Spectroscopic characterization and molecular weight distribution of dissolved organic matter in sediment porewaters from Lake Erhai, Southwest China

Dissolved organic matter (DOM) in sediment porewaters from Lake Erhai, Southwest China was investigated using dissolved organic carbon (DOC) concentration, UV absorbance, fluorescence and molecular weight distribution. DOC exhibited a high concentration at the sediment–water interface with a rapid decrease to the oxic–anoxic interface at approximately 7 cm, and then increased with depth. Similar trends were also found for the UV absorption coefficients at 254 and 280 nm in the porewaters. DNA in the sediment was also measured, which confirmed the high abundance of aerobic bacteria in the upper layer of the sediment. Both humic-like (peaks A and C) and protein-like (peaks B and D) fluorescence were observed in the porewater DOM, and their fluorescence intensities exhibited a similar porewater profile as DOC concentration. A strong correlation was found between the peak fluorescence intensity ratio r(A, C) and r(D, B). Both the fluorescence index and UV absorption coefficient at 254 nm suggested a dramatic increase in aromaticity of porewater DOM across the oxic–anoxic interface. Porewater DOM exhibited a multimodal distribution of molecular weight with a relatively low polydispersity. The results of this study offer significant insight into the nature and properties of DOM in freshwater ecosystems.     

The hyporheic zone as a source of dissolved organic carbon and carbon gases to a temperate forested stream

The objective of this study was to examine chemical changes in porewaters that occur over small scales (cm) as groundwater flows through the hyporheic zone and discharges to a stream in a temperate forest of northern Wisconsin. Hyporheic-zone porewaters were sampled at discrete depths of 2, 10, 15, 61, and 183 cm at three study sites in the study basin. Chemical profiles of dissolved organic carbon (DOC), CO₂, CH₄, and pH show dramatic changes between 61 cm sediment depth and the water-sediment interface. Unless discrete samples at small depth intervals are taken, these chemical profiles are not accounted for. Similar trends were observed at the three study locations, despite each site having very different hydraulic-flow regimes. Increases in DOC concentration by an order of magnitude from 61 to 15 cm depth with a corresponding decrease in pH and rapid decreases in the molecular weight of the DOC suggest that aliphatic compounds (likely organic acids) are being generated in the hyporheic zone. Estimated efflux rates of DOC, CO₂, and CH₄ to the stream are 6.2, 0.79, 0.13 moles m² d^-1, respectively, with the vast majority of these materials produced in the hyporheic zone. Very little of these materials are accounted for by sampling stream water, suggesting rapid uptake and/or volatilization.     

Porewater Stoichiometry of Terminal Metabolic Products, Sulfate, and Dissolved Organic Carbon and Nitrogen in Estuarine Intertidal Creek-bank Sediments

Porewater equilibration samplers were used to obtain porewater inventories of inorganic nutrients (NH₄⁺, NO_x, PO₄³⁻), dissolved organic carbon (DOC) and nitrogen (DON), sulfate (SO₄²⁻), dissolved inorganic carbon (DIC), hydrogen sulfide (H₂S), chloride (Cl⁻), methane (CH₄) and reduced iron (Fe²⁺) in intertidal creek-bank sediments at eight sites in three estuarine systems over a range of salinities and seasons. Sulfate reduction (SR) rates and sediment particulate organic carbon (POC) and nitrogen (PON) were also determined at several of the sites. Four sites in the Okatee River estuary in South Carolina, two sites on Sapelo Island, Georgia and one site in White Oak Creek, Georgia appeared to be relatively pristine. The eighth site in Umbrella Creek, Georgia was directly adjacent to a small residential development employing septic systems to handle household waste. The large data set (>700 porewater profiles) offers an opportunity to assess system-scale patterns of porewater biogeochemical dynamics with an emphasis on DOC and DON distributions. SO₄²⁻ depletion (SO₄²⁻)_Dep was used as a proxy for SR, and (SO₄²⁻)_Dep patterns agreed with measured (³⁵S) patterns of SR. There were significant system-scale correlations between the inorganic products of terminal metabolism (DIC, NH₄⁺ and PO₄³⁻) and (SO₄²⁻)_Dep, and SR appeared to be the dominant terminal carbon oxidation pathway in these sediments. Porewater inventories of DIC and (SO₄²⁻)_Dep indicate a 2:1 stoichiometry across sites, and the C:N ratio of the organic matter undergoing mineralization was between 7.5 and 10. The data suggest that septic-derived dissolved organic matter with a C:N ratio below 6 fueled microbial metabolism and SR at a site with development in the upland. Seasonality was observed in the porewater inventories, but temperature alone did not adequately describe the patterns of (SO₄²⁻)_Dep, terminal metabolic products (DIC, NH₄⁺, PO₄³⁻), DOC and DON, and SR observed in this study. It appears that production and consumption of labile DOC are tightly coupled in these sediments, and that bulk DOC is likely a recalcitrant pool. Preferential hydrolysis of PON relative to POC when overall organic matter mineralization rates were high appears to drive the observed patterns in POC:PON, DOC:DON and DIC:DIN ratios. These data, along with the weak seasonal patterns of SR and organic and inorganic porewater inventories, suggest that the rate of hydrolysis limits organic matter mineralization in these intertidal creek-bank sediments.     

