Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia)

An interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (K_i^equ), total ligands concentration (L_iT) and association/dissociation rate constants (k_i¹,k_i^- 1).A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater–seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K₁^equ: 11.2–13.0, log K₂^equ:8.8–10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter.Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by at-equilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k₁¹:6.1–20 × 10³ (M s)^− 1, k₂¹: 1.3–6.3 × 10³ (M s)^− 1) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h.It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µM_C, i.e. 1 mg_CL^− 1) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM).     

水样中氮磷营养盐的短期保存技术研究

用8种保存方法对淡水和海水水样中四个氮磷营养盐（NH3-N、NO3—N、NO3-N、PO4—P）参数及总氮的稳定性进行了7d保存效果的比较研究。结果表明,淡水与海水氮磷营养盐的最佳保存方法与效果各不相同,但淡水和海水的总氮值在各种方法保存下均十分恒定。综合考虑有效性及可操作性后提出了5d内的短期保存技术：（1）海水水样用5‰氯仿4℃条件下保存,供NH3-N、NO2—N和N03-N三个营养盐的测定,用5‰甲醛4℃条件下保存供PO4-P测定;（2）淡水用5‰氯仿4℃条件下保存,供NH3-N测定,5‰甲醛4℃条件保存供NO2-N、NO3-N和PO4-P测定。     

干湿交替条件下包气带土柱中氮素迁移转化规律实验

干湿交替的回灌方法常被用于解决地面回灌补给地下水的堵塞问题。研究干湿交替条件下地面回灌对地下水的影响对于指导再生水回灌地下水具有重要实际意义。通过室内土柱模拟实验,在入渗强度为10.5 mm/h的条件下,日均进水量3 888 mL;用干湿交替的地面回灌模式持续运行136 d,累计灌入氨氮含量为5 mg/L的模拟再生水23 894 L,研究包气带土柱对氨氮的去除效果及氮素在包气带中的迁移转化规律。研究表明,充分利用包气带的好氧、兼氧和厌氧环境,生物脱氮是地下水回灌过程中脱氮的主要途径。包气带对氨氮的去除机理主要为土壤对氨氮的吸附作用和微生物的降解作用。回灌过程中累积在土颗粒表面的氨氮在干期发生硝化作用,干湿交替会加强氮素在包气带的迁移转化,导致干期后的回灌初期大量硝态氮迁移到饱和带地下水中。     

无人机航空伽马能谱数据处理中大气氡的修正

介绍了无人机航空伽马能谱数据处理中大气氡修正的一种方法——能谱比法的原理与方法、数据处理过程及其在无人机航空伽马能谱数据处理中的应用。使用该方法对喀什地区的无人机航空伽马能谱进行修正,修正后的航放U较好地反映了该区的地质情况,可以应用到生产实践中去。     

扩散法——EA-IRMS测定天然水体铵态氮同位素实验条件研究

稳定氮同位素是研究氮循环和氮污染源示踪的一个有效手段。然而目前国内对水体中铵态氮同位素测定方法研究较少,限制了水体氮循环和污染机理的深入探讨。本文采用改进的扩散法(EA-IRMS)测定水中铵态氮同位素,探讨了样品制备过程中扩散溶液的体积、浓度和扩散时间对回收率及氮同位素测定值的影响。实验得出最佳扩散条件为:1.50 mg/L氯化铵溶液400 mL扩散14天,回收率大于95%,且不会产生氮同位素分馏。本研究为高精度测定天然水体中铵态氮同位素提供了更可靠的实验条件。     

我国氨的排放量和时空分布

根据我国的实际情况讨论了各种氨排放源的排放因子，计算了各种氨源的贡献，以动物的贡献最大，占52%。1993 年我国氨的排放量为12 Mt，排放量最大的是河南、山东和四川，排放密度最大的是上海。在北京、广西、广东、湖南、江西和山东测定了大气氨的浓度，北京大气氨浓度有明显的季节变化，春季平均为16 μg/m3，夏季最高为41μg/m3，冬季只有3.2 μg/m3。一般夜间氨的浓度高于白天。测定了氨的垂直分布，并计算了氨浓度的标高。     

Combined effects of light intensity and NH^＋4-enrichment on growth,pigmentation, and photosynthetic performance of Ulva prolifera （Chlorophyta）

