Mechanisms for trace metal enrichment at the surface microlayer in an estuarine salt marsh

The relative contributions of adsorption to particulate surfaces, complexation with surface-active organic ligands and uptake by micro-organisms were evaluated with respect to their importance in the surface microlayer enrichment (‘partitioning’) of Cd, Pb and Cu. The contributions of each process were inferred from field data in which partitioning of the dissolved and particulate forms of Cd, Pb and Cu, total and dissolved organic carbon, particles and total bacteria were observed. In the South San Francisco Bay estuary, particle enrichment appears to control trace metal partitioning. Trace metal association with the particulate phase and the levels of partitioning observed were in the order Pb > Cu > Cd and reflect the calculated equilibrium chemical speciation of these metals in computer-simulated seawater matrices.     

Metal distributions and their fluxes at the coastal boundary of a semi-enclosed ria

Water column samples have been collected in the outer channel of the Ferrol Ria (NW Spain) during four occasions over a tidal cycle. The objective was to study the exchange of dissolved and particulate Cd, Cu, Pb and Zn and particulate Al, Fe and Si between the ria and the adjacent coastal waters. This study provides the first extensive dataset on dissolved and particulate metal concentrations in the water column of a Galician ria. Typical concentrations of dissolved Cd (96 ± 31 pM), Cu (8 ± 4 nM), Pb (270 ± 170 pM) and Zn (21 ± 10 nM) were similar than in other European Atlantic shelf and coastal waters. The fraction of metals in the particulate phase followed the trend: Pb > Cu Zn > Cd. The outgoing water from the ria was enriched in dissolved and particulate Cu, Pb and Zn compared with incoming waters, whereas Cd concentrations were similar for both waters. The suspended particulate matter was composed of a mixture of marine and continental material. The latter end-member was found to arise from the metal-rich ria bed sediments, which is diluted by the dominant metal-poor marine end-member. The net output flux of Cu from the channel is balanced by the freshwater inputs to the ria, and the net Zn flux gave a positive output to coastal waters. For Pb, the net flux to the coastal waters is less than that input from the rivers, as a result of its particle reactivity and deposition in sediments. On the contrary, a net input flux of dissolved Cd from coastal waters was observed, highlighting the oceanic source of this metal in the Galician rias. Results from the budget calculations are in agreement with the differential geochemical behavior of these elements in coastal waters.     

Distribution of As, Cr and V species in the Po-Adriatic mixing area, (Italy)

The distribution of dissolved and participate concentrations of As, Cr and V was investigated in the mixing area of the Po river in five surveys over the period March 1992-March 1995. The data obtained indicate noticeable contamination of coastal waters of the northern Adriatic with Cr but not As or V. Total dissolved concentrations for As and V were comparable with oceanic levels but were higher by a factor of 4 for Cr. These results suggest either low anthropogenic inputs of As and V, from terrigenous and atmospheric sources, or efficient removal mechanisms. The investigated metals had low reactivity during freshwater-seawater mixing and the distribution of concentrations in the dissolved and solid phases suggests that the dilution process is the main factor controlling the transport of these metals to the sea in low-to-medium solid transport conditions. Further investigations are required to elucidate the behavior of these metals during high solid transport conditions. Significant changes in the speciation of As occurred during the transition between the two end-member matrices. In the coastal waters of the northern Adriatic, the arsenite fraction in winter, and the arsenite and dimethylarsinate fractions in summer increased with respect to riverine waters. Changes in the speciation of chromium were minor, but also showed a small increase in reduced species in marine waters.     

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.     

Land inputs,behaviour and contamination levels of copper in a ria estuary (NW Spain)

Copper concentrations were measured in the sediments and dissolved phase of the water column in the Lérez Estuary (Pontevedra Ria, Galicia), NW Spain, and in the freshwater-sewage inputs to the estuary. Dissolved copper fluxes in the estuary were quantified. Results show that the freshwater end-member in the Lérez Estuary has minimal copper contamination ([Cu](Dissolved)=7+/-4 nM, Sediment Enrichment Factor=1) and the source of dissolved copper inputs is localized in the saline end-member ([Cu](Dissolved)=20-55 nM, Sediment Enrichment Factor=6-7). A non-conservative behaviour of dissolved copper showing a net addition during estuarine mixing was observed. The budgetary calculations and the copper sediment distribution suggest that the major copper input to the estuary-ria system is located at the Marín-Placeres transect, playing an important role in the net addition of copper within the estuarine mixing. The importance of upwelling in the renewal of the Galician coastal waters and dilution of continental inputs is discussed.     

