Factors influencing particulate matter geochemistry in the St. Lawrence estuary turbidity maximum

635 samples of suspended particulate matter (SPM), collected in the St. Lawrence river and estuary during periods of high and low river flow from a series of individual and anchor stations on a transect traversing the turbidity maximum zone, as well as two sediment box cores, were analyzed for Al, Si, Ca, Mg, Fe and Mn.An abrupt change in elemental composition occurs when traversing the front at the landward edge of the turbidity maximum. As the SPM concentration increases across the front from 20–200 mg l^?1, the Ca/Al and Mg/Al ratios of the SPM increase and the Si/Al, Fe/Al and Mn/Al ratios decrease. The almost 50% decrease of the Mn/Al ratio is not related to changes in salinity. Within the turbidity maximum the tidal-averaged Si/Al, Ca/Al, Mg/Al and Fe/Al ratios of the SPM do not differ significantly from the landward to the seaward end of the turbidity zone, but on one tidal station the ratios of Si, Ca and Fe to Al are significantly lower at high river flow than at low flow. The Mn/Al ratio is insensitive to the extreme variations of either salinity (0.6–30‰) or SPM concentrations (10–480 mg l^?1) within the turbidity zone. A tendency for higher Mn/Al ratios to be associated with near-bottom SPM, observed in the center of the turbidity zone during the low river flow period, is well developed in the lower reaches of the zone.Diagenetic mobilization within the rare fine-grained bottom sediments of the turbidity maximum is responsible for changes in Mn and Fe content of particulate matter, and early settling of coarse-grained components and size sorting within the zone are responsible for other compositional changes. Local sources, desorption and precipitation are apparently of secondary importance. The depletion of both Mn and Fe in the SPM and sediment of the upper estuary implies a net seaward escape of diagenetically mobilized metal.     

Dissolved chromium in the St. Lawrence estuary

A study of dissolved chromium in the St. Lawrence estuary and Gulf of St. Lawrence has been carried out. A chromium concentration of 0·7 μg l^?1 was found in the St. Lawrence River. In the turbidity maximum of the upper estuary, chromium is removed from solution onto fine-grained resuspended sediments and internally produced organic-rich floccules. A simple flux calculation shows that these processes remove ～50% of the total dissolved chromium input of the river. At salinities greater than 5‰ dissolved chromium mixes conservatively.     

悬浮泥沙在长江口铀非保守行为中的重要作用

利用高精度的电感耦合等离子体质谱仪对2014年1月长江口表层水中溶解铀浓度及其234U/238U比值、2013年3月长江口表层沉积物中各矿物组分的铀含量及其234U/238U比值进行了测定,研究了其空间分布特征和影响因素。结果表明:除了长江径流和海水之外,长江口还有其他的溶解铀来源。水体中过剩铀与悬浮颗粒物浓度呈现显著相关性（r2=0.96）。对长江口表层沉积物进行的序列提取实验进一步表明,水体中悬浮颗粒物或沉积物中可解吸态和碳酸钙结合态铀可以在河口区域释放进入水体,而铁锰氧化物和有机物结合铀比较稳定,不受河口区混合过程的影响。每千克颗粒物或沉积物能够释放约2 μmol颗粒态铀,使其转化为溶解态。然而,铁氢氧化物和细颗粒物的絮凝吸附作用也可使溶解铀同时从河口水体中清除。在低盐度区,铀的清除和添加过程速率相近,使溶解铀呈现暂时的"伪保守"现象:颗粒态释放的铀具有明显低的234U/238U比值,导致水体的234U/238U低于保守混合值。在中高盐度区域,溶解铀呈现明显的富集现象。但是由于水相和颗粒相中的铀交换,可释放颗粒态铀的234U/238U接近溶解铀的234U/238U比值,从而导致水体的234U/238U比值呈现出保守性。长江口颗粒物的铀释放通量为（3.48±0.41）×105 mol/a,约占输入的总颗粒态铀通量（1.80±0.17）×106 mol/a的19.3%。长江口输入东海的溶解铀总通量（河流溶解态铀与河口添加铀之和）为（2.68±0.13）×106 mol/a,约为世界河流入海铀通量的11.7%。     

Relationship between biogeochemical features of biogenic elements and flocculation in the Changjiang Estuary

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Particle Dynamics and Trace Metal Reactivity in Estuarine Plumes

