北极孔斯峡湾表层沉积物中溶解有机质的来源与转化历史

在北极地区孔斯峡湾采集28个表层沉积物样品,测定了其中水溶性有机质(也称溶解有机质,DOM)的分子量分布、紫外/可见吸收光谱和三维荧光光谱特征,并利用平行因子分析(PARAFAC)模型对DOM的荧光组分和来源进行了解析。结果表明:孔斯峡湾表层沉积物中有色溶解有机质(CDOM)及其中的荧光溶解有机质(FDOM)含量均从内湾向外湾方向呈逐渐累积的趋势,但CDOM中的FDOM所占比例逐渐减小,与DOM趋于老龄化密切相关。沉积作用减弱以及长期的光化学降解和微生物降解作用对此起主要贡献,并导致腐殖质和小分子组分在沉积物DOM中所占的比例呈逐渐递增的趋势。沉积物DOM包含陆源类腐殖质、自生源类腐殖质和类蛋白等三个荧光组分,但是其组成比例空间差异很大。吸收光谱斜率比(S_R)随自生源所占百分比增加而减小,随DOM腐殖质组分中陆源与自生源的比值增加而增加;腐殖化指数(HIX)随类腐殖质与类蛋白质比值和水深的增加而增加,生物源指数(BIX)随自生源比例增加而增加。峡湾沉积物DOM的组成和来源存在着高度的空间差异,在冰川湾区由水体颗粒有机质(POM)的近期转化和迁移而来,而在峡湾中央及口门附近以较老的腐殖质为优势,主要源于水体DOM长期迁移和转化。研究表明,FDOM/CDOM,S_R,HIX和BIX等构成的CDOM光谱指纹信息可以作为揭露沉积物溶解有机质来源及迁移转化历史的工具,对探索海洋与冰川相互作用影响下的峡湾环境演变有着重要意义。     

The effect of seawater magnesium on natural fluorescence during estuarine mixing,and implications for tracer applications

Natural fluorescence, which is thought to result from low molecular weight humic and fulvic compounds, can be used as a tracer to distinguish between individual river waters. Natural fluorescence exhibits conservative mixing with seawater, except for a slight fluorescence increase which is sometimes observed in the low salinity range (0–5‰). This increase is not due to the inner filter effect (internal quenching). Laboratory experiments can reproduce this low-salinity natural fluorescence increase. Of the major seawater ions, only magnesium can cause a similar natural fluorescence increase. Variation in sample pH, ionic strength, or particle content cannot explain the natural fluorescence increase, nor does it appear to be related to the estuarine flocculation of humic material. Addition of seawater magnesium to the fluorescent material with subsequent loss of hydrogen ions could enhance fluorescence by adding crosslinking to the structure. Replacement of a fluorescence-depressing metal like copper or iron by magnesium could also enhance fluorescence, essentially by removing the quenching effect of the metal. Experimental data in this study are consistent with both of these possible mechanisms. Calcium also enhances fluorescence, however the effect of seawater calcium during estuarine mixing is not as apparent as the magnesium effect. The implications of this low-salinity natural fluorescence increase with respect to estuarine and coastal tracer applications depend on whether individual rivers mix in the high or low salinity region of an estuary or coastal area.     

Tracing dissolved organic matter in aquatic environments using a new approach to fluorescence spectroscopy

Dissolved organic matter (DOM) is a complex and poorly understood mixture of organic polymers that plays an influential role in aquatic ecosystems. In this study we have successfully characterised the fluorescent fraction of DOM in the catchment of a Danish estuary using fluorescence excitation–emission spectroscopy and parallel factor analysis (PARAFAC). PARAFAC aids the characterisation of fluorescent DOM by decomposing the fluorescence matrices into different independent fluorescent components. The results reveal that at least five different fluorescent DOM fractions present (in significant amounts) in the catchment and that the relative composition is dependent on the source (e.g. agricultural runoff, forest soil, aquatic production). Four different allochthonous fluorescent groups and one autochthonous fluorescent group were identified. The ability to trace the different fractions of the DOM pool using this relatively cheap and fast technique represents a significant advance within the fields of aquatic ecology and chemistry, and will prove to be useful for catchment management.     