Dissolved Aluminum in the Upper St. Lawrence Estuary

The concentrations of dissolved aluminum (Al) in the upper St. Lawrence Estuary were determined during periods of high and intermediate river-discharge. Laboratory experiments simulating estuarine processes were also conducted in order to examine possible mechanisms controlling the Al distribution. During the high river-discharge, the Al concentration at river end-member was 1.63 µM and decreased exponentially with increasing salinity. An almost complete removal of dissolved Al was observed in the low salinity area up to 10 with an intensive removal in the turbidity maximum zone. Principal mechanisms responsible for the Al removal inferred from the laboratory experiments were flocculation and adsorption onto suspended particulate matter (SPM). During the intermediate river-discharge, the Al concentration was 0.72 µM at the river end-member and again decreased with increasing salinity. However, the removal was less pronounced, being only about 25%. Good fits with model predictions and laboratory experiments suggest that principal removal mechanisms were authigenic aluminosilicate formation and adsorption onto SPM. In the upper St. Lawrence Estuary, Al distribution is controlled by a combination of three removal mechanisms: flocculation, authigenic aluminosilicate formation, and adsorption. Each mechanism can become a dominant factor depending on the concentration level and speciation of dissolved Al in the river water.     

Seasonal variations of dissolved and particulate copper species in estuarine waters

This one-year survey conducted in the macrotidal estuary of Penzé (Brittany, Western part of the Channel, France) was aimed at examining the variations of the various dissolved and particulate copper species. Ten field stations along the whole freshwater–seawater mixing zone were sampled each month. Different biogeochemical parameters (SPM, chl-a, pH and DOC) were also measured. The levels in total dissolved and total particulate copper ranged from 1.8 to 9.5 nM and from 5 to 98 μg g⁻¹, respectively; such amounts are indicative of a pollution-free system. Extractable C₁₈ copper (non-polar hydrophobic organic copper species), in winter and spring, accounted for 30–40% of the total dissolved copper. In summer, this contribution rapidly rose to 60% in the salinity range 20–30; over the same period of time, total particulate copper decreased. The change in dissolved copper speciation and the lowering of particulate copper concentrations were attributed to the release of strong organic ligands by phytoplankton. Our field data evidenced a highly variable behaviour for the various copper species over the seasonal cycle, and then led us to identify the following mechanisms: (i) metal desorption from organic river-flown particles (winter and spring), (ii) metal desorption from resuspended sediment in the upstream section (summer), (iii) competition between particles, non-extractable C₁₈ organic ligands and phytoplankton-released extractable C₁₈ organic ligands to complex copper in the downstream section (summer), and (iv) removal of non-extractable C₁₈ organic copper by adsorption (autumn). Dissolved copper species fluxes were assessed: most of metal inputs to the estuary (60–74%) corresponded to non-extractable C₁₈ organic copper. Winter and spring metal output fluxes were mainly constituted of non-extractable C₁₈ organic complexes; on the other hand, extractable C₁₈ organic complexes were predominant in summer and autumn output fluxes.     

The distribution of Mn,Fe, Zn,Cd and Cu in Baltic seawater; a study on the basis of one anchor station

A total of 150 samples were collected at a 10-days' anchor station in the Bornholm basin (55° 31.1′N, 15° 32.1′E) and analyzed for dissolved (< 0.4 μm) and particulate trace metals. For dissolved Mn, large gradients have been found in the vertical distribution with minimum concentrations (< 0.2 μgl^?1) in the halocline zone and considerably higher values in the deep waters (up to 50 μgl^?1). Ultrafiltration studies indicate that dissolved Mn is probably present as Mn²⁺ in the oxygenated bottom layer. The primary production process was not evident in the particulate Mn profile; the suspended particulate material (SPM), however, shows a considerable enrichment with depth, apparently due to Mn-oxide precipitation.The distribution of dissolved Fe was rather homogeneous, with average concentrations throughout the water column between 0.86 and 1.1 μgl^?1, indicating that the oxidation of Fe²⁺ ions released from the sediments must already be complete in the very near oxidation boundary layer. Relatively high concentrations of particulate Fe were actually measured in the bottom layer, with the maximum mean of 11.2 μgl^?1 at 72 m. Similarly to Mn, the profile of particulate Fe does not reflect the SPM curve of the eutrophic layer. On average, about 70% of the total Fe in surface waters was found to be particulate.The average concentrations of dissolved Zn, Cd and Cu were found to be rather homogeneous in the water column but showed a relatively high variability with time. A simplified model on trace-metal uptake by phytoplankton indicates no significant change in dissolved metal concentrations during the period of investigation. On average, only 1.7% Zn, 3.3% Cd and 9.8% Cu of the total metal concentrations were found in particulate form. SPM analyses showed significant correlations of Zn, Cd and Cu with Fe, indicating that particulate iron is an important carrier for particulate trace metals in Baltic waters.     

