Distribution and speciation of phosphorus along a salinity gradient in intertidal marsh sediments

We examined forms of solid phosphorus fractions in intertidal marsh sediments along a salinity (0–22%.) gradient in a river-dominated estuary and in a marine-dominated salt marsh with insignificant freshwater input. Freshwater marsh sediments had the highest ratio of organic N:P of between 28:1 and 47:1 mol:mol, compared to 211 to 311 molmol in the saltmarshes, which is consistent with a trend toward P-limitation of primary production in freshwater and N-limitation in salt marshes. However, total P concentration, 24.7±11.1mol P g dw^–1 (±1 SD) averaged over the upper meter of sediment, was greatest in the freshwater marsh where bioavailablity of P is apparently limited. In the freshwater marsh the greatest fraction of total P (24–51%.) was associated with humic acids, while the importance of humic-P decreased with increasing salinity to 1–23%. in the salt marshes. Inorganic P contributed considerably less to total sediment P in the freshwater marsh (15–40%.) than in the salt marshes (33–85%.). In reduced sediments at all sites, phosphate bound to aluminum oxides and clays was an important inorganic P pool irrespective of salinity. Inorganic P associated with ferric iron [Fe(III)] phases was most abundant in surface sediments of freshwater and brackish marshes, while Ca-bound P dominated inorganic P pools in the salt marshes. Thus, our results showed that particle-bound P in marsh sediments exhibited changes in chemical association along the salinity gradient of an estuarine system, which is a likely consequence of changes in ionic strength and the availability of iron and calcium.     

Anaerobic Oxidation of Arsenite Linked to Chlorate Reduction

Microorganisms play a significant role in the speciation and mobility of arsenic in the environment. In this study, the oxidation of arsenite [As(III)] to arsenate [As(V)] linked to chlorate (ClO₃⁻) reduction was shown to be catalyzed by sludge samples, enrichment cultures (ECs), and pure cultures incubated under anaerobic conditions. No activity was observed in treatments lacking inoculum or with heat-killed sludge, or in controls lacking ClO₃⁻. The As(III) oxidation was linked to the complete reduction of ClO₃⁻ to Cl⁻, and the molar ratio of As(V) formed to ClO₃⁻ consumed approached the theoretical value of 3:1 assuming the e⁻ equivalents from As(III) were used to completely reduce ClO₃⁻. In keeping with O₂ as a putative intermediate of ClO₃⁻ reduction, the ECs could also oxidize As(III) to As(V) with O₂ at low concentrations. Low levels of organic carbon were essential in heterotrophic ECs but not in autotrophic ECs. 16S rRNA gene clone libraries indicated that the ECs were dominated by clones of Rhodocyclaceae (including Dechloromonas, Azospira, and Azonexus phylotypes) and Stenotrophomonas under autotrophic conditions. Additional phylotypes (Alicycliphilus, Agrobacterium, and Pseudoxanthomonas) were identified in heterotrophic ECs. Two isolated autotrophic pure cultures, Dechloromonas sp. strain ECC1-pb1 and Azospira sp. strain ECC1-pb2, were able to grow by linking the oxidation of As(III) to As(V) with the reduction of ClO₃⁻. The presence of the arsenite oxidase subunit A (aroA) gene was demonstrated with PCR in the ECs and pure cultures. This study demonstrates that ClO₃⁻ is an alternative electron