The role of bacteria in the nutrient exchange between sediment and water in a flow-through system

The contribution of bacteria to phosphorus (P) and nitrogen (N ) release from, or retention in, sediment was studied in a flow-through system. Live and formaldehyde-killed sediment communities were incubated in 25-liter bottles with a continuous flow of P- or P + N-enriched water. Sediment bacteria in the killed communities were inhibited by adding formaldehyde (final concentration 0.04% v/v) to the sediment before the start of the experiment. Bacterial activity in the live sediments measured with [³H]thymidine and [¹⁴C]leucine incorporation techniques did not change essentially during the experiment period (7–8 days). Chemical mechanisms were found to be of principal importance in PO₄-P retention in the sediment. In the live samples, the net retention of PO₄-P was lower than in the killed samples, which was likely due to the reduced O₂ conditions in the sediment as a consequence of bacterial mineralization. In total P exchange, however, bacteria increased the retention rate by recycling dissolved organic P in the sediment. In the live communities the retention of N was very efficient, and all the introduced NH₄ -N and NO₃-N was immobilized by sediment bacteria. Nitrogen enrichment, however, did not alter the P exchange rates. The gradual emergence of bacterial activity (and grazing) in the killed communities, subsequent to the dilution of formaldehyde concentration, enhanced the release of PO₄-P and NH₄-N from sediment.     

A mixing model analysis of stream solute dynamics and the contribution of a hyporheic zone to ecosystem function*

1. We monitored streamwater and streambed sediment porewaters from White Clay Creek (WCC), SE Pennsylvania, for dissolved organic carbon (DOC), dissolved oxygen (DO) and conductivity to investigate organic matter processing within the hyporheic zone. Dissolved organic carbon and DO concentrations were higher in the streamwater than in the porewaters and, in many cases, concentrations continued to diminish with increasing depth into the streambed. 2. Hydrological exchange data demonstrated that the permeability of the stream bed declines with depth and constrains downwelling, effectively isolating porewaters >30 cm from streamwater. 3. End‐member mixing analysis (EMMA) based on conductivity documented a DOC source and DO sink in the hyporheic zone. We calculated hyporheic streambed DOC fluxes and respiration from the EMMA results and estimates of water flux. Based upon our calculations of biodegradable DOC entering the hyporheic zone, we estimate that DOC supports 39% of the hyporheic zone respiration, with the remaining 61% presumably being supported by entrained particulate organic carbon. Hyporheic respiration averaged 0.38 g C m^?2 d^?1, accounted for 41% of whole ecosystem respiration, and increased baseflow ecosystem efficiency from 46 to 59%. 4. Advective transport of labile organic molecules into the streambed concentrates microbial activity in near‐surface regions of the hyporheic zone. Steep gradients in biogeochemical activity could explain how a shallow and hydrologically constrained hyporheic zone can dramatically influence organic matter processing at the ecosystem scale.     

