Predictability of bacterial activity and denitrification in aquatic sediments with continuous measurements of redox potential

Redox potential has been adopted as a qualitative parameter for interpreting solubility changes of nutrients and contaminants and the biological activity within wetland systems for several decades. The majority of studies considering the redox geochemistry in sediments used measurements of bulked material and single point measurement of biogeochemical parameters for interpretation, yet it remains questionable whether this information is reliable for environments that are very dynamic, such as wetlands. In this study it is evaluated whether variations in redox potential reflect dynamics of denitrification and overall bacterial respiration using continuous measurements of redox potential in time-series experiments in laboratory microcosms, in which the biogeochemical variation was enhanced by bioturbation. The results presented here suggest that measurements of redox potential have predictive potential in approximating rates of denitrification and overall bacterial respiration in aquatic sediments. The data clearly suggest that, while sediment bulk measurements and measurements of single profiles of redox potential, denitrification and bacterial activity often fail to provide ecological relevant information in dynamic systems, measurements of spatial and temporal redox potential profiles provide a useful parameter that reflects biogeochemical processes and functioning of sediments.     

Dinosterol δD values in stratified tropical lakes (Cameroon) are affected by eutrophication

In freshwater settings, dinosterol (4α,23,24-trimethyl-5α-cholest-22E-en-3β-ol) is produced primarily by dinoflagellates, which encompass various species including autotrophs, mixotrophs and heterotrophs. Due to its source specificity and occurrence in lake and marine sediments, its presence and hydrogen isotopic composition (δD) should be valuable proxies for paleohydrological reconstruction. However, because the purity required for hydrogen isotope measurements is difficult to achieve using standard wet chemical purification methods, their potential as a paleohydrological proxy is rarely exploited. In this study, we tested δD values of dinosterol in both particulate organic matter (POM) and sediments of stratified tropical freshwater lakes (from Cameroon) as a paleohydrological proxy, the lakes being characterized by variable degrees of eutrophication. In POM and sediment samples, the δD values of dinosterol correlated with lake water δD values, confirming a first order influence of source water δD values. However, we observed that sedimentary dinosterol was D enriched from ca. 19 to 54‰ compared with POM dinosterol. The enrichment correlated with lake water column conditions, mainly the redox potential at the oxic–anoxic interface (E_h OAI). The observations suggest that paleohydrologic reconstruction from δD values of dinosterol in the sediments of stratified tropical lakes ought to be sensitive to the depositional environment, in addition to lake water δD values, with more positive dinosterol δD values potentially reflecting increasing lake eutrophication. Furthermore, in lake sediments, the concentration of partially reduced vs. non-reduced C₃₄ botryococcenes, stanols vs. stenols, and bacterial (diploptene, diplopterol and ββ-bishomohopanol) vs. planktonic/terrestrial lipids (cholesterol, campesterol and dinosterol) correlated with E_h OAI. We suggest using such molecular proxies for lake redox conditions in combination with dinosterol δD values to evaluate the effect of lake trophic status on sedimentary dinosterol δD values, as a basis for accurately reconstructing tropical lake water δD values.     

Arsenic behaviour in gold-ore mill tailings,Massif Central,France: hydrogeochemical study and investigation of in situ redox signatures

