溶解态磷在海洋微藻碱性磷酸酶活力变化中的调控作用

在实验室批量培养条件下,测定了海洋微藻培养体系中碱性磷酸酶活力(APA)和各形态溶解磷的动态变化,分析了二者之间的关系.结果表明,在批量培养过程中,APA的动态变化呈"S"形曲线,各形态溶解磷在其变化过程中所起的调控作用不同,介质中溶解无机磷和小分子溶解有机磷的浓度是激发APA发生变化的主要调控因子,大分子溶解有机磷的浓度对APA的作用不明显,但APA的增大可加速微藻利用大分子溶解有机磷的速率.微藻的种类和丰度不影响APA的动态变化形式及其调控机理.     

气相色谱法测定沉积物中的木质素

河流和海洋沉积物样品在碱性条件下以氧化铜氧化后,用气相色谱分析氧化产物中的酚类化合物,并与木质素的酚类氧化产物进行比较和定量。对硝基苯和氧化铜作为氧化剂的实验结果进行了比较;试验了所生成的酚类化合物的毛细管柱气相色谱定量测定方法及方法的空白和重复性。     

一种手性辅助试剂C_2-对称二亚砜的合成方法研究

采用改良的Ｓｈａｒｐｌｅｓｓ氧化条件,以氢过氧化枯烯为氧化剂,成功地对二硫醚１进行了不对称氧化得到单亚砜６,其光学纯度为１００％,产率为６０％。用臭氧将单亚砜６进一步氧化,以３６％的产率和１００％ｅｅ得到Ｃ２对称二亚砜７,从而建立了合成Ｃ２－对称二亚砜７手性辅助试齐的有效方法。     

海洋褐藻胶生产废水的絮凝-氧化处理研究

使用新型高效的絮凝剂Xp，对海洋褐藻胶生产废水进行絮凝，催化氧化处理试验，确定了絮凝剂Xp的最佳使用条件，催化氧化时间和氧化剂用量，结果表明，经本工艺处理后，废水中主要污染物CODcr的去除率达到83．9％，处理后的废水基本达到国家《污水综合排放标准》（GB8978－1996）限定的二级标准。     

絮凝-CO2曝气-催化氧化处理制革废水研究

使用新型高效的絮凝剂MF,对制革废水进行絮凝吸附、CO2曝气、催化氧化回用处理试验,确定了絮凝剂MF的最佳使用条件、催化氧化时间和氧化剂用量.结果表明,制革废水经工艺处理后,对废水中主要污染物CODCr、S2-、Cr3+、SS、色度的去除率分别达到78.9%、97.5%、95.5%、91.4%、96.5%.处理后的废水基本达到鞣铬工艺用水要求和国家<污水综合排放标准>(GB8978-1996)限定的二级标准.     

海洋环境中氧化还原敏感性微量元素的地球化学行为及环境指示意义

依据国内外最新研究成果,初步讨论了氧化还原敏感性微量元素(RSE)Re、Cd、Mo、U、V等的地球化学行为,其中包括海洋沉积物中RSE的来源、RSE在缺氧和无氧海区的沉淀富集机理及其环境指示意义。在此基础上讨论了利用RSE研究氧化还原环境时应注意的一些问题。RSE的沉淀富集机制不尽相同,但具有以下共同特点:①对底层海水的溶解氧浓度敏感。在正常溶解氧条件下,氧化还原敏感性微量元素在海水中呈溶解态稳定存在,而当底层海水处于缺氧或无氧条件时容易发生还原。②当底层海水处于缺氧或无氧条件时,经过沉积物—海水界面过程,受缺氧程度不同的制约,海水中呈溶解态的RSE依次在沉积物中沉淀,出现不同程度的富集。③持续还原条件下,RSE在沉积物中稳定存在;受氧化作用后,容易在沉积物中发生二次迁移和重新富集。不同的RSE其氧化还原电位不同,在氧化还原序列中的位置不同,Re在U之后Mo之前发生还原。因此,RSE在海洋沉积物中的不同富集特征和富集程度可作为还原程度指标研究底层海水的缺氧程度和底质的氧化还原环境。研究RSE的氧化还原环境指示意义,必须对RSE陆源碎屑来源组分进行剔除,同时,还应充分注意到还原沉积区发生氧化后,RSE在沉积物中会发生重新迁移和二次富集。     

