Arsenic release and attenuation in low organic carbon aquifer sediments from West Bengal

High arsenic concentrations in groundwater are causing a humanitarian disaster in Southeast Asia. It is generally accepted that microbial activities play a critical role in the mobilization of arsenic from the sediments, with metal‐reducing bacteria stimulated by organic carbon implicated. However, the detailed mechanisms underpinning these processes remain poorly understood. Of particular importance is the nature of the organic carbon driving the reduction of sorbed As(V) to the more mobile As(III), and the interplay between iron and sulphide minerals that can potentially immobilize both oxidation states of arsenic. Using a multidisciplinary approach, we identified the critical factors leading to arsenic release from West Bengal sediments. The results show that a cascade of redox processes was supported in the absence of high loadings of labile organic matter. Arsenic release was associated with As(V) and Fe(III) reduction, while the removal of arsenic was concomitant with sulphate reduction. The microbial populations potentially catalysing arsenic and sulphate reduction were identified by targeting the genes arrA and dsrB, and the total bacterial and archaeal communities by 16S rRNA gene analysis. Results suggest that very low concentrations of organic matter are able to support microbial arsenic mobilization via metal reduction, and subsequent arsenic mitigation through sulphate reduction. It may therefore be possible to enhance sulphate reduction through subtle manipulations to the carbon loading in such aquifers, to minimize the concentrations of arsenic in groundwaters.     

Phosphorus–iron interaction in sediments: can an electrode minimize phosphorus release from sediments?

All restoration strategies to mitigate eutrophication depend on the success of phosphorus (P) removal from the water body. Therefore, the inputs from the watershed and from the enriched sediments, that were the sink of most P that has been discharged in the water body, should be controlled. In sediments, iron (hydr)oxides minerals are potent repositories of P and the release of P into the water column may occur upon dissolution of the iron (hydr)oxides mediated by iron reducing bacteria. Several species of these bacteria are also known as electroactive microorganisms and have been recently identified in lake sediments. This capacity of bacteria to transfer electrons to electrodes, producing electricity from the oxidation of organic matter, might play a role on P release in sediments. In the present work it is discussed the relationship between phosphorus and iron cycling as well as the application of an electrode to work as external electron acceptor in sediments, in order to prevent metal bound P dissolution under anoxic conditions.     

Molecular analysis of arsenate-reducing bacteria within Cambodian sediments following amendment with acetate

The health of millions is threatened by the use of groundwater contaminated with sediment-derived arsenic for drinking water and irrigation purposes in Southeast Asia. The microbial reduction of sorbed As(V) to the potentially more mobile As(III) has been implicated in release of arsenic into groundwater, but to date there have been few studies of the microorganisms that can mediate this transformation in aquifers. With the use of stable isotope probing of nucleic acids, we present evidence that the introduction of a proxy for organic matter ((13)C-labeled acetate) stimulated As(V) reduction in sediments collected from a Cambodian aquifer that hosts arsenic-rich groundwater. This was accompanied by an increase in the proportion of prokaryotes closely related to the dissimilatory As(V)-reducing bacteria Sulfurospirillum strain NP-4 and Desulfotomaculum auripigmentum. As(V) respiratory reductase genes (arrA) closely associated with those found in Sulfurospirillum barnesii and Geobacter uraniumreducens were also detected in active bacterial communities utilizing (13)C-labeled acetate in microcosms. This study suggests a direct link between inputs of organic matter and the increased prevalence and activity of organisms which transform As(V) to the potentially more mobile and thus hazardous As(III) via dissimilatory As(V) reduction.     