海洋有机质的光谱分析方法评述

海洋有机质的光谱分析已成为海洋碳循环的研究热点之一。本文从天然有机质吸收光谱和荧光光谱分析的基本原理入手,系统梳理了有机质光谱分析中容易被忽视的基本概念,讨论了过滤与保存方式、p H值、荧光内滤效应等对有机质光谱分析的影响。结合色氨酸、酪氨酸、腐殖酸及大量现场样品的实验结果,对吸收光谱和三维荧光光谱的不同解析方法进行了系统的分析与对比。基于在南海、西菲律宾海获取的现场调查数据,对于文献中常用的荧光指数(FI)、腐殖化指数(HIX)、自生源指数(BIX)等光谱参数的内在含义及其在海洋环境中的适用性进行了评述。此外,还归纳和总结了胶体有机质和颗粒有机质荧光分析的最新进展,并对今后在光谱分析与观测领域有待完善和突破的一些关键领域进行了展望。     

Local remineralization patterns in the mesopelagic zone of the Eastern North Atlantic, off the NW Iberian Peninsula

The short-time-scale variability of the remineralization patterns in the domain of Eastern North Atlantic Central Waters (ENACW) off the NW Iberian Peninsula is studied based on biogeochemical data (oxygen, nutrient salts, total alkalinity, pH, dissolved organic matter and fluorescence of dissolved humic substances) collected weekly between May 2001 and April 2002. The temporal variability of inorganic variables points to an intensification of remineralization during the summer and autumn, with an increase of nutrients, total inorganic carbon and fluorescence and a decrease of oxygen. During the subsequent winter mixing, there is a biogeochemical reset of the system, with lower nutrients, total inorganic carbon and fluorescence and higher oxygen. In contrast to inorganic variables, the levels of dissolved organic matter in the ENACW seem to respond to short-term events probably associated with fast sinking particles, where solubilisation of organic matter prevails over remineralization. Applying a previously published stoichiometric model, we observed a vertical fractionation of organic-matter remineralization. Although there is a preferential remineralization of proteins and P compounds in the entire domain of ENACW, the percentage was higher in the upper ENACW (σ<27.10 kg/m³) than in the lower; the percentage of N and P compounds in the oxidised organic matter was >80% for the upper ENACW and 63% for the lower. Likewise, the redissolution of calcareous structures contributes about 6% and 13% to the carbon regenerated in the upper and lower layers of ENACW, respectively.     

Laser-Dye Imaging of the pH Field in a Laboratory Experiment

We established a precise DeLIF (Dual Emission Laser Light Fluorescence) system for the instant measurement of the pH field in laboratory experiments. This method is very important in studies of the biological impacts of CO₂ sequestration, i.e., effects of pH on organisms. The technique is demonstrated by applying it to the pH measurement around a liquid CO₂ droplet, which has a large gradient of CO₂ concentration near its interface, the concentration value on the boundary being known as the solubility of CO₂. In the Laser Induced Fluorescence (LIF) method using quinine and an ultraviolet laser light source, the relatively unstable pulse of the laser source decreased the measurement reliability. We therefore investigated many kinds of fluorescent dye and demonstrated the DeLIF measurement, identifying a process for cancelling fluctuations of laser light intensity. Quinine and sulforhodamine were used as fluorescence dyes. The molar absorption coefficient and emission intensity of quinine depend on the pH of aqueous solutions, while those of sulforhodamine are not as much affected by pH. The ratio of these fluorescence intensities represents pH at each point of the image. As a result, the pH field was successfully measured with an uncertainty of only approximately ±0.005, for 3.0 < pH. This revised version was published online in July 2006 with corrections to the Cover Date.     

