Transport of particulate organic carbon by the Mississippi River and its fate in the Gulf of Mexico

This study was designed to determine the amount of particulate organic carbon (POC) introduced to the Gulf of Mexico by the Mississippi River and assess the influence of POC inputs on the development of hypoxia and burial of organic carbon on the Louisiana continental shelf. Samples of suspended sediment and supporting hydrographic data were collected from the river and >50 sites on the adjacent shelf. Suspended particles collected in the river averaged 1.8±0.3% organic carbon. Because of this uniformity, POC values (in μmol l^?1) correlated well with concentrations of total suspended matter. Net transport of total organic carbon by the Mississippi-Atchafalaya River system averaged 0.48×10¹² moles y^?1 with 66% of the total organic carbon carried as POC. Concentrations of POC decreased from as high as 600 μmol l^?1 in the river to <0.8 μmol l^?1 in offshore waters. In contrast, the organic carbon fraction of the suspended matter increased from <2% of the total mass in the river to >35% along the shelf at ≥10 km from the river mouth. River flow was a dominant factor in controlling particle and POC distributions; however, time-series data showed that tides and weather fronts can influence particle movement and POC concentrations. Values for apparent oxygen utilization (AOU) increased from ～60 μmol l^?1 to >200 μmol l^?1 along the shelf on approach to the region of chronic hypoxia. Short-term increases in AOU were related to transport of more particle-rich waters. Sediments buried on the shelf contained less organic carbon than incoming river particles. Orgamic carbon and δ¹³C values for shelf sediments indicated 3 that large amounts of both terrigenous and marine organic carbon are being decomposed in shelf waters and sediments to fuel observed hypoxia.     

Nutrient changes in the Mississippi River and system responses on the adjacent continental shelf

The Mississippi River system ranks among the world's top 10 rivers in freshwater and sediment inputs to the coastal ocean. The river contributes 90% of the freshwater loading to the Gulf of Mexico, and terminates amidst one of the United States' most productive fisheries regions and the location of the largest zone of hypoxia, in the western Atlantic Ocean. Significant increases in riverine nutrient concentrations and loadings of nitrate and phosphorus and decreases in silicate have occurred this century, and have accelerated since 1950. Consequently, major alterations have occurred in the probable nutrient limitation and overall stoichiometric nutrient balance in the adjacent continental shelf system. Changes in the nutrient balances and reduction in riverine silica loading to, the continental shelf appear to have led to phytoplankton species shifts offshore and to an increase in primary production. The phytoplankton community response, as indicated by long-term changes in biological uptake of silicate and accumulation of biologically bound silica in sediments, has shown how the system has responded to changes in riverine nutrient loadings. Indeed, the accumulation of biologically bound silica in sediments beneath the Mississippi River plume increased during the past two decades, presumably in response to, increased nitrogen loading. The duration, size, and severity of hypoxia has probably increased as a consequence of the increased primary production. Management alternatives directed at water pollution issues within the Mississippi River watershed may have unintended and contrasting impacts on the coastal waters of the northern Gulf of Mexico.     

A review of water column processes influencing hypoxia in the northern Gulf of Mexico

In this review, we use data from field measurements of biogeochemical processes and cycles in the Mississippi River plume and in other shelf regions of the northern Gulf of Mexico to determine plume contributions to coastal hypoxia. We briefly review pertinent findings from these process studies, review recent mechanistic models that synthesize these processes to address hypoxia-related issues, and reinterpret current understanding in the context of these mechanistic models. Some of our conclusions are that both nitrogen and phosphorus are sometimes limiting to phytoplankton growth; respiration is the main fate of fixed carbon in the plume, implying that recycling is the main fate of nitrogen; decreasing the river nitrate loading results in less than a 1:1 decrease in organic matter sinking from the plume; and sedimenting organic matter from the Mississippi River plume can only fuel about 23% of observed coastal hypoxia, suggesting significant contributions from the Atchafalaya River and, possibly, coastal wetlands. We also identify gaps in our knowledge about controls on hypoxia, and indicate that some reinterpretation of our basic assumptions about this system is required. There are clear needs for improved information on the sources, rates, and locations of organic matter sedimentation; for further investigation of internal biogeochemical processes and cycling; for improved understanding of the rates of oxygen diffusion across the pycnocline; for identification and quantification of other sources of organic matter fueling hypoxia or other mechanisms by which Mississippi River derived organic matter fuels hypoxia; and for the development of a fully coupled physical-biogeochemical model.     