Molecular Analysis of Arsenate-Reducing Bacteria within Cambodian Sediments following Amendment with Acetate

The health of millions is threatened by the use of groundwater contaminated with sediment-derived arsenic for drinking water and irrigation purposes in Southeast Asia. The microbial reduction of sorbed As(V) to the potentially more mobile As(III) has been implicated in release of arsenic into groundwater, but to date there have been few studies of the microorganisms that can mediate this transformation in aquifers. With the use of stable isotope probing of nucleic acids, we present evidence that the introduction of a proxy for organic matter (¹³C-labeled acetate) stimulated As(V) reduction in sediments collected from a Cambodian aquifer that hosts arsenic-rich groundwater. This was accompanied by an increase in the proportion of prokaryotes closely related to the dissimilatory As(V)-reducing bacteria Sulfurospirillum strain NP-4 and Desulfotomaculum auripigmentum. As(V) respiratory reductase genes (arrA) closely associated with those found in Sulfurospirillum barnesii and Geobacter uraniumreducens were also detected in active bacterial communities utilizing ¹³C-labeled acetate in microcosms. This study suggests a direct link between inputs of organic matter and the increased prevalence and activity of organisms which transform As(V) to the potentially more mobile and thus hazardous As(III) via dissimilatory As(V) reduction.     

Microbial ecology of arsenic‐mobilizing Cambodian sediments: lithological controls uncovered by stable‐isotope probing

Microbially mediated arsenic release from Holocene and Pleistocene Cambodian aquifer sediments was investigated using microcosm experiments and substrate amendments. In the Holocene sediment, the metabolically active bacteria, including arsenate‐respiring bacteria, were determined by DNA stable‐isotope probing. After incubation with ¹³C‐acetate and ¹³C‐lactate, active bacterial community in the Holocene sediment was dominated by different Geobacter spp.‐related 16S rRNA sequences. Substrate addition also resulted in the enrichment of sequences related to the arsenate‐respiring Sulfurospirillum spp. ¹³C‐acetate selected for ArrA related to Geobacter spp. whereas ¹³C‐lactate selected for ArrA which were not closely related to any cultivated organism. Incubation of the Pleistocene sediment with lactate favoured a 16S rRNA‐phylotype related to the sulphate‐reducing Desulfovibrio oxamicus DSM1925, whereas the ArrA sequences clustered with environmental sequences distinct from those identified in the Holocene sediment. Whereas limited As(III) release was observed in Pleistocene sediment after lactate addition, no arsenic mobilization occurred from Holocene sediments, probably because of the initial reduced state of As, as determined by X‐ray Absorption Near Edge Structure. Our findings demonstrate that in the presence of reactive organic carbon, As(III) mobilization can occur in Pleistocene sediments, having implications for future strategies that aim to reduce arsenic contamination in drinking waters by using aquifers containing Pleistocene sediments.     

Anaerobic metabolism of particulate organic matter in the sediments of a hypereutrophic lake*

SUMMARY. The anaerobic decomposition of particulate organic matter (POM) was examined in the anoxic pelagic sediments of hypereutrophic Wintergreen Lake. Degradation of sedimented POM occurred rapidly as shown by increased production and release of ammonia, hydrogen sulphide, volatile fatty acids and methane from the sediments 2–3 weeks after large inputs of organic matter. Maximum concentrations of most metabolites were found at the sediment-water interface, indicating that the initial anaerobic degradation of freshly deposited POM occurred at this site. The absence of the inorganic electron acceptors, nitrate and sulphate, suggested that fermentation and methanogenesis were the major anaerobic processes involved in the dissimilation of organic matter in these sediments during stratified periods. The amount of carbon input converted to methane in the sediments was determined from May to early November 1976 and 1977. Carbon output as methane was measured by quantifying methane lost from the sediments by ebullition and by estimating soluble methane lost to the water column by diffusion. Total methane release during summer stratification accounted for 34% of the particulate organic carbon input to the sediments in 1976 and 44% in 1977. Methane release was directly related to the rate of sedimentation of POM. However, methane production was temporarily inhibited following high rates of sedimentation in 1976, suggesting that the rate of organic loading may be an important factor controlling anaerobic decomposition in these sediments.     

