Contrasting behaviour of trace metals in the Scheldt estuary in 1978 compared to recent years

Dissolved and particulate trace metals (Cu, Cd, Pb, Zn, Ni, Fe and Mn) measured at six stations along the Scheldt estuary in October/November 1978 are compared with more recent data. Based on Ca content in the suspended matter, three distinct geochemical regions could be distinguished: the upper estuary (salinity 1–7) dominated by fluvial mud, mid-estuary (salinity 7–17) where the composition of the suspended matter remained relatively constant, and the lower estuary where marine mud prevailed. Re-suspension of sediments is the major factor controlling the composition of the particles in the upstream region. Anoxic conditions prevailed in the upper part of the estuary extending to a salinity of 15 in 1978, while at present the seaward boundary of the anoxic water body is located at less saline waters. Furthermore, the present-day metal load is much lower than in 1978. As a consequence of the changed situation, maxima in dissolved concentrations of redox-sensitive metals in the mid/lower estuary have moved as well, which affects the trace metal re-distribution pattern. In the anoxic zone, exchange processes between dissolved and particulate metal fractions were strongly redox regulated, with Fe and Mn as excellent examples. Iron was removed from the dissolved phase in the early stages of mixing resulting in an increase in the suspended particulate matter of the leachable ‘non-residual' Fe fraction from 2 to 3.5%. Due to its slower kinetics, removal of Mn from solution occurred in mid-estuary where oxygen concentrations increased. Cu, Cd and Zn on the contrary were mobilised from the suspended particles during estuarine mixing. External inputs of Pb, and to a lesser extent of Cu, in the lower estuary resulted in the increase of their particulate and the dissolved concentrations. Calculated K_d (distribution coefficient) values were used to assess the redistribution between the dissolved and particulate phase of the investigated metals. Due to the existence of the anoxic water body in the upper estuary, the importance of redox processes in determining the K_d values could be demonstrated. The sequence of K_d values in the upper estuary (Fe, Cd, Zn, Pb > Cu > Ni, Mn) is significantly different from that in the lower estuary (Fe > Mn > Pb, Ni, Zn, Cu, Cd). Thus, in such a dynamic estuary single metal-specific K_d values cannot be used to describe redistribution processes.     

Sedimentary processes on an intertidal mudflat in the upper macrotidal Seine estuary, France

In order to understand the hydrodynamic parameters that control the fluvial sediment dynamics on an intertidal mudflat located in a sheltered zone in the upper part (fluvial part) of the macrotidal Seine estuary (France), a two-year field study of high-frequency field measurements was carried out. The bed-level evolution of the mudflat surface was measured from the semi-diurnal period to annual time scales using a high-resolution altimeter. The data showed that the sedimentary patterns on the mudflat were mainly controlled by river flows and tides. During high river flows in winter, sedimentation dominated; suspended particulate matter concentrations were higher, submersion was constant and at semi-diurnal scale, sedimentation duration was more important than erosion due to an asymmetrical tide. By contrast during low river flows in summer, erosion dominated mainly as a result of immersion/emersion of tidal flats during semi-diurnal cycle. From this annual sedimentation–erosion cycle we identify a temporary storage of 10–30% of the fine-grained (<63 μm) river-borne particles on mudflats in the upper section of the fluvial Seine estuary during high river flows.River-related sediment fluxes were estimated from the measurement of fine-grained sedimentation zones in the fluvial part of the estuary. The erosion/sedimentation processes were perennial, and the amounts of contributing sediments were directly related to the solid river load. Our results indicate that mudflats in the fluvial part of the Seine estuary play an important role in the downstream transfer of fine-grained suspended particulate matter (SPM) towards the turbidity maximum and the Rouen docks particularly during low river flows, when roughly 30–50% of the SPM originates from the eroded intertidal flats.     