The barnacle Balanus amphitrite as a biomonitor for Cd: Radiolabelled experiments

Radiolabelled experiments were carried out to measure necessary parameters in the development of a biodynamic ecotoxicological simulation model of Cd accumulation in the barnacle biomonitor Balanus amphitrite. The Cd uptake rate constant from the dissolved phase, the Cd assimilation efficiency (AE) from suspended particulate matter (SPM) and the efflux rate constant were obtained using ¹⁰⁹Cd. A Cd uptake rate constant from the dissolved phase (k_u) of 0.0072 L g⁻¹ h⁻¹ was determined for the barnacle under environmentally realistic dissolved Cd concentrations (maximum of 400 ng L⁻¹). Cd AE from SPM was determined from the barnacle feeding on SPM with low and high chl a concentrations, resulting in AEs of 39.0% and 48.7%, respectively, and an efflux rate of 0.0072 d⁻¹. The difference between the AEs resulted from differences in chl a:SPM ratios suggesting a general tendency of higher AE when SPM is enriched with chl a. These results reinforce that the accuracy of ecotoxicological models for metal accumulation in organisms depends on how representative the selected food items are of the organism’s natural diet.     

基于水淘选分级的长江口最大浑浊带附近颗粒有机碳的来源、分布和保存

从分粒级的角度研究大河河口颗粒有机碳的输送特征是深刻理解河口淡咸水混合过程中有机碳的生物地球化学过程的关键。于2011年6月采集了长江口最大浑浊带附近盐度梯度下的表层悬浮颗粒物,采用水淘选方法对其按照水动力直径大小进行了分级分离,分析了这些颗粒物的有机碳含量、稳定碳同位素组成及颗粒物比表面积等参数,讨论了不同粒级颗粒物上有机碳的来源、分布和保存随盐度的变化特点及其影响因素。结果表明,随着盐度的增加和粒径的增大,长江口最大浑浊带附近分级颗粒有机碳逐渐降低,颗粒有机碳含量主要集中在小于32μm的粒级。相对于长江干流,长江口颗粒有机碳含量偏低,可能归因于河口最大浑浊带附近特殊的生物地球化学作用,如细颗粒物絮凝——沉降、微生物分解等。基于蒙特卡洛模拟的三端元混合模型的计算表明长江口分级颗粒有机碳主要来源于河流和三角洲输入,海洋来源贡献较小,三者的平均贡献比例分别为40%、35%和25%。在河口盐度梯度的淡水端,不同粒级颗粒物上三角洲来源的有机碳比例均随着盐度升高而增加,而在咸水端,海源有机碳的贡献比例升高,尤其是在16-32μm粒级,最高达39%。32-63μm粒级的颗粒物单位比表面积有机碳含量均大于1.0mg/m~2,小于32μm的颗粒物单位比表面积有机碳含量均在0.4-1.0mg/m~2的范围之内,符合河流颗粒物的一般特点,同时也说明细颗粒物上的有机碳可能已经发生了一定程度的分解,不过相对于长江口表层沉积物,颗粒物单位比表面积有机碳含量普遍较高,表明这些颗粒有机碳在沉降过程中或沉积之后还要经历进一步的再矿化分解,初步的估算表明,长江所输送的陆源有机碳约71%会在沉积过程中损失掉。本研究有助于深入了解大河河口不同粒级颗粒物在有机碳迁移转化过程中的作用,深化对高浊度河口有机碳生物地球化学过程的认识。     

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%。     

河口水与污水混合有机物和磷的转移动力学

污水与九龙江河口水混合研究表明，ＣＯＤ的降解符合一级动力学模式，降解速率常数ｋ在０．０４－０．１１ｄ＾－１之间，水体有机物的转移以降解作用为主；两种水体混合时，先产生磷的吸附，后释放，整个过程表现为颗业磷向溶解无机磷的转移。     

Some peculiarities of the trace-metal distribution in Baltic waters and sediments

Between 1980 and 1984 extensive studies were carried out in the Baltic Sea on trace metals (Cd, Co, Cu, Fe, Hg, Mn, Ni, Pb and Zn) in water, suspended matter and sediments. The results enabled the influence of different factors on metal distribution patterns to be considered. The vertical profiles of dissolved and particulate metals in waters of the central deep basins reflect influences caused by oxygen deficiency and anoxic conditions in near-bottom water layers. Peculiarities at Station BY15 in the Gotland Deep included high dissolved Fe, Mn and Co concentrations and remarkable enrichment of Zn (0.64%), Cd (51 μg g⁻¹) and Cu (0.15%) in particulate matter from the anoxic zone. Manganese-rich particles were accumulated above this layer.In fine-grained soft sediments below anoxic deep waters, maximum contents of Cd, Cu and Zn were observed, relative to other coring sites, between Bothnian Bay and Lübeck Bight. The Hg content in sediments probably reflects the joint flocculation with organic matter. Land-based sources seem to play the leading part for maximum lead contents.     

