光强和营养盐对伪矮海链藻昼夜节律变化的影响 Ⅰ.细胞分裂、叶绿素α及活体荧光特性

于1989年1月—1989年8月采用连续培养和半连续培养方法进行了伪矮海链藻细胞分裂、叶绿素α含量和活体荧光特性与光、营养盐关系的研究。结果表明,细胞分裂、活体荧光、叶绿素α均呈现光照期的增长速率明显高于黑暗期的增长速率的日变化规律,荧光增强比则在光照期开始后或黑暗期结束时出现最高值;光强和营养盐不仅影响各指标日变化的幅度,而且还可改变荧光增强比峰值出现时间。因此,在研究细胞分裂、叶绿素α和荧光特性的昼夜节律时,必须考虑光和营养盐这两个重要因素。     

Relative molar mass distributions of chromophoric colloidal organic matter in coastal seawater determined by Flow Field-Flow Fractionation with UV absorbance and fluorescence detection

A new method for the characterization of chromophoric colloidal organic matter in seawater has been applied to samples from the Baltic Sea, Kattegatt and Skagerrak seas. Size fractionation of the sample by Flow Field-Flow Fractionation and measurement of the fluorescent and UV absorbing properties of the individual size fractions result in a relative molar mass distribution (RMM) of the optical properties. The RMM distributions have been used to estimate number and weight average relative molar masses, and polydispersity indices. At least two sources of coloured organic matter were identified from the ratio of fluorescence to UV: the Baltic surface water and the Skagerrak deep water. The dominating processes were mixing and dilution, but processes such as photo bleaching of fluorescence are also believed to be important. The RMM distribution derived from UV detection (1150–1300 Dalton) increased with increasing salinity while that derived for fluorescence (1500–1250 Dalton) decreased with increasing salinity. The specific UV absorbance taken as a proxy of the aromaticity of the chromophoric organic material showed decreasing trend with both increasing salinity and increasing UV derived weight average relative molar mass. Increasing polydispersity of the colloidal material was also observed as a function of salinity.     

High-resolution measurements of chromophoric dissolved organic matter in the Mississippi and Atchafalaya River plume regions

Chromophoric dissolved organic matter (CDOM) was measured in the spring and summer in the northern Gulf of Mexico with the ECOShuttle, a towed, instrumented, undulating vehicle. A submersible pump mounted on the vehicle supplied continuously flowing, uncontaminated seawater to online instruments in the shipboard laboratory and allowed discrete samples to be taken for further analysis. CDOM in the northern Gulf of Mexico was dominated by freshwater inputs from the Mississippi River through the Birdfoot region and to the west by discharge from the Atchafalaya River. CDOM was more extensively dispersed in the high-flow period in the spring but in both time periods was limited by stratification to the upper 12 m or so. Thin, subsurface CDOM maxima were observed below the plume during the highly stratified summer period but were absent in the spring. However, there was evidence of significant in situ biological production of CDOM in both seasons.The Mississippi River freshwater end member was similar in spring and summer, while the Atchafalaya end member was significantly higher in the spring. In both time periods, the Atchafalaya was significantly higher in CDOM and dissolved organic carbon (DOC) than the Mississippi presumably due to local production and exchange within the coastal wetlands along the lower Atchafalaya which are absent along the lower Mississippi. Nearshore waters may also have higher CDOM due to outwelling from coastal wetlands. High-resolution measurements allow the differentiation of various water masses and are indicative of rapidly varying (days to weeks) source waters. Highly dynamic but conservative mixing between various freshwater and marine end members apparently dominates CDOM distributions in the area with significant in situ biological inputs (bacterial degradation of phytoplankton detritus), evidence of flocculation, and minor photobleaching effects also observed. It is clear that high-resolution measurements and adaptive sampling strategies allow a more detailed examination of the processes that control CDOM distributions in river-dominated systems.     