Origin of sedimentary organic matter in the north-western Adriatic Sea

In order to evaluate the origin and the transformation of organic matter on the shallow shelf of the NW Adriatic Sea, organic carbon, total nitrogen and stable isotope ratios of organic carbon were analysed in riverine suspended matter and sediments as well as in marine suspended and sedimentary organic matter, in marine phytoplankton and zooplankton.The deposition of organic matter is influenced by fine sediment concentration. Surface sediments were characterised by highly variable biogeochemical conditions on the sea floor, whereas sub-surface sediments showed a more homogeneous hypoxic/anoxic environment.Low C_org/N ratio and high organic carbon and nitrogen concentrations in riverine suspended organic matter indicate an important contribution of freshwater phytoplankton within rivers, particularly during low flow regimes, which adds to the marine phyto- and zooplankton at shelf locations.In order to evaluate the importance of terrestrial, riverine and marine sources of OM in shelf sediments, a three end-member mixing model was applied to shelf surface sediments using ¹³C/¹²C values for organic matter and N/C ratios. The model showed an elevated contribution of terrestrial organic substances at intermediate depths (10–15 m), mostly corresponding to an area of coarser grain-size, whereas the riverine and marine organic fractions were mainly accumulating near the coast and offshore, respectively.     

Isotopic and biochemical composition of particulate organic matter in a shallow water estuary (Great Ouse, North Sea, England)

The biogeochemistry of particulate organic matter was studied in the Great Ouse estuary draining to the North Sea embayement known as the Wash from March 1990 to January 1991. Eleven locations were sampled monthly on a 50 km transect across the shallow estuary from the tidal weir to the middle of the Wash. Particulate organic carbon (POC) and total carbohydrate, protein and lipid analyses were combined with the determination of stable carbon isotopes. δ¹³C often increased from −30‰ in the river to −22‰ in the tidal freshwater reach. The mixing zone between fresh and marine tidal waters displayed only a slight increase in δ¹³C to −19‰. The change in δ¹³C values in the freshwater tidal reach demonstrated that mixing of riverborne and marine suspended POC was not the only process affecting the carbon stable isotope composition. Complementary sources, interfering considerably with the two end-member sources, may be identified as autocthonous primary production and resuspension of sediment that may be transported upstream. The respective importance of these sources is subject to seasonal variation. From March to August, high concentrations in carbohydrate and protein through the whole estuary indicate that despite turbidity significant primary production occurred. The proportional importance of the uncharacterized fraction of POC, which is considered as complex organic matter, was high from September to January and low from March to August. During most of the year, the biochemical compositions of particulate organic matter in the turbidity maximum and the rest of the estuary were similar. This contradicted the principle that owing to the long residence times of particles degradation processes largely dominate the production processes within the turbidity maximum. The occurence of significant in situ production in such shallow water estuaries may partially compensate for the degradation of suspended particulate organics, resulting in a complex relationship between the biogeochemical cycling and the fate of nutrients.     

River or mangrove? Tracing major organic matter sources in tropical Brazilian coastal waters

The influence of mangrove-fringed tropical estuaries on coastal carbon budgets has been widely recognised. However, a quantitative differentiation between riverine and mangrove-derived inputs to the dissolved (DOM) and microparticulate organic matter (POM) pool of these environments has been hitherto not possible. Based on lignin-derived phenols and stable carbon isotopes a chemical signature for mangrove, terrestrial and marine-derived organic matter was established for a mangrove estuary in North Brazil. A mixing model was applied to calculate the contribution of each of the three sources to the DOM and POM pool in the estuary throughout 18 tidal cycles in the course of one year. Best source assignment for POM was reached with the yield of lignin phenols and δ¹³C as paired indicators, while the origin of DOM was best identified by the yield of lignin phenols and the acid to aldehyde ratio of vanillyl phenols. Although only about 6% of the fluvial catchment area is covered by mangroves, their contribution to the estuarine DOM and POM pool generally exceeded several times the terrigenic input from the hinterland. This outwelling of mangrove-derived organic matter was enhanced during the rainy season. DOM and POM were exported from the mangrove to the estuary in similar proportions. Most mangrove-POM was rapidly removed from the water column, while mangrove-DOM behaved conservatively. In contrast, terrestrial DOM was almost entirely removed in the outer part of the estuary, which was accompanied by a concomitant increase in terrestrial POM. This seems to be the result of a geochemical barrier zone for this type of DOM in the estuary. Generally, a high proportion of mangrove-DOM was present in the outer part of the estuary, even at high tide. This indicates DOM outwelling from mangroves in adjacent bays or estuaries and points to similar driving forces controlling this process on a regional scale. Mangroves probably play a more important role than rivers for marine carbon budgets along the North Brazilian coast south of the Amazon estuary.     