Transport of dissolved organic nitrogen in Mississippi River plume and Texas-Louisiana continental shelf near-surface waters

Dissolved organic nitrogen (DON) in near-surface (<20 m depth) waters of the Texas-Louisiana continental shelf is the predominant form of total dissolved nitrogen that is advected by the Mississippi-Atchafalaya River plume. Relatively high DON concentrations associated with low-salinity (<33 psu) waters throughout the year can be traced within the plume along the Texas-Louisiana inner shelf. DON concentrations throughout the shelf were significantly higher near the Mississippi-Atchafalaya outflow region relative to downstream inner Gulf shelf locations. Significant intercruise variations were also evident, with the highest concentrations during May 1992 and lower values in October 1992. At a fixed location off the Mississippi River outflow region DON concentration covaried inversely with salinity on time scales of hours to months, confirming that source water is a determining factor for variations of bulk DON concentrations in the region. Similar variations in upper water DON concentrations at different locations and seasons occurred in both plume and nonplume waters, which resembled the seasonal concentration changes of riverine nitrogen, and show that this pool is useful in tracing the influence of riverine-derived nitrogen on the overall nitrogen balance of the NW Gulf of Mexico’s continental shelf. Plume and nonplume DON concentrations deviated from mixing lines between riverine and oceanic endmembers, suggesting that plume waters may be a sink and nonplume waters may be a source of a labile fraction of DON in the region.     

Records of nutrient-enhanced coastal ocean productivity in sediments from the Louisiana continental shelf

Shelf sediments from near the mouth of the Mississippi River were collected and analyzed to examine whether records of the consequences of anthropogenic nutrient loading are preserved. Cores representing approximately 100 yr of accumulation have increasing concentrations of organic matter over this period, indicating increased accumulation of organic carbon, rapid early diagenesis, or a combination of these processes. Stable carbon isotopes and organic tracers show that virtually all of this increase is of marine origin. Evidence from two cores near the river mouth, one within the region of chronic seasonal hypoxia and one nearby but outside the hypoxic region, indicate that changes consistent with increased productivity began by approximately the mid-1950s when the inorganic carbon in benthic forams rapidly became isotopically lighter at both stations. Beginning in the mid-1960s, the accumulation of organic matter, organic δ¹³C, and δ¹⁵N all show large changes in a direction consistent with increased productivity. This last period coincides with a doubling of the load of nutrients from the Mississippi River, which levelled off in the mid-1980s. These data support the hypothesis that anthropogenic nutrient loading has had a significant impact on the Louisiana shelf.     

Going West: Nutrient Limitation of Primary Production in the Northern Gulf of Mexico and the Importance of the Atchafalaya River

