Geochemical composition of sediments in the Scheldt estuary with emphasis on trace metals

Superficial sediments of the Scheldt estuary were collected with a Van Veen grab at 57 stations between Temse and Vlissingen. They were analysed for major elements (Si, Al, Fe, Ca, Mg, Na, K, Cinorg and Corg) and trace metals (Cd, Pb, Cu, Zn, Cr, Ni, Co, Mn and Li). Factor analysis indicates that 44% of the variance can be explained by one factor which exhibits a high saturation for trace metals, organic matter, Al and Fe, all variables typical of fine mud. The high scores of this first factor are almost exclusively present in the upper estuary except for one area in front of Terneuzen. The second factor, which explains 23% of the variance, is typical of the carbonates and the third one (19% of the variance) is representative of the clay minerals. These two factors are more evenly distributed over the estuary. As usual, a strong influence of granulometry on the distribution of trace elements in the sediments was observed. Intercomparison of their composition within the Scheldt or with those of other aquatic systems requires thus a normalization procedure. This problem has been studied in detail by analysing various size fractions (63–16, 16–8, 8–4, <4 m) obtained by elutriation of the sample or by using a parameter characteristic of the fine fraction such as the concentration of a typical element (Al, Fe, Li, Corg). The normalization of trace metals allowed us to evaluate an enrichment factor of the trace elements in the estuarine deposits due to mans activities. In addition, it demonstrates the decrease of the anthropogenic impact on the composition of sediments by comparing the composition of sediments collected in 1976 and in 1994.     

Suspended matter in the Scheldt estuary

The Scheldt estuary is characterised by a specific energy pattern resulting from the interaction of wave energy, tidal energy and river energy. It divides the estuary into three parts and governs suspended matter transport and distribution pattern. Observation of suspended matter transport shows the existence of three estuarine turbidity maxima (ETM), a marine-dominated ETM in the lower estuary at the river mouth, a river-dominated ETM in the upper estuary with suspended matter concentration reaching up to 300 mg/l, and the most important tide-dominated ETM in the middle estuary with suspended matter concentrations from several hundred milligrams per litre up to a few grams per litre. Resuspension is the dominant phenomenon in this last ETM due to the tidal related bottom scour, which is initiated when a critical erosion velocity of 0.56 m/s is exceeded. An assessment of residual current along the axis of the estuary shows distinctive pattern between the surface water flow and the near bottom water flow. Also the local morphology of the river, natural or man-made, has a prominent effect on the orientation and strength of the residual currents flowing along either side of the river or river bend. Evaluation of suspended matter concentration in relation to the current flow shows no systematic correlation either because of phenomena as scour lag and settling lag mainly in the middle estuary, or because of the current independency character of uniform-suspension mainly in the upper and lower estuary. Quantification of suspended matter load exhibits a net downstream transport from the upper estuary, a near-equilibrium sustainable status in the middle estuary and a net upstream transport of suspended matter from the lower estuary. The characteristic of suspended matter is induced by and is a function of e.g. tidal phase, spring-neap tide, longitudinal and vertical distribution mechanisms, seasons, short and long terms of anthropogenic influence and/or estuarine maintenance. Suspended matter is dominated by complex and cohesive organo-mineral aggregates. It consists of a variable amount of an inorganic fraction (average of 89%) and an organic fraction and occurs largely as flocs, the size of which is remarkably larger in the upper estuary and smallest within the ETM in the middle estuary. Independent time series measurements (1990–2000) of suspended matter property show an increasing sand fraction, a decreasing organic matter content, a rise in ¹³C as well as a decrease in water transparency. These independent measurements exhibit coherent consequences of estuarine maintenance operations. Maintenance dredging of the shipping channel and harbours and dumping operation in the Scheldt strengthen marine influence further landward, resulting in a sustained tidal range increment and upstream flow and transport of suspended matter.     