Natural organics as fluorescent tracers of river-sea mixing

The use of dissolved organic matter fluorescence as a tracer of river-sea mixing was examined in two South Carolina estuaries. Fluorescence declined linearly with seawater dilution in laboratory mixing studies, and also behaved conservatively in an estuary where a single river emptied into a bay. Fluorescence-salinity relationships were also studied in another estuary where a piedmont river (high suspended sediment, low fluorescence) and a coastal plains river (low sediment, high fluorescence) mixed with ocean water. The factor of 2 or greater difference in fluorescence between the two rivers allowed their relative contribution to the estuarine water mass to be distinguished. Petroleum hydrocarbons, measured in estuarine water at 0·7-1·8 μg l⁻¹ concentrations, contributed negligibly to water fluorescence.     

三峡截流后长江口秋季TSM、POC和PN的分布特征

基于2004年11—12月长江口56个站位的悬浮体调查资料,分析了长江口区悬浮体总量(TSM)、颗粒有机碳(POC)和颗粒氮(PN)质量浓度的平面分布特征,探讨该区TSM及颗粒有机质的物质来源和三峡截流对长江三角洲的影响。结果表明,表、底层TSM与POC、PN质量浓度之间存在显著的正线性相关关系并都呈现出南高北低的格局,说明了长江悬浮颗粒物入海后主要沿东南方向输运。POC、PN质量分数与POC、PN的质量浓度不同,它们与TSM质量浓度对数有负相关关系。由于河口区底质再悬浮作用显著,TSM和POC、PN质量浓度呈现表层低、底层高的特点。长江口悬浮体主要来自长江径流和底质沉积物的再悬浮。与三峡截流前数据的对比表明,截流对目前长江口区的TSM和POC尚未造成明显的影响。     

Stable isotopes of carbon and nitrogen in suspended matter and sediments from the Godavari estuary

Spatial distribution of the carbon and nitrogen content and their isotopic enrichment in suspended matter and sediments were measured in the Godavari estuary to identify the sources and transformation mechanism of organic matter. Significant variability in isotopic distribution was found over the entire length of the Godavari estuary, suggesting multiple sources of organic matter. The mean isotopic ratios (δ¹³C_sed −25.1 ± 0.9, δ¹³C_sus −24.9 ± 1, δ¹⁵N_sed 8.0 ± 2 and δ¹⁵N_sus 6.5 ± 0.9‰) and elemental concentrations (C_sed 0.45 ± 0.2%, C_sus 0.9 ± 0.7%, N_sed 0.07 ± 0.05% and N_sus 0.16 ± 0.1%) support a predominantly terrigenous source. Significant enrichment in the isotopic ratios of δ¹³C from the upper to lower estuary in both suspended (−27.5 and −24.3‰, respectively) and sedimentary (−26.2 and −24.9‰, respectively) phases indicates a decrease in the influence of terrigeneous material toward the mouth of the estuary. A significant positive relationship exists between the δ¹³C of suspended and sediment, which indicates that these two organic carbon pools are likely coupled in the form of a significant exchange between the two phases. A positive relationship exists between chlorophyll a and suspended organic matter, which may mean that a significant source of organic carbon is the in situ produced phytoplankton. But, applying a simple mixing model to our isotopes, data yielded about 46% as the contribution of the terrestrial source to suspended matter, which may support the excessive heterotrophic activity in the Godavari estuary reported earlier.     