不同类型含磷营养物质对微小亚历山大藻(Alexandrium minutum)生长和毒素产生的影响

采用显微镜细胞计数和麻痹性贝毒的高效液相色谱分析方法,通过对比磷酸二氢钾、磷酸甘油和三磷酸腺苷（ATP）等含磷营养物质对微小亚历山大藻生长和毒素产生的影响,研究了微小亚历山大藻对不同类型含磷营养物质的利用情况.结果表明,在磷限制条件下,加入磷酸二氢钾、磷酸甘油和ATP均能促进微小亚历山大藻的生长,所获得的最大藻细胞密度分别为22700、28400和27800藻细胞/ml,对数期生长速率分别为0.12/d、0.14/d和0.15/d,溶解态有机磷对藻生长的促进作用稍好于溶解态无机磷.三种含磷营养物质对毒素产生的效应没有明显差别,稳定期藻细胞毒素含量分别为22.87、23.98和21.80fmol/cell.磷限制对毒素组成的影响很大,磷限制条件下膝沟藻毒素GTX1/4的含量占绝对优势,GTX2/3含量很少.在添加含磷营养物质后,GTX1/4所占比例降低,GTX2/3比例增加,说明磷限制显著改变了微小亚历山大藻的毒素组成.对藻体碱性磷酸酶活性分析的结果显示,磷限制组具有最高的碱性磷酸酶活性,添加有机磷化合物实验组的碱性磷酸酶活性显著高于添加无机磷化合物的实验组.研究结果表明,微小亚历山大藻可以利用实验中采用的无机磷化合物和有机磷化合物,但其利用溶解态有机磷化合物的机制尚不清楚,可能是通过诱导合成碱性磷酸酶来水解培养基中的溶解态含磷有机物,从而释放无机磷酸盐用于藻细胞的生长.     

锰细菌对锰、铁金属离子的转移作用

本文报道了锰细菌对锰的氧化和铁的氧化还原作用的实验结果.在好氧的条件下锰细菌能使可溶性的Mn2+氧化为Mn4+.在锰细菌的生长繁殖过程中其环境的pH不断升高,更有利于锰的氧化;环境的温度升高可加快细菌对锰的氧化速度.锰细菌在含低价铁的培养液中可以较快地把Fe2+氧化为Fe3+,它的氧化速度要比锰的氧化速度快;在厌氧的培养条件下,锰细菌可将溶液中的高价铁还原为低价铁,而且使其环境的pH明显下降.     

过硫酸盐氧化法测定海水中溶解总磷

实验研究在碱性和酸性条件下过二硫酸钾高温氧化四种不同类型含磷标准化合物在海水中的回收率和影响回收率的因素。结果表明 :在碱性条件下过二硫酸钾高温氧化可使海水中非聚磷类化合物完全回收 ,而聚磷类化合物回收率不高 ,延长消化时间聚磷类化合物的回收率有一定提高。除个别化合物外 ,各类含磷化合物在酸性条件下可被定量回收。依此 ,建立酸性过硫酸盐氧化法分解测定海水中溶解态总磷的方法。     

光助Fenton氧化法去除水中两种氯乙酸及其动力学研究

以二氯乙酸和三氯乙酸为目标污染物,研究了光助Fenton氧化去除水中卤乙酸的可行性及影响因素,并对其动力学进行了初步研究.结果表明,影响光助Fenton氧化的因素很多,氙灯功率500 W、H2O2和Fe2+投加量分别为5.0和1.0 mmol·L-1、pH=4.0反应60 min是所考察范围内的最佳降解条件,浓度为100 μg·L-1的二氯乙酸和三氯乙酸的降解率分别为90.32％、87.77％;在实际水质pH=7.0时,相同浓度的二氯乙酸和三氯乙酸的降解率分别为75.34％、68.80％.紫外辐射与Fenton氧化对二氯乙酸和三氯乙酸的降解具有协同效应.光助Fenton氧化对二氯乙酸和三氯乙酸的降解符合一级反应动力学,表观活化能分别为30.11、31.09 kJ·mo1-1,受温度影响不大.     

