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。     

小长山岛3种大型海藻组织碳、氮含量和δ15N值的环境指示意义

大型海藻组织碳、氮含量及δ¹⁵N值的变化对于指示营养盐来源及营养盐评价研究具有重要的意义。为探究大型海藻组织碳、氮含量及δ¹⁵N值的变化特征,于2020年7月至2021年6月逐月分析了小长山岛潮间带孔石莼（Ulva pertusa）、角叉菜（Chondrus ocellatus）、鼠尾藻（Sargassum thunbergii）3种大型海藻组织的碳、氮含量和δ¹⁵N值的变化,并对其生长环境中海水的理化因子进行了测定。结果发现：孔石莼组织的氮含量与海水中的NO₃-N和DIN含量之间存在显著的相关性,角叉菜组织的氮含量与海水中的NH₃-N含量之间也存在显著的相关性。然而,大型海藻组织的碳含量和C/N比值与海水中的碳、氮营养盐之间并无显著的相关性。孔石莼组织的δ¹⁵N值与海水中的NO₃-N和DIN含量之间也存在显著的相关性。因此,孔石莼适于用作NO₃-N和DIN来源的指示藻种。结果指示小长山岛潮间带海水中具有供大型海藻生长利用的充足的营养盐,其主要受到生活污水和养殖排放的影响。     

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。     

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。     

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。     

小球藻对不同盐度海水养殖尾水的净化效果研究

微藻处理养殖尾水已成为热点研究方向,有关一定盐度范围内海水养殖尾水的微藻处理研究较少。本试验调配了两种盐度(16和26)的海水养殖尾水,以空白组作对照,设置小球藻(Chlorella salina)初始接种密度梯度(5×10⁵、1×10⁶、2×10⁶和3×10⁶个/mL),研究小球藻对海水养殖尾水中不同形态氮和磷的去除效果。结果表明,小球藻在海水养殖尾水中生长良好,可有效去除尾水中的氮磷营养盐,16盐度组中各初始藻密度组对NH₄⁺、NO₃^-和总溶解态氮(total dissolved nitrogen,TDN)的去除率分别为85.03%~85.87%、60.87%~63.70%和54.53%~57.64%,组间无显著差异(P>0.05);26盐度组中除5×10⁵组外,其余藻密度组对NH₄⁺、NO₃^-和TDN的去除率分别为87.23%~88.16%、56.70%~57.79%和53.31%~54.62%,且组间无显著差异(P>0.05),表明小球藻初始接种密度对尾水中氮盐的去除无显著影响。除5×10⁵个/mL组外,16与26盐度组中对TDN的去除率无显著差异,表明盐度变化对氮的去除无影响。随着初始藻密度的升高,16和26处理组对总溶解态磷(total dissolved phosphorus,TDP)的去除率均上升,分别为76.13%~99.53%和63.72%~96.83%,表明藻初始接种密度的升高可促进尾水中磷的去除,且盐度升高没有影响小球藻对磷的去除。本研究获得了不同初始接种密度小球藻对一定盐度范围的海水养殖尾水的吸收利用特点,可为海水养殖尾水的生态化处理提供一定的理论基础。     

渤海海峡冬季表层海水中溶解无机碳分布特征分析

根据2010 年2 月—2010 年3 月的调查数据, 探讨了冬季渤海海峡及其附近表层海水中溶解无机碳体系的分布特征。结果表明: 表层水体中TA、DIC 和HCO₃^- 的浓度分布总体上呈现出海峡西南部高东北部低的分布趋势。西南部出现的高值区, 与该区域靠近莱州湾, 受莱州湾水体污染影响有关。调查海域TA 与表层水的温度相关性明显, pH 与叶绿素的相关性较高。水温和Chl-a 浓度是影响水体中无机碳体系分布变化的重要因素。其中, 水温对HCO₃^- 的影响要明显强于DIC。海峡南北两侧水体交换的差异, 是导致海峡南部东西两端无机碳体系各参数监测数值的差异明显大于海峡北部的主要原因。     