Porewater acid/base chemistry in near-shore regions of an acidic lake

Sediment porewaters in the near-shore region (within 1 m of the shoreline) of an acidic lake (Dart's Lake) were monitored during the summer of 1983 to investigate whether spatial variations in porewater acid/base chemistry were significant in this region of the lake. Previous investigations of Dart's Lake porewaters have indicated that within deeper waters (>2m depth), sediment porewaters are elevated in alkalinity relative to overlying lake water. Within the near-shore region, porewaters both considerably more and less acidic than the lake water were observed. Both reduction of strong acid anions (SO₄ ^2–, NO₃ ^–) and the mobilization of base cations were significant mechanisms of alkalinity production in porewaters exhibiting reducing conditions. In sediments reflecting oxic conditions, porewaters were generally more acidic than the lakewater. Measurement of groundwater seepage into the lake at the near-shore sites indicated that oxic sites exhibited elevated inputs of groundwater when compared to sites where reducing conditions existed. The acidic porewaters associated with high groundwater flows suggests that groundwater inputs to the lake may be a source of acidity (not alkalinity) on a whole-lake basis.     

Using porewater profiles to assess nutrient availability in seagrass-vegetated carbonate sediments

We measured porewater profiles of inorganic (NH₄ ⁺, NO₃ ^–(+NO₂ ^–), PO₄ ^3– (hereafter referred to as DIP)) and organic (DON, DOP) nutrients in seagrass-vegetated sediments at two sites in a shallow bay in Bermuda within close proximity (200 m) but subject to different nutrient loading. At both sites, total dissolved and inorganic nutrient concentrations were usually 1–2 orders of magnitude higher in the sediments than in the water column, with the exception of NO₃ ^–. Organic N and P were significant components of the total dissolved nutrient pools both in the sediment porewater and in the overlying water column (up to 75% for DON and 40% for DOP), and may be important in meeting plant nutrient demands. We used two approaches to examine how well porewater nutrient concentrations reflected the relative availabilities of N and P for seagrasses: (1) a simple stoichiometric nutrient regeneration model based on the N:P ratio of decomposing organic matter and porewater NH₄ ⁺ concentrations to predict porewater DIP, and (2) fitting of the porewater profiles to estimate rates of net nutrient production (or consumption), which reflects the balance between nutrient sources and sinks in the rhizosphere. The stoichiometric model indicated that sediment porewaters were depleted in P relative to N in the low-nutrient outer bay site, and enriched in P relative to N in the higher-nutrient inner bay site. These results are consistent with the mechanism of carbonate sediments in oligotrophic tropical environments being a strong sink for dissolved inorganic P and our previous work suggesting that nutrient enrichment causes P to become disproportionately more available than N. Net nutrient production rates of porewater P at both sites and N at the inner bay site were low (typically < 2%) relative to the nutrient demands of the seagrasses. The implications of the profile interpretation are two-fold: (1) the low rates of net nutrient production indicate diffusive losses from the root zone were insignificant and that nutrient turnover rates were high, except in the P-limited outer bay where N accumulated in sediment porewaters; and (2) because standing stock nutrient concentrations often represent a small fraction of the total nutrients cycled in the sediments, they are in many cases a poor indicator of nutrient availability. Based on our estimates of losses from the root zone, decomposition, and plant uptake we have constructed a rough budget for the cycling of P and N at our two sites.     

The dual influences of dissolved organic carbon on hypolimnetic metabolism: organic substrate and photosynthetic reduction