acceptor to support the microbial oxidation of As(III).The contamination of drinking water with arsenic (As) is a global public health issue. Arsenic is a human carcinogenic compound (2), which poses a risk to millions of people around the world (31). The most common oxidation states of As in aqueous environments are arsenite [As(III), H₃AsO₃] or arsenate [As(V), H₂AsO₄⁻, and HAsO₄²⁻]. Microbial processes play critical roles in controlling the fate and transformation of As in subsurface systems (22). As(V) binds to aluminum oxides more extensively than As(III) under circumneutral pH conditions (12, 16). Both As(III) and As(V) are strongly adsorbed on iron oxides (9). However, As(III) is more rapidly desorbed compared to As(V) (35).Aerobic bacteria can oxidize As(III) forming As(V) (14, 28), which potentially is less mobile in the subsurface environment. Also, in environments with dissolved ferrous iron [Fe(II)] the oxidation of Fe(II) (both abiotic and biotic) would result in formation of Fe(III) (hydr)oxides such as ferrihydrite which adsorb As. Oxidation processes, therefore, can decrease the mobilization of As in groundwater. However, oxygen (O₂) is poorly soluble in groundwater and may become consumed by microbial activity, creating anaerobic zones. Alternative oxidants aside from O₂ also have the potential to support the microbial oxidation of As(III). Recently, several studies have demonstrated that nitrate-dependent As(III) oxidation is carried out by anaerobic microorganisms to gain energy from As(III) oxidation. As(III)-oxidizing denitrifying bacteria have been isolated from various environments including As-contaminated lakes and soil (21, 25), as well as enrichment cultures (ECs), and isolates from pristine sediments and sludge samples (33, 34). 16S rRNA gene clone library characterization of the ECs indicates that the predominant phylotypes were from the genus Azoarcus and the family Comamonadaceae (34).Beside nitrate, chlorate (ClO₃⁻) can also be considered as a possible alternative oxidant for microorganisms to promote the bioremediation of contaminated plumes (6, 17). (Per)chlorate is commonly used as a terminal electron acceptor by anaerobic bacteria; as a result, it is completely degraded to the benign end product, chloride (Cl⁻). Microbial reduction of perchlorate proceeds via a three-step process of ClO₄⁻ → ClO₃⁻→ ClO₂⁻ → O₂ + Cl⁻ (6). Reduction of perchlorate to chlorate, and chlorate to chlorite is catalyzed by respiratory (per)chlorate reductases (3). Subsequent disproportionation of chlorite into Cl⁻ and O₂ is catalyzed by chlorite dismutase, which is the fastest step, and the O₂ produced is immediately consumed for energy of cell synthesis (6). Although organic compounds are the most well studied electron donors for (per)chlorate reduction, Fe(II) oxidation has also been shown to be linked to microbial ClO₃⁻ reduction (36).The main objective of the present study is to explore the potential use of ClO₃⁻ as an electron acceptor for the microbial oxidation of As(III) by anaerobic bacteria. The theoretical stoichiometry of the reaction is presented below: (1) Based on bioenergetic considerations, the reaction is feasible as indicated by the highly exergonic standard change in Gibbs free energy [ΔG⁰′ = −92.4 kJ mol⁻¹ As(III)] calculated from E^0′ values of 0.618 and 0.139 V for ClO₃⁻/Cl⁻ (6) and As(V)/As(III) (18), respectively.     