The fluorescence of dissolved organic matter in seawater

A total of 28 vertical profiles of seawater fluorescence was measured in the Sargasso Sea, the Straits of Florida, the Southern California Borderlands, and the central Pacific Ocean. In all cases, surface seawater fluorescence was low as a result of photochemical bleaching which occurs on the timescale of hours. Fluorescence of deep water was 2–2.5 times higher than that of surface waters, and was constant, implying a long residence time for fluorescent organic matter, possibly of the order of thousands of years. Fluorescence correlates well with nutrients (NO₃⁻, PO₄³⁻) in mid-depth waters (100–1000 m) in the Sargasso Sea and the central North Pacific, consistent with results in the central Pacific and the coastal seas of Japan. This suggests that regeneration or formation of fluorescent materials accompanies the oxidation and remineralization of settling organic particles.The various sources and sinks of fluorescent organic matter in the global oceans are assessed. The major sources are particles and in situ formation; rivers, rain, diffusion from sediments, and release from organisms are minor sources. The major sink is photochemical bleaching.     

长江口及邻近海域有色溶解有机物的分布及河口混合行为的季节变化研究

于2019年3月、7月和10月对长江口及邻近海域有色溶解有机物(CDOM)的分布及河口混合行为进行分析研究。通过对盐度、吸收光谱斜率S_275～295、吸收系数a_CDOM(355)以及叶绿素a的分析发现,在河口内低盐度区,7月淡水流量大,陆源输入量最大,a_CDOM(355)值最高,3月CDOM来源主要受陆源输入和浮游植物生产活动的影响,a_CDOM(355)值较10月高;在口外高盐度区,3月和7月的a_CDOM(355)值相近,均低于10月,CDOM分布主要受浮游植物生产活动的影响。利用三维荧光光谱?平行因子分析方法共鉴定出4个荧光组分:类蛋白质组分C1(280/330 nm)、类腐殖质组分C2(300/350 nm)、类腐殖质组分C3(260/465 nm)和类腐殖质组分C4(320/410 nm)。在3月、7月及10月,4个荧光组分强度由长江口内到口外呈递减趋势,受陆源输入和浮游植物生产活动的影响,平均荧光强度的季节变化总体上来说,由大到小依次为7月、10月、3月。3个季节CDOM荧光组分均存在偏离理论稀释线的现象,说明CDOM的来源(陆源输入、沉积物再悬浮和现场生物活动)和去除(被颗粒物吸附、光降解和细菌降解)机制复杂多变,揭示了长江口区域CDOM在不同时空下的不保守混合行为。     

高原湖泊溶解有机质的三维荧光光谱特性初步研究

提要近年来,荧光光谱技术被广泛应用于研究天然水体中溶解有机质(Dissolved Organic Matter,DOM)的物理化学特性。为了理解高原湖泊中DOM的组成、荧光光谱特性及其在湖泊水体中的垂直分布情况,作者利用荧光发射光谱、三维荧光光谱研究云贵高原湖泊红枫湖和百花湖中的DOM。结果显示,高原湖泊DOM主要表现为类富里酸荧光,包括可见区和紫外区两种类型的荧光峰,各种天然水体中都有报道的类蛋白荧光在红枫湖DOM中并不明显,而在百花湖DOM中则有较强的类蛋白荧光。溶解有机质所含三种类型荧光峰(PeakA:紫外区类富里酸荧光峰;PeakB:可见区类富里酸荧光峰;PeakC:类蛋白荧光峰)的荧光强度与溶解有机碳之间没有明显的线性相关关系,可能与高原湖泊水体pH值、DOM在湖泊不同深度由于受到光降解、微生物降解等作用存在差异等因素有关。与有机质结构和成熟度有关的荧光峰比值r(A,C)在1.40—2.09范围内,红枫湖南湖、百花湖DOM样品的r(A,C)值随着水体深度有下降的趋势,而红枫湖北湖DOM的r(A,C)值则随着水体深度有较大起伏,揭示了高原湖泊水体中DOM的结构以及分布情况存在差异。另外,r(A,C)值与pH之间具有良好的正相关关系,其相关系数红枫湖南湖DOM为0.95,百花湖两个采样点DOM分别为0.67、0.75,而红枫湖北湖DOM则显示出一定的负相关性(R2=0.45)。     

Production of chromophoric dissolved organic matter fluorescence in marine and estuarine environments: an investigation into the role of phytoplankton