Iron, Mn, Cu, Pb and Zn have been determined in suspended particulate matter (SPM) collected in the estuarine plume regions of the Humber (during winter, spring and summer) and Thames (winter only). Metal concentrations (w/w) were found to increase with SPM concentration and could be defined in terms of the mixing of an ambient, slow settling population, with variable proportions of a diluent population. The end-members of the particle mixing series are fine material derived from coastal erosion, which is modified seasonally by biological production, and contaminated estuarine material which is contained within the estuarine discharge or derived from local resuspension of reworked deposits by tidal currents and wave activity. Iron-normalized metal concentrations exhibited an inverse relationship with SPM concentration in the Humber region and regression analyses enabled seasonal changes in end-member compositions to be evaluated. Since the metal:Fe ratios of the ambient population did not accord with those of local cliff samples, additional sources of metal were proposed whose importance to particle composition increases with a reduction in SPM concentration. Qualitatively, the seasonal variation of end-member compositions was consistent with (i) the coupling between redox processes occurring in the bed sediment and adsorption of metals (Mn, Cu, Zn) released from the pore waters onto ambient and diluent suspended particles in the overlying water column, and (ii) adsorption of metal (Pb) by ambient suspended particles from an extraneous (atmospheric) source. In the Thames plume, an increase in Fe-normalized metal concentrations with increasing particle concentration resulted from the mixing of end-member particles and the effects of additional metal from an internal or extraneous source were less clear, possibly because of metal desorption from suspended particles traversing the salinity gradient in the outer estuary. The processes described in this study regulate the internal cycling of trace metals in estuarine plume regions and the export of metals to neighbouring shelf sea environments.     

Suspended particulate matter in the St. Lawrence estuary and Gulf surface layer and development of a remote sensing algorithm

Remote sensing of chlorophyll concentration is potentially affected by the presence of inorganic matter in the water column. Seasonal variability of total suspended particulate matter (SPM) concentration and its partition into organic and inorganic fractions was thus measured in the estuary and Gulf of St. Lawrence during five cruises. These measures were made in the surface layer down to the depth of the 0.1% light level. Results indicate that vertical variability was small for the entire study area. Data analysis lead to the definition of two main regions having different SPM characteristics: 1) the estuary zone characterized by a strong spatial variability, intermediate SPM concentrations and a clear spring phytoplankton bloom that is combined to an increased inorganic matter load; 2) the gulf region characterized by a relatively low SPM concentration and phytoplankton blooms in the spring and fall periods. Combined with in situ measurements of remote sensing reflectances, the database was used to validate existing inorganic matter retrieval algorithms and develop a new one better adapted to the low concentrations encountered in the St. Lawrence estuary and Gulf.     

钱塘江河口细颗粒泥沙絮凝沉降特性研究

钱塘江口河口上游河流和海域来沙多为细颗粒泥沙,粘性细颗粒泥沙由于其特殊的表面电化学性质遇到强电解质海水而产生絮凝沉降,是形成河口淤积的原因之一。影响絮凝的因素很多,除了电解质,还有泥沙粒径的大小、盐度、含沙量、PH值、温度、有机质含量、矿物成分、水流速度及紊动情况等。本文通过粒度分析、静水沉降、动水沉降等各种实验手段分析钱塘江口泥沙的基本特性,找出最佳絮凝盐度以及泥沙不淤流速等值,初步探讨了细颗粒泥沙的絮凝机理,为治理钱塘江口提供科学依据。     

Geochemistry of rare earth elements in the dissolved,acid-soluble and residual phases in surface waters of the Changjiang Estuary

The concentrations of rare earth elements in the dissolved, acid-soluble and residual phases in surface waters of the Changjiang Estuary were determined using ICP-MS. The main purposes of the study are to understand the estuarine geochemistry of rare earth elements and to explore water-particle interactions in the Changjiang estuarine mixing zone. The results show that there are two distinct processes operating on dissolved rare earth elements in the estuary: large scale removal at low salinities due to salt-induced coagulation and remarkable release at mid to high salinities. These processes result in modification of the effective river water flux and the systematical fractionation of the dissolved rare earth elements toward the East China Sea. The increase in concentration of dissolved rare earth elements in the mid to high salinity waters of the Changjiang Estuary suggests a sediment source in the mixing zone of the estuary, which is located over a shallow, broad shelf where there is extensive physical contact between bottom sediment and estuarine waters. Acid-soluble rare earth elements, the concentrations of which also dropped sharply in the low salinity region, appear to be controlled by salt-induced coagulation process and intense deposition of suspended particulate matter in the low salinity region. In the mid to high salinities, all acid-soluble rare earth element concentrations increase slightly with increasing salinity, suggesting that resuspension of sediments occurred. In contrast, the residual rare earth element concentrations are relatively constant with salinity variation in the Changjiang estuarine surface waters.     

