Geochemical cycling of heavy metals in a marine coastal area: benthic flux determination from pore water profiles and in situ measurements using benthic chambers

Concentrations of the heavy metals Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn were measured in sea water, suspended matter, sediments and pore water samples collected in a coastal area of the middle Tyrrhenian Sea. Concentration factors between pore water (extracted from the first centimeter of the sediments) and the overlying sea water (taken 30 cm above the sea bed) were less than 1 for Cr, Cu and Pb, 1–10 for Cd and Ni, 10–100 for Fe and Co, 100–1000 for Mn, and 1–100 for Zn.The benthic fluxes of heavy metals at the sediment-water interface were measured directly using in situ benthic chambers and calculated using Fick's first law during two experimental periods, one in 1986 and the other in 1988. The fluxes of Cu, Ni, Pb and Zn varied significantly over time; this appeared to be related to their relatively low ( 10) concentration factors. From the benthic chamber experiments, metals with positive fluxes were in the order: Mn > Fe > Co > Cd, while those with negative fluxes were: Zn > Pb > Ni Cu. Fluxes calculated using Fick's Law were: positive – Mn > Fe > Zn (or Zn > Fe) > Ni > Co > Cd, negative fluxes Pb > Cu > Cr.Measured (benthic chamber) and calculated (Fick's first law) fluxes for Co, Cd, Mn, Pb and Fe were comparable within an order of magnitude, although less agreement was found for Cu, Ni and Zn. Removal of Ni and Zn at the sediment-water interface has been proposed to explain the fact that the measured and calculated fluxes have opposite directions for these metals.     

Incidence of mussel culture on biogeochemical fluxes at the sediment-water interface

Upward nutrient fluxes at the sediment-water interface were studied in a mussel farming zone (Carteau, Gulf of Fos, France) in order to estimate the impact of organic matter input from biodeposition. Nitrate, nitrite, ammonia, silicate, phosphate and oxygen were measured. Fluxes were estimated by means of polyacrylate benthic chambers placed at sites located under (UM) and outside (OM) the rope hanging structures. Transformation of biodeposited organic matter increases phosphate, silicate and ammonia fluxes. No variation in nitrite fluxes could be detected and only minor differences were observed in nitrate and the oxygen production/consumption equilibrium at the two stations. Phosphate and silicate fluxes, which were always higher at the UM than at the OM site, decreased from spring to winter. Ammonia fluxes were very high under mussel cultures in May and September and lower in November. The fact that ammonia flux was always higher at the UM than at the OM sites might be explained by degradation of mussel biodeposit, as well as by benthic macrafauna excretion. Discrepancies between fluxes of the nutrients studied at the UM and OM sites increased as organic particulate matter in the water column decreased. Variations of oxygen flux followed a different pattern, since they were correlated with presence and abundance of photosynthetic microphytes on the bottom and in the water. Bottom respiration exceeded production of oxygen only in May 1988 at the UM station.As it now stands, biodeposit input into the sediment under mussel ropes does not affect the ecosystem, although the flow of nutrients towards the water column is higher than in other areas.     

Benthic nutrient fluxes in Cadiz Bay (SW Spain)

During summer and autumn 1988, benthic fluxes of nutrients and oxygen were measured in the Bay of Cadiz. The study was carried out using benthic chambers and in addition by determining gradients of nutrient concentration in interstitial water. Fluxes ranged between 13.5–24.3, 3.4–7.8, 6.1–28.4 and (− 99.4)−(− 188.5) mmol m^{− 2} d⁻¹ for NH₄ ⁺ , o-P, SiO₂ and O₂ respectively. These values are far higher than those reported by other authors for locations at similar latitudes. The stoichiometry of O, N and P transference suggest that benthic degradation of principally allochthonous organic matter takes place mainly through anaerobic pathways.     