Continuous flow analysis of dissolved total phosphorus in seawater by UV-K2S2O8 online digestion method

Several methods for analysis of dissolved total phosphorus in seawater were reviewed. Discussions were focused on UV irradiation and persulphate oxidation methods which are the most popular dissolved organic phosphorus determination methods presently. The compounds used for the phosphorus recovery test were categorized into three groups according to their chemical structure. It was found that low power UV irradiation can decompose P-O-C or P-C bonds efficiently but may be inefficient for P-O-P bonds. Heating-bath in acid condition is useful for decomposing P-O-P bonds. Using the continuous flow analysis system (Auto-analyzer Ⅱ), UV digestion and heating-bath, series experiments were carried out based on the above analysis. Eleven model compounds were employed for the phosphorus recovery test and the factors influencing the decomposition efficiency of dissolved compounds containing phosphorus were clarified. Finally, the optimal design for determination of dissolved total phosphorus in seawater based on the routine continuous flow analysis system was presented. For the organic mono-phosphate, the recovery is more than 90% and a recovery of 33%～51% was obtained for inorganic or organic polyphosphates. Up to now, this is the highest decomposition efficiency for dissolved phosphorus based on the continuous flow analysis system.     

海水中胶体有机碳的测定──高温燃烧法和紫外/过硫酸钾法的比较

利用切向超滤(cross-flow ultrafiltration)技术对海水中胶体有机碳(COC)和真溶解有机碳(UOC)进行了分离,并分别用高温燃烧法和紫外/过硫酸钾法对胶体有机碳和真溶解有机碳进行了测定。测定结果表明,切向超滤能定量分离海水中的胶体有机碳,高温燃烧法和紫外/过硫酸钾法对胶体有机碳和真溶解有机碳的测定结果没有明显的系统误差,表明这两种方法的氧化效率基本相同,胶体粒子的存在,对紫外/过硫酸钾法的氧化效率没有显着影响。     

A preliminary methods comparison for measurement of dissolved organic nitrogen in seawater

Routine determination of dissolved organic nitrogen (DON) is performed in numerous laboratories around the world using one of three families of methods: UV oxidation (UV), persulfate oxidation (PO), or high temperature combustion (HTC). Essentially all routine methods measure total dissolved nitrogen (TDN) and calculate DON by subtracting the dissolved inorganic nitrogen (DIN). While there is currently no strong suggestion that any of these methods is inadequate, there are continuing suspicions of slight inaccuracy by UV methods.This is a report of a broad community methods comparison where 29 sets (7 UV, 13 PO, and 9 HTC) of TDN analyses were performed on five samples with varying TDN and DIN concentrations. Analyses were done in a “blind” procedure with results sent to the first author. With editing out one set of extreme outliers (representing 5 out of 145 ampoules analyzed), the community comparability for analyzing the TDN samples was in the 8–28% range (coefficient of variation representing one standard deviation for the five individual samples by 28 analyses). When DIN concentrations were subtracted uniformly (single DIN value for each sample), the comparability was obviously worse (19–46% cv). This comparison represents a larger and more diverse set of analyses, but the overall comparability is only marginally better than that of the Seattle workshop of a decade ago. Grouping methods, little difference was seen other than inconclusive evidence that the UV methods gave TDN values for several of the samples higher than HTC methods. Since there was much scatter for each of the groups of methods and for all analyses when grouped, it is thought that more uniformity in procedures is probably needed. An important unplanned observation is that variability in DIN analyses (used in determining the final analyte in most UV and PO methods) is essentially as large as the variability in the TDN analyses.This exercise should not be viewed as a qualification exercise for the analysts, but should instead be considered a broad preliminary test of the comparison of the families of methods being used in various laboratories around the world. Based on many independent analyses here, none of the routinely used methods appears to be grossly inaccurate, thus, most routine TDN analyses being reported in the literature are apparently accurate. However, it is not reassuring that the ability of the international community to determine DON in deep oceanic waters continues to be poor. It is suggested that as an outgrowth of this paper, analysts using UV and PO methods experiment and look more carefully at the completeness of DIN conversion to the final analyte and also at the accuracy of their analysis of the final analyte. HTC methods appear to be relatively easy and convenient and have potential for routine adoption. Several of the authors of this paper are currently working together on an interlaboratory comparison on HTC methodology.     