Anodically generated manganese(III) acetate for the oxidation of α — amino acids in aqueous acetic acid: A kinetic study

Summary Manganese(III) acetate was prepared by the oxidation of manganese(II) acetate in aqueous acetic acid by electrolytic method. The anodically generated Mn(III) species was characterised by spectroscopic and redox potential studies. Conditions for the study of kinetics of Oxidation of-amino acids by Mn(III) in aqueous acetic acid was investigated. Plots of log[Mn(III)] versus time for the first order process, or Mn(III) versus time for zero order process were nonlinear. The rate constants computed from [Mn(III)]^1/2 versus time plots were independent of [Mn(III)]₀ indicating that the reaction goes through competitive zero and first order path-ways in [Mn(III)]₀. The kinetic order in [amino acid], [H⁺] and [Mn(II)] were found out. Effect of added anions like CH₃COO^–, F^–, Cl^– and ClO ₄ ^- were investigated. Evidence for the transient existence of the free radical reaction intermediate is given. Dependence of reaction rate on temperature is explained and activation parameters computed from Arrhenius and Eyring plots. A mechanism consistent with the observed results is proposed and discussed.     

Coupled Arsenotrophy in a Hot Spring Photosynthetic Biofilm at Mono Lake,California

Red-pigmented biofilms grow on rock and cobble surfaces present in anoxic hot springs located on Paoha Island in Mono Lake. The bacterial community was dominated (∼ 85% of 16S rRNA gene clones) by sequences from the photosynthetic Ectothiorhodospira genus. Scraped biofilm materials incubated under anoxic conditions rapidly oxidized As(III) to As(V) in the light via anoxygenic photosynthesis but could also readily reduce As(V) to As(III) in the dark at comparable rates. Back-labeling experiments with ⁷³As(V) demonstrated that reduction to ⁷³As(III) also occurred in the light, thereby illustrating the cooccurrence of these two anaerobic processes as an example of closely coupled arsenotrophy. Oxic biofilms also oxidized As(III) to As(V). Biofilms incubated with [¹⁴C]acetate oxidized the radiolabel to ¹⁴CO₂ in the light but not the dark, indicating a capacity for photoheterotrophy but not chemoheterotrophy. Anoxic, dark-incubated samples demonstrated As(V) reduction linked to additions of hydrogen or sulfide but not acetate. Chemoautotrophy linked to As(V) as measured by dark fixation of [¹⁴C]bicarbonate into cell material was stimulated by either H₂ or HS⁻. Functional genes for the arsenate respiratory reductase (arrA) and arsenic resistance (arsB) were detected in sequenced amplicons of extracted DNA, with about half of the arrA sequences closely related (∼98% translated amino acid identity) to those from the family Ectothiorhodospiraceae. Surprisingly, no authentic PCR products for arsenite oxidase (aoxB) were obtained, despite observing aerobic arsenite oxidation activity. Collectively, these results demonstrate close linkages of these arsenic redox processes occurring within these biofilms.Oxyanions of the group 15 element arsenic, arsenate [As(V)] and arsenite [As(III)], have been known for millennia to be potent poisons. Despite its well-established toxicity to life, the phenomenon of arsenic resistance was discovered whereby some microorganisms maintain an otherwise “normal” existence in the presence of high concentrations of As(V) or As(III) (17, 29, 31). More recently it has become recognized that certain representatives from the bacterial and archaeal domains can actually exploit the electrochemical potential of the As(V)/As(III) redox couple (+130 mV) to gain energy for growth. This can be achieved either by employing As(III) as an autotrophic electron donor or by using As(V) as a respiratory electron acceptor (18, 21, 34). The latter phenomenon, although most commonly associated with chemoheterotrophy, can also employ inorganic substances like sulfide or H₂. Indeed, As(V)-respiring anaerobes displaying a capacity for chemoautotrophy with these electron donors have been isolated and described (5, 7, 16). We recently reported that photoautotrophy is supported by As(III) in anoxic biofilms located in hot springs on Paoha Island in Mono Lake, CA (15). This process represented a novel means of As(III) oxidation achieved via anoxygenic photosynthesis occurring in certain photosynthetic bacteria (i.e., Ectothiorhodospira) and possibly within some cyanobacteria as well (e.g., “Oscillatoria”).Whether or not a microbial habitat is overtly oxic or anoxic, or temporally shifts between these two states over a diel cycle, critical energy linkages between aerobes and anaerobes have long been known for the biogeochemical cycles of key elements, such as sulfur, iron, and nitrogen. Most prominently studied is the case of nitrogen, whereby an ecological coupling exists between the processes of nitrification and denitrification (9, 10, 28). The former process provides energy to aerobic nitrifiers, while the latter process consumes the nitrate produced by this reaction, thereby meeting the energy needs of the denitrifiers.For arsenic, the detection of both As(III) oxidation and As(V) reduction in oxic and anoxic incubations of freshly collected periphyton suggested that an analogous coupled process may also occur for this element (12). Similarly, several uncontaminated soils in Japan displayed a capacity for either As(V) reduction or As(III) oxidation upon arsenic oxyanion amendment and whether they were incubated under oxic or anoxic conditions (39). A defined coculture consisting of an aerobic As(III) oxidizer (strain OL1) and an anaerobic As(V) respirer (strain Y5) was shown to function in this fashion under manipulated laboratory conditions of oxygen tension (26). We pursued the phenomenon of coupled arsenic metabolism further by using materials collected from the hot spring biofilms in Mono Lake, but we focused on examination of the cycling of arsenic under anoxic conditions.In this paper we report results obtained by manipulated incubations of red-pigmented biofilms found in the hot springs of Paoha Island. Preliminary community characterizations of these biofilms show that they are dominated by Bacteria from the genus Ectothiorhodospira but also harbor an assemblage of Archaea related to the Halobacteriacaea. Incubation results have demonstrated the presence of the following arsenic metabolic activities: respiratory As(V) reduction, photosynthetic anaerobic As(III) oxidation, and aerobic As(III) oxidation, along with the ecophysiological conditions under which they occur. Surprisingly, we were unable to obtain authentic PCR products for arsenite oxidase genes (aoxB), despite observing aerobic As(III) oxidation activity. These biofilms serve as a model system for how anaerobic cycling of arsenic can be sustained with oxidation of As(III) by anoxygenic photosynthesis coupled to regeneration of this electron donor via dissimilatory As(V) reduction. The significance that such a light-driven anaerobic ecosystem may have played in the Archean Earth is discussed.     