Microphytobenthos activity and fluxes at the sediment-water interface: interactions and spatial variability

In this study oxygen and nutrient fluxes and denitrification rates across the sediment-water interface were measured via intact core incubations with a twofold aim: show whether microphytobenthos activity affects these processes and analyse the dispersion of replicate measurements. Eighteen intact sediment cores (i.d. 8 cm) were randomly sampled from a shallow microtidal brackish pond at Tjarno, on the west coast of Sweden, and were incubated in light and in darkness simulating in situ conditions. During incubation O₂, inorganic N and SiO₂ fluxes and denitrification rates (isotope pairing) were measured. Assuming mean values of 18 cores as best estimate of true average (BEA), the accuracy of O₂, NH₄ ⁺, NO₃ ^- and SiO₂ fluxes calculated for an increasing number of subsamples was tested. At the investigated site, microalgae strongly influenced benthic O₂, inorganic N and SiO₂ fluxes and coupled (D_n) and uncoupled (D_w) denitrification through their photosynthetic activity. In the shift between dark and light conditions NH₄ ⁺ and SiO₂ effluxes (60 and 110 µmol m^-2h^-1) and D_n (5 µmol m^-2 h^-1) dropped to zero, NO₃ ^- uptake (70 µmol m^-2 h^-1) showed a 30% increase, while D_w (20 µmol m^-2 h^-1) showed an 80% decrease. For O₂ and NO₃ ^- dark fluxes, 4 core replicates were sufficient to obtain averages within 5-10% of the best estimated mean, while 10-20% accuracy was obtained with 4-12 replicates for SiO₂ and >10 replicates for NH₄ ⁺ dark fluxes. Mean accuracy was considerably lower for all light incubations, probably due to the patchy distribution of the benthic microalgal community.     

Macrophyte communities and their impact on benthic fluxes of oxygen, sulphide and nutrients in shallow eutrophic environments

The impact of macrophyte communities on benthic fluxes has been analyzed in three shallow coastal environments: Etang du Prévost (Mediterranean coast of France), characterized by the large floating macro-alga Ulva rigida; Certes fishponds (Bassin d'Arcachon), covered by Ruppia cirrhosa; and the inner intertidal mud-flat in the Arcachon Bay (French Atlantic coast), which has extensive Zostera noltii meadows. In these bodies of water, primary production is dependent primarily on the dominant seagrasses and macroalgae that are also responsible for the large quantity of organic matter deposited on the sediment surface. In 1993 and 1994, fluxes of oxygen, sulphide and nutrients were measured in early and late summer, which were selected in order to represent the production and decomposition phases of the dominant macrophytes. Experimental work was undertaken to measure: (1) standing crop of dominant macroalgae and rooted phanerogams and the elemental and macromolecular composition of plant biomass; (2) benthic fluxes of oxygen, sulphide, nitrogen and phosphorus using incubation of multiple dark and light benthic chambers; (3) water-sediment profiles of free-sulphide in sediment cores with rooted phanerogams (Ruppia) as well as with floating Seaweeds (Ulva).At the selected sampling sites, in addition to external (tides) and/or internal (sediment reactivity) factors, we observed differences in benthic fluxes which were clearly related to growth patterns and structure of the macrophyte communities. The Z. noltii meadows were stable and characterized by slow growth and almost constant biomass. In the more sheltered sampling station in the Certes fishponds, R. cirrhosa beds showed a summer decrease due to extensive epiphyte growth. During the decomposition phase, significant fluxes of free-sulphide occurred inside the dark benthic chambers, probably due to the metabolism of the epiphytic layer. In the Etang du Prévost, U. rigida achieved high biomass levels, even though the macroalgal beds exhibited a patchy distribution due to wind action and the hydrodynamics of the lagoon. In the decomposition phase, which was coincident with the annual dystrophic crisis the rapid decomposition of Ulva led to high fluxes of free sulphide.The shift from the production to decomposition phase resulted in substantial changes in nutrient recycling only in the macro-algal-dominated system. During the growth period dissolved inorganic nitrogen and phosphorus were kept at low levels due to macrophyte uptake. In contrast during the decomposition phase when the macroalgal biomass was mineralised, nitrogen and phosphorus were rapidly recycled. The same processes did not occur in the Certes fishponds probably because of the greater internal buffering capacity linked either to plant morphology/physiology or to the properties of the sediment.     