We investigated the effect of dissolved organic carbon (DOC) on hypolimnetic metabolism (accumulation of dissolved inorganic carbon (DIC) and methane (CH₄)) in 21 lakes across a gradient of DOC concentrations (308 to 1540 mol C L^–1). The highly colored nature of the DOC in these lakes suggests it is mostly of terrestrial origin. Hypolimnetic methane accumulation was positively correlated with epilimnetic DOC concentration (Spearman rank correlation = 0.67; p < 0.01), an indicator of allochthonous DOC inputs, but not with photic zone chlorophyll a concentration (Spearman rank correlation = 0.30; p = 0.22). Hypolimnetic DOC concentrations declined in 19 of 21 lakes during the stratified period at rates that ranged from 0.06 to 53.9 mmol m^–2 d^–1. The hypolimnetic accumulation of DIC + CH₄ was positively correlated with, and, in most cases of comparable magnitude to, this DOC decline suggesting that DOC was an important substrate for hypolimnetic metabolism. The percentage of surface irradiance reaching the thermocline was lower in high DOC lakes (0.3%) than in low DOC lakes (6%), reducing hypolimnetic photosynthesis (as measured by the depth and magnitude of the deep dissolved oxygen maxima) in the high DOC lakes. In June, the hypolimnia of lakes with < 400 mol L^–1 DOC had high concentrations of dissolved oxygen and no CH₄, while the hypolimnia of lakes with DOC > 800 mol L^–1 were completely anoxic and often had high CH₄ concentrations. Thus, DOC affects hypolimnetic metabolism via multiple pathways: DOC was significant in supporting hypolimnetic metabolism; and at high concentrations depressed photosynthesis (and therefore oxygen production and DIC consumption) in the hypolimnion.     

Coupled Dynamics of Iron and Phosphorus in Sediments of an Oligotrophic Coastal Basin and the Impact of Anaerobic Oxidation of Methane

Studies of phosphorus (P) dynamics in surface sediments of lakes and coastal seas typically emphasize the role of coupled iron (Fe), sulfur (S) and P cycling for sediment P burial and release. Here, we show that anaerobic oxidation of methane (AOM) also may impact sediment P cycling in such systems. Using porewater and sediment profiles for sites in an oligotrophic coastal basin (Bothnian Sea), we provide evidence for the formation of Fe-bound P (possibly vivianite; Fe₃(PO₄)₂ ^.8H₂O) below the zone of AOM with sulfate. Here, dissolved Fe²⁺ released from oxides is no longer scavenged by sulfide and high concentrations of both dissolved Fe²⁺ (>1 mM) and PO₄ in the porewater allow supersaturation with respect to vivianite to be reached. Besides formation of Fe(II)-P, preservation of Fe-oxide bound P likely also contributes to permanent burial of P in Bothnian Sea sediments. Preliminary budget calculations suggest that the burial of Fe-bound P allows these sediments to act as a major sink for P from the adjacent eutrophic Baltic Proper.     

Biogeochemical cycling of sulfur and iron in sediments of a south-east Asian mangrove,Phuket Island,Thailand

Benthic sulfate reduction and sediment pools of sulfur and iron were examined during January 1992 at 3 stations in the Ao Nam Bor mangrove, Phuket, Thailand. Patterns of sulfate reduction rates (0–53 cm) reflected differences in physical and biological conditions at the 3 stations, and highest rates were found at the vegetated site within the mangrove (Rhizophora apiculata) forest. Due to extended oxidation of mangrove sediments, a large portion of the added³⁵S-label was recovered in the chromium reducible pools (FeS₂ and S⁰) (41–91% of the reduced sulfur). Pyrite was the most important inorganic sulfur component, attaining pool sizes 50–100 times higher than acid volatile pools (FeS). HCl-extractable (0.5 M HCl) iron pools, including Fe(II)_HCl and Fe(III)_HCl, were generally low and Fe(III)_HCl was only present in the upper surface layers (0–5 cm). Maximum concentrations of dissolved Fe²⁺ (35–285 M) occurred just about the depth where dissolved H₂S accumulated. Furthermore Fe²⁺ and H₂S coexisted only where concentrations of both were low. There was an accumulation of organic sulfur in the deep sediment at 2 stations in the inner part of the mangrove. The reoxidation of reduced sulfides was rapid, and storage of sulfur was minor in the upper sediment layers, where factors like bioturbation, the presence of roots, or tidal mixing enhance oxidation processes.Author of correspondence.     

