三价钛还原法分析硝酸根氮氧同位素的方法研究

本研究利用三价钛还原法将标准样品、海水、湖水和雨水中硝酸根转化为N₂O测试其氮氧同位素值,并优化实验条件（NO^-₃浓度、试剂量、反应时间和温度等）。结果表明：4 cm³硝酸根水样（浓度约为20 μmol/dm³）,加入100 mm³TiCl₃溶液（浓度为150 g/dm³）,25 ℃反应24 h,NO^-₃还原为N₂O的平均转化率为86.3%（n=5）。5种丰度硝酸根氮氧同位素标样校准曲线斜率分别为0.947和0.617,相关系数R²分别为0.999和0.994;方法检出限的NO^-3浓度为2.5 μmol/dm³,其δ¹⁵N的标准偏差小于0.7‰(n=5),δ¹⁸O_VSMOW值的标准偏差小于2.5‰(n=5);20 μmol/dm³硝酸根样品δ¹⁵N的标准偏差小于0.5‰（n=5),δ¹⁸O_VSMOW值的标准偏差小于1.0‰（n=5）。该方法测定3种不同类型水样δ¹⁵N的标准偏差分别为0.3‰、0.6‰和0.5‰;δ¹⁸O_VSMOW的标准偏差分别为2.1‰、2.0‰和1.6‰。三价钛还原法分析水体中硝酸根氮氧同位素操作步骤简单,测试效率高,但氧同位素结果需要系统校正。     

球形棕囊藻同化吸收硝酸盐的氮氧稳定同位素分馏研究

球形棕囊藻(Phaeocystis globosa)赤潮是一种全球范围的生态灾害,而硝酸盐稳定同位素技术是研究海洋富营养化与赤潮暴发机制的前沿技术。为将该技术应用于球形棕囊藻赤潮暴发机制方面的研究,首先需了解其同化吸收硝酸盐的稳定同位素分馏特征。为此开展了球形棕囊藻室内培养实验,获取培养过程中氮、磷、硅等营养盐的浓度及硝酸盐氮、氧稳定同位素(δ¹⁵N-NO₃^-、δ¹⁸O-NO₃^-)等参数的变化特征,计算球形棕囊藻同化吸收硝酸盐的稳定同位素分馏系数。结果显示,NO₃^-和PO₄^3-浓度随培养时间均呈现先明显下降后稳定的特征,同时伴随直径2~3mm的囊体出现并生长至2~3cm。NH₄⁺浓度先后两次出现升高,推测可能是受到有机氮矿化过程的补充所致。随NO₃^-浓度降低,δ¹⁵N和δ¹⁸O的值分别在第13天和第7天达到相对峰值。经计算,球形棕囊藻同化吸收硝酸盐过程δ¹⁵N和δ¹⁸O分馏系数分别为3.32‰±0.38‰和3.12‰±0.59‰,而前者的分馏系数呈逐渐降低的特点,原因可能是随球形棕囊藻生长,发生酶还原的NO₃^-较参与跨膜运输的NO₃^-比例逐渐升高。研究首次给出了球形棕囊藻同化吸收硝酸盐过程的氮、氧稳定同位素分馏系数及其变化特征,补充了海洋微藻同位素分馏数据库,为稳定同位素技术研究球形棕囊藻赤潮暴发的营养机制提供了重要的基础数据。     