The environmental risks of pollution in the Scheldt estuary

The ecotoxicological effects of pollution in the Scheldt estuary is evaluated for several routes of exposure by comparing observed concentrations of micro-contaminants in water and tissues of biota with toxicity data in literature. Ecological risks are estimated for dissolved trace metals according to the method of VAN STRAALEN (1990) using published data on NOECs from aquatic toxicity tests concerning reproduction, mortality and growth for cold blooded marine and estuarine organisms. Of eight investigated trace metals, zinc and nickel cause the highest risks, both affecting up to 4% of the aquatic species. The occurrence of bioaccumulation of PCBs and cadmium is investigated in several trophic levels. High concentrations of PCBs are observed in tissues of biota and may indicate adverse effects on top predators (seals, terns), especially in the brackish zone. Environmental risks of other organic micro-contaminants have not been indicated due to the limited number of data on toxicity or environmental concentrations. The effects of a mixture of pollutants in sediments from the Scheldt estuary were investigated with an oyster larvae bioassay showing an increased toxicity in upstream direction. Moreover, in the upper part of the estuary, preconditions regarding the oxygen concentration are not met and overshadow the toxic effects of pollution with micro-contaminants. Especially in the less contaminated part of the estuary more ecotoxicolgical research is required to perform an integral risk evaluation. At present, still little is known about effects that may occur in the field.     

Modelling of water and sediment quality in the Scheldt estuary

In 1987 the Tidal Waters Division (Ministry of Transport, Public Works and Water Management, The Netherlands) initiated the SAWES project (Systems Analysis WEstern Scheldt). In the framework of this project, a water quality model for the Scheldt estuary was made. The model aims to establish the relation between pollution inputs and the concentration of pollutants in the abiotic compartments and to establish the fate of wasted substances. The model includes oxygen, nitrogen and trace metals. Due to the low oxygen content of the upper Scheldt estuary, a new model approach for trace metals had to be developed, taking into account precipitated metal sulphides. The calibration, verification and sensitivity analysis of the model provided a good understanding of the chemistry of the estuary. Afterwards the model was used to support policy making by computing how the water and sediment quality in the estuary respond to reduced inputs of waste.     

The behaviour of copper and zinc in the Scheldt estuary

The behaviour of copper and zinc in the Scheldt estuary, both in the particulate and the dissolved phase, is discussed for the period 1982–1983. The longitudinal particulate copper and zinc profiles fall below the dilution line, which is attributed to mixing and mobilization processes. In the dissolved phase both metals show a production region in the end member of the estuary, for copper a pronounced mid estuarine maximum is observed. Study of the metal speciation suggested that organic ligands might keep heavy metals in solution, especially in area of intensive production, and promote the subsequent export of these metals downstream the estuary.     

Water quality modelling of the western Scheldt estuary

In 1987 the National Institute for Coastal and Marine Management (theNetherlands) initiated the SAWES project (Systems Analysis WEstern Scheldt).The main goals of the project were to acquire knowledge with respect to thepollution problems in the Scheldt estuary and to apply this knowledge tomanagement issues of the Scheldt on an operational level. The main interestwas to understand quantitatively the relation between inputs of pollutingsubstances and effects on the ecosystem. In the framework of the project, awater quality model for the Scheldt estuary was made. In 1995, the modelarea was expanded to include the Belgian coastal region at the mouth of theestuary. The model calculates the fate of discharged substances andestablishes the relation between pollution inputs and the resulting waterquality, including general water quality (oxygen, pH, alkalinity, major ionchemistry and nutrients) as well as pollutant concentrations. The modelincorporates all chemical processes which affect these concentrations,including the precipitation/dissolution of metal sulphides which to a largeextent controls the fate of trace metals. Based on calibration andverification exercises, it has been shown that the model provides a goodrepresentation of the physical and chemical processes taking place withinthe estuary and can therefore be used to support policy development for theestuary. For example, the model can compute how the water and sedimentquality in the estuary will respond to reduced inputs of waste or to suchhuman activities as dredging. This revised version was published online in July 2006 with corrections to the Cover Date.     

Factors affecting metal concentrations in reed plants (Phragmites australis) of intertidal marshes in the Scheldt estuary

We aimed to identify the environmental factors which significantly affect metal uptake by reed plants in the intertidal marshes along the river Scheldt. Transfer coefficients, defined as the ratio of metal concentrations in reed stems to the metal contents in specific sediment fractions (i.e. the exchangeable Cd and Zn fraction and total Cr, Cu, Ni and Pb content), were calculated for each sampling site. They were inversely related to the sediment clay and/or organic matter content. Metal mobility and thus plant availability is higher in sediments with a lower clay or organic matter content. Moreover, the plants might actively accumulate in particular essential elements when concentrations in the sediments are rather low, which is the case in sediments low in clay and organic matter contents. Finally, more sandy sediments are expected to be susceptible to occasional oxidation of sulphides, which leads to an increased metal availability. A higher salinity promoted the uptake of Cu, Cr and Zn.     