Modeling Microbially Induced Carbon Degradation in Redox-Stratified Subsurface Environments: Concepts and Open Questions

The degradation of organic matter, including organic contaminants, in subsurface environments is controlled by the abundances and functional capabilities of the resident microorganisms. As a consequence, modeling approaches simulating the fate of organics and related changes in redox conditions have to account for the effects of microbial activity on the degradation kinetics, as well as for the spatial and temporal distributions of the chemical species (e.g., terminal electron acceptors, nutrients or toxic substances) that control microbial activity. The present paper reviews the principal modeling approaches that are used to simulate the degradation of organic matter in water-saturated porous media. Special attention is devoted to modeling the bioavailability of chemical substrates of microbial reactions, and the sequential occurrence of terminal electron accepting pathways. While the various model approaches found in the literature are capable of reproducing field data sets from various environmental settings, they are rarely compared in terms of performance and predictive ability. Most approaches incorporate simplifications or empirical rate laws, which limit their range of application. Thus, there remains a need for further development of more general, process-based modeling concepts to represent microbially mediated reactive processes.     

Sulfur Cycling in the Terrestrial Subsurface: Commensal Interactions, Spatial Scales, and Microbial Heterogeneity

Abstract Microbiological, geochemical, and isotopic analyses of sediment and water samples from the unconsolidated Yegua formation in east-central Texas were used to assess microbial processes in the terrestrial subsurface. Previous geochemical studies suggested that sulfide oxidation at shallow depths may provide sulfate for sulfate-reducing bacteria (SRB) in deeper aquifer formations. The present study further examines this possibility, and provides a more detailed evaluation of the relationship between microbial activity, lithology, and the geochemical environment on meter-to-millimeter scales. Sediment of varied lithology (sands, silts, clays, lignite) was collected from two boreholes, to depths of 30 m. Our findings suggest that pyrite oxidation strongly influences the geochemical environment in shallow sediments (∼5 m), and produces acidic waters (pH 3.8) that are rich in sulfate (28 mM) and ferrous iron (0.3 mM). Sulfur and iron-oxidizing bacteria are readily detected in shallow sediments; they likely play an indirect role in pyrite oxidation. In consistent fashion, there is a relative paucity of pyrite in shallow sediments and a low ³⁴S/³²S-sulfate ratio (0.2‰) (reflecting contributions from ³⁴S-depleted sulfides) in shallow regions. Pyrite oxidation likely provides a sulfate source for both oxic and anoxic aquifers in the region. A variety of assays and direct-imaging techniques of ³⁵S-sulfide production in sediment cores indicates that sulfate reduction occurs in both the oxidizing and reducing portions of the sediment profile, with a high degree of spatial variability. Narrow zones of activity were detected in sands that were juxtaposed to clay or lignite-rich sediments. The fermentation of organic matter in the lignite-rich laminae provides small molecular weight organic acids to support sulfate reduction in neighboring sands. Consequently, sulfur cycling in shallow sediments, and sulfate transport represent important mechanisms for commensal interaction among subsurface microorganisms by providing electron donors for chemoautotrophic bacteria and electron acceptors for SRB. The activity of SRB is linked to the availability of suitable electron donors from spatially distinct zones. Received: 10 November 1997; Accepted: 10 February 1998     

Nutrient retention and release in a floodplain's aquifer and in the hyporheic zone of a lowland river

Fertilizer applications and other non-point sources result in an increasing diffuse N and P pollution of receiving waters degrading water quality by eutrophication with several adverse impacts. Floodplains are regarded as reactive interfaces between uplands and receiving waters. In the present study groundwater quality on its subsurface flow from an upland area through a lowland floodplain towards the receiving water body of the Spree River was monitored biweekly over 2 years with two transects of 18 groundwater observation wells. Within the floodplain reaction rates of the nutrients are unevenly distributed. On a scale smaller than the floodplain, the hyporheic zone is regarded as reactive interface with unproportional high reaction rates. Therefore, phosphate and dissolved iron were measured with high spatial resolution in the pore water of the riverbed and the oxbow bed to investigate turnover processes and their small-scale spatial variability at the immediate surface–subsurface interface. The biogeochemical composition of subsurface water is characterized by little temporal variability while spatial heterogeneity is high on the hectametre scale of the study site as well as on the centimetre scale of the bed sediments. Nitrate is eliminated very efficiently by denitrification in the anoxic aquifer of the floodplain while ammonium and phosphate concentrations increase under anoxic conditions. Phosphate and ammonium originate from the mineralization of organic matter and phosphate is additionally released by reductive dissolution of iron-bound phosphorus and weathering of bedrock. Sorption–desorption processes equalize temporal fluctuations of phosphate concentrations. Phosphate uptake by plants is assumed as an important process at only one of the groundwater observation wells. Redox conditions required for a phosphate sink are opposite to those involved in nitrate removal by denitrification. Thus, redox patchiness of floodplain aquifers favours nitrate and phosphate removal, i.e. a temporal and spatial sequence of anoxic and oxic conditions eliminates nitrogen and causes phosphate storage. On the groundwater's path from the upland to the river further phosphate is released in the bed sediments. It originates from previously settled particulate compounds containing phosphorus. While the release of iron-bound phosphorus clearly predominates in the riverbed sediments the mineralization of organic matter is an important additional phosphorus release process in the oxbow bed sediments.     

