长江口氧化还原敏感元素的早期成岩过程

通过测试长江口沉积物及间隙水中Fe、Mn、U及Mo的含量,结合早期成岩模型及地球化学热力学分析,探讨了在河口环境中影响间隙水氧化还原敏感元素(Fe、Mn、U及Mo)分布的主要因素.根据Fick第一定律,估算了Fe、Mn、U及Mo在沉积物-水界面的扩散通量.结果表明,间隙水Fe、Mn、U及Mo的含量分别介于0.8~106μmol/L、14.8~258μmol/L、1.9~14.4nmol/L及60~546nmol/L之间.在垂直剖面上,间隙水Fe、Mn峰值分别出现在约5cm或10cm的深度.早期成岩过程是影响长江口沉积物间隙水Fe、Mn分布的主要因素.吸附系数对间隙水Fe、Mn的分布也有重要的影响.吸附系数越高,间隙水Fe、Mn浓度越低.影响间隙水U分布的主要因素为Fe,而Mo与Fe、Mn之间不存在相关性.通量计算结果显示Fe、Mn、U及Mo的扩散通量分别介于3.0~10.5μmol·(m2·d)-1、35.7~439.5μmol·(m2·d)-1、-2.3~0.2nmol·(m2·d)-1及-36.0~94.6nmol·(m2·d)-1之间.沉积物中自生铀组分约占总铀的6%~67%.      

湿地沉积物-水界面营养盐交换的定量估算

为有效控制湖泊内源营养盐的释放,探讨了不同物理改良措施(覆沙、底质疏松)对沉积物-水界面营养盐的释放通量控制效果。利用原位孔隙水采样技术(Peeper)来获得沉积物孔隙水剖面,对改良后湿地沉积物孔隙水营养盐的垂向分布及其扩散通量进行了研究。结果发现,改良后沉积含水率、孔隙率分别提高了91%和54%。水土界面附近,随剖面深度增加,孔隙水中PO₄3-、NH₄+、NO₃-及NO₂-浓度分布符合指数关系,PO₄3-、NH₄+在8 cm左右达到最大值。种植芦苇后沉积物孔隙水中PO₄3-、NH₄+均有不同程度的下降,改良措施能有效降低表层弱结合态磷在总磷中比例但增加铁磷的比例,种植芦苇可强化这一效应。运用Fick第一定律对剖面孔隙水营养盐的扩散通量进行估算,发现沉积物经疏松后,NH₄+、PO₄3-的扩散通量由57.47~72.19μg/(m2·d)和2.55~3.21μg/(m2·d)变为-95.54~-130.94μg/(m2·d)和1.50~2.05μg/(m2·d),可考虑疏松沉积物-水界面附近沉积物来作为控制湖泊内源污染的有效手段之一。     

喀斯特森林雨水的地球化学特征——以贵州茂兰国家级自然保护区为例

贵州茂兰喀斯特原始森林地区25个雨水样品的化学组成研究表明,该区雨水的pH值为4．4～7．2,平均为5．1。雨水样品富NH4^＋、Ca^2＋和SO4^2-、C1^-。NH4^＋是最主要的阳离子,平均值为56．8／μmol／L,占阳离子组成的26％～74％,Ca^2＋次之,平均值为14．8μmol／L,NHg和Ca^2＋之和占了阳离子组成的71％～94％,SO4^2-是最主要的阴离子,平均值为39．2μmol／L,占了阴离子组成的69％～91％,CI一次之,平均值为9．5μmol／L。SO4^2-和C1-占了阴离子组成的71％～96％。与中国其他地区的雨水样品相比,茂兰地区雨水离子含量要低1～2个数量级;物质来源分析表明茂兰地区雨水中溶质主要来源于自然过程的输入,人为活动输入可以忽略不计。     

太湖北部沉积物中铁硫的地球化学特征研究

选择太湖北部柱状沉积物为研究对象,对沉积物及间隙水中铁硫的地球化学特征进行了研究。结果显示．间隙水中Fe^2＋的平均浓度是S^2-平均浓度的82倍,其值为9．6～270．5μmol／L。这说明沉积物中是以Fe^3＋的还原为主,而非SO4^2-。沉积物中还原性无机硫以黄铁矿为主,其次为AVS,最后为单质硫。沉积物中的Fe^2＋的浓度均高于其他形态的铁,约占总铁含量的30％～40％。活性铁的浓度为109．86～208．16μmol／g,仅占总铁的20％左右。沉积物各层中与硫结合的铁仅占总铁的0．12％～2．35％,占活性铁的0．39％～8．36％,通过分析铁硫之间的关系并结合蓝藻爆发的时间推断,铁硫化合物的生成不是PO4^3-释放的原因。太湖北部沉积物中Fe—S及P-S之间相互关系较弱。     