珠江口沉积物有机质特征、来源及其对碳存储的意义

河口沉积物作为承接陆海过程的重要载体, 是有机质赋存的主要形式之一。本文研究了珠江口沉积物总有机碳、总氮含量和沉积物可溶性有机物三维荧光特征, 以及其在口内区、混合区和口外区空间差异和影响因素, 并结合碳稳定同位素(δ¹³C)估算了珠江口各区域沉积物中不同来源有机质的贡献。结果显示: (1)沉积物总有机碳和总氮含量空间变化相似, 口内区和混合区域沉积有机质含量显著高于口外区; 主成分分析发现, 口内区沉积有机质含量主要受径流输入的影响, 口外区主要受Fe³⁺的影响; (2)MixSIAR稳定同位素混合模型结果显示, 口内区和混合区沉积有机质以陆源为主, 口外区则以海源为主; (3)珠江口沉积物新生有机质较多, 可快速被利用, 总体上不利于有机碳存储; 而陆源输入导致口内区和混合区沉积有机质腐殖化程度较高, 有机碳可存储性相对较高, 口外受海源有机质和铁氧化物—有机质复合体的影响, 有机碳可存储性相对较低。本研究可为深入认知河口区沉积有机质的生物地球化学过程及有机碳存储提供参考。     

Plankton distribution and vertical flux of biogenic matter during high summer stratification in the Krka estuary (Eastern Adriatic)

The aim of this study was to investigate phytoplankton abundance, composition and vertical export in the highly stratified Krka estuary, Croatia. The estuary is stratified throughout the year, and an interface between fresh- and brackish water plays an important role in production and degradation of biogenic matter. Vertical export of particulate organic carbon (POC), phytoplankton carbon (PPC) and faecal pellet carbon (FPC) was studied by deploying sediment traps in the middle and lower reach of the estuary and in the adjacent coastal zone. Zooplankton faecal pellet (FP) production experiments were conducted to provide additional information on the potential contribution of FP to the total carbon flux. High suspended concentrations of POC, chlorophyll a and phytoplankton was found in the lower reaches of the Krka estuary, adjacent to a source of anthropogenic eutrophication. The fraction of organic detritus to the total POC flux was 61–69% inside the estuary but only 7% at the marine station. This indicates that the primary producers in the surface layer of the Krka estuary are decomposed in and below the interface and then settle as detritus to the bottom. Low sedimentation rates in the coastal zone outside the estuary revealed that the eutrophication does not spread out of the estuary. Mesozooplankton played a modest role in vertical flux regulation, due to their low abundance and dominance of smaller forms as well as low faecal pellet production rates. It is concluded that processes taking place at the freshwater-seawater interface are of major importance for the vertical carbon flux in the investigated area.     

长江口盐度梯度下不同形态碳的分布、来源与混合行为

河口碳的生物地球化学过程是全球碳循环的重要组成。通过测定溶解无机碳（DIC）及其稳定同位素丰度（δ13C_DIC）,溶解有机碳（DOC）,有色溶解有机物（CDOM）,颗粒有机碳（POC）及其稳定同位素丰度（δ13C_POC）与元素比值（N/C）及相关指标,研究了2014年7月长江口盐度梯度下不同形态碳的分布、来源和混合行为。结果表明,DIC浓度、DOC浓度、POC含量分别为1 583.2~1 739.6 μmol/L,128.4~369.4 μmol/L和51.2~530.8 μmol/L,这些不同形态碳及CDOM的荧光组分的分布模式相似,均是从口内到口外,整体呈现先增大后减小的趋势,并与盐度呈现非保守混合行为。添加作用主要发生在在口门处最大浑浊带附近。与含量相反,从口内到口外,δ13C_DIC和δ13C_POC均呈现逐渐减小再增大的趋势,在口门附近达到最低值,分别为-9.7‰和-26.7‰。在口门附近不同形态碳含量上升及δ13C_DIC、δ13C_POC的降低可能主要与沉积物再悬浮及微生物作用有关。基于蒙特卡洛模拟的三端元混合模型的结果显示,河口内外POC来源变化明显,口内POC以陆源有机碳贡献为主,平均为62.3%,口外海源贡献逐渐增加。CDOM相关参数结果表明长江口CDOM主要来自陆源输入,海源及人类活动等也对其产生影响。     

Origin and fate of particulate organic matter in the southern Beaufort Sea – Amundsen Gulf region,Canadian Arctic