Phosphorus Sequestration in Lake Sediment with Iron Mine Tailings

Internal phosphorus loading can lead to eutrophication in lakes when anoxic sediments release bioavailable phosphorus into the water column. In laboratory experiments, iron mine tailings helped to sequester phosphorus in sediment from a eutrophic lake. Phosphorus release from the sediments after extraction with distilled water or 0.02 N H ₂ SO ₄ was significantly reduced when mine tailings were added (1:1 w/w), even when the system was anaerobic (～ 1 mg O ₂ /L). The degree of sequestration was enhanced when glucose (1% w/w) was added to stimulate the growth of microorganisms, suggesting that the process was microbially mediated. We suggest that oxidized iron in the mine tailings served as an electron sink for microbial respiration via dissimilatory Fe³⁺ reduction. The reduced iron released into solution sequestered phosphorus, either as it re-oxidized and formed hydrous ferric oxide complexes containing phosphorus (HFO-P), or through precipitation. Since mine tailings are inexpensive, they may prove useful for preventing phosphorus from entering surface waters, as well as reducing internal phosphorus loading.     

Dissimilatory Fe(III) and Mn(IV) reduction.

The oxidation of organic matter coupled to the reduction of Fe(III) or Mn(IV) is one of the most important biogeochemical reactions in aquatic sediments, soils, and groundwater. This process, which may have been the first globally significant mechanism for the oxidation of organic matter to carbon dioxide, plays an important role in the oxidation of natural and contaminant organic compounds in a variety of environments and contributes to other phenomena of widespread significance such as the release of metals and nutrients into water supplies, the magnetization of sediments, and the corrosion of metal. Until recently, much of the Fe(III) and Mn(IV) reduction in sedimentary environments was considered to be the result of nonenzymatic processes. However, microorganisms which can effectively couple the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV) have recently been discovered. With Fe(III) or Mn(IV) as the sole electron acceptor, these organisms can completely oxidize fatty acids, hydrogen, or a variety of monoaromatic compounds. This metabolism provides energy to support growth. Sugars and amino acids can be completely oxidized by the cooperative activity of fermentative microorganisms and hydrogen- and fatty-acid-oxidizing Fe(III) and Mn(IV) reducers. This provides a microbial mechanism for the oxidation of the complex assemblage of sedimentary organic matter in Fe(III)- or Mn(IV)-reducing environments. The available evidence indicates that this enzymatic reduction of Fe(III) or Mn(IV) accounts for most of the oxidation of organic matter coupled to reduction of Fe(III) and Mn(IV) in sedimentary environments. Little is known about the diversity and ecology of the microorganisms responsible for Fe(III) and Mn(IV) reduction, and only preliminary studies have been conducted on the physiology and biochemistry of this process.     