不同氮源下南极冰藻Chlamydomonas sp.ICE-L的生物量、氮吸收与脂肪酸组成研究

微藻培养过程中氮缺失有利于油脂和生物量的积累,然而不同氮源条件下微藻生长与生物量的研究有限,限制了生物油脂的相关研究。本文研究通过研究南极冰藻Chlamydomonas sp.ICE-L在不同氮源条件下的细胞生长与油脂积累,进一步探究其作为富集油脂微藻的潜力。研究发现：在含有NH₄CL的培养基中,Chlamydomonas sp.ICE-L生长速率最大;在含有NH₄NO₃的条件下,获得了最大干重量0.28 g/L。最高油脂含量0.21 g/g是在缺氮条件下获得,同时得到干重0.24 g/L。在多不饱和脂肪酸的产出方面,NH₄NO₃和NH₄Cl为氮源培养基时要好于缺氮和KNO₃培养基,在NH₄NO₃和NH₄Cl为氮源的培养条件下ICE-L胞内C18：3和C20：5的含量高。比较而言,缺氮和KNO₃培养基时C16：0、C18：1和C18：2的含量要高。     

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。     

船基围隔条件下沙尘和营养盐添加对近海浮游植物群落结构的影响

为研究沙尘沉降和营养盐输入对中国陆架海域浮游植物群落结构的影响,于2017年3—4月在中国黄、东海进行沙尘和不同营养盐(NO^-₃、PO^-₄、尿素)添加的船基围隔培养实验。结果表明,与对照组相比,沙尘(2 mg/L)和尿素添加实验组的浮游植物群落细胞密度及群落结构变化不显著,叶绿素a含量差异不显著,优势种均为海链藻属 (Thalassiosira)。不同比值的氮、磷无机营养盐添加对水体中叶绿素a含量和细胞密度的影响不同,其中氮磷比为64∶1的实验组叶绿素a含量和细胞密度最高,分别为18.20 μg/L和7.86×10⁵cells/L。沙尘和营养盐添加对浮游植物群落的影响主要表现为叶绿素a含量、细胞密度峰值及不同优势种所占比例的差异,而各个实验组的种类组成及优势种具有一定的相似性。     

Diatoms grow faster using ammonium in rapidly flushed eutrophic Dokai Bay,Japan

The importance of the nitrogen source for phytoplankton growth in a highly eutrophic embayment, Dokai Bay, was investigated. The DIN concentration often exceeded 100 μM of which 40–70% was NH₄ ⁺. During two incubation experiments, the natural assemblage of mainly diatoms took up NH₄ ⁺ instead of NO₃ ⁻. The growth of two Skeletonema species isolated in Dokai Bay were significantly faster on NH₄ ⁺ (1.86 and 1.27 div. d⁻¹ respectively) than on NO₃ ⁻ (1.55 and 1.04 div. d⁻¹ respectively). Our results indicated that these diatoms could grow faster by using NH₄ ⁺ compared to NO₃ ⁻ in this eutrophic bay.     

长江口及邻近海区营养盐结构与限制

通过研究长江口及邻近海域溶解无机氮(DIN=NO₃-+NO₂-+NH₄+)、磷酸盐(PO₄3-)、硅酸盐(SiO₃2-)所表征的营养盐区域结构特征及影响因素,在分析营养盐绝对限制情况的基础上,划分了潜在相对营养限制区域。结果表明,123°E以西近岸表层区域DIN/P比值全年均高于16,而Si/DIN除秋季外基本小于1,显示出长江冲淡水影响下"过量氮"的特征。春夏季河口锋面区(31°~32.5°N,122.5°~124°E)硅藻的大量生长可使DIN/P异常升高和Si/DIN异常降低。秋季研究区域北部DIN/P西低东高且Si/DIN西高东低是由于在高DIN、低PO₄3-的长江冲淡水影响下,近岸受相对低DIN、高SiO₃2-的苏北沿岸流南下入侵影响而被分割而成。冬季长江口门东北部存在的高DIN/P和低Si/DIN区则主要由于寡营养盐的黑潮水深入陆架,向东北输送的部分长江冲淡水和增强的苏北沿岸流共同作用造成DIN升高所致。利用Redfield比值进行了不同站位表层潜在相对营养限制情况的区分。近岸123°E以西受高DIN、SiO₃2-长江冲淡水影响,四季多呈现PO₄3-潜在相对限制,而在春夏季由于浮游植物的大量吸收PO₄3-,造成局部PO₄3-绝对限制及潜在相对限制。春夏季氮限(DIN潜在相对限制)一般发生在外海部分站位,但较为零散。秋季除了东南外海大部分站位外,受苏北沿岸流影响在长江口北部近岸也存在氮限。随着低DIN/P的黑潮表层水(KSW)的入侵加强,冬季外海氮限站位增多。硅限(SiO₃2-潜在相对限制)在夏季发生在赤潮高发区,而冬季南部存在较多硅限站位表明KSW中SiO₃2-相对较为缺乏。     