The influence of salinity on the solubility of Zn and Cd sulphides in the Scheldt estuary

In the estuary of the river Scheldt, where an oxygen gradient exists in addition to the salinity gradient, redox processes will be of major importance for trace metal mobilisation. In this study, the influence of salinity and pH on the redox processes of dissolved Zn and Cd sulphides is investigated together with the effects on the ratio of the dissolved Zn and Cd concentrations. The speciation of these metals is calculated with the chemical equilibrium programme +. Zn sulphides are oxidised at lower oxygen concentrations than Cd sulphides, due to lower stability constants, causing a sudden increase or peak in the dissolved Zn/Cd ratio. The formation of dissolved Cd chloride complexes when oxidation occurs at high salinities (S=15) increases the mobility of Cd, causing a decrease in the Zn/Cd peak of the total dissolved concentrations. The peak is three to four times smaller at S=15 than when oxidation occurs at S=2. The simple model calculations compare very well with field data. The Scheldt estuary is suitable to illustrate these calculations. In the 1970s, the anoxic part of the estuary reached S=15–20, but since the early 1980s it has dropped to S=2–10. Historic data on metals in the estuary from 1978, 1987 and the 1990s were used to compare with the equilibrium calculations. The increase of the dissolved Zn/Cd peak at low salinity as a consequence, of the decreasing anoxic region is confirmed well by the data. The good agreement between model calculations and field data is a proof of the extreme importance of redox processes for the solubility of Zn and Cd sulphides in the estuary.     

Dissolved Cd behaviour in some selected french and chinese estuaries. Consequences on Cd supply to the ocean

Few data on dissolved trace metals in rivers and estuaries are presently available. This paper is an attempt to provide additional data on dissolved concentrations obtained in polluted and so-called unpolluted river estuarine systems. Data for two major French rivers (Gironde, Rhône) have been compared with the Chinese Yellow River (Huanghe) and Yangtze River (Changjiang). Dissolved Cd concentrations have been measured by differential pulse anodic stripping voltammetry. Average concentrations range from 15 ng kg⁻¹ to 50 ng kg⁻¹ (0.13–0.45 nmol kg⁻¹) in the French rivers and are below 4 ng kg⁻¹ (0.040 nmol kg⁻¹) in the Chinese rivers.In all the estuaries studied the dissolved Cd concentrations depict a systematic bulge in the mixing zone which is attributed largely to remobilization processes from particulate matter when the chlorinity increases. Other parameters that may also play a significant role for remobilization are discussed. The processes concerned lead us to reassess the net Cd river input to the oceans, and this should be taken into account for a more precise evaluation of the residence time of oceanic Cd.     

Trace metal (Cd,Cu, Ni and Pb) cycling in the upper water column near the shelf edge of the European continental margin (Celtic Sea)

This study investigates the relative importance of processes that affect trace metal (TM) cycling in the upper water column at the shelf edge of the Celtic Sea on the western European continental margin. The examined processes include external inputs (by atmosphere and river), physical factors (upwelling, winter mixing and water mass advection) and biological processes (in situ uptake, regeneration and export to deep waters). The concentrations of dissolved Cd, Cu, Ni and Pb were measured with this aim in January 1994 and June 1995 at vertical stations across slope, including stations with upwelling, and in the surface waters along the Celtic Sea shelf. Additionally, deep sea (from sediment trap data) and atmospheric fluxes were estimated. The metal profiles over the slope off the Celtic Sea are quite similar to open ocean profiles already described in the northeast Atlantic, and the concentrations in surface waters are only slightly enriched compared to the nearby open ocean (1.2–1.3× for Cd and Ni). The external sources to the system appear to be of weak influence: the fluvial input is locally strong at the coast and then “diluted” along the large continental shelf; the atmospheric deposition is not significant at the annual scale in comparison to the metal content in the upper waters of the shelf edge (at least for Cd, Ni and Cu). In the upwelling zone, a significant increase in concentrations was observed in the summer surface mixed layer (×2 for nitrate and Cd and ×1.5 for Ni) in comparison to the non-upwelling zone. In winter, concentrations of bioreactive metals increased significantly in the surface waters in comparison to the low summer levels (×5 for nitrate and Cd). Our results suggest that upwelling and winter mixing act as regenerated sources that lead to the resupply of the bioreactive elements above the permanent thermocline with a low export to deeper waters. The tracing of the Mediterranean intermediate waters (MIW) from Gibraltar to the studied area shows indeed that its elemental content at the Celtic shelf edge is mainly due to the conservative mixing of the three “end-member” component waters which are thought to make up the MIW. The remineralization of organic matter within this water mass during its transport to the north would contribute only 20% of the nutrients and Cd concentrations recorded at the Celtic Sea shelf edge. According to the correlation found with nutrients in the 10–200-m layer, dissolved Pb would also be subjected to biological uptake and regeneration within the seasonal thermocline. Particulate scavenging removal of Pb would take place below the permanent thermocline throughout the water column.     