Spatial Electron Acceptor Variability: Implications for Assessing Bioremediation Potential

An extensive network of multilevel samplers was established in a hydrocarbon-contaminated wetland aquifer. Results of groundwater sampling for benzene, toluene, ethylbenzene, and xylenes (BTEX), and electron acceptors show that both pristine and contaminated groundwater have spatially variable chemical signatures, owing primarily to microbially mediated oxidation-reduction reactions. Due to these spatial variations, estimates of the efficiency of intrinsic bioremediation can vary significantly depending on how geochemical data are collected. Use of data collected from monitoring wells with screens longer than the vertical extent of the plume will generally underestimate the potential for intrinsic bioremediation for the most chemically active horizon of the plume. A comparison of pristine and contaminated redox patterns demonstrates that, although BTEX exerts the highest demand for electron acceptors, oxidation of natural organic matter also contributes to electron acceptor utilization. If natural and other non-BTEX losses of electron acceptors are ignored, the assimilative capacity, defined as the amount of a contaminant that can potentially be degraded with known amounts of electron acceptors, will be overestimated. Many numerical and analytical models designed to simulate biodegradation are directly or indirectly based on assimilative capacity estimates. Proper estimation of assimilative capacity is crucial if models are to accurately quantify solute concentrations over time and space.     

Organic matter diagenesis at the oxic/anoxic interface in coastal marine sediments,with emphasis on the role of burrowing animals

The present paper reviews the current knowledge on diagenetic carbon transformations at the oxic/anoxic interface in coastal marine sediments. Oxygen microelectrodes have revealed that most coastal sediments are covered only by a thin oxic surface layer. The penetration depth of oxygen into sediments is controlled by the balance between downward transport and consumption processes. Consumption of oxygen is directly or indirectly caused by respiration of benthic organisms. Aerobic organisms have the enzymatic capacity for complete oxidation of organic carbon. Anaerobic decay occurs stepwise, involving several types of bacteria. Large organic molecules are first fermented into small moieties. These are then oxidized completely by anaerobic respirers using a sequence of electron acceptors: Mn⁴⁺, NO₃ ^-, Fe³⁺, SO₄ ^2- and CO₂. The quantitative role of each electron acceptor depends on the sediment type and water depth. Since most of the sediment oxygen uptake is due to reoxidation of reduced metabolites, aerobic respiration is of limited importance. It has been suggested that sediments contain three major organic fractions: (1) fresh material that is oxidized regardless of oxygen conditions; (2) oxygen sensitive material that is only degraded in the presence of oxygen; and (3) totally refractory organic matter. Processes occurring at the oxic/anoxic boundaries are controlled by a number of factors. The most important are: (1) temperature, (2) organic supply, (3) light, (4) water currents, and (5) bioturbation. The role of bioturbation is important because the infauna creates a three-dimensional mosaic of oxic/anoxic interfaces in sediments. The volume of oxic burrow walls may be several times the volume of oxic surface sediment. The infauna increases the capacity, but not the overall organic matter decay in sediments, thus decreasing the pool of reactive organic matter. The increase in decay capacity is partly caused by injection of oxygen into the sediment, and thereby enhancing the decay of old, oxygen sensitive organic matter several fold. Finally, some future research directions to improve our understanding of diagenetic processes at the oxic/anoxic interface are suggested.     

Microbial Community Compositions and Geochemistry of Sediments with Increasing Distance to the Hydrothermal Vent Outlet in the Kairei Field

Abstract

Microbial metabolisms in sediments play a pivotal role in marine element cycling. In hydrothermal sediments chemosynthetic microorganisms likely prevail, while in non-hydrothermally impacted sediment regimes microorganisms associated with organic matter decomposition are primarily recognized. To test how these microorganisms are distributed along the hitherto neglected transition zone influenced to different degrees by hydrothermal input we sampled four sediment sites: these were (i) near an active vent, (ii) the outer rim, and (iii) the inactive area of the Kairei hydrothermal field as well as (iv) sediments roughly 200?km south-east of the Kairei field. Chemistry and microbial community compositions were different at all sampling sites. Against expectations, the sediments near the active vent did not host typical chemosynthetic microorganisms and chemistry did not indicate current, extensive hydrothermal venting. Data from the outer rim area of the active Kairei field suggested microbially mediated saponite production and diffuse hydrothermal flow from below accompanied by increased metal concentrations. A steep redox gradient in the inactive Kairei field points towards significant redox driven processes resulting in dissolution of hydrothermal precipitates and intense metal mobilization. Local microorganisms were primarily Chloroflexi, Bacillales, Thermoplasmata, and Thaumarchaeota.     

