聚苯醚的溴化及其对富氧性能的影响

利用亲电反应及自由基反应分别对聚苯醚进行了不同程度的溴化。测定了不同温度下对O_2和N_2的透过率及相应的玻璃化转变温度和密度。发现苯环上的溴化有利于提高O_2和N_2的透过率,而选择性基本不变。甲基上的溴化大大提高了O_2、N_2的选择性,但透过率下降较多。苯环上溴含量与Tg呈很好的线性关系,密度亦随溴含量的增加而增加。透过率与温度的关系符合Arrhenius方程。溴化后的聚苯醚其透过活化能略有下降,并计算了溴化聚苯醚的摩尔自由体积和摩尔内聚能,发现其比值越大,O_2、N_2的透过率越大。

用X-光电子能谱对热处理的四苯基铁卟啉化学修饰电极的研究

本文用XPS、DTA、和TG分析了解四苯基铁卟啉和四苯基铁卟啉化学修饰电极的热分解行为。由XPS谱图揭示了玻璃炭与四苯基铁卟啉之间的相互作用,进而阐述了经热处理的四苯基铁卟啉化学修饰电极的表面结构与电催化稳定性的关系。从四苯基铁卟啉化学修饰电极的XPS价态谱发现Fe中心离子的3d电子在电极的电催化活性中的作用。

A transglutaminase from Chinese shrimp (Fenneropenaeus chinensis), full-length cDNA cloning, tissue localization and expression profile after challenge

Transglutaminase can catalyze the cross-linking reaction between soluble clotting protein molecules from the plasma for prevention of excess blood loss from a wound and obstructing micro-organisms from invading the wound in crustaceans. A novel transglutaminase (FcTG) gene was cloned from hemocytes of Chinese shrimp Fenneropenaeus chinensis by 3' and 5' rapid amplification of cDNA ends (RACE) PCR. The full-length cDNA consists of 2972 bp, encoding 757 amino acids with a calculated molecular mass of 84.96 kDa and a theoretical isoelectric point of 5.61. FcTG contains a typical transglutaminase-like homologue (TGc domain: E-value = 1.94e-38). Three catalytic sites (Cys-324, His-391 and Asp-414) are present in this domain. The deduced amino acid sequence of FcTG showed high identity with black tiger shrimp TG, kuruma shrimp TG and crayfish TG. Transcripts of FcTG mRNA were mainly detected in gill, lymphoid organ and hemocytes by RT-PCR. RNA in situ hybridization further confirmed that FcTG was constitutively expressed in hemocytes both in the circulatory system and lymphoid organ. The variation of mRNA transcription level in hemocytes and lymphoid organ following injection of killed bacteria or infection with white spot syndrome virus (WSSV) was quantified by RT-PCR. The up-regulated expression of FcTG in shrimp lymphoid organ following injection of bacteria indicates that it is inducible and might be associated with bacterial challenge. (c) 2006 Elsevier Ltd. All rights reserved.

Benthic foraminifera and bottom water evolution in the middle-southern Okinawa Trough during the last 18 ka

A piston sediment core E017 from the middle-southern Okinawa Trough was investigated. A preliminary study of the deep-water evolution since 18 cal. ka BP was performed based on the quantitative census data of benthic foraminiferal fauna, together with planktonic foraminiferal oxygen and carbon isotope, AMS(14)C dating, and the previous results achieved in the southern Okinawa Trough. The result shows that the benthic fauna was dominated by Bulimina aculeata (d'Orbigny), Uvigerina peregrina (Cushman), Hispid Uvigerina and Uvigerina dirupta (Todd) during the glaciation-deglaciation before 9.2 cal. ka BP, while Epistominella exigua (Brady), Pullenia bulloides (d'Orbigny), Cibicidoides hyalina (Hofker), Sphaeroidina bulloides (d'Orbigny) and Globocassidulina subglobosa (Brady) predominated the fauna in the post-glacial period after 9.2 cal. ka BP. The benthic foraminifera accumulation rate (BFAR), paleoproductivity estimates and benthic foraminiferal assemblage conformably indicate that surface water paleoproductivity and organic matter flux during the glaciation-deglaciation were higher than those of the post-glacial period in the middle-southern Okinawa Trough, and gradually enhanced from the southern to the central Okinawa Trough during the glaciation-deglaciation, which could be caused by the discrepancy of the terrigenous nutrients supply. High abundances of E exigua, an indicator of pulsed organic matter input, after 9.2 cal. ka. BP may indicate that the intensity of seasonally riverine pulsed flux during the post-glacial period was stronger than that of the glaciation-deglaciation period, and the seasonal influx in the central trough might be stronger than in the south. The temporal distributions of the typical species indicating bottom water oxygen content and ventilation condition show that the ventilation of the bottom water during the post-glacial period is more active than the glaciation-deglaciation, which reflects that the evolution of the intermediate and deep waters of the northwestern Pacific during the last glaciation has no evident influence on the deep-water of the middle-southern Okinawa Trough. Additionally, the variations in agglutinated benthic foraminiferal abundance and other carbonate dissolution proxies indicate that carbonate dissolution gradually increased since the last 18 ka in the Okinawa Trough and rapidly enhanced at 9.2 cal. ka BP. The modern shallow carbonate lysocline could form at 3 cal. ka BP.