Bioinspired FeIIICdII and FeIIIHgII complexes: synthesis, characterization and promiscuous catalytic activity evaluation

In this work we report on the synthesis, crystal structure, and physicochemical characterization of the novel dinuclear [Fe^IIICd^II(L)(μ-OAc)₂]ClO₄·0.5H₂O (1) complex containing the unsymmetrical ligand H₂L = 2-bis[{(2-pyridyl-methyl)-aminomethyl}-6-{(2-hydroxy-benzyl)-(2-pyridyl-methyl)}-aminomethyl]-4-methylphenol. Also, with this ligand, the tetranuclear [Fe₂^IIIHg₂^II(L)₂(OH)₂](ClO₄)₂·2CH₃OH (2) and [Fe^IIIHg^II(L)(μ-CO₃)Fe^IIIHg^II(L)](ClO₄)₂·H₂O (3) complexes were synthesized and fully characterized. It is demonstrated that the precursor [Fe^III₂Hg^II₂(L)₂(OH)₂](ClO₄)₂·2CH₃OH (2) can be converted to (3) by the fixation of atmospheric CO₂ since the crystal structure of the tetranuclear organometallic complex [Fe^IIIHg^II(L)(μ-CO₃)Fe^IIIHg^II(L)](ClO₄)₂·H₂O (3) with an unprecedented {Fe^III(μ-O_phenoxo)₂(μ-CO₃)Fe^III} core was obtained through X-ray crystallography. In the reaction 2 → 3 a nucleophilic attack of a Fe^III-bound hydroxo group on the CO₂ molecule is proposed. In addition, it is also demonstrated that complex (3) can regenerate complex (2) in aqueous/MeOH/NaOH solution. Magnetochemical studies reveal that the Fe^III centers in 3 are antiferromagnetically coupled (J = − 7.2 cm^− 1) and that the Fe^III-OR-Fe^III angle has no noticeable influence in the exchange coupling. Phosphatase-like activity studies in the hydrolysis of the model substrate bis(2,4-dinitrophenyl) phosphate (2,4-bdnpp) by 1 and 2 show Michaelis-Menten behavior with 1 being ~ 2.5 times more active than 2. In combination with k_H/k_D isotope effects, the kinetic studies suggest a mechanism in which a terminal Fe^III-bound hydroxide is the hydrolysis-initiating nucleophilic catalyst for 1 and 2. Based on the crystal structures of 1 and 3, it is assumed that the relatively long Fe^III…Hg^II distance could be responsible for the lower catalytic effectiveness of 2.     

Hydrothermal synthesis, crystal structures and properties of new Fe, Co, Ni, and Zn complexes with 6-quinolinecarboxylate: Interplay of coordinative and noncovalent interactions

Reactions of Fe^II, Co^II, Ni^II, and Zn^II salts with 6-quinolinecarboxylic acid (HL) under the hydrothermal conditions afford three monomeric complexes [M(L)₂(H₂O)₄] (M = Fe^II for 1, Co^II for 2, and Ni^II for 3) and a 1-D polymeric species {[Zn(L)₂(H₂O)] · H₂O}_n (4). The crystal structures of the ligand HL and these four complexes have been determined by using the X-ray single-crystal diffraction technique. The results suggest that complexes 1-3 are isostructural, displaying novel 3-D pillar-layered networks through multiple intermolecular hydrogen bonds, whereas in coordination polymer 4, the 1-D comb-like coordination chains are extended to generate a hydrogen-bonded layer, which is further reinforced via aromatic stacking interactions. Solid-state properties such as thermal stability and fluorescence emission of the polymeric Zn^II complex 4 have also been investigated.     

Transport of carbon dioxide and ammonium in bioturbated (Nereis diversicolor) coastal, marine sediments