Historical Au-ore exploitation at the Chéni mine in the Massif Central, France, generated 525,000 tonnes of finely ground mill tailings deposited in a heap that has spread with time into three settling basins. The tailings, which are rich in quartz (80%), mica and clay minerals (10% of illite, smectite, kaolinite and chlorite), feldspars (5%) but poor in carbonates (<1%), also contain sulphides (around 5%, mainly pyrite and arsenopyrite). Arsenic content of the tailings is around 6 g kg. This paper describes the geochemistry of drainage waters, with special attention paid to in situ values of the three major redox couples, namely Fe(II)/Fe(III), As(III)/As(V) and S(IV)/S(VI). The water samples range from acidic and oxidized (pH 2.9, E_h +700 mV) to moderate pH and weakly reducing (pH 7.6, E_h 15 mV). The waters are rich in SO₄ and Ca and have variable As (0.05–95 mg L⁻¹) and Fe concentrations (0.07–141 mg L⁻¹). Reduced As(III) species predominate over As(V) species (As(III)/As(V) up to 21), whereas oxidized forms of Fe and S are favoured (Fe(II)/Fe(III) up to 0.5, and S(IV)/S(VI) up to 1).Thermodynamic calculations were performed with the PHREEQC and EQ3NR codes based on a revised As database to evaluate saturation indices (SI) of the waters in relation to the main minerals and define which redox couples control the redox state of the system. The important role of carbonates, though only present in small amounts, explains the acid buffering generated by the oxidation of sulphides for waters in the pH 7–7.5 range. Measured E_h appears to fall between the calculated E_h of the Fe(II)/Fe(III) couple and that of the As(III)/As(V) couple, illustrating redox disequilibrium.     

Variability of dissolved organic carbon in sediments of a seagrass bed and an unvegetated area within an estuary in Southern Texas

Pore-water dissolved organic carbon (PWDOC) concentrations were examined in vegetated and bare sediments of aHalodule wrightii seagrass bed, and in a mud bottom sediment of a southern Texas estuary. Temporal variability was examined at diel (dawn and noon) and bimonthly time scales. Distribution patterns of PWDOC were compared with physical, chemical, and biological factors thought to exert control on PWDOC. Concentration of PWDOC, bacterial production, and resultant PWDOC turnover times displayed statistically significant spatial and temporal variability. Concentration of PWDOC ranged from 14 mg C 1^?1 to 107 mg C 1^?1 of pore water, or 9–71 μg C cm^?3 wet sediment. PWDOC was more variable and was approximately 5 times higher than DOC concentrations in the water column. Low PWDOC concentrations (mean = 14.6 μg C cm^?3) and high bacterial production rates (mean = 1.92 μg C cm^?3 h^?1) were observed at the mud station, whereas PWDOC concentrations were high (mean = 24.6 μg C cm^?3) and bacterial production rates were low (mean = 0.43 μg C cm^?3 h^?1) at the bare station. PWDOC turnover times (T_t), assuming 50% bacterial growth efficiency (1–840 h) were shortest at the mud station (mean=13 h) and longest at the bare station (mean=180 h). In the overlying water column, T_t values were longer, ranging from 1,000–10,000 h. PWDOC concentrations were 25% higher in vegetated sediments than in neighboring bare sediments. This difference was probably due to inputs of labile photosynthetic excretia, since bacterial production rates in vegetated sediments displayed significant diel variability and were 4 times greater than that of bare sediments. Based upon the entire data set, PWDOC was significantly related to macrofaunal biomass, sediment POC, sediment C:N ratios, and oxygen metabolism, but was significantly correlated only to the latter two variables in stepwise multiple regression. Our findings suggest that organism activities and detrital quality are the major determinants controlling variability in PWDOC.     

The onset of anthropogenic activity recorded in lake sediments in the vicinity of the Horne smelter in Quebec,Canada: Sulfur isotope evidence

Contents and δ³⁴S values of several S compounds, enumerations of S-reducing bacteria (SRB) and Fe-reducing bacteria (IRB), and Fe, Pb and In concentrations were determined for ²¹⁰Pb-dated sediment cores from two lakes in Quebec, Canada. Both lakes are located approximately 70 km downwind of the Horne smelter and refinery in Rouyn-Noranda. Increases in Fe, Pb and In concentrations and a decrease in the δ³⁴S values of total S in both lake sediment cores coincide with the start-up of the smelter in 1927. The shift towards more negative δ³⁴S values was primarily caused by an increase in the extent of S isotope fractionation during bacterial (dissimilatory) SO₄ reduction due to SO₄ loading of the lakes after smelting began. Consequently, an enhanced accumulation of ³²S-enriched reduced inorganic S compounds is evident in the sediments. δ³⁴S values of organic S in the sediments decreased only slightly due to the smelter emissions between 1930 and 1980. Hence, due to the sulfide depositing mechanisms, S isotope ratios constitute a useful tracer recording the onset of S pollution in sediments of the two previously SO₄-limited lakes investigated. In contrast, total S concentrations alone are not reliable indicators for anthropogenic S loading in lake sediment records.     