We tested whether phytoplankton are a direct source of chromophoric dissolved organic matter (CDOM) fluorescence in a series of experiments. In the first experiment, sonication of 11 dense algal cultures from several algal classes revealed no immediate release of CDOM fluorescence. In a second experiment, using nutrient addition bioassays from a range of sites in the mid-Atlantic region, we found no increase in CDOM fluorescence when nutrient limitation was alleviated despite large increases in chlorophyll a over 3–5 days. In a third experiment, the change in CDOM fluorescence over a 28-day period in five non-axenic algal batch cultures was measured. There was little or no increase in CDOM fluorescence until the cultures entered the stationary phase, whereupon an exponential increase in CDOM fluorescence was observed. In a fourth set of experiments, the production of CDOM fluorescence was examined in a series of cultures of Skeletonema costatum and Prorocentrum minimum. In the dark, in the absence of autotrophic growth, we observed slow rates of CDOM fluorescence production (0.02–0.05 NFlU day⁻¹). Rates were much higher in parallel lighted cultures (0.1–0.2 NFlU day⁻¹) but were more related to bacterial counts than to algal biomass. In a third phase of this experiment, when illuminated, stationary phase cultures were filtered through 1-μm pore size filters and incubated in the dark, CDOM fluorescence production continued unchanged. These results are consistent with the hypothesis that phytoplankton are not a direct source of CDOM fluorescence in marine and estuarine environments and that CDOM fluorescence is produced by bacteria using non-fluorescent organic matter derived from phytoplankton.     

Tracing of dissolved organic matter from the Sepetiba Bay (Brazil) by PARAFAC analysis of total luminescence matrices

Fluorescent excitation-emission matrices (FEEM) of the fluorescent dissolved organic matter (FDOM) are widely used for DOM characterization and tracing. In this work, a set of FEEM from sampling campaigns in the Sepetiba Bay (Brazil) was decomposed into independent components using the parallel factor analysis (PARAFAC) algorithm. Four independent components were extracted describing the total fluorescence of the FDOM. The well described peaks A, C, M, B and T were found, and a new peak, A', linked to the C peak, was detected. Relative contribution of each of four components to the total fluorescence confirms that the coastal water has DOM of terrestrial origin, except for the 275Ex/400-500Em range (nm), which primarily occurs in marine waters.     

Production and degradation of fluorescent dissolved organic matter derived from bacteria

Dynamics of fluorescent dissolved organic matter (FDOM) in ocean environments has received attention over the past few decades. Although it has appeared that in situ production of oceanic FDOM is mainly due to bacteria, the production and bio- and photodegradation processes of bacterial FDOM have not been elucidated. In this study, a culture experiment with bacteria was carried out to assess the production and biodegradation processes of bacterial FDOM. Photodegradation of bacterial FDOM and dissolved organic carbon (DOC) was also examined by exposure to a solar simulator. Bacterial FDOM consists of six components which were determined by parallel factor analysis (PARAFAC). Fluorescence intensities of protein-like FDOM increased with the bacterial biomass, but the increases of humic-like FDOM lagged behind the protein-like FDOM by 5–10 days. Exposure to simulated sunlight caused significant decreases in fluorescence intensities of all components; 52–94% of the initial intensities were lost during 24 h. While, the DOC concentration exhibited a small decrease through the experiment (1.9–11.1%). These results showed that photodegradability of bacteria derived DOC was much less than the fluorescence, indicating that the lifetime of bacteria-derived DOC is much longer than the length estimated by the fluorescence. The role of photobleached FDOM derived from bacteria may be significant in the biogeochemical cycle at the surface layer.     

On the distribution of UV-blue fluorescent organic matter in the Southern Ocean

The purpose of the work presented in this paper was to study the components of fluorescent organic matter (FOM) resulting from multi-way decomposition of excitation-emission matrices (EEMs) and to find out how their relative distributions and amounts were affected by the changing hydrography and productivity in the Southern Ocean. Data were collected during the austral summer 97/98 along the 6°E meridian covering the area between the spring ice edge and the Subtropical Front. By multiway PARAllel FACtor (PARAFAC) analysis, fluorescence EEMs could be decomposed into components that could be used for relative quantification. It is shown that three components suffice to model the fluorescence in this specific region. Two of the components obtained were protein-like and directly related to in-situ production/degradation; they were correlated with chlorophyll a, and were found to mix down to the core of the Antarctic intermediate water (AAIW) in the Subtropical Front. One component was classified as UV/Visible humic-like and showed a distribution that was very closely related to the qsu-calibrated fluorescence, i.e. indicative of terrestrial input, and of long term processes in the ocean. We suggest that the UV/Visible humic-like component consists of refractory material that is not produced or degraded significantly. It is concluded that a small number of components from PARAFAC analysis were satisfactory representatives of the major types of UV-blue fluorescent structural units present. The qualitative and quantitative results from the PARAFAC model also correlated well with other chemical and physical parameters.     