Two identical experiments with sieved and homogenized sandy and muddy sediment were conducted to determine transport enhancement of porewater solutes (TCO₂ and NH₄ ⁺) by the presence of the polychaeteNereis diversicolor (1000–1500 m^–2). Flux measurements showed thatN. diversicolor enhanced the release of CO₂ and NH₄ ⁺ 1.5–5 times. Accordingly, porewater concentrations of these compounds were reduced considerably in the bioturbated zone of both types of sediments. Two different diagenetic models, effective (eddy) diffusion and nonlocal exchange, were used to describe solute profiles in the bioturbated sediments. In permeable sandy sediments advective porewater movements may occur more readily than in more cohesive muddy sediments. The effective diffusion model (with D_e=1.6–2.0 cm² d^–1) provided an excellent fit to the measured concentrations of both solutes below the bioturbated zone in permeable sandy sediment, whereas this model overestimated the concentration in the bioturbated zone. However, in the less permeable muddy sediment the effective diffusion model overestimated the NH₄ ⁺ profile considerably at all depths. The nonlocal exchange model (with=0.17–0.29 d^–1), on the other hand, provided an excellent fit in the less permeable muddy sediment, suggesting that solute profiles here were controlled by molecular diffusion, even in the presence of burrow irrigation. For the permeable sediment, the nonlocal exchange model (with=0.14 d^–1) underestimated the measured NH₄ ⁺ profile. Accordingly, linear slopes from plots of porewater TCO₂ as a function of porewater NH₄ ⁺ revealed that eddy diffusion (or advective porewater movements) was important in the bioturbated zone of this sediment type. However, combined with the generally more realistic shape of profiles derived by the nonlocal exchange, these evidences suggest that both eddy and molecular diffusion must operate in the bioturbated zone of permeable sediments.     

Ecosystem Modulation of Dissolved Carbon Age in a Temperate Marsh-Dominated Estuary

We measured the concentrations and isotopic values (¹⁴C and ¹³C) of dissolved inorganic, dissolved organic, and particulate organic carbon (DIC, DOC, and POC, respectively) in the Parker River watershed and estuary in Massachusetts, USA, to determine the age of carbon (C) entering the estuary and how estuarine processing affects the quantity and apparent age of C transported to the Gulf of Maine. The watershed measurements indicated the transport of ¹⁴C-enriched modern DIC and DOC and variably aged POC from the watershed to the estuary. The transport of organic matter from the watershed was dominated by DOC transport, with POC making up less than 10% of the total. Surveys within the watershed aimed at determining which land-use type dominated the DOC export indicated that wetlands, although they made up only around 20% of the land use, could be responsible for approximately 75% of the DOC export. We therefore conclude that the wetland land uses of the Parker River watershed are exporting mainly ¹⁴C-enriched modern DOC. DIC isotopes indicate that the source of DIC in the Parker River watershed is dominated by the weathering of noncarbonate parent material by ¹⁴C-enriched carbon dioxide (CO₂) originating from the respiration of young organic matter in soils. Transects in the estuary displayed net additions of all C species. For DOC and DIC, the export of this internally added DOC and DIC was approximately equal to the amount being exported from the watershed, showing the importance of focusing on estuaries when estimating the export of C to the coastal ocean. With respect to DIC, the total input is even larger when the atmospheric exchange of excess pCO₂ is calculated. The ¹⁴C-DOC and ¹⁴C-DIC transects indicate that the internally added DOC and DIC is ¹⁴C-enriched modern material. The source of this material is the fringing marshes and estuarine phytoplankton, with the relative importance of these two sources changing over time. Taken together, the bulk C and ¹⁴C measurements show that the estuary is adding significant quantities of young DOC despite the presence of vast quantities of old marsh peat flanking the entire estuary. Furthermore, the DIC data indicate that ¹⁴C-enriched modern material is what is fueling the majority of heterotrophic respiration within the system.     

Distribution of dissolved organic carbon in lakes of different trophic types

The distributions of dissolved organic carbon (DOC) in the warm season were elucidated in ten lakes of different trophic types in Japan, Russia, and China. DOC showed similar vertical distributions in all the lakes in summer when thermal stratification occurred. DOC in the epilimnion was higher than the value of 0.8mgCl^–1 found in the hypolimnion. In three Japanese lakes, hypolimnion DOC was negatively correlated with apparent oxygen utilization (AOU), reflecting the net oxidation of DOC using the dissolved oxygen in lake water. The DOC:O₂ ratios (0.115–0.179), calculated by the slopes of the regression lines of DOC versus AOU in hypolimnion water, were as low as those of deep-sea water, which indicates low bioavailability of lake water DOC for heterotrophic bacteria. DOC and conductivity did not correlate well except in two Japanese lakes: one showed a positive correlation and the other a negative correlation, indicating DOC loading from the inflowing rivers. Eutrophic lakes tended to have higher DOC values than meso- and oligotrophic lakes, and DOC values in the surface water negatively correlated with Secchi depths.     