细菌反硝化法测试硝酸盐氮、氧同位素的研究与应用

为了验证细菌反硝化法对水体中硝酸盐氮、氧同位素组成测定的适用性、重现性及准确性, 在不同时间(2019年7月28日、8月19日、8月26日)利用反硝化细菌分别将海水、湖水和自来水样品中的硝酸盐转化为氧化亚氮（N₂O）, 并进行氮、氧同位素测定。结果表明, 不同时间段3个批次实验的硝酸盐氮同位素校准曲线斜率都接近理论值1, 相关性系数均高于0.999, 说明反硝化细菌在将样品中的硝酸盐全部还原为N₂O的过程中氮同位素分馏效应很小; 同一样品3个批次测定的硝酸盐的氮同位素值基本相同, 表明细菌反硝化法对硝酸盐氮同位素的测定在长时间周期内具有很好的重现性和准确性。3个批次氧同位素校准曲线斜率稳定在0.61～0.63之间, 相关性系数均高于0.99, 单批次内海水、湖水和自来水3类样品中硝酸盐氧同位素比值的标准偏差范围在0.18‰～0.69‰之间, 表明经过氧同位素校准曲线的校正, 可以准确反映样品中硝酸盐氧同位素组成; 同一样品3个批次测定的氧同位素值差异较大, 其变化范围为1.33‰～16.38‰, 可能是由于样品储存过程中硝酸盐与水之间发生的氧同位素交换作用所致。     

一株嗜碱兼性好氧反硝化菌Marinobacter sp.B3的分离鉴定及脱氮性能研究

为获得反硝化脱氮效率较好的菌株,实验从海水螺旋藻培养体系中分离获得一株嗜碱兼性好氧反硝化菌, 通过观察细菌形态以及16S rRNA基因序列的同源性分析, 鉴定该菌株为海杆菌属, 命名为Marinobacter sp. B3。为明确该海杆菌的反硝化性能及氮转化途径, 研究开展了溶解氧(DO), 碳氮摩尔比(C/N), pH和温度等不同单因素对反硝化性能影响实验和氮平衡实验。单因素影响实验结果表明, 当硝酸钾(KNO₃)作为唯一氮源, NO₃^--N的初始浓度为100 mg/L, 盐度32, 振荡速度为150 r/min (初始DO质量浓度是5.6 mg/L), C/N=10, pH=8.0±0.2, 温度为35 °C时, 可获得最大脱氮效果。氮平衡实验结果得出, 在好氧环境下, 有20.11%的NO₃^--N转化为胞内氮, 5.58 mg/L的NO₃^--N转化为其他形态(NO₂^--N、NO₄⁺-N和有机氮), 74.72%转化为N₂释放; 厌氧环境下, 有26.65%的NO₃^--N转化为胞内氮, 72.86%的NO₃^--N转化为气态产物释放。最终实验结果表明, Marinobactersp. B3在好氧和厌氧条件下, 48 h对NO₃^--N的去除率分别为99.89%和93.80%, 具有较好的反硝化脱氮能力, 且在好氧条件下NO₃^--N去除效率更高, 在海水工厂化循环水养殖尾水处理方面具有良好的应用前景。     

不同规格近江牡蛎的排氨率和耗氧率分析

采用实验生态学方法研究了不同规格近江牡蛎的呼吸和排泄生理生态学参数。结果显示,近江牡蛎耗氧率R_O随软体干重(W )的增加而减小, 体重对近江牡蛎耗氧率(R_O)的影响达极显著水平,R_O = 1.8232W^-0.7600, (R²= 0.8313 , P <0.01); 近江牡蛎的排氨率(R_N)和排磷率(R_P)随软体干重的增加而降低,呈负相关关系;而氧氮比O/N和氮磷比N/P在各组间未达显著水平(P >0.05) , R_N = 0.0930W^-0.6582 (R² = 0.7444, P <0.01)、R_P = 0.0126W^-0.8874 (R² = 0.9224,P <0.01);各组不同规格近(大小)江牡蛎的O/N值较高,而N/P值则随规格增大而呈上升趋势,但差异也不显著(P >0.05)。这些研究结果对牡蛎养殖密度和环境关系分析及牡蛎健康养殖具有重要参考价值。     

Growth of marine bacteria and ammonium regeneration from substrates in different C: N ratios