To investigate controls on phytoplankton production along the Louisiana coastal shelf, we mapped salinity, nutrient concentrations (dissolved inorganic nitrogen (DIN) and phosphorus (P_i), silicate (Si)), nutrient ratios (DIN/P_i), alkaline phosphatase activity, chlorophyll and ¹⁴C primary productivity on fine spatial scales during cruises in March, May, and July 2004. Additionally, resource limitation assays were undertaken in a range of salinity and nutrient regimes reflecting gradients typical of this region. Of these, seven showed P_i limitation, five revealed nitrogen (N) limitation, three exhibited light (L) limitation, and one bioassay had no growth. We found the phytoplankton community to shift from being predominately N limited in the early spring (March) to P limited in late spring and summer (May and July). Light limitation of phytoplankton production was recorded in several bioassays in July in water samples collected after peak annual flows from both the Mississippi and Atchafalaya Rivers. We also found that organic phosphorus, as glucose-6-phosphate, alleviated P limitation while phosphono-acetic acid had no effect. Whereas DIN/P_i and DIN/Si ratios in the initial water samples were good predictors of the outcome of phytoplankton production in response to inorganic nutrients, alkaline phosphatase activity was the best predictor when examining organic forms of phosphorus. We measured the rates of integrated primary production (0.33?C7.01 g C m^?2 d^?1), finding the highest rates within the Mississippi River delta and across Atchafalaya Bay at intermediate salinities. The lowest rates were measured along the outer shelf at the highest salinities and lowest nutrient concentrations (<0.1 ??M DIN and Pi). The results of this study indicate that P_i limitation of phytoplankton delays the assimilation of riverine DIN in the summer as the plume spreads across the shelf, pushing primary production over a larger region. Findings from water samples, taken adjacent the Atchafalaya River discharge, highlighted the importance of this riverine system to the overall production along the Louisiana coast.     

Characterization of nutrient, organic carbon, and sediment loads and concentrations from the Mississippi River into the northern Gulf of Mexico

We synthesize and update the science supporting the Action Plan for Reducing, Mitigating, and Controlling Hypoxia in the Northern Gulf of Mexico (Mississippi River/Gulf of Mexico Watershed Nutrient Task Force 2001) with a focus on the spatial and temporal discharge and patterns of nutrient and organic carbon delivery to the northern Gulf of Mexico, including data through 2006. The discharge of the Mississippi River watershed over 200 years varies but is not demonstrably increasing or decreasing. About 30% of the Mississippi River was shunted westward to form the Atchafalaya River, which redistributed water and nutrient loads on the shelf. Data on nitrogen concentrations from the early 1900s demonstrate that the seasonal and annual concentrations in the lower river have increased considerably since then, including a higher spring loading, following the increase in fertilizer applications after World WarII. The loading of total nitrogen (TN) fell from 1990 to 2006, but the loading of total phosphorus (TP) has risen slightly, resulting in a decline in the TN:TP ratios. The present TN:TP ratios hover around an average indicative of potential nitrogen limitation on phytoplankton growth, or balanced growth limitation, but not phosphorus limitation. The dissolved nitrogen:dissolved silicate ratios are near the Redfield ratio indicative of growth limitations on diatoms. Although nutrient concentrations are relatively high compared to those in many other large rivers, the water quality in the Mississippi River is not unique in that nutrient loads can be described by a variety of land-use models. There is no net removal of nitrogen from water flowing through the Atchafalaya basin, but the concentrations of TP and suspended sediments are lower at the exit point (Morgan City, Louisiana) than in the water entering the Atchafalaya basin. The removal of nutrients entering offshore waters through diversion of river water into wetlands is presently less than 1% of the total loadings going directly offshore, and would be less than 8% if the 10,093 km² of coastal wetlands were successfully engineered for that purpose. Wetland loss is an insignificant contribution to the carbon loading offshore, compared to in situ marine production. The science-based conclusions in the Action Plan about nutrient loads and sources to the hypoxic zone off Louisiana are sustained by research and monitoring occurring in the subsequent 10 years.     

Sources and distribution of terrigenous organic matter delivered by the Atchafalaya River to sediments in the northern Gulf of Mexico