Molecular and cultivation-dependent analysis of metal-reducing bacteria implicated in arsenic mobilisation in south-east asian aquifers

The reduction of sorbed As(V) to the potentially more mobile As(III) by As-respiring anaerobic bacteria has been implicated in the mobilisation of the toxic metalloid in aquifer sediments in SE Asia. However, there is currently only a limited amount of information on the identity of the organisms that can respire As(V) in these sediment systems. Here experiments are described that have targeted As(V)-respiring bacteria using cultivation-independent molecular techniques, and also more traditional microbiological approaches that have used growth media highly selective for organisms that can grow using arsenate as the sole electron acceptor supplied for anaerobic growth. The molecular techniques used have initially targeted DNA from microcosms displaying maximal rates of arsenate reduction, both with and without added electron donor. More recent studies from the authors’ laboratory have used stable isotope probing techniques, targeting DNA from the active microbial fraction in microcosms labelled with [¹³C]acetate supplied as an electron donor for arsenate reduction. Phylogenetic analyses using a highly conserved genetic marker (the 16S rRNA gene) have suggested the involvement of Sulfurospirillum and Geobacter species in arsenate-respiration, and this has been supported further by complimentary experiments using more traditional microbiological techniques. Additional research required to clarify the role of these organisms in the mobilisation of As in situ are discussed.     

Archaea mediate anaerobic oxidation of methane in deep euxinic waters of the Black Sea

We evaluate anaerobic oxidation of methane (AOM) in the Black Sea water column by determining distributions of archaea-specific glyceryl dialkyl glyceryl tetraethers (GDGTs) and ¹³C isotopic compositions of their constituent biphytanes in suspended particulate matter (SPM), sinking particulate matter collected in sediment traps, and surface sediments. We also determined isotopic compositions of fatty acids specific to sulfate-reducing bacteria to test for biomarker and isotopic evidence of a syntrophic relationship between archaea and sulfate-reducing bacteria in carrying out AOM. Bicyclic and tricyclic GDGTs and their constituent ¹³C-depleted monocyclic and bicyclic biphytanes (down to −67‰) indicative of archaea involved in AOM were present in SPM in the anoxic zone below 700 m depth. In contrast, GDGT-0 and crenarchaeol derived from planktonic crenarchaeota dominated the GDGT distributions in the oxic surface and shallow anoxic waters. Fatty acids indicative of sulfate-reducing bacteria (i.e., iso- and anteiso-C₁₅) were not strongly isotopically depleted (e.g., −32 to −25‰), although anteiso-C₁₅ was 5‰ more depleted in ¹³C than iso-C₁₅. Our results suggest that either AOM is carried out by archaea independent of sulfate-reducing bacteria or those sulfate-reducing bacteria involved in a syntrophy with methane-oxidizing archaea constitute a small enough fraction of the total sulfate-reducing bacterial community that an isotope depletion in their fatty acids is not readily detected. Sinking particulate material collected in sediment traps and the underlying sediments in the anoxic zone contained the biomarker and isotope signature of upper-water column archaea. AOM-specific GDGTs and ¹³C-depleted biphytanes characteristic of the SPM in the deep anoxic zone are not incorporated into sinking particles and are not efficiently transported to the sediments. This observation suggests that sediments may not always record AOM in overlying euxinic water columns and helps explain the absence of AOM-derived biomarkers in sediments deposited during past periods of elevated levels of methane in the ocean.     