Nitrogen uptake kinetics in the Ross Sea, Antarctica

The first estimates of uptake kinetic parameters for NH₄⁺, NO₃⁻, and urea in the Ross Sea, Antarctica were measured on three cruises during austral late winter–early spring 1996 (pre-bloom), late spring 1997 (bloom development), and summer 1997 (bloom decline). Nitrogen (N) uptake experiments were conducted with water collected at the 50% light penetration depth using trace-metal clean protocols and ¹⁵N tracer techniques. At all sites, ambient NO₃⁻ concentrations ranged from 5.8 to 30.5 μg-at N l⁻¹ and silicic acid concentrations were greater than 62.0 μg-at Si l⁻¹. The following trends were observed. First, based on maximum uptake rates (V_max), apparent N utilization followed the order NO₃⁻>NH₄⁺>urea during the pre-bloom and bloom development cruises. During the summer cruise, as the bloom was declining, the apparent order of utilization was NH₄⁺>NO₃⁻>urea. Second, evidence for possible repression of NO₃⁻ uptake by elevated NH₄⁺ concentrations was only observed at one site. Third, the kinetic parameters of NH₄⁺ uptake rates corrected for isotope dilution were compared with the kinetic parameters determined from uncorrected rates. In this comparison, the measure of substrate affinity, α (α=V_max/K_s) increased by an average of 4.6-fold when rates were corrected for isotope dilution, but values of V_max remained unchanged. Fourth, using bacterial production data, the magnitude of bacterial N uptake was estimated. Assuming that all bacterial N demands were met with NH₄⁺, the estimated bacterial portion of NH₄⁺ uptake ranged from <1%, when the ratio of bacteria to autotrophic biomass was low, to 35%, when bacterial abundance and biomass were highest. Finally, dramatic changes in NH₄⁺ uptake capacity were observed at one station (Stn. O), where kinetic parameters were measured during all three cruises. We hypothesize that a mutualistic relationship exists between phytoplankton and heterotrophic bacteria, and that the creation of microzones of high NH₄⁺ concentrations contributed to the changes seen at this station.     

Inorganic and organic nitrogen cycling in the Southern California Bight

On the basis of mass balance calculations performed for nitrogen (N) uptake experiments in the Southern California Bight (SCB), it has been suggested that a significant portion of dissolved inorganic N (DIN) uptake results in the production of dissolved organic N (DON). To investigate this process, the fate of ammonium (NH₄⁺) and nitrate (NO₃⁻) uptake was quantified within the euphotic zone at three coastal stations in the SCB using ¹⁵N tracer techniques. Several trends in the fate of DIN and the production of DON were observed. First, production of particulate N (PN), from both NH₄⁺ and NO₃⁻, was quantitatively more important in near surface waters, while DON release dominated within the nitracline. Second, the percentage of gross N uptake released as DON was generally higher when NO₃⁻, rather than NH₄⁺, was the substrate. Third, the percentage of N released as DON was higher at night, relative to the day. Fourth, rates of DON release were significantly correlated to NH₄⁺ regeneration, suggesting that similar mechanisms are responsible for both processes—presumably grazing. The results of this study indicate that the DON pool is a sink for DIN uptake on the time scale of hours. One implication of this finding is that new production estimates based on ¹⁵NO₃⁻ uptake rates will likely underestimate particle flux out of the surface layer because the rate of NO₃⁻ uptake is underestimated due to loss of DO¹⁵N during the incubation. On time scales of months to years, however, the N that is taken up as NO₃⁻ and released as DON will likely contribute to export flux via incorporation of the dissolved phase during seasonal mixing into sinking particles or transport. The export of DON on these time scales argues for the use of gross uptake rates to calculate f-ratios.     