Contribution a l'etude chimique du materiel dissous et particulaire de l'estuaire de la riviere rimouski

Temperature, pH, total alkalinity, dissolved oxygen, silicate, nitrate, phosphate and the Mn, Fe and Al contents of suspended particulate matter (SPM) were measured in the Rimouski River estuary as functions of chlorinity during the period May—September 1980.At any given time, total alkalinity (TA) is conservative within the estuary with respect to chlorinity. However, the total alkalinity (TA) of the freshwater is related to river flow. This is attributed to dilution of the river water with bicarbonate-poor rainwater.Generally, pH follows the same pattern observed for TA in freshwater. Dissolved oxygen is usually more concentrated in freshwater and decreases linearly with increasing chlorinity. Freshwater is always saturated or supersaturated with respect to O₂. Seasonal fluctuations are attributed to temperature variations.There is no evidence for removal of soluble silicate from the freshwater entering the sea. The concentration of silicate in the freshwater is strongly influenced by rainfall. Soil leaching, conditioned by high rainfall increases the concentration of soluble silicate in freshwater. Nitrate behaves similarly whereas phosphate is complicated by the presence of sewage.Analysis of the Mn, Fe and Al contained in the SPM indicates dilution of river-borne particles rich in Mn by others less rich in this element. A decrease in Mn content with increasing chlorinity and SPM concentration as well as increasing concentrations of SPM with increasing chlorinity indicate that the composition is controlled primarily by physical mixing of material from two sources rather than by chemical processes. Within the analytical precision the Fe/Al ratio does not vary with the chlorinity.     

盐度和腐殖酸共同作用下的长江口泥沙絮凝过程研究

长江河口有机质含量丰富,盐度变化较大,因此研究长江河口以细颗粒泥沙为主的多因子共同作用下的絮凝有助于了解最大浑浊带的形成机制.通过实验研究盐度和腐殖酸共同作用对长江口细颗粒泥沙浊度变化影响的过程,从浊度相对变化率、絮团粒径和电位变化三方面综合分析了其絮凝机理,并且对絮凝体进行了红外和电镜分析,探讨了絮凝体的微观结构.结果表明:(1)随着盐度增大细颗粒泥沙浊度相对变化率逐渐增大,粒径增大,而电位绝对值变小;(2)随着腐殖酸浓度增大细颗粒泥沙浊度相对变化率先略有升高后迅速降低,粒径增大,电位绝对值增大;(3)微观结构的分析表明腐殖酸是以腐殖酸盐的形式包覆在泥沙表面,同时也验证了河口中C-P-OM(C代表黏土,P代表阳离子,OM代表有机化合物)的泥沙絮凝模式.     

伶仃洋河口泥沙絮凝特征及影响因素研究

泥沙絮凝对河口细颗粒泥沙运动过程起着极其重要的作用。本文通过LISST-100激光粒度仪等仪器实测伶仃洋河口2013年洪季悬浮泥沙絮凝体现场粒径及水动力、泥沙条件,结合实验室悬沙粒径分析,研究大小潮期间伶仃洋河口泥沙絮凝特征,探讨紊动剪切强度、含沙量、盐度分层及波浪等因素对伶仃洋河口泥沙絮凝的影响。结果表明:伶仃洋河口水体中现场粒径平均值为148.53 μm,大于实验室悬沙分散粒径36.74 μm,河口絮凝现象明显;沉速与有效密度、粒径呈正相关,絮团平均有效密度为153.49 kg/m3,平均沉速达1.13 mm/s;小潮时絮团平均粒径大于大潮,垂向上表底层絮团粒径小、中层大,中底层絮团沉速大于表层。伶仃洋河口水动力、泥沙条件是影响其泥沙絮凝的重要因素,低剪切强度（小于5 s-1）、低含沙量（小于50 mg/L）及高体积浓度有利于细颗粒泥沙之间的相互碰撞,促进絮凝作用;当剪切强度与颗粒间碰撞强度高于絮团所能承受的强度时,絮团易破碎分解成小絮团或更细的泥沙颗粒;伶仃洋河口盐度层化引起的泥沙捕获现象增大中层泥沙体积浓度,有利于中层絮凝体的发育;观测期相对较大的波浪增强水体紊动,增大了水体细颗粒泥沙的碰撞几率,表层絮团粒径随波高峰值的出现而增大。     