A cohesive sediment balance for the Scheldt estuary

This article present a method to generate a cohesive sediment balance for the Scheldt estuary (The Netherlands and Belgium). In this balance the net transports have been determined on a regional scale. The complicated circulation patterns on a smaller scale are considered as a black box. The cohesive sediments in the balance are defined as the inorganic sediment with a particle size smaller than 63 μm. In the balance a distinction is made between the relatively ‘clean’ marine mud fraction and the more polluted fluvial fraction. The calculations are made on a basis of field data. The field data of the morphological changes in the estuary are based on the period of 1975–1985. The net natural transport of fluvial mud is estimated to reach beyond the mouth of the estuary. The net marine import of mud is estimated to reach beyond the brackish part of the estuary, located in Belgium. The sediment balance also provides the time scale for the response of an estuary. The time scale related to the reduction in pollution proves to be quite large. Calculations with a simple analytic model with typical values for the Scheldt estuary indicate that several decades will pass until a significant improvement in bottom sediment quality is reached even after a 100% reduction of the loading of pollutants. The presented balance is not the final answer. Improvements can be achieved by more accurate field data, smaller morphological units and verification by other methods (cf. tracer methods, mathematical models).     

Political aspects of the closure of the Eastern Scheldt estuary

Summary A chronological survey is given of the discussions about the aspects of the closure of the Eastern Scheldt, an estuary in the SW Netherlands (Delta Area).Delta Plans were made already before World War II. After the Disaster of 1953 the main objective was to obtain a sufficient safeguard against superfloods. The ecological losses in the Delta Area were not yet recognized. Due to the activities of action groups this aspect was put into the interest of political parties. In 1973 a special commission investigated the possibilities of a synthesis between ecology and land protection. The commission proposed to maintain a reduced tidal range in the Eastern Scheldt by means of a storm-surge barrier. In Government and Parliament this proposal was evaluated, adapted and finally accepted. Dike-raising, according to the pressure groups the most simple and cheapest way to get the necessary protection, was definitely rejected. The most important consequence of these decisions was the extra costs of 2000 million guilders.Up till now discussions are focussed on the most acceptable tidal reduction. The Parliament accepted because of financial reasons 25% reduction. The action groups advocate at most 10%.Communication nr. 173 of the Delta Institute for Hydrobiological Research.     

Geochemistry of mercury in an intertidal flat of the Scheldt estuary

Sediments were sampled on the ‘Groot Buitenschoor’, an intertidal flat located at about 60 km from the Scheldt's river mouth. Hg concentrations ranged from 30 to 1756 ng g⁻¹. The concentrations were strongly correlated with fine grain fraction, organic matter content and sulphide concentrations. Incubation experiments were performed in order to determine the potential methylation rate of Hg as well as biotic and abiotic factors influencing this transformation. About 1 to 2% of the added inorganic Hg is converted into methylmercury. This conversion rate points to the same equilibrium ratio as was observed in natural sediments, indicating an equilibrium between methylation and demethylation reactions in the sediments. Incubation of a sterilised sediment sample significantly decreased the methylation rate, but the methylmercury concentrations observed are still ten times higher than the natural (unspiked) sediment. This result could be due to a chemical (non-enzymatic) methylation of mercury. Sulphate reducing bacteria are the main species responsible for the methylation of Hg at this site. Addition of Na₂MoO₄, a specific inhibitor of sulphate reducing bacteria, decreased the methylation rate to the abiotic level (sterilised sediment). High sulphate reduction rates, however, lead to lower methylation rates. Increased formation of sulphides due to microbial sulphate reduction leads to enhanced HgS formation and this reaction competes with the methylation process. HgS is in fact the major product formed by the reaction of sulphate reducing bacteria with Hg species. About 50% of the Hg spiked to the sediments is transformed into HgS during the incubation experiments, and that compound is practically unavailable for methylation in contrast to other bound forms of Hg.     

Use of nitrifying activity measurements for describing the effect of salinity on nitrification in the Scheldt estuary.

Nitrifying activity measurements, carried out on freshly collected samples from an estuarine environment, show that the composition of the nitrifier population undergoes a progressive modification during the mixing of freshwater masses in seawater, with increasing tolerance to salt. As a result, the overall effect of increasing salinity on nitrification is much less severe than the direct effect of salt on the freshwater nitrifying population.     

