Priming effect of benthic gastropod mucus on sedimentary organic matter remineralization.

Mucous gels are produced by benthic animals rapidly and in copious amounts, and consequently they are a possible priming substrate whose addition in modest amounts may affect sedimentary organic matter (SOM) remineralization. The priming effect of benthic infaunal mucus was tested using mucus of the common gastropod Neverita duplicata as model substrate. Its composition is typical of marine molluscan mucus, consisting primarily of water (>96% by weight). Salt-free dry weight constitutes 0.7% of total mucus. Relationships between C, N and S content show the presence of N-free and S-free fractions, indicative of mucopolysaccharides, that account for approximately half of the total C present. The C/N ratios of the N-containing fraction (6.1 and 8.75 for pedal and hypobranchial mucus, respectively) are indicative of a carbohydrate-protein complex. Relatively low C/S ratios for the S-containing fraction (21.8 and 10.5 for pedal and hypobranchial mucus, respectively) and positive staining with Alcian Blue dye are indicative of S-ester and alkyl-SO42- groups bridging mucopolysaccharide and glycoprotein components. Anaerobic incubations of pedal mucus, sediment and mucus-sediment mixture resulted in the generation of ΣCO2 and NH4+ at ratios lower than substrate C/N ratios, indicating the preferential decomposition of N-rich components. Production rates of ΣCO2 and NH4+ in mucus-sediment incubations are higher, by 9±16% and 29±11%, respectively, than those predicted from linear addition of mucus-only and sediment-only rates. The accelerated remineralization rate of N in the presence of modest mucus contribution suggests that benthic mucus addition can affect SOM remineralization processes through a "priming" effect.

Medically-Derived (131)I as a Tool for Investigating the Fate of Wastewater Nitrogen in Aquatic Environments.

Medically derived (131)I (t1/2 = 8.04 d) is discharged from water pollution control plants (WPCPs) in sewage effluent. Iodine's nutrient-like behavior and the source-specificity of (131)I make this radionuclide a potentially valuable tracer in wastewater nitrogen studies. Iodine-131 was measured in Potomac River water and sediments in the vicinity of the Blue Plains WPCP, Washington, DC, USA. Dissolved (131)I showed a strong, positive correlation with δ(15)N values of nitrate (δ(15)NO3(-)) in the river, the latter being a traditional indicator of nutrient inputs and recycling. Surface water δ(15)NO3(-) values ranged from 8.7 to 33.4‰; NO3(-) + NO2(-) concentrations were 0.39-2.79 mg N L(-1) (26-186 µM). Sediment profiles of particulate (131)I and δ(15)N indicate rapid mixing or sedimentation and in many cases remineralization of a heavy nitrogen source consistent with wastewater nitrogen. Values of δ(15)N in sediments ranged from 4.7 to 9.3‰. This work introduces (131)I as a tool to investigate the short-term fate of wastewater nitrogen in the Potomac River and demonstrates the general utility of (131)I in aquatic research.

Nitrogen transformations in constructed wetlands: A closer look at plant-soil interactions using chemical imaging.

Constructed wetlands have long been used for domestic wastewater treatment. Despite the widespread application of constructed wetlands for wastewater remediation, they are still regarded as a black box in terms of the complex biogeochemical processes occurring internally, particularly with respect to plant-soil (and nitrogen) interactions. Additionally, many critical processes pertaining to nitrogen transformations in constructed wetlands are thought to occur in microzones within the rhizosphere, highlighting the need for studies with sub-cm spatial resolution. In this study we coupled nitrogen porewater measurements with chemical imaging to determine spatio-temporal patterns in porewater O2 and pH to assess the extent of plant-induced changes in soil redox dynamics that influence nitrogen biogeochemical cycling during dosed application of nitrogen-rich artificial wastewater. Planar optode imaging revealed extensive O2 fluxes to otherwise anoxic sediment via radial oxygen loss (ROL) from Typha latifolia roots. The contribution of photosynthetic O2 from this plant species was minimal as a strong oxic signal persisted in darkness (diel cycles). NH4+ and NOx- removal were strongly correlated with the extent of oxic and anoxic areas, a function largely attributed to the presence of plants and the associated enhanced microbial communities supported. The distribution of nitrogen species within the Typha rhizosphere exhibited reproducible trends as a function of distance from roots, with concentrations highest close to roots (1-5 mm from root surface) and subsequently decreasing at greater distances. Microscale spatio-temporal redox heterogeneity within the rhizosphere due to ROL imposed by plants promoted nitrogen removal likely by stimulating the coupling between nitrification and denitrification in these systems. Collectively, this study highlights the profound importance of plants in exerting controls on soil conditions and nitrogen cycling in constructed wetland systems. With careful considerations, constructed wetlands designed to promote wetland plants' functions may enhance nitrogen removal and mitigate nitrogen pollution.