Profiles of dissolved and acid-leachable selenium in a sediment core from the lower St. Lawrence estuary

Concentrations of Se in the pore-water and in the solid phase, and the concentrations of other diagenetic constituents (Fe, Mn, phosphate, ammonium and I) in pore-water, were determined in a sediment core from a 350-m deep station in the lower St. Lawrence Estuary. The concentration of dissolved Se in pore-water was 2.1 nmol kg⁻¹ at the surface of the core, increasing to a maximum of 7.6 nmol kg⁻¹ at a depth of 12 cm, and thereafter decreasing gradually with depth. This profile is similar to the profiles of Fe and phosphate, whose concentration maxima occur around 10 cm. The concentration of total sedimentary Se remained almost constant with depth (≈ 0.75 mg kg⁻¹); however, a significant enrichment of oxalate-leachable Se was observed in the top 2 cm. The sedimentary cycling of Se appears to be closely related to that of Fe: adsorption of Se onto Fe oxyhydroxide at or near the sediment-water interface, release of the adsorbed Se by the reduction of Fe oxyhydroxide, and removal by formation of ferroselite (FeSe₂) at depth. The pore-water flux of Se was estimated by two different methods, firstly from the pore-water gradient, and secondly by applying a box model to the oxalate-leachable solid-phase Se data. The methods agree well both giving values for the flux of 0.11 nmol cm⁻² year⁻¹. This agreement suggests that the loss of labile Se in the sediment is balanced by the upward flux of dissolved Se.     

PHYSICOCHEMICAL PROCESSES OF SILICATES IN THE ESTUARINE REGION: Ⅴ. A SIMULATION EXPERIMENT ON THE FORMATION OF AUTHIGENIC SILICATE MINERALS BY ADSORPTION

Authigenic silicate minerals similar to Chamosite were synthesized under laboratory conditions, demonstrating that there may exist a geochemical process of authigenic silicate minerals formation by coagulation, adsorption, structural rearrangement and crystallization from dissolved substances in estuarine and marine environments. This also further confirms our previous geochemical removal pattern of dissolved silica in the estuarine region. Results show that the authigenic silicate minerals is one of the significant sinks of the chemical removal of dissolved silica from seawater.     

Rare earth elements in suspended and bottom sediments of the Mandovi estuary, central west coast of India: Influence of mining

Rare earth elements (REEs) in the suspended particulate matter (SPM) of the Mandovi estuary indicated that the mean total-REEs (∑REE) and light REE to heavy REE ratios are lower than that of the average suspended sediment in World Rivers and Post-Archean average Australian shale. High ∑REE were associated with high SPM/low salinity and also with high SPM/high salinity. Although the ∑REE broadly agree with SPM levels at each station, their seasonal distributions along transect are different. SPM increased seaward in the estuary both during the monsoon and pre-monsoon, but consistently low at all stations during the post-monsoon. The mean ∑REE decreased marginally seaward and was <25% at sea-end station than at river-end station. Spatial variations in ∑REE are maximum (64%) during the pre-monsoon. Strong to moderate correlation of ∑REE with Al, Fe and Mn in all seasons indicates adsorption and co-precipitation of REEs with aluminosilicate phases and Fe, Mn-oxyhydroxides. The ratio of mean ∑REE in sediment/SPM is low during the monsoon (1.27), followed by pre-monsoon (1.5) and post-monsoon (1.62). The middle REE- and heavy REE-enriched patterns with positive Ce and Eu anomalies are characteristic at every station and season, both in SPM and sediment. They also exhibit tetrad effect with distinct third and fourth tetrads. Fe-Mn ore dust is the most dominant source for REEs. However, the seasonal changes in the supply of detrital silicates, Fe-Mn ore dust and particulates resuspended from bottom sediments diluted the overall effect of salinity on fractionation and distribution of REEs in the estuary.     

Vertical mixing at the head of the Laurentian Channel

Temperature, salinity and velocity profiles taken over a 5-day period in the St. Lawrence Estuary at the head of the Laurentian Channel are used to describe the semidiurnal tidal period isopycnal oscillations occurring in this region. The observed variation in the degree of vertical mixing over the tidal cycle is used to support the concept of nutrification of the estuarine surface waters and suggests an explanation for the quarter-diurnal variability of primary production in this region.     