Suspended sediments (SS) from the Atchafalaya River (AR) and the Mississippi River and surficial sediment samples from seven shallow cross-shelf transects west of the AR in the northern Gulf of Mexico were examined using elemental (%OC, C/N), isotopic (δ¹³C, Δ¹⁴C), and terrigenous biomarker analyses. The organic matter (OM) delivered by the AR is isotopically enriched (∼−24.5‰) and relatively degraded, suggesting that soil-derived OM with a C4 signature is the predominant OM source for these SS. The shelf sediments display OC values that generally decrease seaward within each transect and westward, parallel to the coastline. A strong terrigenous C/N (29) signal is observed in sediments deposited close to the mouth of the river, but values along the remainder of the shelf fall within a narrow range (8-13), with no apparent offshore trends. Depleted stable carbon isotope (δ¹³C) values typical of C3 plant debris (−27‰) are found near the river mouth and become more enriched (−22 to −21‰) offshore. The spatial distribution of lignin in shelf sediments mirrors that of OC, with high lignin yields found inshore relative to that found offshore (water depth > 10 m).The isotopic and biomarker data indicate that at least two types of terrigenous OM are deposited within the study area. Relatively undegraded, C3 plant debris is deposited close to the mouth of the AR, whereas more degraded, isotopically enriched, soil-derived OM appears to be deposited along the remainder of the shelf. An important input from marine carbon is found at the stations offshore from the 10-m isobath. Quantification of the terrigenous component of sedimentary OM is complicated by the heterogeneous composition of the terrigenous end-member. A three-end-member mixing model is therefore required to more accurately evaluate the sources of OM deposited in the study area. The results of the mixing calculation indicate that terrigenous OM (soil-derived OM and vascular plant debris) accounts for ∼79% of the OM deposited as inshore sediments and 66% of OM deposited as offshore sediments. Importantly, the abundance of terrigenous OM is 40% higher in inshore sediments and nearly 85% higher in offshore sediments than indicated by a two-end-member mixing model. Such a result highlights the need to reevaluate the inputs and cycling of soil-derived OM in the coastal ocean.     

Input of Nutritionally Rich Organic Matter from the Mississippi River to the Louisiana Coastal Zone

Isotopes have often been used to discern riverine subsidies to coastal food chains, but there are few direct measurements of nutritional quality of riverine particulates. We tested for nutritionally enriched organic matter in the Mississippi River suspended sediment and evidence for its delivery to Louisiana coastal sediments by measuring enzymatically hydrolysable amino acids (EHAA). Riverine suspended sediments contained EHAA concentrations of up to 5 mg g^?1, higher than reported in any coastal sediment. Pigment concentrations indicated that EHAA in some river samples were dominated by phytoplankton, but many samples contained significant non-algal EHAA. Coastal sediments showed EHAA concentrations lower than riverine sediments but still higher than most reported shelf values. Incubation of riverine sediment showed losses of 28–34% of their EHAA over 6 days, similar to differences found between riverine and coastal sediments. EHAA concentrations decreased more rapidly than total nitrogen, indicating the relative lability of this pool of material in the studied region. These EHAA-enriched materials provide fuel for various coastal biota whose composition likely depends on factors such as disturbance regimes.     

Comparison of nutrient and trace element distributions in the delta and shelf outflow regions of the Mississippi and Atchafalaya Rivers

Nutrient and trace element distributions were determined in the outflow region of the Mississippi and Atchafalaya rivers during high river discharge. This outflow region can be divided into two physiographic areas: the broad, shallow Louisiana Shelf off the Atchafalaya River and the narrow shelf off the Mississippi Delta. The physiographic differences between these two areas lead to observable differences in the chemical distributions. During high discharge conditions, nutrient depletion occurs at lower salinities on the Louisiana Shelf, relative to the delta outflow plume, and significant uptake of nickel and cadmium is apparent in these shelf waters, too. Important factors that appear to connect the physiographic to the chemical include the fate of the fluvial suspended load, rates of mixing, and the extent of productivity supported by recycled nutrients. The results suggest that the Mississippi-Atchafalaya outflow region may provide a natural laboratory for examining the possible effects of sea-level change on the biogeochemistry of estuarine and coastal environments.     