Influence of ecosystem engineers on ecosystem processes is mediated by lake sediment properties

Invasive species may impact biotic community structure, ecosystem processes, and associated goods and services. Their impact may be especially strong when they also serve as ecosystem engineers (i.e. organisms affecting the physical habitat and resources for other species). Dreissenid mussels fill both these roles, having invaded the Laurentian Great Lakes in the late 1980s, and also serve as ecosystem engineers by altering nutrient fluxes and influencing the microbial food web through direct nutrient release and excretion of feces and pseudo‐feces at the water–sediment interface. We conducted laboratory experiments to investigate how the different functional traits of invasive quagga mussels (filtering activity and direct nutrient release) and native chironomid larvae (tube building and bioirrigation) interact with lake sediment of differing organic matter content to influence biogeochemical fluxes and water quality. Our results showed that sediment reworking and ventilation activities by chironomid larvae increased oxygen penetration in the sediment, affecting primarily pore water chemistry, whereas invasive mussels enhanced nutrient releases in the surface water. However, sediment organic matter modulated the effects of ecosystem engineers on system‐level processes; chironomids had a greater influence on sediment reworking and microbial‐mediated processes in organic‐rich sediments, whereas quagga mussels enhanced nutrient concentrations in the overlying water of organic‐poor sediments. These results have management implications, as the effects of invasive mussels on the biogeochemical functioning in the Great Lakes region and elsewhere can alter system bioenergetics and promote harmful algal blooms.     

Ecology, physiology, and phylogeny of deep subsurface Sphingomonas sp

Several new species of the genus Sphingomonas including S. aromaticivorans, S. stygia, and S. subterranea that have the capacity for degrading a broad range of aromatic compounds including toluene, naphthalene, xylenes, p-cresol, fluorene, biphenyl, and dibenzothiophene, were isolated from deeply-buried (>200 m) sediments of the US Atlantic coastal plain (ACP). In S. aromaticivorans F199, many of the genes involved in the catabolism of these aromatic compounds are encoded on a 184-kb conjugative plasmid; some of the genes involved in aromatic catabolism are plasmid-encoded in the other strains as well. Members of the genus Sphingomonas were common among aerobic heterotrophic bacteria cultured from ACP sediments and have been detected in deep subsurface environments elsewhere. The major source of organic carbon for heterotrophic metabolism in ACP deep aquifers is lignite that originated from plant material buried with the sediments. We speculate that the ability of the subsurface Sphingomonas strains to degrade a wide array of aromatic compounds represents an adaptation for utilization of sedimentary lignite. These and related subsurface Sphingomonas spp may play an important role in the transformation of sedimentary organic carbon in the aerobic and microaerobic regions of the deep aquifers of the ACP. Received 12 May 1999/ Accepted in revised form 25 July 1999     

Sediments as a source for contaminants?

This review article covers the processes affecting trace metals in deposited sediments. The sediment-water system can be divided in three parts: the oxic layer, the anoxic layer and the oxic-anoxic interface. Available data show that trace metals like Cu, Zn and Cd occur as sulphides in marine and estuarine anoxic sediments. Calculations show that organic complexation is unlikely and the dominant species are sulphide and bisulphide complexes. Chromium and arsenic are probably present as adsorbed species on the sediments; their concentrations in the pore waters, therefore depend on the concentrations in the sediments. The oxic-anoxic interface plays the major role in the potential flux of trace metals from the sediments, however this interface is not well studied at present. Changes from an anoxic to an oxic environment as occurs during dredging and land disposal of contaminanted sediments may cause a remobilization of some trace metals.     