Autotrophic carbon sources for heterotrophic bacterioplankton in a floodplain lake of central Amazon

The relative contribution of autotrophic carbon sources (aquatic macrophytes, flooded forest, phytoplankton) for heterotrophic bacterioplankton was evaluated in a floodplain lake of the Central Amazon. Stable carbon isotopes (¹³C) were used as tracers. Values of ¹³C of different autotrophic sources were compared to those of dissolved organic carbon (DOC) and those of bacterially produced CO₂.The percentage of carbon derived from C₄ macrophytes for bacterially produced CO₂ was the highest, on average 89%. The average ¹³C value of CO₂ from bacterial respiration was –18.5 ± 3.3. Considering a fractionation of CO₂ of 3 by bacterial respiration, ¹³C value was –15.5, near C₄ macrophyte ¹³C value (–13.1).The average value of total DOC ¹³C was –26.8 ± 2.4. The percentage of C₄ macrophytes carbon for total DOC was on average 17%. Considering that bacteria consume mainly carbon from macrophytes, the dominance of C₃ plants for total DOC probably reflects a faster consumption of the former source, rather than a major contribution of the latter source.Heterotrophic bacterioplankton in the floodplain may be an important link in the aquatic food web, transferring the carbon from C₄ macrophytes to the consumers.     

Impact of sampling methods on sulfate reduction rates and dissolved organic carbon (DOC) concentrations in vegetated salt marsh sediments

The impact of sediment coring on measured rates of sulfate reduction(SRR) by the whole core ³⁵S-injection technique was assessed inmarshsediment vegetated by Spartina anglica. Simultaneously,therole of extraction method (centrifugation vs. sippers) for determination ofporewater DOC in vegetated sediment was evaluated. SRR was measuredinsitu with radiotracer injected directly into the sediment and in atime series from 1 to 24 h after coring. SRR incubations carriedout within 6 h (June) or 12 h (August) of coringyielded up to an order of magnitude higher rates than measured insitu. The enhancement of SRR was instantaneous but temporary andcorrelated with measured porewater DOC concentrations. Cores sampled fromrootedsediments should therefore not be used for sulfate reduction incubations withinthe first 12 h due to the effect of DOC leaching from roots cutduring the coring procedure. The labile fraction of leached DOC appears to beexhausted after a pre-incubation period of at least 12 h.Measurement of porewater DOC is also problematic in vegetated sediment.Porewater extraction by centrifugation of sediment may result in up to oneorderof magnitude higher DOC concentrations than in porewater obtained by anondestructive sipper technique. DOC is probably forced out of roots duringcentrifugation resulting in erroneously high porewater DOC concentrations.     

Predominance of phytoplankton-derived dissolved and particulate organic carbon in a highly eutrophic tropical coastal embayment (Guanabara Bay,Rio de Janeiro,Brazil)

We investigate the carbon dynamics in Guanabara Bay, an eutrophic tropical coastal embayment surrounded by the megacity of Rio de Janeiro (southeast coast of Brazil). Nine sampling campaigns were conducted for dissolved, particulate and total organic carbon (DOC, POC and TOC), dissolved inorganic carbon (DIC), partial pressure of CO₂ (pCO₂), chlorophyll a (Chl a), pheo-pigments and ancillary parameters. Highest DOC, POC and Chl a concentrations were found in confined-shallow regions of the bay during the summer period with strong pCO₂ undersaturation, and DOC reached 82 mg L^?1, POC 152 mg L^?1, and Chl a 800 μg L^?1. Spatially and temporally, POC and DOC concentrations varied positively with total pigments, and negatively with DIC. Strong linear correlations between these parameters indicate that the production of TOC translates to an equivalent uptake in DIC, with 85% of the POC and about 50% of the DOC being of phytoplanktonic origin. Despite the shallow depths of the bay, surface waters were enriched in POC and DOC relative to bottom waters in periods of high thermohaline stratification. The seasonal accumulation of phytoplankton-derived TOC in the surface waters reached about 105 g C m^?2 year^?1, representing between 8 and 40% of the net primary production. The calculated turnover time of organic carbon was 117 and 34 days during winter and summer, respectively. Our results indicate that eutrophication of coastal bays in the tropics can generate large stocks of planktonic biomass and detrital organic carbon which are permanently being produced and partially degraded and buried in sediments.     