Optical properties of low molecular weight and colloidal organic matter: Application of the ultrafiltration permeation model to DOM absorption and fluorescence

Cross-flow ultrafiltration (CFF) is often used to obtain separation and concentration of colloids from bulk natural water samples. Application of the ultrafiltration permeation model allows the quantitative determination of the low molecular weight material (LMW, < 1 kDa) and colloids in bulk dissolved organic matter (DOM) from measurements of time series permeate samples obtained from CFF. Detailed analysis of a Yukon River water sample shows that DOM absorption coefficient and fluorescence follow the permeation model and that the complex spectral optical properties of LMW DOM can be reconstructed from CFF data. A combination of measured and modeled data indicates that the LMW contribution to bulk DOM optical properties obtained from CFF can be grossly underestimated by the use of a low concentration factor (CF, the ratio of initial sample volume to retentate volume). Even at a relatively high CF of 19, optical properties of LMW DOM calculated from measurements of the retentate or integrated permeate would underestimate true values by 5–36%. In the Yukon River sample, LMW dissolved organic carbon represented 26% of the bulk concentration, but only 3–14% of the colored DOM was in the LMW fraction while 31–33% of bulk DOM florescence was due to LMW DOM. The contrasting optical properties of LMW and colloidal DOM support the concept that analysis of bulk DOM absorption and fluorescence properties reveals information about DOM molecular weight.     

Continuous Multi‐probe Measurements in Fastflowing Waters Using a Hydrographic Slot

Taking continuous spatiotemporal in situ measurements with multi‐probes in fast‐flowing waters/rivers can be problematic because the sensors may be damaged by high shear forces and flotsam. To protect the multi‐probe and to enable easy access for the maintenance and calibration of the sensors, a special multi‐probe holder fixed in a hydrographic slot was developed. The validation of the probe system revealed a “memory effect” at short time scales (< 10 s) within sharp gradients caused by the overflow container of the multi‐probe rack keeping the sensors submerged in the sample water. Continuously recorded data (conductivity, temperature, pH, oxygen concentration and saturation, as well as in vivo fluorescence of chlorophyll‐a) from a research cruise on board the RV ALBIS along the river Elbe (river km 309) and entering the river Saale are presented. This river stretch upstream of the city of Magdeburg to the mouth of the Saale tributary was found to have a complex physicochemical character, which is attributable to the long mixing process of water from the river Saale and the river Elbe.     

泡沫塑料吸附分离富集-电感耦合等离子体质谱法测定稀土矿石中的镓

采用电感耦合等离子体质谱法(ICP-MS)测定稀土矿石中的镓,高含量的稀土元素会造成严重的质谱干扰。本文采用聚氨酯泡沫塑料在6 mol/L盐酸介质中吸附样品溶液中的镓后,以0.5 mol/L氯化铵水浴加热解脱30 min,镓的吸附-解脱效率超过99%,稀土元素等干扰物质基本不进入解脱液中,即在富集镓的同时实现了镓与基体元素的高效分离,降低了质谱干扰。本方法检出限低(0.022μg/g),经土壤及水系沉积物标准物质验证,镓的测定值与标准值吻合(绝对偏差为0.38%~4.70%),实际稀土矿石样品的加标回收率为94.1%~100.6%,精密度(RSD)低于4%(n=12),可应用于分析一般地质样品以及稀土矿石中的镓。     

无内标-多外标校正激光剥蚀等离子体质谱法测定磁铁矿微量元素组成

激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)常用于磁铁矿原位微量元素分析,按照校正策略不同,主要分为内标法和无内标法。内标法需要用电子探针(EMPA)预先测定磁铁矿中内标元素Fe的含量,过程较繁琐,且待测元素含量会受到内标元素含量测定的影响。本文采用铁含量较高的玄武质玻璃BCR-2G、BIR-1G、BHVO-2G和GSE-1G作为外标,避免了内标元素含量的测定,建立了无内标-多外标校正LA-ICP-MS测定磁铁矿微量元素组成的分析方法。利用该方法测定了科马提岩玻璃GOR-128g和自然岩浆磁铁矿BC 28的微量元素组成以评估方法的可靠性。结果表明,科马提岩玻璃的测定结果与推荐值及前人内标法的测定值一致,多数元素的相对标准偏差RSD5%;自然岩浆磁铁矿的测定结果与推荐值相比,多数元素的RSD7%,低于前人内标法的RSD(15%)。由此说明无内标-多外标法可以实现富铁硅酸岩或磁铁矿微量元素含量的准确校正,克服了基体效应的影响。因此,无内标-多外标法是一种原位测定磁铁矿微量元素含量的快速、准确方法,具有一定的应用潜力。     