To establish the relative importance of terrigenous and marine organic matter in the southern Beaufort Sea, we measured the concentrations and the stable isotopic compositions of organic carbon and total nitrogen in sediments and in settling particles intercepted by sediment traps. The organic carbon content of surface sediment in the Chukchi and southern Beaufort Seas ranged from 0.6 to 1.6% dry wt., without a clear geographical pattern. The C_ORG:N_TOT ratio ranged from 7.0 to 10.4 and did not vary significantly downcore at any one station. Values of δ¹³C_ORG and δ¹⁵N_TOT in the sediment samples were strongly correlated, with the highest values, indicative of a more marine contribution, in the Amundsen Gulf. In contrast, the organic matter content, elemental (C_ORG:N_TOT ratio) and isotopic (δ¹³C_ORG and δ¹⁵N_TOT) composition of the settling particles was different from and much more variable than in the bottom sediments. The isotopic signature of organic matter in the Beaufort Sea is well constrained by three distinct end-members: a labile marine component produced in situ by planktonic organisms, a refractory marine component, the end product of respiration and diagenesis, and a refractory terrigenous component. A three-component mixing model explains the scatter observed in the stable isotope signatures of the sediment trap samples and accommodates an apparent two-component mixing model of the organic matter in sediments. The suspended matter in the water column contains organic matter varying from essentially labile and marine to mostly refractory and terrigenous. As it settles through the water column, the labile marine organic matter is degraded, and its original stable isotope signature changes towards the signature of the marine refractory component. This process continues in the bottom sediment with the result that the sedimentary organic matter becomes dominated by the refractory terrigenous and marine components.     

长江口最大浑浊带及邻近水域营养盐的分布特征

根据2003年11月~2004年8月4个航次的调查数据,探讨了长江口最大浑浊带及邻近水域营养盐的分布特征。结果表明,营养盐浓度一般随盐度的增加而减小,不同营养盐表现出不同的平面分布和季节变化特点。最大浑浊带所处地理位置、水动力状况、高悬浮体含量以及生物活动等决定了营养盐分布不同于整个调查水域。与整个调查水域相比,最大浑浊带营养盐浓度更高;无机N的硝化作用进行得更为充分;高的DIN/PO4-P和SiO3-Si/PO4-P比(远高于Redfield比),相对低的SiO3-Si/DIN比等。透明度是最大混浊带浮游植物生长的主要限制因素。营养盐在河口的转移除了海水稀释作用外,还有部分的生物转移以及受悬浮体-沉积物系统的影响,特别是PO4-P。在最大浑浊带,富营养化现象更为严重。     

鸭绿江河口地区沉积物特征及悬沙输送

根据鸭绿江河口区4个站位的潮周期测量数据和3个柱状样的粒度数据，对悬沙的输送规律以及口门地区最大浑浊带的形成机制、悬沙输送方向以及物质来源和动力条件进行了分析。计算分析表明，鸭绿江是一条落潮流占优势的河流，平均流作用、斯托克斯漂移效应以及水深与悬沙浓度的潮变化引起的悬沙输送是其河口区最主要的悬沙输送机制。3个柱状样粒度参数自东向西的变化反映了鸭绿江辽口西侧沿岸地区动力条件和沉积环境的变化：沉积物的平均粒径变小，分选变差，并且更正偏，物源的多元化特征逐渐增强。物源和河口区沿岸沉积动力环境的差异以及潮相的周期变化使3个柱状样中的环境敏感粒度组分对应着不同的粒径分布区间。     

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.     

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.     