Natural assemblages of marine bacteria were chosen in a batch culture experiments. The impact of varying nitrogen substrate concentrations and the substrate C:N ratios (C:N_S) on the bacterial C:N ratio (C:N_B), the bacterial growth efficiency (BGE) and ammonium regeneration was mainly examined. The C:N_S ratios varied from 5:1 (carbon limitation) to 40:1 (nitrogen limitation) with varying combinations of glucose and NO₃^-. The C:N_B ratio had positive relationship with the C:N_S ratio (r=0.93, n=8), whose value was 3.77 when the C:N_S ratio was 5:1 but increased to 6.47 when the C:NS ratio was 40:1. These results indicate that the C:N_B ratio is a potential diagnostic tool for determining the bacterial growth in natural waters controlled by either, carbon or nitrogen. BGE decreased with the declining nitrate concentration and negatively related to C:N_s (r=-0.51, n=8). The average value of BGE was 0.20. This value was a little lower than other reports, which could be induced by the nitrogen source used in our experiments. Finally, regeneration time of ammonium delayed with the increasing C:N_S ratio, which indicates that there were different metabolism mechanisms when bacterial growth was limited by carbon source and nitrogen source.     

Retrieval of total ozone in the mesosphere with a new model of electronic-vibrational kinetics of O<Subscript>3</Subscript> and O<Subscript>2</Subscript> photolysis products

The paper presents a new model of electronic-vibrational kinetics of the products of ozone and molecular oxygen photodissociation in the terrestrial middle atmosphere. The model includes 45 excited states of the oxygen molecules O₂(b ¹, Σ _g ⁺ ,v= 0−2), O₂ (a ¹Δ _g , v= 0−5), and O₂(X ³Σ _g ⁻ , v= 1−35) and of the metastable atom O (¹ D) and over 100 aeronomic reactions. The model takes into account the dependence of quantum yields of the production of O₂(a ¹Δ _g , v= 0−5) in a singlet channel of ozone photolysis in the Hartley band on the wavelength of photolytic emission. Taking account of the electronic-vibrational kinetics is important in retrieval of the vertical profiles of ozone concentration from measured intensities of the Atm and IR Atm emissions of the oxygen bands above 65 km and leads to an increase in the ozone concentration retrieved from the 1.27-μm emission, in contrast to the previous model of pure electronic kinetics. Sensitivity analysis of the new model is made for variations in the concentrations of atmospheric constituents ([O₂], [N₂], [O(³P)], [O₃], [CO₂]), the gas temperature, rate constants of the reactions, and quantum yields of the reaction products. A group of reactions that most strongly affect the uncertainty of ozone retrieval from measured intensities of atmospheric emissions of molecular oxygen O₂(b ¹Σ _g ⁺ , v) and O₂(a ¹Δ _g , v) has been determined. Original Russian Text ? V.A. Yankovsky, V.A. Kuleshov, R.O. Manuilova, A.O. Semenov, 2007, published in Izvestiya AN. Fizika Atmosfery i Okeana, 2007, Vol. 43, No. 4, pp. 557–569.     

光谱法测定海水中溶解态无机氮的研究进展

溶解态无机氮（dissolved inorganic nitrogen, DIN）主要由亚硝酸盐-氮（NO^-₂-N）、硝酸盐-氮（NO^-₃-N）和铵氮（NH⁺₄-N）组成,它们在海洋的生物地球化学循环过程中起重要作用。但人类活动向海洋输入了大量无机氮,导致一系列环境问题。为了更好地开展海洋氮循环研究和环境污染管理,需对海水中的DIN进行测定。在众多分析方法中,光谱法因其通用性好、适用范围广、所需设备简单,成为测定海水DIN的首选。本文总结了近10年来基于光谱法测定海水DIN的研究进展,包括紫外分光光度法测定NO^-₃-N、萘乙二胺分光光度法测定NO^-₂-N和NO^-₃-N、次溴酸盐氧化-分光光度法测定NH⁺₄-N、靛酚蓝分光光度法测定NH⁺₄-N、酸碱指示剂-分光光度法测定NH⁺₄-N、荧光法和化学发光法测定DIN等,比较了各分析方法的特点,并展望了光谱法测定海水DIN的发展趋势。总的来说,在分析方法上,新试剂的使用以及一些新合成材料的出现,丰富了DIN的分析手段;在分析仪器上,以流动分析技术为基础的分析仪器在DIN的实验室及现场分析中得到了广泛应用。DIN的分析方法均朝着简单便捷、全自动化、分析速度快、精确度高、可适用范围广的方向发展。     