The manganese cycle in Lac Léman,Switzerland: the role ofMetallogenium

The manganese pathways in Lac Léman have been investigated on the basis of chemical analyses undertaken on water, suspended solids, bottom sediments and interstitial water samples. The various modes of occurrence of Mn have been determined by means of visual examination using SEM and TEM (scanning and transmission electron microscopy), by microanalysis (EDAX) of various sediment fractions, by chemical analysis of the dissolved phase, and by chemical speciation and XRD of bottom sediments. Fluxes to and from the sediment have also been computed. The time-depth variations of Mn in the water column are characterized by (a) a very steep gradient of Mn sol. from the sediment interstitial water (15 mg l⁻¹) to the overlying water, 2 m above the bottom(500 μg l⁻¹), (b) an accumulation of Mn part. between 280 m and the interface at 310 m, consisting of mineralized colonies ofMetallogenium. The abundance ofMetallogenium colonies is inversely related to O₂ concentration; the optimal value for the bacterium Mn fixation is around 1 mg l⁻¹. Because of the quasi-anoxic state of the bottom sediments and overlying water, Mn diffuses from a ‘source layer’, 2–5 cm below the interface (a) upwards across the interface, before being taken up byMetallogenium, and (b) downwards to a ‘sink layer’, in which large amounts of Mn-carbonate precipitate. Particulate Mn sedimentation rates measured in traps show that downwards Mn flux due toMetallogenium settling approximately balances the upwards soluble flux due to diffusion. Quantitatively, the process of Mn cycling in Lac Léman is, therefore, limited to the lowermost part of the hypolimnion. Although Zn and Cd seem to follow the same cycle as Mn, Fe behaves in a different manner; it was not taken up byMetallogenium at the time of our study.     

Manganese K-edge X-ray absorption spectra of the cyclic S-states in the photosynthetic oxygen-evolving system

A set of Mn K-edge XANES spectra due to the redox states S₀–S₃ of the OEC were determined by constructing a highly-sensitive X-ray detection system for use with physiologically native PS II membranes capable of cycling under a series of saturating laser-flashes. The spectra showed almost parallel upshifts with relatively high K-edge half-height energies given by 6550.9±0.2 eV, 6551.7±0.2 eV, 6552.5±0.2 eV and 6553.6±0.2 eV for the S₀, S₁, S₂ and S₃ states, respectively. The successive difference spectra between S₀ and S₁, S₁ and S₂, and S₂ and S₃ states were found to exhibit a similar peak around 6552–6553 eV, indicating that one Mn(III) ion or its direct ligand is univalently oxidized upon each individual S-state transition from S₀ to S₃. The present data, together with other observations of EPR and pre-edge XANES spectroscopy, suggest that the oxidation state of the Mn cluster undergoes a periodic change; S₀: Mn(III,III,III,IV) S₁: Mn(III,IV,III,IV) S₂: Mn(III,IV,IV,IV) S₃: Mn(IV,IV,IV,IV) or Mn(III,IV,IV,IV)·L⁺ with L being a direct ligand of a Mn(III) ion.Abbreviations Chl chlorophyll - D tyrosine 160 on the D2 protein, an accessory electron donor in PS II - D⁺ the oxidized form of D - EDTA ethylene-diaminetetraacetic acid - EPR electron paramagnetic resonance - EXAFS extended X-ray absorption fine structure - HL py-2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol - Mes 2-(N-morpholino)ethanesulfonic acid - N4 py-tris(2-pyridylmethyl)amine - OEC oxygen evolving complex - P680 primary electron donor of PS II - PS II Photosystem II - Q₄₀₀ a high spin Fe³⁺ of the iron-quinone acceptor complex in PS II - SSD solid state detector - XAFS X-ray absorption fine structure - XANES X-ray absorption near edge structure     

A Microbial Arsenic Cycle in Sediments of an Acidic Mine Impoundment: Herman Pit,Clear Lake,California