Temporal and spatial trends in heavy metal concentrations in the marine mussel Mytilus edulis from the Western Scheldt estuary (The Netherlands)

Since the first North Sea Conference (1984, Bremen), all countries bordering the North Sea made commitments to reduce discharge of hazardous substances into the North Sea. From Belgium and The Netherlands, large reductions (upto 90) in heavy metal emissions from land-based sources have been reported between 1985 and 2000. Recently, some studies in the Western Scheldt estuary (WS) have shown that total metal concentration in the water, sediments and suspended particles have decreased compared to levels in the 70s. However, data on aquatic organisms is still very limited and it is therefore difficult to confirm whether the reductions in pollution input and generally improving water quality in the WS have a corresponding impact on the levels of heavy metals in aquatic organisms. The current study measured metal concentrations in the soft tissues of mussels, Mytilus edulis (known to be good indicators of environmental metal pollution) during the period 1996–2002. Spatial (salinity and pollution gradients), temporal and seasonal variations were also studied. Results showed a down-stream decreasing trend for the metals studied (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn) during all sampling campaigns. There was also a significant seasonal effect on tissue metal concentrations, with a peak observed around spring in both WS and the nearby less polluted Eastern Scheldt (ES). On temporal trends, a clear drop of metals in mussels was observed in the early 80s coinciding with the start of the efforts to reduce chemical pollution input into the North Sea. Since those early reductions, metal concentrations in mussels generally remained unchanged upto mid 90s. However, in recent times metal concentration in mussels have increased significantly, for example Cd in 2002 was almost 10 times the values in 1983 and similar to levels seen during the peak in the 70s. Other metals also increased in the 90s also reaching levels seen in the 70s. As there is no indication of recent increase in metal input into the estuary, we suggest that increased metal concentrations observed in mussels in recent years especially in the upper estuary are most likely a result of changes in physical and chemical speciation and metal bioavailability. Such changes may be caused by changes in some water quality parameters in the estuary (i.e. increased dissolved oxygen, concentration of organic matter), resulting in conditions that favour releases of sediment-bound metals into the water column. The relationship between metal content and season showed very similar annual profiles in the polluted WS and less polluted ES. Thus, seasonal variations in metal concentrations appear to be largely controlled by biological processes, while total body burdens are dependent on environmental levels and bioavailability.     

Seasonal variation of floc characteristics on tidal flats, the Scheldt estuary

The flocculation mechanism dominates the fate of suspended matter in the estuarine environment. By modifying the texture of suspended matter, flocculation is one of the principle factors determining the transport and deposition of suspended matter in estuaries. Surveys of the seasonal variation of dispersed particle and non-dispersed particle characteristics, organic matter content as well as suspended matter deposition in two contrasting intertidal environments, one freshwater and one brackish water, in the Scheldt estuary were undertaken at fortnightly intervals for a year. The study of non-dispersed particle, i.e. floc, is mainly focused on floc size, shape, and microstructure, properties presumed to be significant in the suspended matter transport processes in the estuary. In this study, floc size as well as floc sphericity correlate positively with the change of organic matter content and reveal that floc grows in a three-dimensional way with increasing organic matter. It is observed that relatively condensed, small and elongated flocs appear in winter and spring periods, while loose, large and spherical flocs occur during the summer. The study also reveals that suspended matter transported as dense flocs with size range of ca. 105–250 m have a greater effect on its short-term deposition than loose flocs with size range of ca. 250–500 m. As the measured suspended matter deposition is much higher in winter–spring than in summer, it is deduced here that highly compact and relatively dense flocs contribute to deposition during winter and spring periods resulting in a stable layer, while loosely formed flocs likely lead to an easier erodible layer during the summer. This study concludes that floc structure-related density is a more significant parameter than floc size in the suspended matter deposition processes.     

Ecophysiological responses of the mangrove Avicennia marina to trace metal contamination

