Sea, known as the Pechora Sea. Cesium-137 and ^239,24OPu activities in surface sediments are generally less than 30 Bq/kg, with the highest levels being measured in sediments off the southwestern coastline of the island of Novaya Zemlya. High correlations between both ¹³⁷Cs and ^239,24OPu and the concentration of fine (< 63 μm) particles in surface sediments indicate that much of the variance in radionuclide concentrations throughout the Pechora Sea can be explained by particle size fractionation. However, elevated activities of ¹³⁷Cs (138 Bq/kg), ⁶⁰Co (92 Bq/kg), ²⁴¹Am (433 Bq/kg), and especially ^239,24OPu (8.47 × 103 Bq/kg) were measured in one surface sediment sample from the fjord of Chernaya Bay on the southern coast of Novaya Zemlya. The source of radioactive contamination is two underwater nuclear tests conducted in Chernaya Bay in 1955 and 1957.The ²³⁸Pu/^239,240Vu activity ratio of 0.0245 in Chernaya Bay is equivalent to values measured in global fallout. The ²⁴⁰Pu/²³⁹Pu atom ratio (0.0304), measured by mass spectrometry, is much lower than values (0.18) typical of global fallout, but is consistent with ratios measured for fallout from the early (1951–1955) series of weapons tests at the Nevada Test Site. The timing of the Chernaya Bay source term, estimated from the ²⁴¹Am/²⁴¹Pu ratio, is consistent with the timing of the 1955 and 1957 underwater nuclear tests. Relatively low initial yields of ²⁴¹Pu (²⁴¹Pu/²³⁹Pu atom RATIO = 0.00 123) in these tests have resulted in relatively low ²⁴¹Am/^239,240Pu activity ratios (0.05) in recent sediments in Chernaya Bay.Radionuclide tracer profiles in cores from the Pechora Sea can be simulated using a two-layer biodiffusion model with rapid, near-homogeneous mixing in the surface mixed layer and reduced mixing in the deep layer. Lead-210 profiles are consistent with a wide range of sedimentation and mixing rates in the deep sediment layer. However, the ¹³7Cs and ^239,240Pu results further constrain the model parameters and indicate that the downward transport of radionuclides in the sediments is governed primarily by sediment mixing, with sediment burial playing a secondary role.     

Artificial radionuclides in the western Northwest Pacific (II):137Cs and239,240Pu inventories in water and sediment columns observed from 1980 to 1986

Concentrations and inventories of¹³⁷Cs and^239,240Pu were determined in sea waters and sediments columns from the western North Pacific from 1980 to 1986.The^239,240Pu/¹³⁷Cs activity ratio in the water column shows a tendency to increase from the surface (10^–3) to bottom waters (10^–1), but the ratio in sediment is within a rather narrow range (10^–2 to 10^–1), indicating more effective removal of plutonium from the water column than¹³⁷Cs. In regions south of 40N, the radionuclide inventories in the water column significantly exceed the estimated global fallout (stratospheric fallout due to the atmospheric nuclear explosion), especially in the case of^239,240Pu. These excess inventories imply that local or close-in fallout derived from nuclear explosions in the equatorial North Pacific are well-preserved and retained in the regions, despite about 20 years since the atmospheric nuclear explosion moratorium. Data suggesting lateral transport of¹³⁷Cs in surface water from north of 40N to southern regions is shown. Some data on⁹⁰Sr contents are also shown.     

Radionuclides in Arctic sea ice: Tracers of sources,fates and ice transit time scales