The involvement of prokaryotes in the redox reactions of arsenic occurring between its +5 [arsenate; As(V)] and +3 [arsenite; As(III)] oxidation states has been well established. Most research to date has focused upon circum-neutral pH environments (e.g., freshwater or estuarine sediments) or arsenic-rich “extreme” environments like hot springs and soda lakes. In contrast, relatively little work has been conducted in acidic environments. With this in mind we conducted experiments with sediments taken from the Herman Pit, an acid mine drainage impoundment of a former mercury (cinnabar) mine. Due to the large adsorptive capacity of the abundant Fe(III)-rich minerals, we were unable to initially detect in solution either As(V) or As(III) added to the aqueous phase of live sediment slurries or autoclaved controls, although the former consumed added electron donors (i.e., lactate, acetate, hydrogen), while the latter did not. This prompted us to conduct further experiments with diluted slurries using the live materials from the first incubation as inoculum. In these experiments we observed reduction of As(V) to As(III) under anoxic conditions and reduction rates were enhanced by addition of electron donors. We also observed oxidation of As(III) to As(V) in oxic slurries as well as in anoxic slurries amended with nitrate. We noted an acid-tolerant trend for sediment slurries in the cases of As(III) oxidation (aerobic and anaerobic) as well as for anaerobic As(V) reduction. These observations indicate the presence of a viable microbial arsenic redox cycle in the sediments of this extreme environment, a result reinforced by the successful amplification of arsenic functional genes (aioA, and arrA) from these materials.     

Experiments on the reproductibility of results from EUF soil extracts with possible improvements resulting from these experiments

Summary The reproducibility of EUF-Ca, K, Na, P, B, NO₃–N and EUF extractable N for fraction 1 (200 V, 20° C, 30 minutes) was within a CV range of 4.54–12.28%.The summation of results for fraction 1 (200 V, 20°C, 30 minutes) and fraction 2 (400 V, 80°C, 5 minutes) gave an improved CV range of 4.23–8.81%.EUF-Mg obtained from fraction 1 (200 V, 20°C, 30 minutes), fraction 2 (400 V, 80°C, 5 minutes) and the acid fraction gave a CV of 6.81%.Results from the acid fraction gave poor reproducibility for Zn, (CV=45.1%). The CV of 12.5% for Mn is low compared to the CV of 30–40% usually obtained.The recovery of Zn, Mn and Mg from the acid fraction was improved. The reproducibility of Zn and Mg was also improved by (a) reducing the sources of contamination; (b) introducing a second filter at the cathode; (c) steeping the filters for 48 hours.     

The characterization of amidohydrolases in a freshwater lake sediment

The properties of three amidohydrolases, i.e., urease (I) EC 3.5.1.5, L-asparaginase (II) EC 3.5.1.1, and L-glutaminase (III) EC 3.5.1.2, were studied in sediment samples taken from a shallow eutrophic freshwater lake.Sediment samples were air dried (ADS) and stored for at least 3 months before being enzymically characterized. The pH optimum of I, II, and III were pH 7.0, 8.4, and 6.5–7.0, respectively, while III in soluble extracts from ADS was most active between pH 8.0 and 9.0. The temperature response of the three enzymes in ADS gave E_a values of 38.9, 41.6, and 35.9 kJmol^–1 for I, II, and III, respectively. K_m and V_max values for ADS I, II, and III were 1.2 mM and 1.9mol NH₃ g^–1h^–1; 0.8 mM and 4.1mol NH₃ g^–1h^–1; and 1.25 mM and 17.4mol NH₃ g^–1h^–1. K_m values for all three enzymes in ADS extracts were at least an order of magnitude greater than those of the ADS. The susceptability of each enzyme to proteolysis was followed in ADS and fresh wet sediment and compared with that of III in an ADS extract. All sediment enzymes were found to be more resistant than the commercial preparation of bacterial L-glutaminase subjected to the same treatment. These results suggested that I, II, and III all exist to some extent as colloid-immobilized enzyme fractions in freshwater sediments and are analogous to the stable enzyme fractions in soils.     

Relation between phosphate and organic matter in fish-pond sediments of the Deroua fish farm (Béni-Mellal, Morocco): implications for pond management

An experimental approach of the phosphate exchange across the water–sediment interface in fish ponds of the Deroua farm (Béni-Mellal, Morocco) is needed to understand the phosphate dynamics in these ponds in relation to their water quality. During this study, we conducted experiments to determine the P-fractions of the different pond sediments and to estimate the release from these sediments of phosphate available for algal uptake. We also determined the amount of phosphate needed to saturate the sediments of two different fish ponds under anoxic and oxic conditions. Phosphate release from sediments comes mainly from Fe(OOH)P and is more important in ponds lined with sheets. The accumulation of organic matter in sediments favours the installation of anoxic conditions and enhances the phosphate release from CaCO₃P, labile in these pond sediments. Under experimental conditions, org-P plays a minor role in the P-release. Oxic conditions, to the contrary, have an inhibitory effect on the P-release from sediments. About 80–98% of the P-adsorbed onto different pond sediments was recovered in the inorg-P-fractions. Aeration induces the oxidation of FeS to Fe(OOH) which can adsorb phosphate from solution. Besides, the presence of bacteria in pond sediments was essential to promote phosphate release under anoxic conditions by controlling the oxidation state of iron and the mineralization of the organic matter. Sheet-lined ponds, when insufficiently dried, accumulate a large quantity of organic matter in their sediments. After a decrease in pH, P is released from CaCO₃P and enhances the phytoplankton productivity responsible for renewed accumulation of organic matter. Org-C concentrations in sediments over 20 mg g^–1 d.w. favour the formation of toxic factors (Fe²⁺, Mn²⁺, NO₂ ^– and H₂S) harmful for carp growth. An extended period of drying efficiently enhances the mineralization of organic matter.     