Denitrification-nitrification process in permeable coastal sediments: An investigation on the effect of salinity and nitrate availability using flow-through reactors

Permeable coastal sediments act as a reactive node in the littoral zone,transforming nutrients via a wide range of biogeochemical reactions.Reaction rates are controlled by abiotic factors,e.g.,salinity,temperature or solute concentration.Here,a series of incubation experiments,using flow-through reactors,were conducted to simulate the biogeochemical cycling of nitrate (NO_3~?) and phosphorus (P) in permeable sediments under differentNO_3~?availability conditions (factor I) along a salinity gradient (admixture of river and seawater,factor II).In an oligotrophic scenario,i.e.,unamendedNO_3~?concentrations in both river and seawater,sediments acted as a permanent net source ofNO_3~?to the water column.The peak production rate occurred at an intermediate salinity(20).IncreasingNO_3~?availability in river water significantly enhanced netNO_3~?removal rates within the salinity range of 0 to 30,likely via the denitrification pathway based on the sediment microbiota composition.In this scenario,the most active removal was obtained at salinity of 10.When both river and seawater were spiked with NO_3~?,the highest removal rate switched to the highest salinity (36).It suggests the salinity preference of theNO_3~?removal pathway by local denitrifiers (e.g.,Bacillus and Paracoccus) and thatNO_3~?removal in coastal sediments can be significantly constrained by the dilution relatedNO_3~?availability.Compared with the obtained variation forNO_3~?reactions,permeable sediments acted as a sink of soluble reactive P in all treatments,regardless of salinity andNO_3~?input concentrations,indicating a possibility of P-deficiency for coastal water from the intensive cycling in permeable sediments.Furthermore,the net production of dissolved organic carbon (DOC) in all treatments was positively correlated with the measuredNO_3~?reaction rates,indicating that the DOC supply may not be the key factor forNO_3~?removal rates due to the consumption by intensive aerobic respiration.Considering the intensive production of recalcitrant carbon solutes,the active denitrification was assumed to be supported by sedimentary organic matter.     

Flocculation process of fine-grained sediments by the combined effect of salinity and humus in the Changjiang Estuary

1 IntroductionThe flocculation of fine-grained particles is onof the main reasons for the estuarine depositionWith the combination of salt water and freshwaterfine-grained particles in estuaries will experiencdrastic changes: flocculation, settlement, res…     

The conservative and non-conservative behavior of chromophoric dissolved organic matter in Chinese estuarine waters

The spectral absorption properties of chromophoric dissolved organic matter (CDOM) and their distributions in two Chinese estuaries, the Yangtze River Estuary and the Jiulong River Estuary, were studied during August 2003 (wet season) and during different seasons between 2003−2005, respectively. The CDOM concentrations (a₃₅₅) of fresh end members in the Jiulong River Estuary varied seasonally, while its quality remained relatively stable. However, the a₃₅₅ of the marine end members exhibited less variability. Application of a conservative mixing model indicated that CDOM behaved conservatively in the Yangtze River Estuary. No photobleaching removal was observed at high salinity region of this estuary. Although CDOM showed conservative behavior for many cruises in the Jiulong River Estuary, there was evidence for removal in the low salinity regions during some cruises. Laboratory mixing experiments and a salt addition experiment suggested that particle sorption of CDOM maybe the possible reason for the removal. These results showed that absorption properties of CDOM can be used as a tool to observe the quantitative and qualitative dynamics of DOM during estuarine mixing.     

西南黄海2018年夏季溶解氧分布特征及其影响因素的初步分析

利用2018年夏季在西南黄海的现场调查资料,分析了海温、盐度和溶解氧(dissoloved oxygen,DO)分布特征.海区西侧的江苏沿海有明显的冷水带,冷水带对应表层较高的DO浓度.在海区南侧的长江口附近,盐度由南向北升高,上部海水DO浓度高,下部海水DO浓度低.综合现场观测数据、CCMP (Cross Calib...     

FLOCCULATION OF DISSOLVED Fe, Al, Mn, Si, Cu, Pb AND Zn DURING ESTUARINE MIXING

This is the first study of the flocculation of dissolved Fe, Al, Mn, Si, Cu, Pb and Zn during mixing in Zhujiang Estuary, based on the experiment on a series of solutions of salinities ranging from 0 to 24 by mixing the Zhujiang water near Zhongshan University and the seawater in Wan-shan Archipelago area. The mechanism of flocculation of the 7 elements is explored, and the effects of time, acidity and temperature on flocculation are discussed. The results show that the flocculation rates of Fe and Pb in the Zhujiang water are almost a hundred per cent, while that forCu reaches 76%; for Mn, 51%; for Al, 48%; for Zn, 28%; and for Si, 1.2%, indicating that Si is conservative.