Iodine diagenesis in non-pelagic deep-sea sediments

Measurements of sediment geochemistry and porewater speciation have been made using eight cores containing turbidite sections from the Madeira and Nares Abyssal Plains. The results have been used to evaluate how the diagenetic chemistry of iodine in these sediments compares with that in sediments undergoing steady-state diagenesis. The behaviour of iodine is related to the development of a redox front within the turbidite, between the organic-rich anoxic sediment and its oxic cap, and the downward migration of the front through the turbidite with time. In contrast to the steady-state case, sediment I contents and I/ C ratios increase downwards through the oxidised section reaching a maximum at the redox front (up to ~ 100 μ/g I; molar I/C~ 20 × 10⁻⁴) below which values drop dramatically (I/C ~ 5 × 10⁻⁴). A strong iodate enrichment (up to ~3 μmol kg⁻¹) is observed in the oxidised section of the sediment. At the front interconversion of I⁻ and IO⁻₃ species occur and below the front porewater IO⁻₃ is absent and I~ concentrations increase with depth (as in other cases of anoxic diagenesis) up to ~ 10 μmol kg⁻. In the oxidised section of the sediment the I enrichment has been supplied by upward transport of iodide with the increasing I content, with depth being accounted for by progressive diagenetic enrichment with time.     

Kinetics of microbial sulfate reduction in estuarine sediments

Kinetic parameters of microbial sulfate reduction in intertidal sediments from a freshwater, brackish and marine site of the Scheldt estuary (Belgium, the Netherlands) were determined. Sulfate reduction rates (SRR) were measured at 10, 21, and 30 °C, using both flow-through reactors containing intact sediment slices and conventional sediment slurries. At the three sites, and for all depth intervals studied (0-2, 2-4, 4-6 and 6-8 cm), the dependence of potential SRR on the sulfate concentration followed the Michaelis-Menten rate equation. Apparent sulfate half-saturation concentrations, K_m, measured in the flow-through reactor experiments were comparable at the freshwater and marine sites (0.1-0.3 mM), but somewhat higher at the brackish site (0.4-0.9 mM). Maximum potential SRR, R_max, in the 0-4 cm depth interval of the freshwater sediments were similar to those in the 0-6 cm interval of the marine sediments (10-46 nmol cm⁻³ h⁻¹ at 21 °C), despite much lower in situ sulfate availability and order-of-magnitude lower densities of sulfate-reducing bacteria (SRB), at the freshwater site. Values of R_max in the brackish sediments were lower (3.7-7.6 nmol cm⁻³ h⁻¹ at 21 °C), probably due to less labile organic matter, as inferred from higher C_org/N ratios. Inflow solutions supplemented with lactate enhanced potential SRR at all three sites. Slurry incubations systematically yielded higher R_max values than flow-through reactor experiments for the freshwater and brackish sediments, but similar values for the marine sediments. Transport limitation of potential SRR at the freshwater and brackish sites may be related to the lower sediment porosities and SRB densities compared to the marine site. Multiple rate controls, including sulfate availability, organic matter quality, temperature, and SRB abundance, modulate in situ sulfate-reducing activity along the estuarine salinity gradient.     

Mercury in sediments from gold and copper exploitation areas in the Camaquã River Basin,Southern Brazil

Mercury concentrations were determined in stream sediments from the Camaquã River Basin, located in the shield region of the state of Rio Grande do Sul, southern Brazil. The resulting geochemical data show that overbank floodplain deposits exhibit higher concentrations than sediments collected from the active channel bed. In addition, higher Hg concentrations were measured in the fine(<63 μm) sediment fraction of the samples. Total Hg concentrations in the fine fraction of active stream sediments from Lavras do Sul County, which have been influenced by past gold mining activities, have decreased during the last five years to values ≤142 ng g⁻¹. However, in a settling pond containing abandoned mine wastes, the Hg concentration of a bulk sample remained exceptionally high (5220 ng g⁻¹). Preliminary speciation results show that Hg⁰ is the predominant species in most of the samples. This was the form of Hg released by the gold amalgamation activities in the area, and appears to be relatively stable under the existing E_h and pH conditions.     