The role of denitrification on arsenite oxidation and arsenic mobility in an anoxic sediment column model with activated alumina

Arsenite (As(III)) is the predominant arsenic (As) species in reducing environments. As(III) is less strongly adsorbed than As(V) at circumneutral pH conditions by common non‐iron metal oxides in sediments such as those of aluminum. Therefore, oxidation of As(III) to As(V) could contribute to an improved immobilization of As and thus help mitigate As contamination in groundwater. Microbial oxidation of As(III) is known to readily under aerobic conditions, however, the dissolved oxygen (O₂) concentration in groundwater may be limited due to the poor solubility of O₂ and its high chemical reactivity with reduced compounds. Nitrate (${\rm NO}_{3}^{{-} } $ ), can be considered as an alternative electron acceptor, which can support oxidation of As(III) to As(V) by denitrifying bacteria. In this study, two up‐flow sediment columns packed with activated alumina (AA) were utilized to demonstrate the role of denitrification on the oxidation of As(III) to As(V) and its contribution to improved As adsorption onto AA. One column was supplied with ${\rm NO}_{3}^{{-} } $ (C1) and its performance was compared with a control column lacking ${\rm NO}_{3}^{{-} } $ (C2). During most of the operation when the pH was in the circumneutral range (days 50–250), the release of arsenic was greater from C2 compared to C1. The effluent As concentrations started increasing on days 60 and 100 in C2 and C1, respectively. Complete breakthrough started on day 200 in C2; whereas in C1, complete breakthrough was never achieved. The effluent and solid phase As speciation was dominated by As(V) in C1, indicating the occurrence of As(III) oxidation due to ${\rm NO}_{3}^{{-} } $ ; whereas in C2, only As(III) was dominant. This study illustrates a bioremediation or natural attenuation process based on anoxic microbial ${\rm NO}_{3}^{{-} } $ ‐dependent oxidation of As(III) to more readily adsorbed As(V) as a means to enhance the immobilization of As on alumina oxide particles in subsurface environments. Biotechnol. Bioeng. 2010;107: 786–794. © 2010 Wiley Periodicals, Inc.     

Contributions of three subsystems of a freshwater marsh to total bacterial secondary productivity

Rates of bacterial production were measured in the water column, on the surface of plant detritus, and in the surface sediments of a freshwater marsh in the Okefenokee Swamp, Georgia, USA. Bacterioplankton production rates were not correlated with several measures of quantity and quality of dissolved organic matter, including an index of the relative importance of vascular plant derivatives. Bacterioplankton productivity was high (mean: 63 g C liter^–1 day^–1) compared with rates reported for other aquatic ecosystems. Somewhat paradoxically, bacterial productivity on plant detritus (mean: 13 g C g^–1 day^–1) and sediments (mean: 15 g C g^–1 day^–1) was low relative to other locations. On an a real basis, total bacterial productivity in this marsh ecosystem averaged 22 mg C m^–2 day^–1, based on sample dates in May 1990 and February 1991. Marsh sediments supported the bulk of the production, accounting for 46% (May) and 88% (February) of the total. The remainder was contributed approximately equally by bacteria in the water column and on accumulated stores of plant detritus. Send offprint requests to: M. A. Moran.     

Manganese and Arsenic Oxidation Performance of Bacterium-Yunotaki 86 (BY86) from Hokkaido,Japan, and the Bacterium's Phylogeny

We examined the Mn(II) oxidation performance of a bacterium, BY86, collected at Yunotaki Falls Hokkaido, Japan. The bacterium showed rapid oxidation of Mn(II), and brown precipitates containing Mn formed within a few days of incubation. The presence of higher oxidation states of Mn than Mn(II) was ascertained by the UV-vis and XANES sutdy. This bacterium did not oxidize As(III) to As(V) in the absence of Mn. In the presence of Mn, however, As(III) was rapidly oxidized to As(V) on the cell surfaces. These findings indicate that BY86 does not have the ability to directly oxidize As(III) to As(V) within a short period of contact, but indirectly oxidizes it by the Mn oxides generated on the cell surfaces. A phylogenetical study disclosed that BY86 was most closely related to Bacillus cereus with an identity of 99.90%. It is expected that our findings in this study will contribute to the study of Mn(II)-oxidizing bacteria, which play an important role in the biogeochemical cycling of Mn as well as other trace elements including As.     