河口水与污水混合有机物和磷的转移动力学

污水与九龙江河口水混合研究表明，ＣＯＤ的降解符合一级动力学模式，降解速率常数ｋ在０．０４－０．１１ｄ＾－１之间，水体有机物的转移以降解作用为主；两种水体混合时，先产生磷的吸附，后释放，整个过程表现为颗业磷向溶解无机磷的转移。     

Features of winter sedimentation processes in Curonian Bay of the Baltic Sea

The concentration distribution was studied for dissolved oxygen, phosphorus forms, and particulate matter in Curonian Bay of the Baltic Sea in poorly known consolidated ice cover conditions during the winter seasons of 2010, 2011, and 2013. The surface and near-bottom waters were sampled at 51 stations. The ice cover exerts no significant effect on the typical seasonal variation of all considered parameters in the basin. The concentrations of mineral and organic phosphorus in the bay appeared to be lower by factors of 2–4 compared to summer values. A two- to threefold decrease in the concentrations of organic phosphorus since 2010 to 2011 and then to 2013 was recorded in the bay, which resulted from a decrease in phosphorus production by phytoplankton. Despite water being isolated from air by ice, the absence of wave mixing, and the decrease in oxygen production owing to the seasonal winter decrease in the intensity photosynthetic processes, no oxygen deficiency was found in the basin. This is because oxygen supplied to the bay by river runoff and production by photosynthesis in the bay exceed the utilization for oxidation of organic matter resulting from low bioproductivity of the waters during winter. The winter decrease in the fraction of biogenic particulate matter is seen as a four- to sevenfold drop in its total concentration in the waters compared to summer seasons. The absence of wave roiling of bottom sediments also caused a decrease in the secondary supply of biogenic particulate matter from sediments into near-bottom waters. No negative trends of geoecological conditions in the bay were revealed by the studied parameters under consolidated ice cover conditions.     

Wet-oxidation and automated colorimetry for simultaneous determination of organic carbon, nitrogen and phosphorus dissolved in seawater

We developed a simple and reliable method which allows simultaneous determination of organic forms of carbon (DOC), nitrogen (DON) and phosphorus (DOP) dissolved in seawater. Conversion of dissolved organic matter (DOM) to inorganic products (carbon dioxide, nitrate+nitrite and soluble reactive phosphate) is performed by a persulfate wet-oxidation in low alkaline condition. After oxidation, the concentration of the inorganic products dissolved in the sample was measured automatically by colorimetry using a 3-channel Technicon AutoAnalyzer system. A number of pure organic compounds were tested in the concentration range encountered in coastal and open ocean, indicating a high efficiency of the digestion procedure. The recovery range is similar to that obtained by other wet-oxidation procedures and by high-temperature catalytic oxidation techniques. Direct comparisons with usual methods used for separate determination of DOC, DON and DOP indicated a high efficiency of the procedure. Reproducibility tests demonstrated a very good precision (around 5%) for lagoonal and coastal waters, while precision was sometimes around 10–25% in oligotrophic oceanic waters, especially for DOP where values approached limits of detection for measuring phosphate. This method is highly suitable for routine analysis and especially appropriate for shipboard work.     

Laboratory Simulation on Phosphorus Releasing near the Water／Sediment Interface in the East China Sea off the Changjiang Estuary

Surface sediment samples taken from the East China Sea off the Changjiang estuary are used as raw materials for phosphorus releasing experiment. It is found that after being thoroughly mixed with seawater for about 10 minutes, phosphorus released from the sediments reaches its maximum value. Adsorption kinetics can be fitted with both Elovich equation and two-constant rate equation. The releasing amount is closely related to the composition of the sediments. Phosphorus release from silty and muddy sediment is higher than from that dominated by sandy composition. For the desorption reaction, iron-phosphorus(Fe-P) is the most active one, with a releasing ratio higher than other phosphorus forms,followed by absorbed-phosphorus (Ad-P) and organic bound phosphorus (OP). All of them can be referred to as bio-available phosphorus. The results demonstrate that phosphorus in sediments can be released into seawater under suitable hydrodynamic conditions, and have a great impact on the nutrition state and primary productivity of marine biosphere.