Recent 2000-year geological records of mud in the inner shelf of the East China Sea and their climatic implications

AXIS(14)C dating and grain-size analysis for Core DD2, located at the north of the Yangtze River-derived mud off the Zhejiang-Fujian coasts in the inner shelf of the East China Sea, provide us a high-resolution grain-size distribution curve varying with depth and time. Data in the upper mud layer of Core DD2 indicate that there are at least 9 abrupt grain-size increasing in recent 2000 years, with each corresponding very well with the low-temperature events in Chinese history, which might result from the periodical strengthening of the East Asian Winter Monsoon (EAWM), including the first-revealed maximum temperature lowering event at around 990 a BP. At the same time, the finer grain size section in Core DD2 agrees well with the Sui-Tang Warming Period (600-1000 a AD) defined previously by Zhu Kezhen, during which the climate had a warm, cold and warm fluctuation, with a dominated cooling period of 750-850 a AD. The Little Ice Age (LIA) can also be identified in the core. It starts around 1450 a AD and was followed by a subsequent cooling events at 1510, 1670 and 1840 a AD. Timing of these cold events revealed here still needs to be further verified owing to some current uncertainty of dating we used in this study.

The sedimentation rates in the Okinawa trough during the Late Quaternary

On the basis of accelerator mass spectrometer radiocarbon (AMS C-14) dating, sedimentation rates of 11 cores collected from the northern to southern Okinawa Trough are discussed. The sedimentation rates in the Okinawa Trough roughly range from 11 to 39 cm/ka, and the average is 23.0 cm/ka. China's continental matter is the main sediment source of the middle Okinawa Trough and has important contribution to the northern and southern Okinawa Trough. The sedimentation rates during the marine oxygen isotope (MI5) 2 are uniformly higher than those during MIS 1 in the northern and middle Okinawa Trough while they are on the contrary in the southern Okinawa Trough. Sedimentation rates in the Okinawa Trough can be one of the proxies of sediment source and an indicator of cooling events.

The history of the Yangtze River entering sea since the last glacial maximum: a review and look forward

This review paper provides a brief review on the development of ideas in the fields of the sea level change of the ECS (East China Sea), the history of the Yangtze River entering the sea and paleochannels in the shelf of the ECS since the Last Glacial Maximum (LGM). The paper summarizes two opposite theories about the Yangtze River entering the sea during the LGM. One theory is that the Yangtze River input a lacustrine in the north of Jiangsu province which was defunct in middle Holocene, and the river was once dry. The other was that the Yangtze River still existed and entered into the Okinawa Trough during the LGM, but scholars share different opinions on which course the river ran across and which place the river input the trough. This paper concludes future work is to study the evolution of the Yangtze River and the paleoclimate and the corresponding events as a whole from the view of regional and even global change, and more attention should be paid to the study on mud sediment, the Yangtze River's response to the changes in climate and sea-level, and the channel metamorphosis.