The dynamics of cable bacteria colonization in surface sediments: a 2D view.

Cable bacteria that are capable of transporting electrons on centimeter scales have been found in a variety of sediment types, where their activity can strongly influence diagenetic reactions and elemental cycling. In this study, the patterns of spatial and temporal colonization of surficial sediment by cable bacteria were revealed in two-dimensions by planar pH and H2S optical sensors for the first time. The characteristic sediment surface pH maximum zones begin to develop from isolated micro-regions and spread horizontally within 5 days, with lateral spreading rates from 0.3 to ~ 1.2 cm day-1. Electrogenic anodic zones in the anoxic sediments are characterized by low pH, and the coupled pH minima also expand with time. H2S heterogeneities in accordance with electrogenic colonization are also observed. Cable bacteria cell abundance in oxic surface sediment (0-0.25 cm) kept almost constant during the colonization period; however, subsurface cell abundance apparently increased as electrogenic activity expanded across the entire surface. Changes in cell abundance are consistent with filament coiling and growth in the anodic zone (i.e., cathodic snorkels). The spreading mechanism for the sediment pH-H2S fingerprints and the cable bacteria abundance dynamics suggest that once favorable microenvironments are established, filamentous cable bacteria aggregate or locally activate electrogenic metabolism. Different development dynamics in otherwise similar sediment suggests that the accessibility of reductant (e.g., dissolved phase sulfide) is critical in controlling the growth of cable bacteria.

Worm tubes as conduits for the electrogenic microbial grid in marine sediments.

Electrogenic cable bacteria can couple spatially separated redox reaction zones in marine sediments using multicellular filaments as electron conductors. Reported as generally absent from disturbed sediments, we have found subsurface cable aggregations associated with tubes of the parchment worm Chaetopterus variopedatus in otherwise intensely bioturbated deposits. Cable bacteria tap into tubes, which act as oxygenated conduits, creating a three-dimensional conducting network extending decimeters into sulfidic deposits. By elevating pH, promoting Mn, Fe-oxide precipitation in tube linings, and depleting S around tubes, they enhance tube preservation and favorable biogeochemical conditions within the tube. The presence of disseminated filaments a few cells in length away from oxygenated interfaces and the reported ability of cable bacteria to use a range of redox reaction couples suggest that these microbes are ubiquitous facultative opportunists and that long filaments are an end-member morphological adaptation to relatively stable redox domains.

Evidence of the activity of dissimilatory sulfate-reducing prokaryotes in nonsulfidogenic tropical mobile muds.

In spite of the nonsulfidic conditions and abundant reactive iron(III) commonly found in mobile tropical deltaic muds, genes encoding dissimilatory sulfite reductase (dsr) were successfully amplified from the upper approximately 1 m of coastal deposits sampled along French Guiana and in the Gulf of Papua. The dsr sequences retrieved were highly diverse, were generally represented in both study regions and fell into six large phylogenetic groupings: Deltaproteobacteria, Thermodesulfovibrio groups, Firmicutes and three groups without known cultured representatives. The spatial and temporal distribution of dsr sequences strongly supports the contention that the sulfate-reducing prokaryote communities in mobile mud environments are cosmopolitan and stable over a period of years. The decrease in the (35)SO(4) (2-) tracer demonstrates that, despite abundant reactive sedimentary iron(III) ( approximately 350-400 mumol g(-1)), the sulfate-reducing prokaryotes present are active, with the highest levels of sulfide being generated in the upper zones of the cores (0-30 cm). Both the time course of the (35)S-sulfide tracer activity and the lack of reduced sulfur in sediments demonstrate virtually complete anaerobic loss of solid phase sulfides. We propose a pathway of organic matter oxidation involving at least 5-25% of the remineralized carbon, wherein sulfide produced by sulfate-reducing prokaryotes is cyclically oxidized biotically or abiotically by metal oxides.

Behavior of medically-derived 131I in the tidal Potomac River.