钪原子的自电离里德伯能级3d4s(1 D2)nf2 D3/2,3d4s(1 D2)nf2 F5/2和3d4s(1 D2)np2 D3/2的理论研究

在多通道量子亏损理论框架下,利用相对论多通道理论,分别在冻结实近似和考虑偶极极化下计算钪原子的J^π=(3/2)^-,(5/2)^-的三个收敛于 3d4s(¹D₂)的自电离里德伯系列的能级.对3d4s(¹D₂)np²D_3/2和3d4s(¹     

离子色谱法测定海水中氯离子和硫酸根离子

氯离子和硫酸根离子是海水中重要的无机阴离子，在研究海洋生态变化、海洋循环作用过程与海洋全球气候变化等领域具有重要的指示意义。其测定方法较多，但缺少相应的测试方法。本文对测定海水中Cl^-，SO₄^2-的离子色谱方法进行了优化，选用IonPacAS14碳酸盐选择性离子色谱柱，以3.5 mmol/L Na₂CO₃+1 mmol/L NaHCO₃为流动相，可消除海水样品中碳酸盐及其他阴离子的干扰。该方法对Cl^-检出限为0.29 mg/L，线性相关系数r²=0.999 2，对SO₄^2-检出限为0.42 mg/L，线性相关系数r²=0.997 9。样品的加标回收率在95%~102%，Cl^-和SO₄^2-的相对标准偏差分别为1.92%和4.18%。该方法简便、迅速、灵敏、准确度高，可满足批量海水样品中Cl^-与SO₄^2-的准确测试。     

同位素示踪技术在海洋环境研究中的应用

综合δD、δ18O、224Ra、226Ra、228R、钍系同位素和210Pb、14C等同位素示踪技术研究的最新成果,概述了同位素示踪技术在海洋水体运动、颗粒动力学、海洋生物生产力、沉积动力学、古海洋学等方面的研究进展,提出了在这一领域应重点发展的研究方向,以期推动同位素示踪技术在海洋环境研究中的应用。     

中国近海沉积物中钍同位素的分布

本文对采自中国7个近岸海域的沉积物中钍(铀)同位素的分布进行了研究。发现表层沉积物中,~(230)Th/~(232)Th)_(A.R.)均小于1.0且呈均匀分布的态势。但~(230)Th/~(232)Th)_(A.R.)的数值及其深度分布特征与深海沉积物截然不同。~(230)Th/~(232)Th)_(A.R.)与水深呈良好的正相关。钍系不平衡普遍存在,其特征是~(228)Th/~(232)Th)_(A.R.)<1.0,据此推测了沉积物中可溶化学物质与上覆海水发生交换的深度。研究了沉积物中~(232)Th的含量、比度和~(232)Th/~(238)U)_(C.R.)的分布特征。从~(234)Th_(ex.)的深度分布求出秀屿站的表层混合系数(0.49×10~(-6)cm~2/s)和沉积柱中~(234)Th_(ex.)的总量。     

夏季大亚湾悬浮颗粒有机物碳、氮同位素组成及其物源指示

2015年夏季开展了大亚湾悬浮颗粒有机物碳（POC）、氮含量（PN）及其同位素组成的研究,结果表明,δ13C_POC和δ15N_PN的变化范围分别为-25.7‰~-17.4‰和-6.3‰~10.4‰,平均值分别为-20.2‰和8.2‰。大亚湾悬浮颗粒有机物含量及其碳氮同位素组成的空间变化反映了不同有机质来源的影响:喜洲岛附近海域表现出高POC、PN、δ13C_POC和δ15N_PN的特征,指征着浮游植物水华的主导贡献;东北部范和港附近海域具有高POC、PN、低δ13C_POC和高δ15N_PN的特征,反映了河流/河口水生有机物的影响;湾顶白寿湾附近海域的δ13C_POC和δ15N_PN出现低值,体现了陆源有机质和人类污水排放的影响。借助δ13C_POC和δ15N_PN的三端元混合模型,定量出海洋自生有机质、陆源有机质、河流/河口水生有机质等3个来源的贡献平均分别为70%、13%和17%,其中海洋自生有机质是夏季大亚湾悬浮颗粒有机物的最主要来源。从这3种来源颗粒有机物含量的空间变化看,海洋自生有机质含量由湾内向湾外减少,与初级生产力的空间变化相对应;河流/河口水生有机质含量在大亚湾东北部出现高值;陆源有机质含量在表、底层出现不同态势,表层陆源有机物含量在湾中部海域最低,而底层则呈现出自湾内向湾口增加的趋势,主要受控于离岸距离和珠江冲淡水、粤东沿岸上升流输送的影响。     