Radiolarian fauna in surface sediments of the northeastern East China Sea

Radiolarian abundance and species composition have been determined in 72 surface: sediment samples from the northeastern East China Sea. The results are compared with chemical and physical properties of the overlying water masses, and with sediment conditions. In the study area, radiolarian abundance and species number increase markedly from northwest to southeast, and their distributions can be divided into three provinces: the low-density zone corresponding to the shelf, the middle-density zone corresponding to the western slope of the Okinawa Trough and the high-density zone corresponding to the central part of the Okinawa Trough. The distribution of radiolarians correlates well with modem sea surface temperature and sea surface salinity, but shows a negative relation with nutrients and primary productivity of the overlying water. This distribution pattern is also strongly affected by the sediment type and terrigenous material input. Also, the Kuroshio Current has an important effect on controlling the distribution and species composition of radiolarian fauna in this area. Based on three Q-mode factors (accounting for 90.2% of the variance), three radiolarian assemblages have been distinguished, and their distributions are clearly correlated with oceanographic current patterns in the region. The mixed water assemblage dominated by Tetrapyle circularis, Tetrapyle quadriloba and Ommatartus tetrathalamus tetrathalamus is restricted to the area of the Mixed Water, but mainly influenced by the Shelf Water. The Kuroshio Water assemblage, which is dominated by Lithelius minor, Dictyocoryne profunda, Stylodictya multispina, Acrosphaera spinosa, Dictyocoryne truncatum, Spongaster tetrars, Stylodictya arachnia and Ommatartus tetrathalamus tetrathalamus, is basically controlled by the Kuroshio Surface Water. And the transition assemblage dominated by Tetrapyle quadriloba and Monozonium pachystylum is associated with the Tsushima Warm Current Water. The boundaries among these assemblages approximately coincide with the oceanographic front. And the changes in the distribution of these assemblages could be,regarded as-not only modifications of the water masses, but also indicators of the possible movements of the oceanic front. (C) 2003 Elsevier Science B.V. All rights reserved.

Paleoceanographic records in the sedimentary cores from the middle Okinawa Trough

Two gravity piston cores (Cores 155 and 18) involved in this study were collected from the middle Okinawa Trough. Stratigraphy of the two cores was divided and classified based on the features of planktonic foraminifera oxygen isotope changes together with depositional sequence, millennium-scale climatic event comparison, carbonate cycles and AMS(14)C dating. Some paleoclimatic information contained in sediments of these cores was extracted to discuss the paleoclimatic change rules and the short-time scale events presented in interglacial period. Analysis on the variation of oxygen isotope values in stage two shows that the middle part of the Okinawa Trough may have been affected by fresh water from the Yellow River and the Yangtze River during the Last Glacial Maximum (LGM). The oxygen isotope value oscillating ranges of the cores have verified that the marginal sea has an amplifying effect on climate changes. The delta(13)C of benthic foraminifera Uvigerina was lighter in the glacial period than that in the interglacial period, which indicates that the Paleo-Kuroshio's main stream moved eastward and its influence area decreased. According to the temperature difference during the "YD" period existing in Core 180 and other data, we can reach the conclusion that the climatic changes in the middle Okinawa Trough area were controlled by global climatic changes, but some regional factors had also considerable influence on the climate changes. Some results in this paper support Fairbanks's point that the "YD" event was a brief stagnation of sea level rising during the global warming up procession. Moreover, the falling of sea level in the glacial period weakened the exchange between the bottom water of the Okinawa Trough and the deep water of the northwestern Pacific Ocean and resulted in low oxygen state of bottom water in this area. These procedures are the reasons for carbonate cycle in the Okinawa Trough area being consistent with the "Atlantic type" carbonate cycle.

Benthic foraminiferal distribution in surface sediments along continental slope of the southern Okinawa Trough: dependance on water masses and food supply

Benthic foraminiferal analysis of 29 samples in surface sediments from the southern Okinawa Trough is carried out. The results indicate that benthic foraminiferal abundance decreases rapidly with increasing water depth. Percentage frequencies of agglutinated foraminifera further confirm the modem shallow carbonate lysocline in the southern Okinawa Trough. From continental shelf edge to the bottom of Okinawa Trough, benthic foraminiferal fauna in the surface sediments can be divided into 5 assemblages: (1) Continental shelf break assemblage, dominated by Cibicides pseudoungerianus, corresponds to subsurface water mass of the Kuroshio Current; (2) upper continental slope assemblage, dominated by Cassidulina carinata, Globocassidulina subglobosa, corresponds to intermediate water mass of the Kuroshio Current; (3) intermediate continental slope assemblage, dominated by Uvigerina hispida, corresponds to the Okinawa Trough deep water mass above the carbonate lysocline; (4), lower continental slope - trough bottom assemblage, dominated by Pullenia bulloides, Epistominella exigua and Cibicidoides hyalinus, corresponds to deep water mass of the Okinawa Trough; and (5) trough bottom agglutinated assemblage, dominated by Rhabdammina spp., Bathysiphon flavidus, corresponds to I strongly dissolved environment of the trough bottom. The benthic foraminiferal fauna in the southern Okinawa Trough are controlled jointly by water masses and food supply. Water temperature, oxygen concentration and carbonate dissolution of the water masses are important controlling factors especially for the continental shelf break and trough bottom assemblages. The food supply also plays an important role in these benthic foraminiferal assemblages along the western slope. of the Okinawa Trough. Both the abundance and the 5 assemblages of benthic foraminifera correspond well to the organic matter supply along the continental slope and a lateral transport of TSM (total suspended matter) and POC (particulate organic carbon) from the shelf break to the deep water is also an important food supply for benthic fauna in this region.

