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1.
Nitrogen isotope compositions of particulate organic matter and nitrate were analyzed for seawater sampled at five stations at the Alaskan Gyre, Western Subarctic Gyre and East China Sea, focusing on the samples from the surface to 5000 m water to characterize the nitrogen cycling in the subarctic North Pacific Ocean and its marginal sea. The 15N of particulate organic matter showed little agreement with a conceptual closed model that interprets isotopic variation as being caused by isotope discrimination on nitrate utilization. The 15N and 13C of particulate organic matter varied with the water depth. A correlation between isotope compositions and C/N elemental ratio was found generally at all stations, although some irregular data were also found in deep layers. We developed a hypothetical nitrogen balance model based on N2 fixation and denitrification in seawater and attempted to apply it to distinguish nutrient cycling using both 15N-NO3 and N* variation in seawater. This model was applied to the observed data set of 15N-NO3 and N* in the North Pacific water and estimated the 15N-NO3 of primordial nitrate in the North Pacific deep water as 4.8. The North Pacific intermediate water for all stations showed similar 15N-NO3 and N* values of 6 and –3 µmol/kg, respectively, suggesting a similar nitrogen biogeochemistry. In the East China Sea, analysis showed evidence of water exchange with the North Pacific intermediate water but a significant influence of nitrogen from the river runoff was found in depths shallower than 400 m.  相似文献   

2.
A method for the determination of the δ15N of nitrate in seawater described by Cline and Kaplan (1975) has been modified for application to low-level nitrate samples. We have minimized the reagent blank problem by replacing the Devarda's alloy with an aluminum reagent, and have also established a procedure that yields quantitative (93 ± 2%) extraction of nitrogen even at low nitrate levels. Though the amounts and the δ15N of the blank N varied from one reagent set to another, with these modifications, an overall N blank was reduced to approximately 0.80 ± 0.33 μmole N having an estimated δ15N value of −1.8‰. After blank and yield corrections, the measured isotopic composition of nitrate differed by approximately 0.1‰ from the actual value while the precision was within ±0.2‰ at the 1.25 μM level. The modified procedure was applied to seawater samples collected from the equatorial Pacific in order to compare the N blanks in field samples with those derived from laboratory experiments. The results support the suitability of the modified approach for isotopic analysis of oceanic nitrate in shallow water. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

3.
A fluorescence-based chemistry has been developed for the detection of nitrite and nitrate (as excess nitrite following reduction of nitrate to nitrite). Detection limits are 4.6 and 6.9 nM, respectively. The technique capitalizes on the triple bond between the two nitrogen atoms within the diazonium ion formed via the well-known reaction between an acidified nitrite sample and an aromatic primary amine. Fluorescence of π-electrons within this bond allows this reaction to be probed with standard fluorescence spectroscopy. Reverse Flow Injection Analysis (rFIA) is used to correct for background fluorescence from leachates and naturally occurring dissolved organic matter (DOM). Comparisons of samples analyzed for nitrite with this technique and with a highly-sensitive chemiluminescent method [Braman, R.S., Hendrix, S.A., 1989. Nanogram nitrite and nitrate determination in environmental and biological materials by vanadium (III) reduction with chemiluminescence detection. Analytical Chemistry, 61 (24) 2716–2718] showed excellent agreement between the two methods (slope=0.9996 and r2=0.9956). These fluorescent nitrite and nitrate + nitrite chemistries were coupled in a sensor package with a modified version of a fluorescent ammonia chemistry [Jones, R.D., 1991. An improved fluorescence method for the determination of nanomolar concentrations of ammonia in natural waters, Limnology and Oceanography. 36(4) 814–819], which also has a nanomolar detection limit. The throughput rate of the fully automated three-channel instrumentation is 18 samples per hour. A field experiment demonstrated the capability of the nutrient sensor package to determine horizontal gradients in nitrate, nitrite, and ammonia in oligotrophic surface waters.  相似文献   

4.
海洋中的氮循环是海洋生物地球化学研究的热点领域之一,而硝化过程是氮循环的关键一环,准确获取硝化速率对于丰富海洋氮循环的认识至关重要。15N标记同位素技术是目前国际上最为广泛使用的硝化速率测定方法,该方法的核心在于准确测定15N加富样品产生的15NO2-15NO3-的含量,但目前的方法普遍存在测试时间较长、测试成本较高、所需样品体积较大或者检测限较高等问题。研究以低成本的膜进样质谱作为15N加富样品测试设备,建立了基于镉柱与氨基磺酸双还原体系测定15N加富样品中15NO3-含量的方法。经条件优化实验确定的具体方法:采用1 mol/L HCl配制15 mmol/L的氨基磺酸(SA)作为反应试剂除去样品原有的NO2-,然后利用镉柱将15NO  相似文献   