Seasonality of materials transport through a coastal freshwater marsh: Riverine versus tidal forcing

Transports of nitrate and suspended solids were measured six times from January 1984 until January 1985 in a small freshwater tidal bayou in south-central Louisiana. The bayou and adjacent marshes are influenced by Atchafalaya River discharges, tides, and coastal weather patterns. Large net ebb-directed water transports occurred in winter, spring, and summer, coincident with high river discharges, indicating riverine dominance. A very small net flood-directed water transport occurred in fall, indicating tidally dominated hydrology. Nitrate and suspended solids transports were net ebb-directed in all seasons, but were two orders of magnitude higher during high river flow. Exports changed as hydrology switched from river dominated to tidally dominated, and as concentrations of materials changed. Comparison of suspended solids and nitrate concentrations in the river and bayou shows that these materials were usually lower in the bayou, indicating retention by the marsh/aquatic system.     

Temporal variability in sources of dissolved organic carbon in the lower Mississippi river

Here we report on the temporal changes in the composition of dissolved organic carbon (DOC) collected in the tidal freshwater region of the lower Mississippi River. Lignin-phenols, bulk stable carbon isotopes, compound-specific isotope analyses (CSIA) and ¹³C nuclear magnetic resonance (NMR) spectrometry were used to examine the composition of high molecular weight dissolved organic matter (HMW DOM) at one station in the lower river over 6 different flow regimes in 1998 and 1999. It was estimated that the annual input of DOC delivered to the Gulf of Mexico from the Mississippi River was of 3.1 × 10⁻³ Pg, which represents 1.2% of the total global input of DOC from rivers to the ocean. Average DOC and HMW DOC were 489 ±163 and 115 ± 47 μM, respectively. ¹³C-NMR spectra revealed considerably more aliphatic structures than aromatic carbons in HMW DOC. Lignin phenols were significantly ¹³C-depleted with respect to bulk HMW DOM indicating that C₄ grass inputs to the HMW DOM were not significant. It is speculated that C₄ organic matter in the river is not being converted (via microbial decay) to HMW DOM as readily as C₃ organic matter is, because of the association of C₄ organic matter with finer sediments. The predominantly aliphatic ¹³C NMR signature of HMW DOM suggests that autochthonous production in the river may be more important as a source of DOC than previously thought. Increases in nutrient loading and decreases in the suspended load (because of dams) in the Mississippi River, as well as other large rivers around the world, has resulted in significant changes in the sources and overall cycling of riverine DOC.     

Late Quaternary coastal and inner shelf stratigraphy, Apalachicola Delta region, Florida

Since the beginning of the Tertiary the sedimentology of the Gulf of Mexico Basin has been dominated by the depositional activity of the Mississippi River. The sedimentologic influence of the Mississippi diminishes with distance east or west of the Louisiana shelf, however. The Texas and northwest Florida shelf margins, for example, are characterized by a series of smaller deltas. In the inner and mid-shelf areas of these regions the near-surface sedimentary units include infilled stream channels and small deltas. Such features are commonly observed in sub-bottom seismic records from the middle and inner shelf of the northeastern Gulf, along the Apalachicola River coast of northwest Florida.

The Apalachicola River is the principal source of clastic sediment to the northeastern Gulf of Mexico. During the late Holocene virtually all of the river's sediment load has been deposited in the modern Apalachicola Delta and in the river's estuary, Apalachicola Bay, which has been filling rapidly. During late Quaternary lowstands, prior to the development of the modern estuary, the river traversed the present-day inner and mid-shelf, incising a network of channels. Based on seismic records, many of these buried shelf channels were considerably larger than their modern counterparts.

During lowstands the Apalachicola River also deposited coarse sediment on the shelf as deltaic and associated river-mouth sediments. These deposits comprise the modern near-surface sediments of the inner and middle shelf. An investigation of subsurface sedimentary features observed in seismic profiles provides details on the late Quaternary development of the northeastern Gulf of Mexico shelf. Seismic reflection profiles obtained on the inner and mid-shelf regions of northwest Florida reveal an approximately 50 m thickness of late Quaternary sediments, comprised of two and sometimes three discrete clastic sequences. Two lower fluvial sequences total as much as 40–50 m in thickness. A transgressive marine sand deposit overlies the older features in some places, varying in thickness from 0 to 5 m. Identification of seismic facies, combined with stratigraphic data from a suite of coastal boreholes, enables correlation of offshore seismic stratigraphic units with late Tertiary and Quaternary coastal stratigraphy.     