The aim of this study was to investigate the effects of light intensity and enhanced nitrogen supply on the growth and photosynthesis of the green-tide macroalga, Ulva prolifera. Thalli of U. prolifera were grown in natural or NH 4 +-enriched seawater under two different light intensities for 7 days, and then the growth rate, pigmentation, and photosynthetic performance of the thalli were evaluated. The results show that the relative growth rate(RGR) was markedly higher under the high light level than under the low light level. Enrichment with NH 4 + enhanced the RGR under high light intensity, but did not affect RGR under low light intensity. In low light conditions, NH 4 +-enrichment resulted in a marked decrease in the maximal photosynthetic rate( P m) and the maximum carbon fixation rate( V max), but it did not affect the half saturation constant for carbon( K 0.5) or the ratio of V max to K 0.5, which reflects the carbon acquisition efficiency. In high light conditions, P m, K 0.5, and the dark respiration rate( R d) increased under NH 4 + enrichment, but V max and the V max / K 0.5 ratio decreased. Regardless of the light intensity, NH 4 +-enrichment did not affect the apparent photosynthetic efficiency( α), which refl ects the ability of the alga to use light energy at low light levels. Under both low and high light intensities, the chlorophyll a(Chl a), chlorophyll b(Chl b), and carotenoids(Car) contents in thalli were higher in NH 4 +-enriched than in natural seawater, except that there was a decrease in the Chl b content of thalli in NH 4 +-enriched seawater under low light intensity. Therefore, NH 4 + enrichment improved the growth and photosynthetic performance of U. prolifera under high light intensity, but not under low light intensity. We discuss the possible mechanisms underlying these physiological responses.     

柴达木盆地石炭系地球物理特征及解释

柴达木盆地具有丰富的油气资源,柴北缘、柴西、粜东三湖地区分别以侏罗系、古近系、新近系和第四系为主要勘探目的层.随着北疆石炭系研究的进展和钻探的成功,石炭系已经成为中国西部地区重要的勘探层系,柴达木盆地的石炭系也引起了勘探家的注意,地面地质调查表明石炭系为柴达木盆地一套潜在烃源岩.为了落实石炭系在柴达木盆地内的分布,笔者充分利用近10年来在柴达木盆地及周缘完成的重、磁、电等资料进行了针对石炭系的资料解释、剥层反演和综合研究,明确了石炭系的分布特征,为柴达木盆地石炭系油气勘探指明了方向.     

南美洲鳗鲡(Anguilla rostrata)的耗氧率(ROC)、窒息点(AP)和适温范围(RT)及对非离子氨(NIA)、NO2-的LC50和SC的研究

为研究南美洲鳗鲡(Anguillarostrata)的耗氧率及其对水温、低溶氧、非离子氨和亚硝酸盐耐受性,本研究采用自制的鱼类呼吸装置测定其耗氧率和窒息点,以黑仔鳗为试验材料,探索其对水温、非离子氨、亚硝酸盐耐受性。结果表明,南美洲鳗鲡耗氧率存在昼夜变化,其昼间耗氧率为(86.46±37.77)mg/(kgh),夜间耗氧率为(123.58±22.56)mg/(kgh),二者存在显著性差异(P0.05);在15—30°C范围内,耗氧率随温度升高逐渐增大,耗氧率和水温的回归方程y=–0.1316x2+9.4507x–13.712(R2=0.9993);南美洲鳗鲡的耗氧率随体质量增大而降低,耗氧量随体质量增加而增大,耗氧量和体重的回归方程为y=0.2321x0.8334(R2=0.9979);在水温25°C时其窒息点随鱼体质量的增大而降低,均重10g、40g和160g的鳗鲡窒息点溶解氧浓度分别为(0.98±0.25)、(0.46±0.06)和(0.32±0.02)mg/L;13—29°C为南美洲鳗鲡的适温范围,25—29°C为其生长适宜水温,在一定范围内的短时低水温或高水温环境对其损伤是可逆的;水中非离子氨对南美洲鳗鲡的LC50和SC分别为12.22mg/L和1.22mg/L,亚硝酸盐氮对南美洲鳗鲡的LC50和SC分别为61.68mg/L和6.17mg/L。     

四川稀土精矿的稀土元素和微量元素地球化学特征及开发利用意义

产自广东省梅州市玉水铜矿的景文矿,属于含水、重稀土-矾-铝硅酸盐矿物(简写为HREE-V-铝硅酸盐矿物),其化学结构式为Y₂Al₂V₂⁴⁺(SiO₄)₂O₄(OH)₄,该矿物在全球属首次发现,暂未开展相关研究。相对于含轻稀土矿物,含重稀土矿物在电子探针分析过程中,当被高压电子束轰击时,被激发出来的特征X射线线系繁多,线系之间分布更加密集,彼此之间相互重叠的现象也更为严重,要获得理想数据的难度很大,是亟待解决和突破的技术难题。本文对该矿物进行了精细的电子探针定量分析,获得理想的化学成分数据,为新矿物命名提供了理论数据技术支撑。通过对实验方法的探索和总结获得以下结果：①利用15kV加速电压、100nA束流对试样进行全元素扫描,以此确定出17种元素;②在定量分析过程中,对重叠峰进行了剥离;③利用仪器软件中的Zoom-Peak ID程序,选择出17种元素的分析线系、精确的峰位及上下背景值;④选取合适的标样及测试时间等定量分析条件,最终获得理想的定量分析结果(平均总量97.41wt%)。上述四条也是确保获得理想定量分析数据的关键因素。