Molecular weight and chemical reactivity of dissolved trace metals (Cd,Cu, Ni) in surface waters from the Mississippi River to Gulf of Mexico

It is generally assumed that estuarine mixing is continuous for metals from terrestrial sources, gradually decreasing towards the open ocean endmember. Here we show that, chemical reactivity, determined by ion exchange method, and molecular weight distributions, obtained using cross-flow ultrafiltration, of dissolved Cd, Cu, and Ni in the surface waters of the Gulf of Mexico varied systematically across the estuarine mixing zone of the Mississippi River. Most size or chemical affinity fractions of dissolved metals (<0.4 μm) were linearly related to salinity (10.8–36.6), suggesting that the distribution of these elements was mainly controlled by continuous mixing processes. Dissolved concentrations across the salinity gradient ranged for Cd: 87–187 pM; Cu: 1.4–18.3 nM; and Ni: 2.6–18.8 nM, with highest values near the Mississippi river mouth, and lowest concentrations in a warm core ring in the Gulf of Mexico. Dissolved Cd was mostly present as a truly dissolved (<10 kDa, 97 ± 1%) and cationic fraction (Chelex-100 extractable, 94 ± 4%). A novel observation across the estuarine mixing zone was that colloidal metal concentrations were identical to either inert (for Cu, Ni) or AMPG-labile anionic (Cu, Cd) fractions. The difference in behavior between Cu and the other two metals might indicate differences in the biopolymeric nature of the metal–organic chelates. In particular, the anionic-organic Cd fractions accounted for just 3 ± 1%, on average. However, for Cu, it was 24 ± 4%, and for Ni, it was 9 ± 6%. The fractions of the total dissolved metal fractions that were “inert” averaged 31 ± 10% for Cu and 29 ± 12% for Ni. Small but noticeable amounts (6 ± 3%) of dissolved inert Cd fractions were also present. Apparent non-local transport processes, likely associated with cross-shelf sediment resuspension processes, could have been responsible for the relatively high concentrations of ‘inert’ and ‘anionic’ metal fractions in high salinity coastal waters, and accounting for the persistence of metals bound to humic substances in the Gulf of Mexico.     

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.     

Manganese recycling in coastal waters

Both water and suspended particulate matter in the deep water of the Gulf of St. Lawrence are greatly enriched in manganese. Maximum dissolved manganese concentrations are encountered close to the sediment-water interface whereas the particulate matter with highest manganese content occurs 30–100 m above the bottom. The elevated concentrations are attributed to the diagenetic release of dissolved manganese from the underlying fine-grained sediments and its subsequent precipitation in the water column. The rate of manganese precipitation is rapid compared to the rates of diffusion and mixing in the bottom water. Part of the manganese-enriched particulate matter becomes mixed throughout the water column by advection and diffusion. Thus, particles enriched in manganese can ultimately be carried into the open ocean by prevailing currents. This process, which appears to be widespread in eastern Canadian coastal waters, enables manganese originally associated with rapidly settling terrigenous particles to be transferred to slowly settling fine-grained suspended particles entering the ocean from coastal environments. In this way, riverborne manganese of terrigenous origin may well account for a major proportion of the excess manganese in pelagic sediments.     

污水与海水混合后海水颗粒物对磷的吸附-释放实验

本文模拟研究了厦门污水与海水混合后,海水颗粒物对磷的吸附-解吸过程,结果表明:颗粒物对磷的吸附只在混合后的1d内进行,之后即产生颗粒磷的释放,并表现为颗粒磷→溶解磷→溶解无机磷的转移过程。溶解无机磷是水体中磷的重要存在形式,其浓度的增加速率基本符合一级动力学模式。颗粒磷的释放过程可用交换吸附动力学模式(t/X)=(t/X_(eq))+B′处理。