Exchange of Cu and Cd across the sediment-water interface in intertidal mud flats from Ria Formosa (Portugal)

Depth profiles of Fe, Mn, (HS)_t, Cu and Cd concentrations in pore water were determined on a seasonal scale in intertidal sediments of Ria Formosa. Concentrations of Cu and Cd were also determined in near-bottom water during the short period that water inundates the sediment. A maximum near the sediment-water interface was observed in depth profiles of Mn and Fe concentrations followed by a decrease with depth. Otherwise, depth profiles of (HS⁻)_t were irregular but peak concentrations was observed below Mn and Fe maximum. Although subsurface maximum was observed at deeper layers for Cu and Cd, the profiles shape varied among sites and sampling dates. This suggests site specificity and alterations associated with early diagenetic reactions. In order to assess exchanges of Cu and Cd across the sediment water interface, diffusive fluxes and advective transport were estimated. Both contribute substantially to the daily transfer of Cd from intertidal sediments to the water column of Ria Formosa. In the case of Cu, the flux associated with tidal flooding (advective flux) was the major contributor. Presumably, the exchange of trace elements between the sediment-water interface in intertidal areas of macro- and meso-tidal systems are underestimated since do not take into consideration the pulse contribution associated with tidal flooding.     

Factors affecting the distribution of benthic and littoral rotifers in a large marine lagoon,together with the description of a new species

Diffusion plays an important role in the exchange processes between lake sediments and the overlying water. Compounds entering the sediments usually have to penetrate through a certain mud thickness, where a reaction may then occur, while compounds being released have to diffuse through the interstitial water before escaping into the lake water.In this article mathematical functions are given which describe certain cases. They are all based on the differential diffusion equation of Fick, but for different boundary conditions different mathematical solutions of partial differential equations are needed. Four of these are presented in this paper, covering the cases of a compound diffusing into the sediments, with or without a chemical reaction occurring in the sediments, combined with either a constant or a non-constant concentration in the water.Furthermore a numerical approach is proposed in which the calculations are made by an iteration process over time and space. The results are presented as a series of concentrations as a function of time and depth in the sediment layer. It is shown in the first place that the time and the space steps must be sufficient small in agreement with the dimensions and time scale of the processes studied in order to obtain a satisfactory precision. The results can be fitted to a simplified exponential equation of the form (A · e^{–·t b} – B), which can be used for a quick assessment of special cases, depends on porosity, ratio between water and mud height; b 0.667. Furthermore this equation can be used to extrapolate from laboratory experiments with the sediments of a specific lake to results valid for the lake itself.The numerical model has also been used to describe the backward diffusion of an eventual product of a chemical reaction, which will diffuse further downward, but also upward. This is e.g. the case for the N₂O production during denitrification experiments when acetylene is applied as an inhibitor.Finally, the application of so called peepers and benthic chambers is discussed, while many of their disadvantages are explained.     

Bacteria in the cold deep-sea benthic boundary layer and sediment-water interface of the NE Atlantic

This is a short review of the current understanding of the role of microorganisms in the biogeochemistry in the deep-sea benthic boundary layer (BBL) and sediment-water interface (SWI) of the NE Atlantic, the gaps in our knowledge and some suggestions of future directions. The BBL is the layer of water, often tens of meters thick, adjacent to the sea bed and with homogenous properties of temperature and salinity, which sometimes contains resuspended detrital particles. The SWI is the bioreactive interface between the water column and the upper 1 cm of sediment and can include a large layer of detrital material composed of aggregates that have sedimented from the upper mixed layer of the ocean. This material is biologically transformed, over a wide range of time scales, eventually forming the sedimentary record. To understand the microbial ecology of deep-sea bacteria, we need to appreciate the food supply in the upper ocean, its packaging, passage and transformation during the delivery to the sea bed, the seasonality of variability of the supply and the environmental conditions under which the deep-sea bacteria grow. We also need to put into a microbial context recent geochemical findings of vast reservoirs of intrinsically labile organic material sorped onto sediments. These may well become desorped, and once again available to microorganisms, during resuspension events caused by deep ocean currents. As biotechnologists apply their tools in the deep oceans in search of unique bacteria, an increasing knowledge and understanding of the natural processes undertaken and environmental conditions experienced by deep-sea bacteria will facilitate this exploitation.     