5.
Isotopic analyses of nitrate by the denitrifier method, and indeed by many other analytical methods, do not discriminate between nitrate and nitrite. For samples containing both chemical species, accurate isotopic analysis of nitrate requires either removal of nitrite or independent isotopic analysis of nitrite and subtraction of its contribution to the mixed isotopic signal. This study evaluates the application of a variety of available analytical approaches to the isotopic analysis of mixed nitrate and nitrite solutions, with the goal of producing accurate coupled isotopic analyses of both nitrate and nitrite. These methods are tested on mixtures of standard solutions of nitrate and nitrite, and then applied to the coupled δ15N and δ18O analyses of nitrate and nitrite in waters of the Eastern Tropical North Pacific (ETNP). Results from standard mixtures show that even for extreme values of nitrate and nitrite δ15N and δ18O, both nitrite removal by ascorbate and nitrite isotopic analysis and subtraction from the mixed isotopic signal yield nitrate δ15N and δ18O values that are close to the expected values. Application of these analyses to samples from the ETNP yielded δ15NNO3 and δ18ONO3 values as high as 21‰ vs. AIR and 19‰ vs. VSMOW, respectively. Conversely, very low δ15N values were observed in nitrite, with values ranging from − 7.2 to − 18.5‰ vs. AIR. Removal of nitrite from ETNP samples thus revealed differences of up to 5‰ between NO3- and NO2- + NO3- for both δ15N and δ18O. Moreover, the δ15N offset between co-occurring nitrate and nitrite is greater than expected from the action of denitrification alone and may provide a unique constraint on the processes involved in the cycling of nitrite in and around oxygen deficient zones. Finally, subtraction of the nitrite δ15N and δ18O from ETNP samples allows the extension of the Δ(15,18) tracer into suboxic regions containing nitrite. The magnitude and distribution of Δ(15,18) in these samples suggests an important role for nitrite reoxidation in nitrate isotope variations.  相似文献   

6.
海水中硝酸盐铜镉柱还原测定操作步骤的优化研究   总被引:2,自引:0,他引:2  
本文比较了硝酸盐测定的铜镉柱还原法在两个规范中技术指标和操作工艺的差异.针对本实验室具体条件,对该测定方法的某些步骤(如镉柱制备、蠕动泵、流速选择、加氯化铵缓冲液方法等)进行优化研究,选择适宜的改进方法,以便将硝酸盐铜镉柱还原测定方法结合进本实验室已有的营养盐测定系统中.  相似文献   

7.
A chemiluminescent analysis technique for the determination of nanomolar quantities of nitrate, nitrate plus nitrite or nitrite alone in seawater is described. The method depends on the selective reduction of these species to nitric oxide which is then determined by its chemiluminescent reaction with ozone, using a commercial nitrogen oxides analyzer. The necessary equipment is compact and sufficiently sturdy to allow shipboard use. A precision of ±2 nM is claimed with analytical rates of 10–12 samples h?1, and modifications are discussed to allow doubling the analytical rate.  相似文献   

8.
We have developed an ecosystem model including two nitrogen isotopes (14N and 15N), and validated this model using an actual data set. A study of nitrogen isotopic ratios (δ15N) using a marine ecosystem model is thought to be most helpful in quantitatively understanding the marine nitrogen cycle. Moreover, the model study may indicate a new potential of δ15N as a tracer. This model has six compartments: phytoplankton, zooplankton, particulate organic nitrogen, dissolved organic nitrogen, nitrate and ammonium in a two-box model, and has biological processes with/without isotopic fractionation. We have applied this model to the Sea of Okhotsk and successfully reproduced the δ15N of nitrate measured in seawater and the seasonal variations in δ15N of sinking particles obtained from sediment trap experiments. Simulated δ15N of phytoplankton are determined by δ 15N of nitrate and ammonium, and the nitrogen f-ratio, defined as the ratio of nitrate assimilation by phytoplankton to total nitrogenous nutrient assimilation. Detailed considerations of biological processes in the spring and autumn blooms have demonstrated that there is a significant difference between simulated δ15N values of phytoplankton, which assimilates only nitrate, and only ammonium, respectively. We suggest that observations of δ 15N values of phytoplankton, nitrate and ammonium in the spring and autumn blooms may indicate the ratios of nutrient selectivity by phytoplankton. In winter, most of the simulated biogeochemical fluxes decrease rapidly, but nitrification flux decreases much more slowly than the other biogeochemical fluxes. Therefore, simulated δ15N values and concentrations of ammonium reflect almost only nitrification. We suggest that the nitrification rate can be parameterized with observations of δ15N of ammonium in winter and a sensitive study varying the parameter of nitrification rate.  相似文献   

9.
建立了测定天然海水中硝酸盐氮同位素组成的蒸馏法,该方法主要是在碱性条件下利用戴氏合金将海水中的硝酸盐还原为氨,后利用稀盐酸吸收生产的氨,将得到的氨吸收液浓缩后干燥结晶,利用同位素比值质谱仪测定所得晶体的氮同位素组成。研究中开展了戴氏合金添加量及氨吸收溶液在不同条件下干燥结晶对氮同位素测值的影响研究。结果表明,戴氏合金添加量为3.0 g及60 ℃下直接干燥结晶为最佳的实验条件。所建立的氨蒸馏法氮空白值仅为(0.90±0.19) μmol,低于此前文献报道的氮空白值;氮同位素组成(δ15N)空白值为(-14.7±4.1)×10-3。运用所建立的氨蒸馏法实测得到的硝酸盐δ15N值与氨扩散法、硝酸盐直接测定法得到的数值非常吻合,进一步证明所建立氨蒸馏法的可靠性。改进后的氨蒸馏法适用于硝酸盐浓度在2~50 μmol/dm3内的天然海水硝酸盐氮同位素组成的测定,方法的标准偏差为±0.3×10-3。  相似文献   

10.
A high sensitivity manifold for the determination of trace quantities (nanomolar concentrations) of nitrate+nitrite and nitrite alone is described. The method uses a classical Technicon AutoAnalyzer II usually employed for shipboard analysis. A reproducibility of ± 1 nmol dm−3 for nitrate plus nitrite and nitrite alone was obtained, with an analytical rate of 40 samples h−1.  相似文献   

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