Volatile fatty acid cycling in organic-rich marine sediments

Volatile fatty acid (VFA) apparent turnover rates were determined by measuring whole sediment VFA concentrations and the corresponding reaction rate constants. The following ranges of VFA concentrations were measured in Cape Lookout Bight, N.C. sediments (μmole·l_s^?1): acetate 54–660, propionate 1–24, butyrate <0.5–22, iso-butyrate <0.5–6. Apparent turnover rates measured over a one-year period ranged from 18–600 μmole·l_s^?1·h^?1 for acetate and 0.7–7 μmole·l_s^?1·h^?1 for the carboxyl carbon of propionate. Methane production was observed only with acetate and only in sulfatedepleted sediments; total acetate turnover attained approximately the same maximum value in both sulfate-reducing and sulfate-depleted sediments.Apparent turnover rates for acetate and propionate appeared to be controlled by similar factors: in sulfate-reducing (surface) sediments the turnover rates were stimulated by autumn storm-mediated deposition/resuspension events; in deeper sulfate-depleted sediments the turnover rates followed changes in the ambient temperature. Changes in VFA poolsizes were proportionally much larger than changes in corresponding rate constants. The ratio of CO₂ to CH₄ produced from acetate vs. depth suggested that non-methanogenic bacteria accounted for 60% of the acetate turnover in sulfate-depleted sediments.VFA concentrations were much lower in N.C. continental slope mud than in Cape Lookout sediments; acetate was the only VFA detectable throughout the top 40 cm of the slope sediments. The estimated production rate of CO₂ from acetate decreased rapidly with depth. The surface rate was approximately 20 times less than that measured at similar temperatures in sulfate-reducing Cape Lookout sediments.     

Study on redox state and grain size of sediments in a mud flat of the Venice Lagoon

An extensive investigation based on the redox potential and grain size distributions was made on the sediment of a Venice Lagoon mud flat subjected to excessive growth of macroalgae. Redox potential and grain size measurements are proved useful tracers for, respectively, oxygen bearing and consuming processes in the water-sediment column and hydrodynamical behavior inside the mud flat. Depth measurements and a considerable number of sites with respect to the size of the area studied are needed to obtain an outline of the behavior of the water body in response to stress conditions caused by human activities. With respect to the top 15-cm-thick sediment layer where E_H variations occur, the mud flat is subdivisible into sectors with different characteristics. Positive or near-zero E_H values were recorded in zones characterized by sparse macroalgae growth and a high content of coarse sediments (diameter 44 µm). On the contrary, very negative E_H values were found in zones affected by overabundant macroalgae bloom and with a higher presence of fine-grained sediment (diameter 44 µm). The clear relationships between algae presence in the mud flat and both the redox potential and grain size characteristics of the sediment emphasize the hydrodynamics as a critical factor determining the variations of the environmental conditions in the ecosystem.     

Carbohydrates in recent marine sediments—I. Origin and significance of deoxy- and O-methyl-monosaccharides

A qualitative and partly quantitative survey of the carbohydrates encountered in acid hydrolyzates of some recent marine sediments reveals the presence of a large variety of known and hitherto unknown monosaccharides. Apart from the well known major monosaccharides a great number of minor components (notably O-methyl and deoxy monosaccharides) are encountered. These minor components are considered to originate from bacteria. Since significantly larger amounts of major monosaccharides are encountered in carbohydrates associated with bacterial cell-walls the greater part of the carbohydrate carbon in these sediments is ascribed to these structures. Superimposed on the bacterial contribution the characteristics of the carbohydrates originating from the primary producers are recognizable. The results indicate that bacterial biopolymers formed by de novo synthesis in the sediment should be considered as a potential source for the insoluble organic matter in these sediments.     