赤道东北太平洋表层沉积物间隙水中营养盐的剖面分布及其海底扩散通量

对赤道东北太平洋海域表层沉积物间隙水中硅酸盐、磷酸盐和硝酸盐等营养盐的剖面分布三个航次的研究表明,研究区在采样深度内沉积物中有机质的分解以硝化作用为主.在水-沉积物界面附近硅酸盐、磷酸盐和硝酸盐都存在着极陡的浓度梯度, Fick扩散定理的计算结果表明,研究区内硅酸盐、磷酸盐和硝酸盐的海底扩散通量分别为- 886.45～ 42.62 μ mol/(m2· d)、- 3.04～ 5.83 μ mol/(m2· d)和- 189.43～ 21.05 μ mol/(m2· d),且硅酸盐和硝酸盐主要是从沉积物向底层水体扩散,是底层水体营养盐的来源之一;研究区内硅酸盐、磷酸盐和硝酸盐的海底扩散通量存在着一定的时间和空间变化, 这可能与因全球气候变化而导致的沉积环境的改变有关.     

北京官厅水库沉积物-水界面磷的分布和迁移特征

研究官厅水库一个沉积物柱及上覆水体磷的含量和形态特征,指出水体中的磷以颗粒态为主,界面上覆水中磷以无机磷酸盐为主,孔隙水中以有机磷占优势;界面附近湖水中总溶解磷、总无机磷、正磷酸盐和有机磷酸盐从远离界面到界面逐渐升高,孔隙水中总溶解磷、总无机磷、正磷酸盐在界面下10 cm左右达到最大值,有机磷含量由界面向下有增加趋势;计算了沉积物-水界面磷的沉降和扩散通量,分别为1967.5μg/a@cm2和0.5μg/a@cm2,结合沉积物中矿物组成、磷与Fe、Mn、SO2-4的关系,探讨影响磷分布和迁移的影响因素.     

河口沉积物孔隙水营养盐分布特征及扩散通量

通过2010年夏季在李村河口潮滩区3个站位的采样分析,研究了孔隙水营养盐的分布特征,并利用Fick第一定律估算了沉积物-水界面间营养盐的扩散通量。结果表明,孔隙水营养盐在不同站位间质量浓度不同,呈现出自河口上游向下游逐渐降低的分布趋势。NH₄⁺-N质量浓度为26.21~53.10 mg/L,是孔隙水中营养盐的主要组分。沉积物中有机物的降解反应主要在还原状态下进行,营养盐质量浓度在垂向上的变化受有机质含量及沉积物氧化还原环境改变的综合影响。除NO₃^--N外其他营养盐均由沉积物向上覆水体扩散,沉积物是底层水体营养盐的重要来源。     

喀斯特山区溪流上覆水—孔隙水—沉积物中不同形态氮的赋存特征及其迁移——以麦西河为例

选取贵州百花湖入湖支流麦西河为对象,研究了上覆水—孔隙水—沉积物体系氮的形态差异,结果表明:麦西河上覆水中,以硝态氮(NO-3-N)为主,氨态氮(NH+4-N)次之,亚硝态氮(NO-2-N)最低;孔隙水中,溶解无机氮中以NH+4-N为主, NO-3-N次之, NO-2-N最低;沉积物中,总氮(TN)的含量为1110.67～4413.16mg/kg;固定态铵含量为34.56～170.05mg/kg,占TN的1.47%～6.25%;可交换态氮以NH+4-N为主, NO-3-N次之, NO-2-N最低。孔隙水NH+4-N是上覆水NH+4-N的2.65～19.51倍,上覆水NO-3-N是孔隙水NO-3-N的7.14～20.43倍。沉积物TN与孔隙溶解水无机氮(DIN)、孔隙水NH+4-N、沉积物可交换态氮和沉积物可交换性NH+4-N呈显著正相关;在沉积物中,可交换性NO-3-N与可交换性NH+4-N及可交换态氮呈显著正相关,可交换性NH+4-N与可交换态氮呈极显著正相关;孔隙水溶解无机氮与孔隙水NH+4-N呈极显著正相关。麦西河不同介质中氮的迁移关系则表现为:由于浓度梯度,上覆水中的NO-3-N扩散到孔隙水中,进而累积到沉积物中;沉积物的可交换性NH+4-N,进入孔隙水,最终扩散到上覆水中。      