Effect of artificial destratification on iron,manganese, and zinc in the water,sediments, and two species of benthic macroinvertebrates in an Oklahoma lake

Ham's Lake was destratified in the summers of 1977 and 1978 by pumping surface water to the bottom. However, an arm was prevented from mixing by a submerged dam of a former farm pond and remained stratified. The concentration of manganese in the water increased to over 5 000 µg 1^–1 in the hypolimnion of the anoxic arm in summer. Soluble manganese averaged 28% of total concentration. Total iron concentrations were relatively high in the water and sorbed iron values were extremely low in the sediments. Soluble iron averaged 12% of total concentration. Zinc values were low in the water and sediments. Chaoborus punctipennis and Chironomus riparius concentrated iron and zinc and discriminated against manganese. Concentration factors were unaffected by mixing.     

Benthic fluxes of nutrients and some trace metals in the Tamar estuary,SW England

Pore water concentration gradients and fluxes of chemical components have been studied in sediments from six intertidal sites in the Tamar Estuary, SW England over the course of a year. Fluxes of nutrients (ammonia, nitrate, nitrite, phosphate and silicate) and trace metals (iron, manganese, zinc, copper and cadmium) were determined using a laboratory microcosm incorporatingin situ pore water samplers. Nutrients (except nitrate) were transported out of the sediment throughout the year, but nitrate fluxes were directed into the sediment in the summer (denitrification) and out of the sediment in the winter (nitrification). The activities of benthic macrofauna resulted in enhanced fluxes but these differed between sites depending on population structure and density and whether irrigation or sediment reworking predominated. Fluxes of trace metals were seasonally and spatially variable and specific differences were observed that could be attributed to both chemical and biological activity.     

Evaluation of six process‐based forest growth models using eddy‐covariance measurements of CO2 and H2O fluxes at six forest sites in Europe

Reliable models are required to assess the impacts of climate change on forest ecosystems. Precise and independent data are essential to assess this accuracy. The flux measurements collected by the EUROFLUX project over a wide range of forest types and climatic regions in Europe allow a critical testing of the process‐based models which were developed in the LTEEF project. The ECOCRAFT project complements this with a wealth of independent plant physiological measurements. Thus, it was aimed in this study to test six process‐based forest growth models against the flux measurements of six European forest types, taking advantage of a large database with plant physiological parameters. The reliability of both the flux data and parameter values itself was not under discussion in this study. The data provided by the researchers of the EUROFLUX sites, possibly with local corrections, were used with a minor gap‐filling procedure to avoid the loss of many days with observations. The model performance is discussed based on their accuracy, generality and realism. Accuracy was evaluated based on the goodness‐of‐fit with observed values of daily net ecosystem exchange, gross primary production and ecosystem respiration (gC m^?2 d^?1), and transpiration (kg H₂O m^?2 d^?1). Moreover, accuracy was also evaluated based on systematic and unsystematic errors. Generality was characterized by the applicability of the models to different European forest ecosystems. Reality was evaluated by comparing the modelled and observed responses of gross primary production, ecosystem respiration to radiation and temperature. The results indicated that: Accuracy. All models showed similar high correlation with the measured carbon flux data, and also low systematic and unsystematic prediction errors at one or more sites of flux measurements. The results were similar in the case of several models when the water fluxes were considered. Most models fulfilled the criteria of sufficient accuracy for the ability to predict the carbon and water exchange between forests and the atmosphere. Generality. Three models of six could be applied for both deciduous and coniferous forests. Furthermore, four models were applied both for boreal and temperate conditions. However, no severe water‐limited conditions were encountered, and no year‐to‐year variability could be tested. Realism. Most models fulfil the criterion of realism that the relationships between the modelled phenomena (carbon and water exchange) and environment are described causally. Again several of the models were able to reproduce the responses of measurable variables such as gross primary production (GPP), ecosystem respiration and transpiration to environmental driving factors such as radiation and temperature. Stomatal conductance appears to be the most critical process causing differences in predicted fluxes of carbon and water between those models that accurately describe the annual totals of GPP, ecosystem respiration and transpiration. As a conclusion, several process‐based models are available that produce accurate estimates of carbon and water fluxes at several forest sites of Europe. This considerable accuracy fulfils one requirement of models to be able to predict the impacts of climate change on the carbon balance of European forests. However, the generality of the models should be further evaluated by expanding the range of testing over both time and space. In addition, differences in behaviour between models at the process level indicate requirement of further model testing, with special emphasis on modelling stomatal conductance realistically.     