A broad deglacial delta C-13 minimum event in planktonic foraminiferal records in the Okinawa Trough

The equatorial Pacific upwelling zone has been suspected of playing an important role in the global atmospheric CO2 changes associated with glacial-interglacial cycles. In order to assess the influencing scope of the surface water deglacial delta(13)C minimum in the tropical low-latitude Pacific, the core DGKS9603, collected from the middle Okinawa Trough, was examined for 4513 C records of planktonic foraminifera N. dutertrei and G. ruber. The planktonic foraminiferal delta(13)C records show a clear decreasing event from 20 to 6 cal. kaBP., which is characterized by long duration of about 14 ka and amplitude shift of 0.4 x 10(-3). Its minimum value occurred at 15.7 cal kaBP. The event shows fairly synchrony with the surface water deglacial delta(13)C minimum identified in the tropical Pacific and its marginal seas. Because there is no evidence in planktonic foraminiferal fauna and 45180 records for upwelling and river runoff enhancement, the broad deglacial delta(13)C minimum event in planktonic foraminiferal records revealed in core DGKS9603 might have been the direct influencing result of the deglacial surface water of the tropical Pacific. The identification for the event in the Okinawa Trough provides new evidence that the water evolution in the tropical low-latitude Pacific plays a key role in large regional, even global carbon cycle.

Heinrich event imprints in the Okinawa Trough: evidence from oxygen isotope and planktonic foraminifera

Planktonic foraminiferal faunas, oxygen isotope and modern analog technique sea surface temperature records were obtained in piston core DGKS9603 (28degrees08.869'N, 127degrees16.238'E, water depth 1100 in) collected from the middle Okinawa Trough. During the last glaciation, four cold events were identified and correlate Heinrich events (HE) H2-5 of the last 45 ka. During the last deglaciation, core DGKS9603 has begun to be influenced by the Kuroshio since about 16 cal ka BP. Three weakenings of this warm current occurred at about 2.8-5.3, 11.4 and 15.5 cal ka BP respectively. Among the three fluctuations, the oldest one is synchronous with HE1 and could be a response to the strong cooling observed in the North Atlantic Ocean. The fluctuation occurring at about 11.4 cal ka ago corresponds to the Younger Dryas within the age error bars. Our observations provide new evidence that the HEs documented from Greenland and the northern North Atlantic had a global climatic impact. Changes in the intensity of the East Asian monsoon could be the main mechanism responsible for the paleoccanographic variations observed in the Okinawa Trough. (C) 2001 Elsevier Science B.V. All rights reserved.

The paleoclimatic events and cause in the Okinawa Trough during 50 kaBP

Planktonic foraminiferal delta O-18 record for core DGKS9603 from the Okinawa Trough shows a series of climatic fluctuations and sudden cooling events in short time scale during 50 kaBP, which appear to correlate closely to the Younger Dryas and Heinrich events H1-5 recorded in Chinese loess, the South China Sea, the North Atlantic cores and the Greenland ice cores. Three polarity reversal events, correlating to Gothenburg, Mungo and Laschamp events, approximately correspond to Heinrich events H1, H3 and H5 respectively, which could be a cause of global climate changes. The delta O-18 curve of the Okinawa Trough is well associated with the grain size record of the Lijiayuan loess profile in northwestern China and is somewhat different from the climate fluctuations documented in the Greenland ice cores. These correlation results indicate that regional factors play an important role in controlling the climate changes in the East Asia, and the East Asian Monsoon could be the prominent regional controlling factor.