东沙群岛海域沉积物游离烃和孔隙水特征及其地球化学意义

对东沙群岛海域HD170和HD196A两个站位，通过系统的顶空气和孔隙水离子取样测试，对柱状样沉积物和底层水中游离甲烷的含量和沉积物孔隙水的离子组成特征以及孔隙水的来源进行了分析。游离气的分析表明，多数沉积物样品中游离甲烷的含量小于20μL／kg，但在HD196A站位，随着沉积物在海底以下埋深的增加，其中的游离甲烷含量迅速增加，在754～774cm，沉积物中游离甲烷的含量达到了7468．66μL／kg，推测其下存在巨大的烃类供应源。孔隙水的^86St／^87Sr同位素测试显示，本文所研究的两个站位沉积物孔隙水来源于正常的海洋沉积过程，而δ^11B的特征表明，沉积物中存在着与海水交换的吸附水，并且HD170站位的交换更多。柱状样沉积物孔隙水中，Ca^2＋、Mg^2＋与SO4^2-浓度表现出随着深度增加而明显降低的趋势，其中HD196A站位的硫酸盐甲烷界面小于10mbsf，暗示了该站位深部很可能赋存天然气水合物。     

珠江口海域沉积物-水界面营养盐释放特征研究

在2015年春季(3月),采用实验室培养法对珠江口海域5个站位的沉积物样品进行了沉积物-水界面营养盐交换速率的实验。结果显示,河口区交换速率较大,海湾地区交换速率较小。NH~+_4、NO~-_3、PO_4~(3-)由沉积物向水体释放,NO~-_2由水体向沉积物迁移,交换速率均值分别为90.6μmol·d~(-1)·m~(-2)、106.9μmol·d~(-1)·m~(-2)、13.8μmol·d~(-1)·m~(-2)和-21.9μmol·d~(-1)·m~(-2)。NH~+_4、NO~-_3和NO~-_2在水体贫氧环境下的交换速率高于富氧条件下的交换速率,贫氧条件下沉积物是PO_4~(3-)的释放源,富氧条件下沉积物是PO_4~(3-)的汇。扰动条件下NH~+_4和PO_4~(3-)的交换速率都大于非扰动条件,但NO~-_3则相反。NO~-_3和NO~-_2的交换速率主要受沉积物-水界面浓度扩散影响,NH~+_4和PO_4~(3-)更多的受界面吸附-解吸控制;在增氧和扰动条件下由于沉积环境由强还原性向氧化性剧变,对沉积物-海水界面营养盐的交换影响比较复杂。与国内近岸海区相比,珠江口沉积物-水界面营养盐的交换速率处于中等水平。     

南海西部海底巨型麻坑活动性示踪研究

南海西部陆坡海域海底广泛发育麻坑,其规模和数量在世界范围内均属罕见,但关于它们目前的活动特征尚不清楚。通过对西沙隆起西南部麻坑区采集的两根沉积柱样孔隙水SO^2–4、K^＋、Mg^2＋、Ca^2＋、Sr^2＋以及溶解有机碳（DIC）含量随深度的变化特征的研究,揭示麻坑内与硫酸根消耗有关的生物地球化学过程,并推断麻坑目前的活动状况。采集于麻坑外的C9柱样SO^2–4浓度变化整体呈向下凹的形态降低,减少的硫酸根是被有机质硫酸盐还原作用消耗。采集于麻坑内的C14柱样SO^2–4浓度梯度呈现明显的三段式变化,0.00-0.66 m内SO2–4浓度变化主要受有机质硫酸盐还原作用控制,0.66-3.70 m受有机质硫酸盐还原和甲烷缺氧氧化共同控制,3.70 m以下部分主要受甲烷缺氧氧化作用的影响。根据C14柱样3.7 m以下孔隙水硫酸根浓度梯度计算的硫酸根-甲烷交接带（SMI）约在14.3 m处,甲烷向上扩散的通量约为0.0144 mol/（m^2·a）。此外,2个柱样沉积物孔隙水的Ca^2＋浓度均随深度明显降低,而Mg2＋浓度略微降低,主要与自生碳酸盐矿物沉淀有关。C14的Mg/Ca和Sr/Ca随深度变化指示该柱样沉积物中自生碳酸盐岩矿物主要为高镁方解石。2个柱样的孔隙水地球化学特征显示目前研究区麻坑活动不活跃, C14麻坑中含甲烷流体发生微弱渗漏,可能处于麻坑活动的衰落期。     