X射线荧光光谱-电子探针在中酸性火山岩鉴定中的应用

中酸性火山岩多具斑状结构,基质可见微晶状结构、隐晶状结构、玻璃质结构等,由于基质矿物颗粒多细小,常用的偏光显微镜受放大倍数的限制,很难准确鉴定矿物种属及含量,这类岩石仅依靠偏光显微镜分类命名会存在误差。本文采用X射线荧光光谱(XRF)、电子探针(EMPA)和偏光显微镜下观察相结合的方法,对中酸性火山岩进行鉴定。结果表明:对于基质呈隐晶质、显微晶质的中酸性火山岩,基质特征相似,偏光显微镜下无法确定长石、石英的含量,因此无法对岩石准确命名;再通过XRF进行主量元素分析,并对分析结果进行标准矿物QAPF双三角图解分类、TAS图解分类及李氏火山岩定量分类,对比结果显示三种分类命名方法存在差异;通过电子探针对矿物进行校验显示,QAPF及李氏火山岩定量分类图解与显微镜下鉴定相符,TAS图解与其他分析结果存在一定偏差。因此,对于中酸性火山岩准确命名,应采用多种分析方法相结合的方式,避免测试单一引起的误差。     

便携式Li-K分析仪的研制及其在锂辉石中锂的分析应用

我国锂钾主要矿产资源大多分布在西部偏远地区,其勘查找矿或综合利用迫切需要现场快速分析技术的支持。本文介绍了自行开发的便携式Li-K分析仪的主要性能及其在锂辉石中锂的分析应用。Li-K分析仪是一种基于大气压的液体阴极辉光放电光谱仪,以待测液体为放电阴极,实现了样品中Li、K等元素的原子化和激发。该仪器以光纤传导CCD光谱仪作为检测器,其波长范围为345~1015 nm,分辨率3 nm;以Li 670.78 nm和K 769.90 nm分析谱线,在仪器最佳工作条件下测定Li、K的精密度(RSD,n=14)均低于2%,检出限为0.03μg/m L,检测范围0.1~10μg/m L。研究表明,不同酸度和酸的类型对谱线强度影响较大,且存在显著的样品基体效应,标准曲线法分析锂辉石中Li的结果偏差高达267%;而标准加入法可克服基体效应的影响,获得与ICP-OES一致性较好的分析结果,为现场开展固体样品中Li的测定奠定了基础。     

熔融制样-X射线荧光光谱法测定电气石中12种主次量元素

电气石是一类含硼的铝硅酸盐矿物,化学成分复杂、化学稳定性强,不易湿法分解,B_2O_3含量较高,导致其主次量元素的同时测定存在一定困难。本文采用熔融法制样,建立了X射线荧光光谱法测定电气石Na_2O、MgO、Al_2O_3、SiO_2、P_2O_5、K_2O、CaO、TiO_2、V_2O_5、Cr_2O_3、MnO、TFe_2O_3等主次量元素的分析方法。样品与四硼酸锂-偏硼酸锂-氟化锂(质量比为4.5∶1∶0.4)混合熔剂的稀释比例为1∶10,消除了粒度效应和矿物效应;在缺少电气石标准物质的情况下,选择土壤、水系沉积物及多种类型的地质标准物质绘制校准曲线,利用含量与电气石类似的标准物质验证准确度,测定结果的相对标准偏差小于4.2%。采用所建方法测定四种不同类型电气石实际样品,测定值与经典化学法基本吻合。本方法解决了电气石不易湿法分解和硼的干扰问题,测定结果准确可靠,与其他方法相比操作简便,分析周期短。