海水中硝酸盐铜镉柱还原测定操作步骤的优化研究

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.     

锌镉还原法测定海水硝酸盐的改进

提出在锌镉法中添加含氨的氯化铵溶液,称铵锌镉还原法,其还原率94.3%,精密度2.0%,比锌镉法还原率和精密度高,无盐效应,又有锌镉法操作简便之优点.铵锌镉法反应机理:由于氨使Zn2+形成络合物,NH4+电离出H+,二者使N03-还原更完全.     

镉2铜法测定海水中硝酸盐的过度还原问题

认为用镉－铜法测定硝酸盐时还原率低的原因是过度还原，并介绍了判断过度还原存在与否的实验方法，研究了影响过度还原程度的因素及解决方法。     

铵锌镉还原法测试硝酸盐氮、氧同位素方法研究

本研究利用铵锌镉还原法将海水、湖水和自来水水体中硝酸盐转化为N₂O气体测试氮、氧同位素, 结果表明当反应体系的pH值在6～8之间, NO₃^-还原为NO₂^-的转化率大于95%, NO₂^-还原为N₂O的转化率大于99%。配置5种丰度的硝酸盐氮、氧同位素标样, 将实验结果与理论值绘制校准曲线, 氮同位素校准曲线斜率为0.48, 相关性良好(R²=0.999 8), 5种丰度δ¹⁵N_N2O标准偏差在0.18‰～0.43‰之间(n=5);氧同位素校准曲线斜率为0.70, 相关性良好(R²=0.999 6), 5种丰度δ¹⁸O_N2O标准偏差在0.27‰～0.46‰之间(n=5)。铵锌镉还原法与镉柱还原法测定硝酸盐氮、氧同位素结果的精密度和准确度一致, 同时海水、湖水和自来水3种不同类型水样的硝酸盐氮、氧同位素测试数据满足实验要求, 而且在实验流程的简洁性和高效性方面更具优势。     

天然海水硝酸盐氮同位素组成的蒸馏法测定

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。     

长江口附近氮的地球化学Ⅰ、长江口附近海水中的硝酸盐

海水中NO3—N的含量，在浮游植物大量繁殖时，可以使之消耗殆尽．但有机质的分解，可以使之获得再生．海水垂直对流作用，可以将底部再生的N03-N带到上层．大陆水也会带来大量的NO3-N．     

海洋沉积物中反硝化细菌的分离及去除硝酸盐氮的模拟试验

从长江口沉积物中筛选分离出了海洋反硝化细菌,模拟了该细菌对不同浓度水平硝酸盐氮的去除效率。研究结果表明,分离出的海洋反硝化细菌能有效去除海水中硝酸盐氮,在硝酸盐氮的初始浓度为 1 mg/L,1 d 内硝酸盐氮去除率就达到了 70 %;在 100 mg/L 硝酸盐氮模拟试验中,约在一周内能将 90 % 硝酸盐氮去除。试验证明反硝化细菌的生长与水体中硝酸盐氮浓度有一定的相关关系,一旦生物修复过程完成,反硝化细菌就会大量死亡,水体重新恢复到清澈透明状况。     

国产沸石的改性处理及其在海水硝酸盐氮同位素预处理中的应用

使用多种改性方法对几种国产天然沸石进行改性处理,提高其铵氮吸附率,制备符合海水硝酸盐氮同位素预处理要求的沸石。发现重力筛选可提高沸石铵氮吸附率16%以上,钠改性及酸改性后钠改性可提高沸石铵氮吸附率80%以上,微波改性和超声波改性均可进一步提高沸石铵氮吸附率。改性处理后,几种沸石在酸性条件下对低浓度铵氮吸附率达90%以上,其氮同位素分馏较美国UOP沸石分馏系数更小,且更稳定。改性后的国产沸石更适于海水硝酸盐氮同位素预处理。应用改性后沸石对长江口海域硝酸盐水样进行了分析,结果表明,改性后沸石可以应用于海水中溶解态硝酸盐的氮同位素分析,为海水中溶解态氮的来源问题及循环机理研究等提供了有效信息。     

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。     

Determination of experimentally enriched15N in nitrate nitrogen based on an improved method of azo dye formation

A method has been developed for determination of¹⁵N isotope ratio in nitrate nitrogen, which is a major analytical step in tracer experiments for studies of nitrate metabolism in the marine environment. The method is based on diazotization of nitrite with sulfanilic acid following reduction of nitrate to nitrite by a cadmium-copper column. The diazonium compound is then subject to the azo coupling reaction with 2-naphthol, and the azo dye formed is extracted by a solid phase extraction column. The dye eluted from the column is collected, and total nitrogen and¹⁵N content of the dye are determined by mass spectrometry. Sulfanilic acid can also remove preexisting nitrite by heating the sample under acidic conditions before passing through the cadmium-copper reduction column. The average recovery of nitrate nitrogen was 86%. A procedure for reducing the background nitrogen that derives from the analytical operations has been developed; background nitrogen was limited to about 0.25 μg-atomN. The variation in the background nitrogen levels reflects the range of error in¹⁵N determination of nitrate nitrogen by this method. Application of the present method to a¹⁵NO₃ ⁻ isotope dilution experiment for determination of nitrification rate in sea water is demonstrated.     