A new heterobinuclear FeIIICuII complex with a single terminal FeIII–O(phenolate) bond. Relevance to purple acid phosphatases and nucleases

A novel heterobinuclear mixed valence complex [Fe^IIICu^II(BPBPMP)(OAc)₂]ClO₄, 1, with the unsymmetrical N₅O₂ donor ligand 2-bis[{(2-pyridylmethyl)aminomethyl}-6-{(2-hydroxybenzyl)(2-pyridylmethyl)}aminomethyl]-4-methylphenol (H₂BPBPMP) has been synthesized and characterized. A combination of data from mass spectrometry, potentiometric titrations, X-ray absorption and electron paramagnetic resonance spectroscopy, as well as kinetics measurements indicates that in ethanol/water solutions an [Fe^III–()OH–Cu^IIOH₂]⁺ species is generated which is the likely catalyst for 2,4-bis(dinitrophenyl)phosphate and DNA hydrolysis. Insofar as the data are consistent with the presence of an Fe^III-bound hydroxide acting as a nucleophile during catalysis, 1 presents a suitable mimic for the hydrolytic enzyme purple acid phosphatase. Notably, 1 is significantly more reactive than its isostructural homologues with different metal composition (Fe^IIIM^II, where M^II is Zn^II, Mn^II, Ni^II, or Fe^II). Of particular interest is the observation that cleavage of double-stranded plasmid DNA occurs even at very low concentrations of 1 (2.5 M), under physiological conditions (optimum pH of 7.0), with a rate enhancement of 2.7×10⁷ over the uncatalyzed reaction. Thus, 1 is one of the most effective model complexes to date, mimicking the function of nucleases.Electronic Supplementary Material Supplementary material is available for this article at .     

Pyrite accumulation in salt marshes in the Eastern Scheldt,southwest Netherlands

Pore water composition, pyrite distribution and pyrite crystal morphology of sediments from salt marshes in the Eastern Scheldt, southwestern Netherlands, were examined from July 1984 to October 1986.Hydrology and marsh vegetation were the chief determinants of pyrite accumulation. In the bare sediments of pans in the low marsh, highly reducing conditions prevailed just below the surface. At these sites, practically all the incoming detrital pyrite (0.5–1% FeS₂) was preserved. The in-situ formation of pyrites was negligible in these anoxic sediments.All incoming detrital pyrite was oxidized in the surface layers (0–10 cm) of the medium-high marsh overgrown withSpartina anglica. Pyrite was formed at a rate of 2.6–3.8 mol S-FeS₂m^–2yr^–1 in a narrow range of depths (15–20cm), at the interface of the oxidizing and underlying reducing sediment. At this interface the concentration profiles of Fe²⁺ and dissolved S intersected. The role of the rhizosphere is discussed in connection with pyrite formation. No further pyrite formation occurred deeper in the sediment. This resulted in the build up of high concentrations of dissolved S and acid volatile sulfides (AVS). The decrease with depth in oxalate-extractable Fe indicated that most of the iron oxyhydroxides (70–80%) had been transformed to pyrite. Another 10–20% of oxalate-extractable Fe was present as AVS. The abundance of framboidal pyrite particles and the high concentrations of AVS and dissolved S indicated that the formation of pyrite occurred via iron monosulfide intermediatesThere was a linear relationship between the organic carbon and the S-FeS₂ content in theSpartina overgrown reducing sediment. The mean C/S ratio was 4.2.