Nitrate δ15N and δ18O evidence for active biological transformation in the Changjiang Estuary and the adjacent East China Sea

The Changjiang Estuary has been considered as one of the most polluted estuaries in the world due to high nitrate (NO-3) input, especially in spring and summer. In this study, δ15N and δ18O of NO-3 , along with other chemical parameters in this area, were measured in spring to evaluate NO-3 biogeochemical processes. A simple two end-members mixing model was used to examine the relative contribution of the Changjiang River Diluted Water and marine water to NO-3 sources in the Changjiang Estuary and the adjacent East China Sea. The isotopic signals show that NO-3 behaved relatively and conservatively in Transect F and Transect P where assimilation was weak possibly due to vertical mixing, while active assimilation and weak nitrification occurred in Transect D. Spatial difference in assimilation was indicated by the～1:1 enrichment of δ15N and δ18O in the three transects, while spatial difference in nitrification was reflected by deviations of δ15 N and δ18O from assimilation line. Our results suggest that the input of the Changjiang River Diluted Water promoted NO-3 assimilation possibly by stratifying the water column which favored the phytoplankton growth.     

植物生长过程中碳同位素分馏对气候的响应

探讨C4植物的碳同位素组成对气候的响应是碳同位素示踪研究的重要任务。观察了典型的C4植物玉米生长过程的碳同位素效应，结果表明，玉米在其生长季节里碳同位素组成有明显的变化。不同部位的叶片碳同位素组成变化不一样，顶部叶片变化较大，下部叶片变化则相对较小。这种变化受温度、水分和光照强度等多种气候要素的影响。同一株玉米，其顶部的叶片δ^13C值比下部叶片要偏正，而且随着玉米的不断生长，这一现象更加明显，温度和光照强度则是引起这一现象的主要气候因子。     

太平洋结核结壳中的锶铅同位素关系研究

依据多金属结核、铁锰结壳的记录 ,研究了太平洋海水结核结壳中锶、铅同位素的关系 ,结果表明 ,太平洋海水中锶同位素与铅同位素无明显的相关性。作者认为这是由于太平洋海水中锶、铅的滞留时间相差很大 ,达 4个数量级 ,锶同位素记录了 10 0 0 0 0 a至百万年时间尺度上全球性大洋范围内海水物质来源的变化 ,而铅同位素能在较小的时间尺度上反映局部的大洋海水物质来源的信号 ,是高分辨率的物源示踪剂     

Geochemical characteristics of gases from the largest tight sand gas field (Sulige) and shale gas field (Fuling) in China

This study performed a detailed geochemical analyses of the components, stable carbon isotopes of alkane gas and CO₂, stable hydrogen isotopes of alkane gas and helium isotopes of reproducing gas from the largest tight gas field (Sulige) and shale gas (Fuling) field in China. The comparative study shows that tight gas from the Sulige gas field in the Ordos Basin is of coal-derived origin, which is characterized by a positive carbon and hydrogen isotopic distribution pattern (δ¹³C₁ > δ¹³C₂ > δ¹³C₃ > δ¹³C₄; δ²H₁ > δ²H₂ > δ²H₃), i.e., the carbon and hydrogen isotopes increase with increasing carbon numbers. Carbon dioxide from this field are of biogenic origin and the helium is crust-derived. Shale gas from the Fuling shale gas field belongs to oil-derived gas which has complete carbon and hydrogen isotopic reversal of secondary alteration origin (δ¹³C₁ < δ¹³C₂ < δ¹³C₃; δ²H₁ < δ²H₂ < δ²H₃), i.e., the carbon and hydrogen isotopes decrease with increasing carbon numbers. Such complete isotopic reversal distribution pattern is due to the secondary alteration like oil or gas cracking, diffusion and so on under high temperature. In that case, positive carbon or hydrogen isotopic distribution pattern will change into complete isotopic reversal as the temperature increases. Carbon dioxide is of abiogenic origin resulting from the thermal metamorphism of carbonates and helium is crust-derived.     