Growth responses of Avicennia marina seedlings to contamination by different concentrations of two essential (Cu, Zn) and two non-essential (Pb, Hg) trace metals were studied under glasshouse conditions. We tested the hypothesis that soil retention and root ultrafiltration would exclude most of the trace metals, and that those that are absorbed and translocated to the shoots would interfere with plant performance and be excreted via leaf salt glands. One-month-old seedlings were subjected to Cu, Zn, Pb and Hg at concentrations of 0, 40, 80, 120 and 160 μg g⁻¹ sediment for 12 months in a randomized complete block design (n = 6). Photosynthesis was measured at the end of 12 months of trace metal exposure with a portable gas exchange system and chlorophyll fluorescence with a pulse-modulated fluorometer. After morphometric measurements, plants were harvested and analyzed for Cu, Zn, Pb and Hg by atomic absorption spectroscopy. Total dry biomass decreased with increasing trace metal concentration for all metals. In the 160 μg g⁻¹ Cu, Zn, Hg and Pb treatments, total biomass was significantly lower than the control value by 43%, 37%, 42% and 40%, respectively. Decreases in plant height and number of leaves followed trends similar to those for total biomass and ranged from 37% to 60%, compared to the controls. Decreases in chlorophyll content in the trace metal treatments ranged from 50% to 58% compared to the control. Carbon dioxide exchange, quantum yield of photosystem II (PSII), electron transport rate (ETR) through PSII and photosynthetic efficiency of PSII (F_v/F_m) were highest in the control treatment and decreased with increasing trace metal concentrations. Decreases in CO₂ exchange in the 160 μg g⁻¹ treatments for all trace metals ranged from 50% to 60%. Concentrations of all trace metals in plant organs increased with increasing metal concentrations and were higher in roots than in shoots, with concentrations of Cu and Zn being considerably higher than those of Hg and Pb. Qualitative elemental analyses and X-ray mapping of crystalline deposits over the glands at the leaf surfaces indicated that Cu and Zn were excreted from the salt glands, while Hg and Pb were absent, at least being below the limits of detection. These results demonstrate that growth processes are sensitive to trace metals and therefore can be considered as a cost of metal tolerance, but salt glands of this mangrove species do contribute eliminating at least part of physiologically essential trace metals if taken up in excess.     

Dynamics and distribution of microphytobenthic chlorophyll-a in the Western Scheldt estuary (SW Netherlands)

The temporal dynamics and spatial distribution of microphytobenthic chlorophyll-a in the layer 0–1 cm were determined in the Western Scheldt estuary over the period 1991–1992. Connections between the annually averaged benthic chlorophyll-a and station elevation and sediment composition (as a measure of the hydrodynamic energy caused by currents and waves) were also examined.Microphytobenthic chlorophyll-a showed one main peak in early summer and a smaller peak in autumn. The mean chlorophyll-a concentration of 113 mg Chl-a m^–2 in the upper centimeter is of the same order of magnitude as in other estuarine areas. The average annual primary production of the microphytobenthos has been estimated at 136 g C m^–2 y^–1 The primary production of sediment inhabiting microalgae is at least 17% of the total primary production in the estuary.Considerable differences in annually averaged chlorophyll-a emerges between the stations. These differences are related mainly to the interaction between station elevation and clay content of the sediment.     

Modeling growth and carbon allocation in two reed beds (Phragmites australis) in the Scheldt estuary

Common reed (Phragmites australis) is a prominent species in the upstream part of the eutrophic Scheldt estuary (Belgium, The Netherlands). From 1996 till 1998, seasonal growth dynamics of the species were studied in two monospecific stands subjected to different salinity regimes (seasonal means 1.6 and 13.3 PSU, respectively). We addressed the following questions: how are these reed vegetations affected by meteorological conditions and by the growth site, what are the important growth processes and what is the fate of the annually fixed carbon. A mathematical model was developed and calibrated using the data from the oligohaline site. Subsequent application of the model to the mesohaline stand required adaptation of parameters relating to the partitioning of resources and timing of growth initiation only. At their peak, the aboveground biomass was 587–1678 g DW m⁻² at the 13.3 PSU site and 1116–2179 g DW m⁻² (1.6 PSU); more than 60% of the biomass was located underground. In 1996, biomasses were 2–3 times lower than in the other 2 years, caused by a retarded growth initiation. Probably due to a lower temperature in early 1996, rhizome bud burst occurred more than 1 month later compared to the other years. In addition, growth initiation was several weeks later in the mesohaline site. This appeared mainly responsible for the large difference in maximal aboveground biomass between both stations. Architecture of the plants was also affected, with a higher shoot density (about 50% more shoots), better-developed root system (15% of total belowground biomass compared to 5%) and more, but smaller leaves at the higher salinity site. Notwithstanding large differences in aboveground biomass, annual growth was similar at both stations (154 and 132 mol C m⁻² per year at the oligo- and mesohaline station, respectively). Primary production accounted for about 80% of all growth processes, rhizome remobilization for almost 20%, translocation of mass before sloughing of leaves accounting about 3%. Within a year, some 44% (oligohaline) and 36% (mesohaline) of new assimilates produced by photosynthesis accumulated as dead litter. The other part was respired by the plant itself, either to provide the energy for growth (23%) or maintenance costs (33–41% at the oligo- and mesohaline station, respectively). Calculated annual turnover rates of aboveground biomass, rhizomes and roots were 100, 62 and 73%, respectively.