Arctic sea ice can incorporate sediment and associated chemical species during its formation in shallow shelf environments and can also intercept atmospherically transported material during transit. Release of this material in ice ablation areas (e.g. the Fram Strait) enhances fluxes of both sediments and associated species in such areas. We have used a suite of natural (⁷Be, ²¹⁰Pb) and anthropogenic (¹³⁷Cs, ²³⁹Pu, ²⁴⁰Pu) radionuclides in sea ice, sea-ice sediments (SIS), sediment trap material and bottom sediments from the Fram Strait to estimate transit times of sea ice from source to ablation areas, calculate radionuclide fluxes to the Fram Strait and investigate the role of sea-ice entrained sediments in sedimentation processes. Sea ice intercepts and transports the atmospherically supplied radionuclides ⁷Be and ²¹⁰Pb, which are carried in the ice and are scavenged by any entrained SIS. All of the ⁷Be and most of the excess ²¹⁰Pb measured in SIS collected in the Fram Strait are added to the ice during transit through the Arctic Ocean, and we use these radionuclides as chronometers to calculate ice transit times for individual ice floes. Transit times estimated from the ²¹⁰Pb inventories in two ice cores are 1–3 years. Values estimated from the ⁷Be/²¹⁰Pb_excess activity ratio of SIS are about 3–5 years. Finally, equilibrium values of the activity ratio of ²¹⁰Pb to its granddaughter ²¹⁰Po in the ice cores indicate transit times of at least 2 years. These transit times are consistent with back-trajectory analyses of the ice floes. The latter, as well as the clay-mineral assemblage of the SIS (low smectite and high illite content), suggest that the sampled sea-ice floes originated from the eastern Siberian Arctic shelf seas such as the eastern Laptev Sea and the East Siberian Sea. This result is in agreement with the relatively low activities of ^239,240Pu and ¹³⁷Cs and the ²⁴⁰Pu/²³⁹Pu atom ratios (∼0.18, equivalent to that in global fallout) in SIS, indicating that prior global atmospheric fallout, rather than nuclear fuel reprocessing facilities, forms the main source of these anthropogenic radionuclides reaching the western Fram Strait at the time of sampling (1999). Transport of radionuclides by sea ice through the Arctic Ocean, either associated with entrained SIS or dissolved in the ice, accounts for a significant flux in ablation areas such as the Fram Strait, up to several times larger than the current atmospheric flux in the area. Calculated fluxes derived from sea-ice melting compare well to fluxes obtained from sediment traps deployed in the Fram Strait and are consistent with inventories in bottom sediments. ²⁴⁰Pu/²³⁹Pu atomic ratios lower than 0.18 in bottom sediments from the Fram Strait provide evidence that plutonium from a source other than atmospheric fallout has reached the area. Most likely sources of this Pu include tropospheric fallout from atomic weapons testing of the former Soviet Union prior to 1963 and Pu released from nuclear reprocessing facilities, intercepted and transported by sea ice to the ablation areas. Future work is envisaged to more thoroughly understand the actual mechanisms by which radionuclides are incorporated in sea ice, focusing on the quantification of the efficiency of scavenging by SIS and the effect of melting and refreezing processes over the course of several years during transit.     

239,240Pu and137Cs in the East China and the Yellow Seas

The distribution and inventory of artificial radionuclides,^239,240Pu and¹³⁷Cs were determined in the East China and the Yellow Seas in 1987. Almost all of^239,240Pu and 50 to 80% of¹³⁷Cs in the continental shelf area are retained in the sediment column.^239,240Pu sediment inventory in the sea area is larger than the fallout input and tends to increase southwardly. This excess^239,240Pu and the lateral distribution are attributable to the supply of^239,240Pu by the Yangtze River discharge. On the contrary,¹³⁷Cs sediment inventory shows a decrease to the south, and the fact can be accounted for by the southward dispersion of fine silt particles discharged from the Yellow River. Total¹³⁷Cs inventory is smaller than the estimated fallout input, and the fact seems to indicate dispersion of¹³⁷Cs out of the shelf region. Vertical profiles of^239,240Pu and¹³⁷Cs contents in sediments differ from that of natural²¹⁰Pb, implying the effect of varied accumulation rates of the artificial radionuclides over the sediment particle mixing by benthic organisms. Apparent maximum sediment particle mixing coefficient (D _B ) calculated from the excess²¹⁰Pb profiles in stations located between the inner and outer shelves ranged from 1.4 to 8.3 cm²y^–1. ThisD _B value is higher than that in the Okinawa Trough (1.0 cm²y^–1), but lower than previously estimatedD _B value (26 cm²y^–1) in the outer shelf mud.