桑沟湾养殖海域营养盐和沉积物-水界面扩散通量研究

利用2006年4,7,11月和2007年1月4个航次对桑沟湾养殖海域的观测资料,分析了该海域营养盐分布、结构特征、主要控制过程以及沉积物-水界面扩散通量,结果表明,该海域的营养盐分布具有明显的季节变化,海水中NO3-,NO2-,PO43-,DOP,TDP和SiO32-浓度皆是秋季最高,而NH4+,DON,TDN浓度则为夏季最高;各种营养盐的最低值除DON外都出现在春季。春季湾内外海水交换不畅,再加上大型藻类海带等生长旺盛期的消耗,使营养盐浓度处于较低水平,在夏秋两季丰水期沿岸河流注入对该海域营养盐的影响较大,冬季无机营养盐浓度分布主要受沿岸流的影响。磷的结构变化较大,其中DOP百分含量在夏季最高,达到81%。从春季到秋季海水中TDN的结构变化从以DON为主转变成以DIN为主。硅和氮的原子比值全年变化不大,硅和氮和氮和磷原子比值春夏两季的高于秋冬季的。分析营养盐化学计量限制标准和浮游植物生长的最低阈值结果表明,磷是春夏两季桑沟湾浮游植物生长的限制性因素;春季硅浓度低于浮游植物生长的最低阀值,也是一个潜在的限制因素。计算结果显示桑沟湾沉积物释放的NH4+,SiO32-和PO43-对初级生产力的贡献较小,与其他浅海环境相比,桑沟湾沉积物-水界面的营养盐通量处于较低或中等水平。     

长江水体溶解态无机氮和磷现状及长期变化特点

于2006年2、5、8和11月对长江从攀枝花至河口和上游的两条支流雅砻江和嘉陵江的溶解态无机氮(NO-3-N、NO-2-N和NH+4-N)和磷酸盐(PO43--P)进行了取样调查,同时结合长江营养盐的历史数据,分析了长江水体中溶解态无机氮、磷的长期变化特点。结果表明,长江NO-3-N、NH+4-N、DIN(包括NO-3-N、NO-2-N和NH+4-N)和PO3-4-P浓度从上游到下游显示出增加趋势,但存在季节差异;NO2-N浓度总体较低,在长江中下游(武汉—南京)浓度较高。长江从上游到下游DIN通量的变化主要受径流量的影响,从上游到下游单位面积年产N量逐渐升高;PO3-4-P输送通量从上游往下游呈增加趋势,也主要受径流量控制,但从季节变化来讲,PO3-4-P的月输送通量受其浓度的控制更加明显。自20世纪60年代来,长江水体中NO3--N、NO2--N、DIN和PO3-4-P的浓度都处于缓慢上升趋势,但到80年代上升速度明显加快;不同阶段DIN和34PO-P的季节变化特点也不尽相同,反映了其来源的差异。目前,长江水体中溶解态无机氮、磷浓度与国内及国际河流相比处于中等水平。     

浒苔对NH+4-N与NO-3-N吸收的相互作用

在国内首次研究了大型海洋绿潮藻浒苔(Ulva prolifera)对NH4+-N与NO 3--N两种氮源的选择吸收作用。结果表明:当两种氮源等浓度比例存在时,随着NH4+-N与NO3--N浓度升高,藻体对NH4+-N的吸收速率逐渐升高,而对NO3--N吸收受到抑制;当NO3--N和NH 4+-N高浓度比存在时,藻体对NH4-N的吸收速率随着NO3--N/NH4+-N比例的升高和NH4-N浓度的下降而降低;当NO3--N和NH4+-N低浓度比存在时,藻体对NH+4-N保持较高的吸收速率,而对NO3--N的吸收效率随着NO3--N浓度的降低而降低;浒苔具有同时利用水体中较高浓度的NH+4-N和NO3--N的能力,只有当NH4+-N或NO3--N浓度较低时,才以吸收相对应的氮源为主。这说明浒苔能够快速、大量地吸收水体中氮源,为爆发性增殖贮备物质条件。同时,即便两种氮源同时存在,浒苔对NH+4-N的吸收速率也远高于对NO3--N的吸收速率,因此,控制NH4+-N的大量输入仍是预防浒苔绿潮爆发的关键。     

Seasonal variability in nitrogenous nutrition of phytoplankton assemblages in the northeastern subarctic Pacific Ocean