Distribution et caractérisation par fluorescence de la matiére organique dissoute dans les eaux de la Manche centrale

Intensity and spectral characteristics of the fluorescence of water samples collected along the transect Cherbourg-Isle of Wight during four cruises for excitations at 370, 313 and 270 nm have been investigated within the framework of the FluxManche II program. Seasonal and spatial differences appeared to reflect on the one hand, variations in terrestrial inputs, and on the other hand, waters masses structuring. The observed linear variation of the fluorescence intensity with salinity indicates a gradual dilution of the continental humic material in going from the coasts to the central part of the English Channel. The largest signal was observed for the English coastal waters in agreement with important terrestrial inputs from the Solent river. While the fluorescence intensity was not found to be correlated with the DOC, it shows a good correlation with the nutrients. This result could indicate both a supply from terrestrial inputs and an almost simultaneous autochtonous regeneration. As similarly reported for waters in the eastern part of the French coastal zone, excitation at 313 nm gives evidence for the presence of two classes of fluorescent dissolved organic matter. These two fluorescent components are indicative of the simultaneous presence of continental humic substances and substances whose assignment to marine humic substances or to heterotrophic related substances are still an open question. As compared to the eastern part of the Channel along the French coasts, excitation at 270 nm indicates a lower content of protein-like compounds which may be related to a lower biological activity along the transect or may be due to the fact that the samplings were made out of the phytoplanktonic bloom period (April–May 1995).     

Relative molar mass distributions of chromophoric colloidal organic matter in coastal seawater determined by Flow Field-Flow Fractionation with UV absorbance and fluorescence detection

A new method for the characterization of chromophoric colloidal organic matter in seawater has been applied to samples from the Baltic Sea, Kattegatt and Skagerrak seas. Size fractionation of the sample by Flow Field-Flow Fractionation and measurement of the fluorescent and UV absorbing properties of the individual size fractions result in a relative molar mass distribution (RMM) of the optical properties. The RMM distributions have been used to estimate number and weight average relative molar masses, and polydispersity indices. At least two sources of coloured organic matter were identified from the ratio of fluorescence to UV: the Baltic surface water and the Skagerrak deep water. The dominating processes were mixing and dilution, but processes such as photo bleaching of fluorescence are also believed to be important. The RMM distribution derived from UV detection (1150–1300 Dalton) increased with increasing salinity while that derived for fluorescence (1500–1250 Dalton) decreased with increasing salinity. The specific UV absorbance taken as a proxy of the aromaticity of the chromophoric organic material showed decreasing trend with both increasing salinity and increasing UV derived weight average relative molar mass. Increasing polydispersity of the colloidal material was also observed as a function of salinity.     

Synchronous fluorescence spectra of natural waters: tracing sources of dissolved organic matter

The fluorescence of North Carolina river samples observed simultaneously by scanning excitation and emission wavelengths at a fixed wavelength difference of 25 nm produced synchronous spectra characteristic of each sample's dissolved organic matter. Examination of the spectra of two river samples for pH, copper, magnesium and ferric iron effects revealed that the metals affect only fluorescence intensity whereas pH alters both intensity and spectral shape. Mixtures of up to four rivers were resolved using linear regression analysis and the synchronous spectrum of each component in the mixture. A similar analysis of field samples may be useful for tracing the source, circulation and mixing of dissolved organic matter in coastal waters, lakes or estuaries.     