长江口吴淞-浏河滨岸带沉积物AVS和SEM含量的空间分布特征

对长江口吴淞-浏河滨岸带37个站位沉积物中酸可挥发性硫化物（AVS）和同时可提取态重金属（SEM）含量及其空间分布特征进行了研究。结果表明,SEM在37个站位沉积物中浓度范围为0．20～1．37μmol／g,平均值为0．74μmol／g;AVS的浓度范围为0．20—0．80μmol／g,平均值为0．23μmol／g;沉积物中AVS含量与总有机碳（TOC）和含水率呈显著正相关关系,而SEM分别与TOC和含水率呈显著正相关关系,与沉积物中值粒径呈显著负相关关系。依据SEM／AVS比值评价方法以及美国EPA（SEM—AVS）差值评价方法对沉积物中重金属的生物有效性的判断表明,除了B2站点无显著生物毒性外,吴淞-浏河滨岸带沉积物中重金属对水生生物均处于中等毒性水平。     

The influence of upwelling and short-term changes in concentrations of nutrients in the water column on fluxes across the surface of a salt marsh

Oceanic upwelling results in the intermittent intrusion of cold ocean water enriched in nitrate, and to a lesser extent soluble reactive phosphorus (SRP), into the Kariega Estuary (South Africa). Laboratory measocosm experiments were conducted to determine the effects of such changes on fluxes of dissolved nutrients across the surface of a salt marsh within the estuary. When replicate mesocosms of the tidal creek and salt marsh were inundated with nonupwelled water (at 25°C and nitrate concentrations of 4.5 μmoll^?1), nitrate fluxes in both regions were small, and the tidal creek exhibited net uptake (negative value) of nitrate from the water column (?85 μmol m^?2 tide^?1), and the marsh, net release (positive values; 113 μmol m^?2 tide^?1). When the mesocosms were inundated with upwelled water, at 16°C and with nitrate concentrations of 24.2 μmol l^?1, both regions exhibited large net uptakes of nitrate (?514 μmol m^?2 tide^?1 and ?226 μmol m^?2 tide^?1 for the tidal creek and salt marsh, respectively). In contrast to nitrate, the fluxes of nitrite, ammonium, and SRP were not significantly different under upwelling and nonupwelling conditions, probably because initial concentrations in the two water types were similar. To determine the extent to which the nitrate uptakes were caused by decreased water temperatures or increased concentrations of nitrate, experiments were conducted in which mesocosms were inundated with water with a range of nitrate concentrations (1.8–25 μmol l^?1), at two temperatures representative of summer upwelling (16°C) and nonupwelling conditions (25°C). In both regions, the net fluxes of nitrate were positively correlated with initial concentrations of nitrate in the water column. For any given concentration, the fluxes at 16°C fell within the range of values at 25°C, indicating that the shifts in fluxes caused by upwelling occurred in response to increased concentrations in the water column and not reduced temperatures.     

Elements of the iron and manganese cycles in Lake Baikal

Using data obtained in recent years, we considered the external mass balance and characteristics of internal iron and manganese cycles in Lake Baikal (biological uptake, remineralization, sedimentary and diffusive fluxes, accumulation in sediments, time of renewal, etc.). Some previous results and common concepts were critically reevaluated.     

Phosphorus Cycling in a Freshwater Estuary Impacted by Cyanobacterial Blooms

The availability of reactive phosphorus (P) may promote cyanobacterial blooms, a worldwide increasing phenomenon. Cyanobacteria may also regulate benthic P cycling through labile organic input to sediments, favouring reduced conditions and P release, ultimately acting as self-sustainment mechanism for the phytoplankton blooms. To analyse P–cyanobacteria feedbacks and compare external versus internal loads, we investigated P cycling in the Curonian Lagoon, a freshwater estuary with recurrent summer blooms. At two sites representing the dominant sediment types, we characterised P pools and mobility, via combined pore water analysis, calculation of diffusive exchanges and flux measurements via sediment core incubations. Annual P budgets were also calculated, to analyse the whole lagoon role as net sink or source. Muddy sediments, representing nearly 50 % of the lagoon surface, displayed higher P content if compared with sandy sediments, and most of this pool was reactive. The muddy site had consequently higher pore water dissolved inorganic phosphorus (DIP) concentrations maintaining high diffusive gradients. However, measured fluxes suggested that both sediment types were mostly P sinks except for a large DIP regeneration (nearly 30 μmol m^?2 h^?1) recorded at the muddy site during an intense cyanobacteria bloom. Such internal regeneration had the same order of magnitude as the annual external P load and may offset the net annual DIP sink role of the estuary. It may also prolong the duration of the bloom. Our results suggest that positive feedbacks can regulate N-fixing cyanobacteria blooms and internal P recycling, through either diffusive fluxes or sediment settling and resuspension.     