Burial of organic carbon and carbonate on inner shelf of the northern South China Sea during the postglacial period

Two vibrocores from the inner shelf off Hong Kong are investigated to compare the contents of organic and inorganic carbon in postglacial sediments. The compositions of organic elements and carbonate are highly variable in the core sediments, but overall drop within the compositional ranges of modern seabed sediments in the Zhujiang estuarine and its shelf area. The Holocene sediments in the inner shelf have never been subject to subaerial exposure and the organic matter and carbonate can be preserved well. The burial of carbon in river-dominated shelf environments is highly dependent on the river flux with time. Nevertheless, it is difficult to establish a simple relationship between carbon burial in sediments in relation to climatic changes of basin-wide scale due to complex controls of production, transport and deposition of organic matter and carbonate. Our study suggests that the organic carbon to nitrogen ratio can not reliably identify the sources of depositional organic matters because of selective decomposition of organic matter components during humification and sedimentation. Caution is therefore needed in using organic elemental compositions as indicators of organic matter sources and paleoenvironmental changes in the East Asian continental shelves where intense river-sea interaction and variable carbon flux in geologic record occur.     

Spatial and temporal variations in terrestrially-derived organic matter from sediments of the Delaware estuary

Terrestrially-derived organic matter in sediments of the Delaware Estuary originates from riverine transport of soils and fresh litter, sewage and industrial wastes, and marsh export of organic matter. The quantity, composition, and spatial distribution of terrigenous organic matter in sediments was determined by elemental (C and N), lignin, and stable carbon isotope analyses. Sediments in the upper Delaware Estuary had low organic carbon content and high lignin content. In contrast, sediments in the lower Delaware Estuary had high organic carbon content and low lignin content. There was a slight decrease in the proportion of syringyl and cinnamyl phenols relative to vanillyl phenols between the upper estuary and lower estuary. Differences in lignin and stable carbon isotope compositions between sediments of the Delaware Estuary and sediments of the Broadkill River estuary (an adjoining salt-marsh estuary) supported previous observations that marshes do not export substantial quantities of organic matter to estuaries. Additional results suggested that lignin-rich sediments were concentrated in the upper estuary, most likely in the zone of high turbidity. Furthermore, algal material diluted lignin-rich sediments, particularly in the lower estuary. The weaker algal signal in bottom sediments compared to that in suspended particulate matter suggested algal material was decomposed either in the water column or at the sediment-water interface. Physical sorting of sediments prior to deposition was also indicated by observations of compositional differences between the upper and lower estuary bottom sediments. Finally, seasonal variations in primary productivity strongly influenced the relative abundance of terrestrial organic matter. In fall, however, the proportion of lignin was greatest because of a combination of greater inputs of terrestrially-derived organic matter, lower river discharge, and a decrease in algal biomass.     

Effects of discharge of municipal waste on water quality of the lower Mississippi River