A sensor package for the simultaneous determination of nanomolar concentrations of nitrite, nitrate, and ammonia in seawater by fluorescence detection

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.     

模拟添加氮对海水溶解无机碳体系的影响

碳和氮作为主要的生源要素对维持海洋生态系的正常运转起着至关重要的作用,碳与氮的变化是相互耦合的且呈双向作用,为探讨海水无机碳与氮的相互作用规律,研究了室内模拟添加硝酸盐对海水无机碳体系pH、溶解无机碳(DIC)、HCO3-、二氧化碳分压(Pco2)的影响。结果表明,在室内培养的条件下,单纯添加硝酸盐(增加至原海水硝酸盐浓度的5-20倍)可引起培养体系浮游生物量的变化,但不能引起海水pH及DIC、HCO-3含量的明显变化,对DIC而言,其变化率仅仅在1%以内,但可导致海水Pco2的相对明显升高,其最终结果导致海水碳汇强度的减弱,碳源强度的增加。     

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.     

Spatial and temporal distribution of cadmium and copper in water and zooplankton in the Bahía Blanca estuary,Argentina

Cadmium and copper in the dissolved and particulate phase and in zooplankton were determined in the Bahía Blanca estuary during six surveys from March to December 2005. Temperature, pH, salinity, dissolved oxygen, suspended particulate matter, particulate organic matter and chlorophyll-a were also considered. Dissolved Cd was below the detection limit (0.2 μg L⁻¹) for almost the entire study period whereas Cu concentrations (0.5–2.4 μg L⁻¹) indicated a continuous dissolved Cu input. Particulate Cd concentrations ranged from below the detection limit (<0.01) to 28.6 μg g⁻¹ d.w. while particulate Cu ranged from below the detection limit (<0.04) to 53.5 μg g⁻¹ d.w. Cd in mesozooplankton ranged from below the detection limit (<0.01) to 37.4 μg g⁻¹ d.w. Some of the Cd levels were higher than those reported for other aquatic ecosystems. Cu in the mesozooplankton ranged from 1.3 to 89.3 μg g⁻¹ d.w., values which were within the reported values or higher than other studies. The log of the partition coefficients (log (K_d)) of Cd was 0.04, while log (K_d) for Cu ranged from −0.39 to 2.79. These values were lower than both those calculated for other estuaries and the typical coefficients for marine environments. The log of the bioconcentration factor (log BCF) of Cd was 1.78, indicating that Cd concentration was higher in the zooplankton than in the dissolved phase. Log BCF of Cu ranged from 1.15 to 3. The logs of the biomagnification factors (log BMF) of Cd were low, with a range between −3.45 and 2.21 and those for Cu ranged from −0.1 to 3.35. Positive values indicate biomagnification while negative values indicate biodiminution. In general, no significant dissolved Cd concentration appeared to be present in the Bahía Blanca estuary and Cu values did not indicate a critical environmental status. The particulate phase seemed to be the major carrier for Cd and Cu and TPCu values were within the normal values for an anthropogenically stressed estuary but not for a strongly polluted system. This fraction was the most important metal source for the mesozooplankton. Moreover, the highest metal concentrations were in the mesozooplankton since most of the bioconcentration and biomagnification factors were positive, especially for Cu.     

海水中总溶解氮测定的高温燃烧法和湿化学氧化法的比较

对测量海水中总溶解氮(TDN)的两种常用方法——高温燃烧法和过硫酸钾氧化法进行了比较。结果表明,两种方法在空白、精密度和准确度实验中不存在显著差异。对不同化合物的回收率均在92%～107%之间,加标回收实验回归曲线的斜率分别为0.93和0.92。对于现场海水样品的测定结果,两个断面拟合的斜率分别为0.92和0.97。HTC法比PO法对实际海水样品的氧化效率略高,在操作上也更方便、快捷。因此,高温燃烧法更适合海水中总溶解氮(TDN)的测定。     

基于分光光度法的多量程海水营养盐原位传感器检测系统设计

针对传统海水营养盐检测方法不能满足海水营养盐长期原位监测需求的问题,研制了一种基于分光光度法的多量程海水营养盐原位传感器检测系统,通过对系统的高度集成及对多量程检测、低功耗技术、漏液保护技术的应用,实现了对海水5项营养盐参数快速、宽范围、高精度的原位测量。经过实验室和青岛中苑码头现场测试,表明本营养盐传感器检测系统具有低功耗、高可靠性能,可满足对5项营养盐参数的快速精确测量要求,实现了对海水营养盐参数的原位监测,为相关部门及时了解海洋生态环境和水体富营养化程度提供了数据支持,具有重大现实意义。