长江口滨岸潮滩重金属源汇通量估算

根据2002～2003年长江口滨岸潮滩16个站位1年的沉积物重金属含量、粒度和密度等季节性测试数据,结合其他文献的沉积物累积速率资料,初步估算了长江口滨岸潮滩重金属的源汇通量。结果表明,2002年徐六泾以下的河口地区,沉积物中Cu、Pb、Fe、Mn、Zn、Cr的年滞留量分别为3425t/a、2751t/a、3451599t/a、69505t/a、14045t/a和3176t/a,石洞口排污口和黄浦江仍然是这几种重金属的主要污染输入来源之一。潮滩能有效滞留河口水体中的重金属,在长江口0m线以上的潮滩沉积物中,Cu、Pb、Fe、Mn、Zn、Cr的年沉降量分别占到整个河口区重金属沉降量的24.3%、27.6%、32.3%、32.4%、20.5%和23.2%。从潮滩重金属的沉降通量来看,南汇边滩的沉降通量最大,长江口南岸潮滩明显高于长江口北支潮滩,说明位于排污口下游的滩地能有效削减入海重金属污染负荷。     

High-resolution profiles of iron, manganese, cobalt, cadmium, copper and zinc in the pore water of estuarine sediment

The remobilization of iron, manganese, cobalt, cadmium, copper and zinc in the pore water of estuarine sediment cores at Yingkou was assessed using diffusive equilibrium in thin films and diffusive gradients in thin films techniques. A relatively anoxic system (+33.7 to ?224.1 mV) in the sediment cores might cause the reductive release of iron, manganese and cobalt into pore water from the estuarine sediment. High-average concentrations of iron (47.85 μg ml^?1) and manganese (3.81 μg ml^?1) were observed using diffusive equilibrium in thin films on the sediment core, but the concentration of cobalt (18.02 ng ml^?1) was relatively low. A strong correlation between iron and cobalt was observed based on the vertical profiles of the metals. Manganese and iron were more readily released from the solid phase to the solution. The peak cobalt, copper and zinc concentrations were observed in the upper layer (2–4 cm) measured using diffusive gradients in thin films. However, the peak iron, manganese and cobalt concentrations were located in the deeper layer (≥7 cm). In addition, the concentration profiles measured using diffusive gradients in thin films of cobalt, copper and zinc were independent of the iron, manganese and cobalt distribution with respect to depth.     

铁（氢）氧化物悬液中磷酸盐的吸附-解吸特性研究

铁（氢）氧化物对P的吸持和释放在一定程度上决定着P的生物有效性和水体富营养化。以两种环境中常见晶质铁氧化物（针铁矿和赤铁矿）为对照,采用X射线衍射（XRD）、透射电镜（TEM）、热重分析（TGA）和孔径分析以及动力学和吸附-解吸热力学平衡等技术方法,研究了弱晶质水铁矿对P吸附-解吸特性,并探讨了相关机制。实验表明,三种矿物对P的吸附分为起始的快速反应和随后的慢速反应,它们均符合准一级动力学过程,反应中OH释放明显滞后于P吸附,P吸附经历了从外围到内囤配位、单齿到多齿配位过渡的过程,与晶质氧化铁比,水铁矿吸附容量和OH释放量更大、慢速吸附反应更快、存在缓慢扩散反应阶段,吸附容量依次是：水铁矿（436μmol／m^2）〉针铁矿（262μmol／m^2）〉赤铁矿（228μmol／m^2）,针铁矿和赤铁矿吸附P符合L（Langmuir）模型,而水铁矿更符合F（Fremldlictl）模型。中性盐介质（KCl）中在最大吸附量时P的解吸率依次为：水铁矿（85％）〈针铁矿（10％）〈赤铁矿（125％）,柠檬酸通过配体解吸和诱导溶解两种机制促进P的解吸,最大吸附量时解吸率依次是：针铁矿（25％）〈水铁矿（32％）〈赤铁矿（50％）。