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.     

Biogeochemical transformations of arsenic in circumneutral freshwater sediments

Arsenic is a wide-spread contaminant of soils and sediments, andmany watersheds worldwide regularly experience severe arsenic loading. While the toxicityof arsenic to plants and animals is well recognized, the geochemical and biological transformationsthat alter its bioavailability in the environment are multifaceted and remain poorly understood.This communication provides a brief overview of our current understanding of the biogeochemistryof arsenic in circumneutral freshwater sediments, placing special emphasis on microbialtransformations. Arsenic can reside in a number of oxidation states and complex ions. The commoninorganic aqueous species at circumneutral pH are the negatively charged arsenates(H₂As^VO₄ ^- and Has^VO₄ ^2-) and zero-charged arsenite(H₃As^IIIO₃ ⁰). Arsenic undergoes diagenesis in response to both physicaland biogeochemical processes. It accumulates in oxic sediments by adsorption on and/orco-precipitation with hydrous iron and manganese oxides. Burial of such sediments in anoxic/suboxicenvironments favors their reduction, releasing Fe(II), Mn(II) and associatedadsorbed/coprecipitated As. Upward advection can translocate these cations and As into theoverlying oxic zone where they may reprecipitate. Alternatively, As may be repartitioned tothe sulfidic phase, forming precipitates such as arsenopyrite and orpiment. Soluble and adsorbedAs species undergo biotic transformations. As(V) can serve as the terminal electronacceptor in the biological oxidation of organic matter, and the limited number of microbes capableof this transformations are diverse in their phylogeny and physiology. Fe(III)-respiring bacteriacan mobilize both As(V) and As(III) bound to ferric oxides by the reductive dissolution ofiron-arsenate minerals. SO₄ ^2--reducing bacteria canpromote deposition of As(III) as sulfide minerals via their production of sulfide. A limited number of As(III)-oxidizing bacteriahave been identified, some of which couple this reaction to growth. Lastly, prokaryotic andeukaryotic microbes can alter arsenic toxicity either by coupling cellular export to its reductionor by converting inorganic As to organo-arsenical compounds. The degree to which each ofthese metabolic transformations influences As mobilization or sequestration in differentsedimentary matrices remains to be established.     

Rates and controls of anaerobic microbial respiration across spatial and temporal gradients in saltmarsh sediments

This study was undertaken to determine the rates and controls ofanaerobic respiration reactions coupled to organic matter mineralization as afunction of space and time along a transect from a bioturbated creekbank to themidmarsh in Georgia saltmarsh sediments. Sulfate reduction rates (SRR) weremeasured at 3 sites during 5 sampling periods throughout the growth season. Thesites differed according to hydrologic regime and the abundance of dominantplants and macrofauna. SRR and pore water / solid phase geochemistry showedevidence of enhanced sediment oxidation at sites exposed to intensebioturbation. Iron(III) reduction rates (FeRR) were directly determined insaltmarsh sediments for the first time, and in agreement with measured SRR,higher rates were observed at the bioturbated, unvegetated creekbank (BUC) andbioturbated, vegetated levee (BVL) sites in comparison to a vegetated mid-marsh(MM) site. An unexpected result was the fact that SRR varied nearly as muchbetween sites (2–3 x) as it did with temperature or season (3–4 x).The BVL site, vegetated by the tall form of Spartinaalterniflora, always exhibited the highest SRR and carbon oxidationrates (> 4000 nmol cm^–3 d^–1) with high activity levels extending deep ( 50 cm)into the sediment, while the MM site, dominated by the short form ofSpartina, always exhibited the lowest SRR which werelocalized to the top 15 cm of sediment. SRR and FeRR at BUC wereintermediate between those measured at the BVL and MM. Acetate was the mostabundant microbial fermentation product (concentrations up to > 1mM) in marsh porewaters, and its distribution reflectedrespirationactivity. Chemical exchange, caused by bioturbation, appeared to be the primarycontrol explaining trends in rates of sulfate and Fe(III) reduction withmacrophytes and carbon source acting as secondary controls.     