亚热带河口陆基养虾塘水体溶解性碳浓度及沉积物-水界面碳通量时空动态特征

以福建闽江和九龙江河口陆基养虾塘为研究对象,通过野外原位观测和室内模拟培养实验,开展了河口陆基养虾塘养殖期间水体溶解性有机碳(DOC)和溶解性无机碳(DIC)及养虾塘沉积物-水界面碳交换通量变化特征的研究。结果表明:时间变化上,养虾塘水体溶解性碳浓度及沉积物-水界面碳通量在闽江河口呈现8月中旬10月中旬6月中旬的特征,在九龙江河口表现为随养殖阶段推移而增加的趋势;空间变化上,闽江河口养虾塘水体溶解性碳浓度及沉积物-水界面碳通量显著高于九龙江河口;沉积物释放溶解性碳速率与水体溶解性碳浓度呈现显著正相关关系,沉积物碳释放过程是引起养虾塘水体溶解性碳浓度时空变化的重要因素。表明河口区水产养虾塘碳循环研究时需考虑不同形态碳生物地球化学循环的时空差异性。     

Bioturbation by Nereis sp. and its effects on the phosphate flux across the sediment-water interface in the Palmones River estuary

The effects of Nereis sp. on the flux of dissolved phosphate across the sediment-water interface has been studied in Palmones River estuary using benthic flux-chambers and intact cores. Diffusive fluxes of phosphate were calculated from pore water gradient concentration and compared with those obtained from benthic chambers experiments. The high abundance of Nereis in the upper sediment layers appears to play an important part in the dissolved oxygen profiles in the overlying water, but had no effect on the redox potential. A negative relationship was found between the Nereis abundance and the phosphate gradient; this gradient ranged between 40 µmol 1^–1 cm^–1 with 340 Nereis individuals m^–2 and 20 µmol 1^–1 cm^–1 with 900 Nereis individuals m^–2. The ratio of the in situ flux to the flux gradient concentration for dissolved phosphate increased with the abundance of Nereis (from 1.7 at low abundance to 5.8 at high abundance).     

Mathematical models and simulations of bacterial growth and chemotaxis in a diffusion gradient chamber

The diffusion gradient chamber (DGC) is a novel device developed to study the response of chemotactic bacteria to combinations of nutrients and attractants [7]. Its purpose is to characterize genetic variants that occur in many biological experiments. In this paper, a mathematical model which describes the spatial distribution of a bacterial population within the DGC is developed. Mathematical analysis of the model concerning positivity and boundedness of the solutions are given. An ADI (Alternating Direction Implicit) method is constructed for finding numerical solutions of the model and carrying out computer simulations. The numerical results of the model successfully reproduced the patterns that were observed in the experiments using the DGC. Received: 3 June 1997 / Revised version: 15 August 2000 / Published online: 20 December 2000     