Biogeochemical characterization of bacterial assemblages in relation to release of arsenic from South East Asia (Bangladesh) sediments

Arsenic release experiments using natural indigenous microbial assemblages and natural sediment samples in Bangladesh have been performed. The As release appears to be facilitated by moderate organic input. Addition of some nutrients caused reducing conditions, which may generate the appropriate environment for Fe-reducing bacteria to become active. Detailed cellular phospholipid fatty acid (PLFA) analysis suggests the presence of SO₄-reducing and Fe-reducing bacteria in the sediments. These Fe-reducing bacteria may serve as the agents catalyzing As release in the organic-rich sediments. 16S rDNA analysis of one cultured sample suggests the presence of clostridia, some of which are known to mediate Fe reduction. Based on new PLFA analyses, it is proposed that combined microbial processes of SO₄ reduction to generate anaerobic conditions and Fe reduction to co-reduce As are important biogeochemical factors for As release in the Bangladesh sediments.     

The Influence of Oyster Farming on Sediment Bacterial Communities

Aquaculture currently provides half of all fish for human consumption, and this proportion is expected to increase to meet the growing global demand for protein. As aquaculture, including oyster farming, expands, it is increasingly important to understand effects on coastal ecosystems. The broad-scale ecological effects of oyster aquaculture are well documented; however, less is known regarding the influence of oyster aquaculture on sediment bacterial communities. To better understand this relationship, we compared three different oyster farming practices that varied in oyster biomass and proximity of oysters to the sediment. We used high-throughput sequencing and quantitative polymerase chain reaction to examine the effect of oyster farming on sediment bacterial communities. We examined the entire bacterial community and looked specifically at bacteria that support essential estuarine ecosystem services (denitrifiers), as well as bacteria that can be detrimental to human health (members of the Vibrio genus). We found that oyster biomass increased Vibrio richness and sediment carbon content, which influenced bacterial community composition. When compared to reference sites, the overall abundance of bacteria was increased by the bottom planting method, but the associated increases in denitrifiers and Vibrio were not significant. We were unable to detect V. parahaemolyticus, V. vulnificus, or V. cholera, the three most common Vibrio pathogens, in any sample, suggesting that oyster farming did not enhance these potential human pathogens in sediments at the time of sampling. These results highlight how differences in oyster farming practice can affect sediment bacterial communities, and the ecosystem services they provide.     

Bacterial contribution to sedimentary organic matter; a comparative study of lipid moieties in bacteria and Recent sediments

A systematic study of the lipid composition of thirteen bacterial species and three Recent sediments (methanogenic sediment, cyanobacterial mat and evaporative gypsum crust) was undertaken in an attempt to recognize bacterial organic matter in sediments. A sequential method, which distinguishes between three different modes of occurrence of lipid moieties (free, OH⁻- and H⁺-labile), was applied. The acid-labile fractions are discussed.The three main groups of bacteria, archaebacteria, gram-positive eubacteria and gram-negative eubacteria, are easily distinguished. Methanogenic and extremely halophilic archaebacteria are characterized by the presence of diphytanyl glyceryl ether and the absence of fatty acids. The gram-positive eubacteria contain primarily iso- and anteiso-branched fatty acids whereas the gram-negative bacteria and sediments are dominated by β- and α-hydroxy fatty acids. A wide variety of H⁺-labile hydroxy fatty acids was observed which included several, as yet unknown, structures.β-Hydroxy fatty acids in this H⁺-labile mode of occurrence are exclusively present in bacteria. Their distribution patterns in sediments are considered “fingerprints” of past and present bacterial populations. The specific differences in β -hydroxy fatty acid compositions observed in the different bacteria and the three sediments investigated, suggest that amide-linked β-hydroxy fatty acid patterns are useful as markers of bacterial populations and therefore of environmental conditions.     