Millennial-scale paleoceanography in Okinawa Trough during Late Quaternary period

Based on the analyses of foraminifer and accelerator mass spectrometer radiocarbon dating in DGKS9603 core from mid-Okinawa Trough close to bottom, oscillation curve, which expressed the relation between the surface water temperature and the depth, has been obtained by using foraminifer analysis and calculation of FP-12E transfer function. The whole core indicated seven cold phases and eight warm phases. Obvious expression of low temperature event during Middle and Late Holocene, YD,H1,H2,H3 and H4 events, as well as the short cold phase during the middle last glacial period, implied that short shifts since 50 kaBP would have been global significance. Sedimentation rate during cold phases is usually faster than that in warm stages, with the lowest rate in Holocene, which may be connected with rising sea level and principal axial of Kuroshio Current moving to west. Volcanic activities highly developed in Okinawa Trough during the Quaternary period, thus abundant volcanic glass and pumice were well preserved.

长江口水域富营养化的形成、演变与特点研究

本文以我国长江口水域富营养化为研究对象，对长江水体溶解态无机氮、磷分布特点和通量变化进行了分析，基于长江流域氮“输入-输出”关系模型探索了水体氮的来源；分析了长江口水域富营养化长期演变及特点；探索了长江口海域低氧区的发生机制。结果如下： 长江水体中NO3--N、NH4+-N、DIN和DIP浓度从上游往下游呈增加趋势，但存在季节差异。长江流域从上游往下游的DIN输送通量的变化主要受水流量的影响，但从上游往下游单位面积年产N量逐渐升高；DIP输送通量从上游往下游呈增加趋势，同时也主要受水流量控制，但从季节变化来讲，DIP的月输送通量受其浓度的控制更加明显。自20世纪60年代来，长江水体中NO3--N、NO2--N、DIN和DIP浓度都处于缓慢上升趋势，但到80年代上升速度明显加快；不同历史时期DIN和DIP的季节变化特点也不尽相同，反映出其来源的差异。同时，本研究采用长江流域氮“输入-输出”关系模型（污染负荷统计模型）对长江水体氮来源进行了分析，估算了各种氮源对水体氮的贡献率。结果表明，2006年向长江流域输入氮的总量为17.6 Tg，其中20%的输入氮转移到了水体（3.5 Tg）。本年度长江大通水文站实测氮输送通量为1.8 Tg，表明约50%的氮在水体输送过程中发生了生物、化学、物理损耗。对于长江水体氮的来源来讲，饲养牲畜粪便氮流失和大气干/湿沉降氮的贡献率较大，分别为26%和25%；农业氮肥流失和城市生活污水排放的贡献率相同，都为17%；农村人口粪便氮流失和工业废水排放的贡献率分别为6%和9%。 自20世纪60年代以来，长江口口门内和外海（盐度>30psu）水体中营养盐浓度增加显著。在表层水体盐度大于22psu海域DIN: PO43--P值表现出了明显升高的历史变化趋势。SiO3: PO43--P值从1959年到1985-86年显著下降，然后到2003-06年有所上升。根据SiO3: PO43--P值和DIN: PO43--P值的长期变化趋势，可以推出，SiO3: DIN值从20世纪50-60年代以后呈现下降趋势。在长江口海域，随着营养盐浓度的增加，浮游生物量的大幅度升高在本研究中得到证实。同时，长江口水域浮游植物种群结构对营养盐结构的长期变化产生响应，研究结果表明，硅藻种类比重从1985-86年84.6% 下降到2004-05年69.8%；年均硅藻丰度占浮游植物总丰度比重在1985-86年达到99.5%，但到2004-05年降低为75.5%，而甲藻丰度比重则由0.7%增大到25.4%。 底层水体DO浓度与Delta S（底层水体与表层水体的盐度之差）和Delta T（表层水体与底层水体的温度之差）成显著负相关，这表明了水体层化或者垂直水体交换是控制长江口水域底层水体溶解氧变化的主要因素，但水体温度层化要比盐度层化在控制低氧区形成上起到更大的作用。上升流在该海域低氧的形成和分布上起到很重要的作用，显著影响低氧水团的垂直分布，也显著影响到溶解氧的水平分布。现场生产的浮游植物可能是低氧区的形成的生物基础，日益增加的叶绿素a浓度和大规模的有害藻华可能是长江口低氧区逐渐增大的原因。本研究认为，此海域低氧区的形成主要受长江冲淡水、台湾暖流的入侵、地形、尤其是温跃层的形成和现场生产的有机物质控制。