九龙江河口区养虾塘沉积物-水界面营养盐交换通量特征

通过对九龙江河口区陆基养虾塘水样和沉积物样品采集分析及结合室内模拟实验,探讨了虾塘在不同养殖阶段沉积物-水界面营养盐通量时间变化特征及其主要影响因素。虾塘沉积物向上覆水体释放NO_x~--N(NO_2~--N和NO_3~--N)、NH_4~+-N和PO_4~(3-)-P能力均呈现随养殖时间推移而降低的特征。沉积物在养殖中期和后期分别呈现对上覆水体NO_x~--N和PO_4~(3-)-P的吸收现象,但总体表现为释放(平均通量分别为(1.87±1.15)、(1.58±0.52)mg m~(-2)h~(-1)和(1.22±0.62)mg m~(-2)h~(-1))。沉积物-水界面溶解无机氮交换以NH_4~+-N为主(沉积物平均释放通量为(46.18±13.82)mg m~(-2)h~(-1))。沉积物间隙水与上覆水间的营养盐浓度差(梯度)及温度对上述交换通量的时间动态特征具有重要调控作用。研究结果表明养殖初期或中期沉积物较高的无机氮(尤其是NO_2~--N和NH_4~+-N)释放是养殖塘水质恶化的一个极具潜力的污染内源,可能会对虾的健康生长产生负面效应,控制沉积物无机氮释放是养虾塘养殖初期和中期重要的日常管理活动之一。     

Mathematical modeling of elution curves for a protein mixture in ion exchange chromatography and for the optimal selection of operational conditions

Elution curves in ionic exchange chromatography (IEC) for a three-protein mixture (alpha-lactoalbumin, ovalbumin, and beta-lactoglobulin), carried out under different flow rates and ionic strength conditions, were simulated using two different mathematical models. These models were the Plate Model and the more fundamentally based Rate Model. Relatively low protein concentrations were used to avoid protein-protein interactions. Simulated elution curves were compared with experimental data not used for parameter identification. Deviation between experimental data and the simulated curves using the Plate Model was less than 0.0189 (absorbance units); a slightly higher deviation [0.0252 (absorbance units)] was obtained when the Rate Model was used. A cost function was built that included the effect of the different production stages, namely fermentation, purification, and concentration. These considered the effect on the performance of IEC; yield, purity, concentration and the time needed to accomplish the separation. Operational conditions in the IEC such as flow rate, ionic strength gradient and the operational time can be selected using this model in order to find the minimum cost for the protein production process depending on the characteristics of the final product desired such as purity and yield. This cost function was successfully used for the selection of the operational conditions as well as the fraction of the product to be collected (peak cutting) in IEC. It can be used for protein products with different characteristics and qualities, such as purity and yield, by choosing the appropriate parameters.     

A new approach for estimating the efficiencies of the nucleotide substitution models

In this article, a new approach is presented for estimating the efficiencies of the nucleotide substitution models in a four-taxon case and then this approach is used to estimate the relative efficiencies of six substitution models under a wide variety of conditions. In this approach, efficiencies of the models are estimated by using a simple probability distribution theory. To assess the accuracy of the new approach, efficiencies of the models are also estimated by using the direct estimation method. Simulation results from the direct estimation method confirmed that the new approach is highly accurate. The success of the new approach opens a unique opportunity to develop analytical methods for estimating the relative efficiencies of the substitution models in a straightforward way.     

Instantaneous benthic response to different organic matter quality: In situ experiments in the Benguela Upwelling System

The benthic community in continental slope and deep-sea sediments of the Benguela Upwelling System was supplied with ¹³C-labelled organic matter (OM) of two different qualities using a benthic chamber lander. Freeze-dried cultures of Skeletonema costatum served as 'fresh' OM. 'Altered' OM of the same material had been additionally dialysed to remove low-molecular weight compounds. In order to investigate the benthic response pattern, mineralization of labelled OM, uptake by macrofauna and incorporation into bacteria were followed over 18-36 h. Total oxygen uptake was not affected beyond natural variation by the OM addition. Mineralization dominated the ¹³C-labelled phytodetritus processing, constituting 71-95% of the total processed OM. Bacterial incorporation of phytodetrital carbon exceeded macrofaunal uptake at all stations. Stations situated in a major centre of OM deposition showed phytodetritus processing rates on average twice as high as outside the depocentre. Phytodetritus processing was 1.5, 2.5 and 4.3 times higher for fresh than for altered OM at 605, 1019 and 1335 m water depth, respectively. Our observations clearly indicate the importance of OM quality on mineralization rates.