长江中下游部分湖泊沉积物碱性磷酸酶分布及其作用研究

沉积物磷负荷在湖泊富营养化的发生与恢复过程中具有关键作用,其释放受物理、化学与生物机制调节,而碱性磷酸酶催化有机磷的矿化,故当为促进沉积物磷循环的重要因素。本文讨论了长江中下游部分湖泊沉积物碱性磷酸酶分布及其在磷释放过程中的作用。五里湖疏浚与未疏浚区以及太湖、巢湖、龙感湖、东湖、月湖、龙阳湖、莲花湖等不同湖泊的不同区域表层沉积物碱性磷酸酶活性(APA)明显不同,这种空间异质性与湖泊富营养化程度相联系。此外,APA随沉积物的深度递减,或在中间与较深层次出现峰值,且具明显的季节性。上述事实以及APA对抑制剂的不同响应方式暗示酶存在形态的多样性(同工酶)。苯丙氨酸(Phe)明显提高月湖与五里湖沉积物APA,沉积物与Phe相互作用并静置一天之后,生物可利用性磷(SRP)的释放量明显增加。再者,Phe可抑制月湖沉积物APA,沉积物与Phe相互作用并静置一天之后,SRP释放量无明显变化,溶解有机磷(DOP)的释放量则明显增加。因此,释放的SRP部分来自某些活跃的有机磷的酶促水解,沉积物碱性磷酸酶在内源磷的释放以及富营养化过程中具有重要作用。     

Entrapment of pollutants in Mediterranean sediments and biogeochemical indicators of their impact

The transit and fate of certain pollutants (Cd, Pb, Zn and P) transported to the western Mediterranean sea-floor and a method to assess their impact are described. The spatial distribution of pollutant concentrations in the Rhône prodelta shows that their decline with distance from their source is due both to mixing with unpolluted sediments, release from contaminated particles during transit and release from sediments after deposition. Beyond the continental shelf, metals of anthropogenic origin, mainly incorporated in faecal pellets, sink and become entrapped in deep sea sediments. Because subsaturating concentrations of trace metals are often found in surface pore waters and storage, therefore, still occurs, co-precipitation with other metal ions existing in slightly supersaturated states has also to be considered. Although phosphate tends to precipitate as apatite after entering sea water, its `definitive' storage in sediments is hindered by certain forms of pollution. Low pH and reducing conditions in sediments enhance phosphate release to the overlying water . Eutrophication may then occur in localised areas. The effects of urban waste water contamination on biogeochemical processes in sediments are examined, in particular processes responsible for the transformation of organic nitrogen. Sediment quality appears to be better defined by the effectiveness of diagenetic processes than by pollutant concentration per se. In general, polluted sediments possess weak capacities to transform organic nitrogen relative to the quantities of organic matter that are available. Such sediment characteristics are indicated by the preferential growth of Caulerpa taxifolia over that of Posidonia oceanica.     

Organic Matter Mineralization with Reduction of Ferric Iron in Anaerobic Sediments

The potential for ferric iron reduction with fermentable substrates, fermentation products, and complex organic matter as electron donors was investigated with sediments from freshwater and brackish water sites in the Potomac River Estuary. In enrichments with glucose and hematite, iron reduction was a minor pathway for electron flow, and fermentation products accumulated. The substitution of amorphous ferric oxyhydroxide for hematite in glucose enrichments increased iron reduction 50-fold because the fermentation products could also be metabolized with concomitant iron reduction. Acetate, hydrogen, propionate, butyrate, ethanol, methanol, and trimethylamine stimulated the reduction of amorphous ferric oxyhydroxide in enrichments inoculated with sediments but not in uninoculated or heat-killed controls. The addition of ferric iron inhibited methane production in sediments. The degree of inhibition of methane production by various forms of ferric iron was related to the effectiveness of these ferric compounds as electron acceptors for the metabolism of acetate. The addition of acetate or hydrogen relieved the inhibition of methane production by ferric iron. The decrease of electron equivalents proceeding to methane in sediments supplemented with amorphous ferric oxyhydroxides was compensated for by a corresponding increase of electron equivalents in ferrous iron. These results indicate that iron reduction can outcompete methanogenic food chains for sediment organic matter. Thus, when amorphous ferric oxyhydroxides are available in anaerobic sediments, the transfer of electrons from organic matter to ferric iron can be a major pathway for organic matter decomposition.