A kinetic approach to describe trace-element distribution between particles and solution in natural aquatic systems

The partitioning of radioactive trace elements between seawater and particulate matter from surface sediments and sediment traps was investigated in laboratory experiments. For the elements Na, Zn, Se, Sr, Cd, Sn, Sb, Cs, Ba, Hg, Th and Pa (group I) constant distribution coefficients (K_d) were found after a few days of equilibration, whereas the elements Be, Mn, Co and Fe (group II) showed an increasing K_d over the whole time of observation of 108 days. The time dependence of K_d is described by an adsorption-desorption equilibrium (group I elements), followed by a lattice transport reaction step (group II elements). The reaction rate constants are compared to Mn oxidation rates and to adsorption rate constants derived from in situ measurements of the $\text{U}\text{Th}$ disequilibrium as available from literature.     

Fatty acids of bacterial origin in contemporary marine sediments

Contributions by bacteria to recent sediments have been recognized as one important source of input for the extractable lipids. It has, however, proved difficult so far to conclusively relate the components identified to the contributing bacteria. This fact is primarily related to the lack of information on both the lipid chemistry of marine bacteria, and of detailed structures of the sedimentary lipids. In this paper a study of the fatty acids from a tropical marine sediment selected because of its high biomass content is reported, and relationships between the sedimentary extracts of the surface layer to fatty acid components of bacteria cultured from the sediment sample are detailed. By selecting specific structural features, a group of fatty acids have been identified as valid markers for bacteria in this environment: these include iso- and anteiso-branched chain acids; 10-methylpalmitic acid; cyclopropyl 17:0 and 19:0 acids of which ▽19:0 (11,12) is unique to bacteria; cis-vaccenic acid; and the 15:1, 17:1 ω6 and ω8 isomers especially when these occur in pairs; iso Δ7–15: 1 and iso Δ9–17:1 are branched unsaturated acids apparently unique to bacteria. Trans-monoene fatty acids are likely to be a direct bacterial input, and the hydroxy acids identified are probably of bacterial cell wall origin. This study, whilst emphasizing the necessity for detailed structural information on fatty acids in order to use them validly as biological markers, considerably extends the range of fatty acids as markers of bacterial input to contemporary sediments.     

Nitrogen losses through sediment denitrification in Boston Harbor and Massachusetts Bay

Sediment denitrification is a microbial process that converts dissolved inorganic nitrogen in sediment porewaters to N₂ gas, which is subsequently lost to the atmosphere. In coastal waters, it represents a potentially important loss pathway for fixed nitrogen which might otherwise be available to primary producers. Currently, data are lacking to adequately assess the role of denitrification in reducing or remediating the effects of large anthropogenic nitrogen loads to the coastal zone. This study describes the results of 88 individual measurements of denitrification (as a direct flux of N₂ gas) in sediment cores taken over a 3-yr period (1991–1994) from six stations in Boston Harbor, nine stations in Massachusetts Bay, and two stations in Cape Cod Bay. The dataset is unique in its extensive spatial and temporal coverage and includes the first direct measurements of denitrification for North Atlantic shelf sediments. Results showed that rates of denitrification were significantly higher in Boston Harbor (mean=54, range<5–206 μmol N₂ m^?2 h^?1) than in Massachusetts Bay (mean=23, range<5–64 μmol N₂ m^?2 h^?1). Highest rates occurred in areas with organic-rich sediments in the harbor, with slower rates observed for low-organic sandy sediments in the harbor and at shallow shelf stations in the bay. Lowest rates were found at the deepest shelf stations, located in Stellwagen Basin in Massachusetts Bay. Observed rates were correlated with temperature, sediment carbon content, and benthic macrofaunal activity. Seasonally, highest denitrification rates occurred in the summer in Boston Harbor and in the spring and fall in Massachusetts Bay, coincident with peak phytoplankton blooms in the overlying water column. Despite the fact that sediment denitrification rates were high relative to rates reported for other East Coast estuaries, denitrification losses accounted for only 8% of the annual total nitrogen load to Boston Harbor, a consequence perhaps, of the short water-residence times (2–10 d) of the harbor.