Manganese inhibition of microbial iron reduction in anaerobic sediments

Potential mechanisms for the lack of Fe(II) accumulation in Mn(IV)‐con‐taining anaerobic sediments were investigated. The addition of Mn(IV) to sediments in which Fe(III) reduction was the terminal electron‐accepting process removed all the pore‐water Fe(II), completely inhibited net Fe(III) reduction, and stimulated Mn(IV) reduction. In a solution buffered at pH 7, Mn(IV) oxidized Fe(II) to amorphic Fe(III) oxide. Mn(IV) naturally present in oxic freshwater sediments also rapidly oxidized Fe(II). A pure culture of a dissimilatory FE(III)‐ and Mn(FV)‐reducing organism isolated from the sediments reduced Fe(III) to Fe(II) in the presence of Mn(IV) when ferrozine was present to trap Fe(II) before Mn(IV) oxidized it. Depth profiles of dissolved iron and manganese reported in previous studies suggest that Fe(II) diffusing up from the zone of Fe(III) reduction is consumed within the Mn(IV)‐reducing zone. These results demonstrate that preferential reduction of Mn(IV) by Fe(III)‐reducing bacteria cannot completely explain the lack of Fe(II) accumulation in anaerobic, Mn(IV)‐containing sedments, and indicate that Mn(IV) oxidation of Fe(II) is the mechanism that ultimately prevents Fe(II) accumulation.     

Rates and regulation of microbial iron reduction in sediments of the Baltic-North Sea transition

The rates and pathways of anaerobic carbon mineralization processes were investigated at seven stations, ranging from 10 to 56 m water depth, in the Kattegat and Belt Sea, Denmark. Organic carbon mineralization coupled to microbial Mn and Fe reduction was quantified using anaerobic sediment incubation at two stations that were widely separated geographically within the study area. Fe reduction accounted for 75% of the anaerobic carbon oxidation at the station in the northern Kattegat, which is the highest percentage so far reported from subtidal marine sediment. By contrast, sulfate reduction was the dominant anaerobic respiration pathway (95%) at the station in the Great Belt. Dominance of Fe reduction was related to a relatively high sediment Fe content in combination with active reworking of the sediment by infauna. The relative contribution of Fe reduction to anaerobic carbon oxidation at both stations correlated with the concentration of poorly crystalline Fe(III), confirming that the concentration of poorly crystalline Fe(III) exerts a strong control on rates of Fe reduction in marine sediments. The dependence of microbial Fe reduction on concentrations of poorly crystalline Fe(III) was used to quantify the importance of Fe reduction at sites where anaerobic incubations were not applied. This study showed that Fe reduction is an important process in anaerobic carbon oxidation in a wider area of the seafloor in the northern and eastern Kattegat (contribution 60 – 75%). By contrast, Fe reduction is of little significance (6 – 25%) in the more coarse-grained sediments of the shallower western and southern Kattegat, where a low Fe content was an important limiting factor, and in fine-grained sediments of the Belt Sea (4 – 28%), where seasonal oxygen depletion limits the intensity of bioturbation and thereby the availability of Fe(III). A large fraction of the total deposition of organic matter in the Kattegat and Belt Sea occurs in the northern Kattegat, and we estimate 33% of benthic carbon oxidation in the whole area is conveyed by Fe reduction.     

Microbial cycling of iron and sulfur in sediments of acidic and pH-neutral mining lakes in Lusatia (Brandenburg, Germany)

A vast number of lakes developed in the abandoned opencast lignite mines of Lusatia (East Germany) contain acidic waters (mmolSm^–2a^–). Potential Fe(III) reduction measured by the accumulation of Fe(II) during anoxic incubation yielded similar rates in both types of sediments, however, the responses towards the supplementation of Fe(III) and organic carbon were different. Sulfate reduction rates estimated with ³⁵S-radiotracer were much lower in the slightly acidic sediment than in the pH-neutral sediment (156 v.s. 738mmolSO₄ ^2–m^–2a^–1). However, sulfate reduction rates were increased by the addition of organic carbon. Severe limitation of sulfate-reducing bacteria under acidic conditions was also reflected by low most probable numbers (MPN). High MPN of acidophilic iron- and sulfur-oxidizing bacteria in acidic sediments indicated a high reoxidation potential. The results show that potentials for reductive processes are present in acidic sediments and that these are determined mainly by the availability of oxidants and organic matter.