Iodine-131 (t1/2=8.04 d) is administered to patients for treatment of thyroid disorders, excreted by patients and discharged to surface waters via sewage effluent. Radionuclides generally behave like their stable analogs; therefore, medically-derived (131)I is useful as a transport-reaction tracer of anthropogenic inputs and the aquatic biogeochemistry of iodine. Iodine-131 was measured in Potomac River water and sediments in the vicinity of the Blue Plains Water Pollution Control Plant (WPCP), Washington, DC, USA. Concentrations measured in sewage effluent from Blue Plains WPCP and in the Potomac River suggest a relatively continuous source of this radionuclide. The range of (131)I concentrations detected in surface water was 0.076±0.006 to 6.07±0.07 Bq L(-1). Iodine-131 concentrations in sediments ranged from 1.3±0.8 to 117±2 Bq kg(-1) dry weight. Partitioning in the sewage effluent from Blue Plains and in surface waters indicated that (131)I is associated with colloidal and particulate organic material. The behavior of medically-derived (131)I in the Potomac River is consistent with the nutrient-like behavior of natural iodine in aquatic environments. After discharge to the river via sewage effluent, it is incorporated into biogenic particulate material and deposited in sediments. Solid phase sediment profiles of (131)I indicated rapid mixing or sedimentation of particulate debris and diagenetic remineralization and recycling on short time scales.

The fate of terrestrial organic carbon in the marine environment.

Understanding the fate of terrestrial organic carbon (Corg) delivered to oceans by rivers is critical for constraining models of biogeochemical cycling and Earth surface evolution. Corg fate is dependent on both intrinsic characteristics (molecular structure, matrix) and the environmental conditions to which fluvial Corg is subjected. Three distinct patterns are evident on continental margins supplied by rivers: (a) high-energy, mobile muds with enhanced oxygen exposure and efficient metabolite exchange have very low preservation of both terrestrial and marine Corg (e.g., Amazon subaqueous delta); (b) low-energy facies with extreme accumulation have high Corg preservation (e.g., Ganges-Brahmaputra); and (c) small, mountainous river systems that sustain average accumulation rates but deliver a large fraction of low-reactivity, fossil Corg in episodic events have the highest preservation efficiencies. The global patterns of terrestrial Corg preservation reflect broadly different roles for passive and active margin systems in the sedimentary Corg cycle.

High-performance planar pH fluorosensor for two-dimensional pH measurements in marine sediment and water.

A new plate fluorosensor foil was developed for two-dimensional pH measurement in marine sediments and overlying waters. The fluorescent dye 8-hydroxy-1,3,6-pyrenetrisulfonic acid trisodium salt (HPTS) was covalently linked onto a transparent poly(vinyl alcohol) membrane backed by polyester sheet. Both excitation and emission bands of the immobilized HPTS showed large red shifts in comparison to HPTS in free solution. The ratio of fluorescence emission intensities at 540 nm following successive excitation at 506 and 428 nm was pH-sensitive and correlated with pH changes from 5.5 to 8.6. These properties are robust and insensitive to factors such as intensity of light source, temperature, and oxygen concentration. The plate sensor responded rapidly (< 2 min), reversibly, and with high precision to pH changes in solution and in sediment. The stability of the sensor was also tested by continually changing the pH between 6 and 8. Performance of the sensor did not vary after > 200 pH cycles. Furthermore, the sensor foil retained its original properties after continuous exposure to natural marine sedimentfor 2 months. The plate optode has been successfully used to measure two-dimensional pH distributions in intertidal flat and subtidal sediment. Images are readily obtained with inexpensive light-emitting diode (LED) excitation and commercial-grade digital cameras with typical pixel resolution of approximately 50 x 50 microm over areas > 150 cm2.

Biogeochemistry of nonylphenol ethoxylates in urban estuarine sediments.

We have examined the concentrations and distributions of nonylphenol ethoxylate (NPEO) surfactants and their primary neutral metabolites in two dated sediment cores collected in 1988 and 1996 from a depositional area proximal to a wastewater treatment plant within Jamaica Bay, NY. Total NPEO concentrations ranged from >50 microg/g near the surface (4-6 cm, deposited ca. 1990) to below detection limits (<0.1 microg/g) at 50 cm depth (deposited ca. 1940). The general decrease in NPEO concentrations with increasing depth in sediment reflected increased commercial use of these compounds over the last 50 yr. NPEO ethoxymer distributions in recent sediments were dominated by NP(0-3)EO, consistent with the increased relative input of these particular ethoxymers to the estuary following the upgrade of local biological sewage treatment processes to full activated sludge in the late 1970s. NPEO ethoxymer profiles in deeper sediments were characterized by relatively higher proportions of unmetabolized, highly ethoxylated NPEOs. Depth profiles of NP1EO and NP in the upper portion of the sediment core showed evidence for in situ diagenetic conversion of NP1EO to NP. However, comparison of NPEO concentrations in selected strata from the core collected in 1996 with those in matched strata from a core collected from the same location in 1988 provided no evidence for in situ degradation of total NPEOs during the elapsed 8 yr between collection dates.