Vertical and horizontal distribution of fluorescent dissolved organic matter in the Southern Ocean

The vertical and horizontal distribution of fluorescent dissolved organic matter (FDOM), determined by fluorescence intensity at 320 nm excitation and 420 nm emission, were clarified in nine stations on two transects at the Southern Ocean, including a subtropical, subantarctic, polar frontal and Antarctic zone. All vertical profiles of fluorescence intensity showed that levels were lowest in the surface waters, increased with increasing the depth in mid-depth waters ( 2000 m), and then stayed within a relatively narrow range from there to the bottom. Such vertical profiles of FDOM were similar to those of nutrients, but were adverse to dissolved oxygen. In water columns below the temperature-minimum subsurface water (dichothermal waters) in the Antarctic zone and below the winter mixed layer in the other zones, we determined the relationships of fluorescence intensity to concentrations of nutrients and apparent oxygen utilization (AOU) over the entire area of the present study, and found significant linear correlations between the levels of fluorescence intensity and nutrient concentrations (r =  0.70 and 0.71 for phosphate and nitrate + nitrite, respectively) and AOU (r = 0.91). From the strong correlation coefficient between fluorescence intensity and AOU, we concluded that FDOM in the Southern Ocean is formed in situ via the biological oxidation of organic matter. The regeneration of the nutrients/consumption of the oxygen/formation of FDOM was active in mid-depth waters. However, the correlations between fluorescence intensities and nutrients and AOU were different in the mid-depth water masses, Subantarctic Mode Water (SAMW), and Antarctic Intermediate Water (AAIW), indicating that the sources of organic matter responsible for FDOM formation were different. A considerable amount of FDOM in the SAMW is thought to be produced by the remineralization of DOM in addition to sinking particulate organic matter, while DOM is less responsible for FDOM formation in the AAIW.     

The determination of total dissolved free primary amines in seawater: Critical factors, optimized procedure and artefact correction

The paper reviews the methods described in the literature for the determination of total dissolved free primary amines (TDFPA) by fluorescence. A wide set of reaction conditions can be found, but they rely on few experiments for their validation. Among fluorogenic compounds, o-phthaldialdehyde (OPA) is more sensitive than fluorescamine and was thus examined here. However, the use of mercaptoethanol (ME) in the reaction (as an additional derivatization compound) is able to generate unreliable results, in particular when standardization relies on glycine. We suggest replacing ME with 3-mercaptopropionic acid (MPA) which induces more stable and comparable fluorescence among amine compounds. A systematic study was therefore undertaken to define reagent concentrations and pH effects on the reaction rates for a variety of primary amines with particular focus on amino acids. The reaction rate is increased by increasing OPA concentration and pH, but slowed by excess MPA. Ammonium interference is influenced by several factors, but spectral investigation showed that the choice of conditions can drastically reduce it. The magnitudes of natural and OPA-induced background fluorescence signals have been assessed in various mediums and it is shown that their contribution to the signal amounts to a large fraction, when not most, of the measured fluorescence. A segmented flow method is proposed with a protocol for adequate correction of biases.     

海带中昆布素的荧光定量检测及提取工艺优化

针对昆布素检测技术的难点,利用昆布素与苯胺蓝能特异性结合的特点,采用荧光分光光度计建立了昆布素含量的荧光快速检测方法。实验结果表明:NaOH浓度对昆布素立体结构影响较大,在昆布素解旋过程中加入70μL 3 mol/L的NaOH能使昆布素-苯胺蓝荧光复合物具有最大的荧光信号;通过三维荧光扫描,确定昆布素-苯胺蓝荧光复合物的最佳激发和发射波长分别为398 nm和502 nm,在此条件下昆布素-苯胺蓝荧光复合物浓度与其荧光值正相关(R2=0.999 4);方法学分析表明:该测定方法具有较高的精密度(RSD为2.52%)和稳定性(RSD为2.09%),检测范围为20~80 mg/L。基于所建立的昆布素含量快速检测方法,本文设计了有关提取温度、提取时间、pH以及乙醇浓度四个因素三个水平的正交试验对海带中昆布素的提取条件作了初步优化,结果表明:海带中昆布素的最佳提取条件是:置于稀盐酸(pH为1)溶液中于25℃下提取4 h,90%乙醇沉淀。     

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.