镭、氡同位素示踪调水调沙对黄河口水体运移及营养盐分布特征的影响

为研究调水调沙影响下的镭、氡同位素和营养盐在黄河口的分布特征,于2013年7月调水调沙期间在黄河口及其邻近海域进行了多点的连续观测。研究发现:(1)黄河口海域镭、氡同位素分布呈现明显的“分区”现象,南北两区分别为“调水调沙影响非显著区域”和“调水调沙影响显著区域”,北部海域镭、氡同位素浓度高值主要来源于陆源输入(包括河流输入和海底地下水排放);(2)调查期间,北部海域水体年龄为(2.9±1.6)d,南部海域水体年龄为(5.0±2.1)d;水龄随潮汐变化表现出涨潮时水龄增大、落潮时水龄减小的波动趋势;(3)北部海域溶解无机氮(DIN)和溶解硅(DSi)含量明显高于南部海域,而溶解无机磷(DIP)在两个区域的含量相差不大。     

Stable carbon and nitrogen isotopes of sinking particles in the eastern bransfield strait (Antarctica)

A time-series sediment trap was deployed at 1,034 m water depth in the eastern Bransfield Strait for a complete year from December 25, 1998 to December 24, 1999. About 99% of total mass flux was trapped during an austral summer, showing distinct seasonal variation. Biogenic particles (biogenic opal, particulate organic carbon, and calcium carbonate) account for about two thirds of annual total mass flux (49.2 g m^-2), among which biogenic opal flux is the most dominant (42% of the total flux). A positive relationship (except January) between biogenic opal and total organic carbon fluxes suggests that these two variables were coupled, due to the surface-water production (mainly diatoms). The relatively low δ¹³C values of settling particles result from effects on C-fixation processes at low temperature and the high CO² availability to phytoplankton. The correspondingly low δ¹⁵N values are due to intense and steady input of nitrates into surface waters, reflecting an unlikely nitrate isotope fractionation by degree of surface-water production. The δ¹⁵N and δ¹³C values of sinking particles increased from the beginning to the end of a presumed phytoplankton bloom, except for anomalous δ¹⁵N values. Krill and the zooplankton fecal pellets, the most important carriers of sinking particles, may have contributed gradually to the increasing δ¹³C values towards the unproductive period through the biomodification of the δ¹³C values in the food web, respiring preferentially and selectively¹²C atoms. Correspondingly, the increasing δ¹⁵N values in the intermediate-water trap are likely associated with a switch in source from diatom aggregates to some remains of zooplankton, because organic matter dominated by diatom may be more liable and prone to remineralization, leading to greater isotopic alteration. In particular, the tendency for abnormally high δ¹⁵N values in February seems to be enigmatic. A specific species dominancy during the production may be suggested as a possible and speculative reason.     

海洋铪同位素演化及其对大陆物源与洋流变化的启示

尽管海洋铪(Hf)同位素早在20世纪80年代就有报道,但直到最近几年随着分析测试技术的发展,它作为示踪陆源风化输入和洋流循环改变的新指标才越来越受到关注。综述了全球大洋Hf同位素现代分布以及新生代演化特点,其中最重要的现象是Nd-Hf同位素投影图上海水与岩石具有不一致的趋势线。在这些观测资料的基础上着重讨论了围绕海洋Hf同位素物源争议的一系列问题,阐述了海洋热液系统、大陆差异风化、洋岛陆架沉积物溶解等对海洋Hf的贡献以及Hf,Nd存留时间不一致等对海洋Hf同位素的影响等。弄清Hf的海洋地球化学行为,对深入认识海洋Hf的循环以及古海洋演化具有着重要的意义。