Biogeochemical processes affecting total arsenic and arsenic species distributions in an intermittently anoxic fjord

Total arsenic, arsenate and arsenite concentration profiles for the water column of Saanich Inlet, an intermittently anoxic fjord located on Vancouver Island, B.C., Canada, were measured using independent analytical techniques for total arsenic and arsenic speciation to evaluate the accuracy of the speciation technique in both oxic and anoxic marine environments. Total arsenic profiles indicate a mid-depth minimum of about 1.0 ppb above the oxic—anoxic interface and an enrichment in the anoxic zone to about 2.0 ppb. This minimum may be due to either advection of arsenic-poor water into Saanich Inlet at mid-depth or arsenic incorporation onto solid phases within a bacteria- and manganese-rich particulate layer located immediately above the oxic—anoxic interface and subsequent removal via sinking particulate material. Ratios of total arsenic to phosphorus in the deep, anoxic waters of the basin are similar to those reported for marine algae, suggesting that the enrichment of total arsenic within the anoxic bottom layer may be due to its release upon organic matter decomposition.Arsenate and arsenite concentration versus depth profiles indicate a rapid (but incomplete in a thermodynamic sense) response to the oxic—anoxic interface. The arsenate/ arsenite concentration ratio is 15/1 in the oxic region of the water column and 1/12 in the anoxic zone. Arsenate—arsenite interconversion occurs at a depth shallower than ferric-ferrous but deeper than MnO₂ —Mn²⁺ interconversions.Measurements of arsenite oxidation rates at near-ambient arsenite concentrations and temperatures using an ⁷⁴As³⁺ radioactive tracer technique indicate that arsenite oxidation is initially ten times faster in seawater taken from the manganese-rich particulate layer at 165 m depth than in seawater collected near the surface at 50 m depth. Addition of antibiotics to seawater from 165 m depth initially suppressed the rate of arsenite oxidation, indicating that it may be partially microbially mediated.     

Sources and Transport of Particulate Hydrocarbons in the Meso-tidal Changjiang Estuary

n-Alkanes and polyaromatic hydrocarbons (PAHs) were analysed on suspended particles from surface waters of the Changjiang Estuary to assess the sources and fate of river-borne material in a meso-tidal riverine system. The n -alkane and PAH assemblages indicated prevailing terrestrial and anthropogenic inputs. Measurements performed at several stations within the estuary showed lower concentrations in the North than in the South Channel. These observations were in agreement with the dynamics and flow pattern of the Changjiang in this part of the estuary. Concentrations measured at a tidal series station over two tidal cycles exhibited a significant increase in flooding of more saline waters. Total suspended particles were also higher, reaching their maximum value (1·9 g l^-1) at high tide during the first flood. These findings were attributed to the landwards transport of the turbidity maximum zone from the outer estuary, as the Taiwan Warm Current funnels into the Changjiang River mouth. Saltier and less turbid waters with a more pronounced marine character could reach the tidal series site at the final stage of the second flood. During the ebb, suspended n-alkane and PAH concentrations were lower but their compositional features remained similar to those during the flood. A high total suspended particle concentration was observed during the ebb, presumably due to the Huang Pu waters flushing. The n -alkane and PAH content of the particles during such an event pointed out stronger contamination of the waters after crossing the highly populated and industrialized area of Shanghai. Flux calculations based on current meter data indicated significant differences between flood and ebb transports.     

Authigenic iron oxide formation in the estuarine mixing zone of the Yangtze River

Estuaries are elementary geochemical fronts where river water and seawater mix. Within this mixing zone, iron and other non-conservative elements can undergo complex reactions to form new solid phases. In order to understand authigenic iron oxide formation in the Yangtze River Estuary, two onsite water-mixing sets of experiments were conducted, one by mixing variable amounts of unfiltered Yangtze River water with filtered East China Sea water of different salinity (set 1), the other by mixing variable amounts of filtered Yangtze River water with filtered East China Sea water of different salinity (set 2). In set 2, the minerals newly formed in the course of mixing were investigated by means of a scanning electron microscope fitted with an energy-dispersive X-ray analytical system. It was found that ferrihydrite and lepidocrocite were formed in these mixing experiments, coexisting in nearly equal amounts. These iron oxides appear as aggregated particles with a large grain-size range of several microns to more than 100 μm. The electrolytic properties of seawater played an important role in the formation of these authigenic iron oxides. Kaolinite and organic aggregates were also found in the experimentally mixed pre-filtered waters. Amounts of newly formed suspended matter (set 2) were one to three orders of magnitude lower than those of total suspended matter (TSM) (set 1). This implies that newly formed minerals represent only a very small proportion of TSM in the estuarine mixing zone of the Yangtze River.     

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.