Nitrogen uptake rates, and physical, chemical and biological characteristics of the euphotic zone were studied in winter, spring and late summer during the period 1992–1994 along a transect (Line P) extending from the continental slope off the southwest corner of Vancouver Island (British Columbia, Canada; station P4; 49°N, 127°W) to open waters in the NE Pacific (OSP; 50°N, 145°W). Nitrate (NO₃⁻) and silicic acid (Si(OH)₄) concentrations increased offshore during every season. Lowest NO₃⁻ and Si(OH)₄ values were observed during late summer and spring, and highest during winter throughout the euphotic zone. For spring and late summer, surface depletion of NO₃⁻ was observed at the inshore end of the transect, while offshore concentrations were never limiting for phytoplankton growth. Silicic acid was never depleted at any depth or station during the period covered by this study. Ammonium (NH₄⁺) and urea concentrations exhibited a patchy distribution along the transect, with no seasonal variations. Chlorophyll a and particulate nitrogen did not show a consistent longitudinal pattern from year to year. In general, the highest concentrations of chlorophyll a and particulate nitrogen were measured during the late summer cruises, with lower values in spring and lowest in winter. Phytoplankton assemblages were numerically dominated by flagellates <5 μm throughout the water column on each cruise transect. Ammonium, urea and NO₃⁻ uptake rates represented on average 55, 24 and 21% of the depth-integrated total nitrogen uptake, both longitudinally and seasonally; hence, phytoplankton utilized nitrogen in the following order: NH₄⁺>urea>NO₃⁻ along Line P. Ammonium may have inhibited the uptake rates of NO₃⁻ and urea. Urea uptake rates were lower than those of NH₄⁺, but higher values were occasionally observed at a few depths along the transect, particularly during the spring of 1993. Depth-integrated NH₄⁺ uptake rates were generally higher inshore, while NO₃⁻ uptake rates showed higher values offshore during most seasons. In contrast, urea uptake rates did not exhibit a consistent longitudinal trend. The depth-integrated f-ratio ranged from 0.05 to 0.37 with an average of 0.21 for all stations and cruises, and was overestimated on average by 36% when urea was excluded from the calculation. On a yearly basis, primary productivity in the NE subarctic Pacific was based on regenerated nitrogen.     

Benthic fluxes in a tropical Estuary and their role in the ecosystem

In-situ measurements of benthic fluxes of oxygen and nutrients were made in the subtidal region of the Mandovi estuary during premonsoon and monsoon seasons to understand the role of sediment–water exchange processes in the estuarine ecosystem. The Mandovi estuary is a shallow, highly dynamic, macrotidal estuary which experiences marine condition in the premonsoon season and nearly fresh water condition in the monsoon season. The benthic flux of nutrients exhibited strong seasonality, being higher in the premonsoon compared to the monsoon season which explains the higher ecosystem productivity in the dry season in spite of negligible riverine nutrient input. NH₄⁺ was the major form of released N comprising 70–100% of DIN flux. The benthic respiration rate varied from −98.91 to −35.13 mmol m⁻² d⁻¹, NH₄⁺ flux from 5.15 to 0.836 mmol m⁻² d⁻¹, NO₃⁻ + NO₂⁻ from 0.06 to −1.06 mmol m⁻² d⁻¹, DIP from 0.12 to 0.23 mmol m⁻² d⁻¹ and SiO₄⁴⁻ from 5.78 to 0.41 mmol m⁻² d⁻¹ between premonsoon to monsoon period. The estuarine sediment acted as a net source of DIN in the premonsoon season, but changed to a net sink in the monsoon season. Variation in salinity seemed to control NH₄⁺ flux considerably. Macrofaunal activities, especially bioturbation, enhanced the fluxes 2–25 times. The estuarine sediment was observed to be a huge reservoir of NH₄⁺, PO₄³⁻ and SiO₄⁴⁻ and acted as a net sink of combined N because of the high rate of benthic denitrification as it could remove 22% of riverine DIN influx thereby protecting the eco system from eutrophication and consequent degradation. The estuarine sediment was responsible for ∼30–50% of the total community respiration in the estuary. The benthic supply of DIN, PO₄³⁻ and SiO₄⁴⁻ can potentially meet 49%, 25% and 55% of algal N, P and Si demand, respectively, in the estuary. Based on these observations we hypothesize that it is mainly benthic NH₄⁺ efflux that sustains high estuarine productivity in the NO₃⁻ depleted dry season.