The effects of discharge of municipal wastes on water quality within the lower Mississippi River below Old River have been reevaluated using published water quality data in the Louisiana reach of the river for the water years 1974–1984. A novel graphical technique has facilitated the evaluation of upriver controls on water quality and the identification of sources and sinks along the lower Mississippi. Comparison of calculated annual fluxes at different downstream monitoring stations has simplified some of the problems inherent in evaluating analyses of samples collected from different water masses during a typical sampling run. The absolute concentrations of chloride, nitrite plus nitrate, total phosphorous, dissolved oxygen, BOD, and COD are all strongly dependent on processes occurring upriver. Nonpoint influx of materials from agricultural wastes and natural plant debris may be the dominant upstream sources of N, P, BOD, and COD. Increases in chloride and phosphorous downstream within the Lower Mississippi appear to be caused by discharge of industrial wastes. Nitrogen fluxes decrease downriver, except where there is local discharge of high-N, high-P industrial waste water, possibly from fertilizer plants. Removal of N and increases in BOD may be due in part to biological uptake. High river discharge rates and efficient, natural processes of reaeration maintain high oxygen saturation levels. With the exception of an increase in bacterial count, the discharge of municipal waste into the Mississippi River in Louisiana appears to have had no significant effect on water quality, a finding consistent with the earlier U.S. Geological Survey study of Wells (1980). It would be highly desirable for future mass balance studies if existing water quality programs on the Mississippi River were to adopt a Lagrangian sampling approach.     

An organic carbon budget for the Mississippi River turbidity plume and plume contributions to air-sea CO2 fluxes and bottom water hypoxia

We investigated seasonal variability in organic carbon (OC) budgets using a physical-biological model for the Mississippi River turbidity plume. Plume volume was calculated from mixed layer depth and area in each of four salinity subregions based on an extensive set of cruise data and satellite-derived suspended sediment distributions. These physical measurements were coupled with an existing food web model to determine seasonally dependent budgets for labile (reactive on time scales of days to weeks) OC in each salinity subregion. Autochthonous gross primary production (GPP) equaled 1.3×10¹² g C yr⁻¹ and dominated labile OC inputs (88% of the budget) because riverine OC was assumed mostly refractory (nonreactive). For perspective, riverine OC inputs amounted to 3.9×10¹² g C yr⁻¹, such that physical inputs were 3 times greater than biological inputs to the plume. Annually, microbial respiration (R) accounted for 65% of labile OC losses and net metabolism (GPP—R) for the entire plume was, autotrophic, equaling 5.1×10¹¹ g C yr⁻¹. Smaller losses of labile OC occurred via sedimentation (20%), advection (10%), and export to higher trophic levels (5%). In our present model, annual losses of labile OC are 10% higher than inputs, indicating future improvements are required. Application of our model to estimate air-sea carbon dioxide (CO₂) fluxes indicated the plume was a net sink of 2.0×10⁹ mol CO₂ yr⁻¹, of which 90% of the total drawdown was from biotic factors. In all seasons, low salinity waters were a source of CO₂ (pCO₂=560–890 μatm), and intermediate to high salinity waters were a sink of CO₂ (pCO₂=200–370 μatm). Our model was also used to calculate O₂ demand for the development, of regional hypoxia, and our spring and early summer budgets indicated that sedimentation of autochthonous OC from the immediate plume contributed 23% of the O₂ demand necessary for establishment of hypoxia in the region.     

Methane-derived carbonate cements in barrier and beach sands of a subtropical delta complex

Highly negative δC¹³ values, ?18 to ? 40%., for carbonate cements found in Recent barrier and beach sands of the Mississippi River Delta complex strongly suggest that considerable carbon is furnished to the CaCO₃ cements by either chemical or biological oxidation of CH₄. These cemented sands are commonly found on beaches of the Chandeleur barrier island chain and other sites along the Louisiana coast where Holocene sands are rapidly transgressing over highly organic marsh deposits. Generation of CH₄ from underlying anoxic marsh sediments, followed by vertical migration and oxidation to CO₂ in the porous overlying sand, appears to be the unique set of conditions regulating this process of carbonate cementation.     

Biodegradation of riverine dissolved organic carbon in five estuaries of the southeastern United States

The biological turnover of riverine dissolved organic carbon (DOC) discharged into five southeastern United States estuaries was examined in long-term respiration bioassays. Measures of bacterial oxygen consumption indicated surprisingly large differences in the inherent biodegradability of DOC among the five estuaries, despite their close geographic proximity. Differences of up to 13-fold in biodegradation rates were also found temporally within a single estuary. For most of the southeastern United States estuaries, measured rates of riverine DOC biodegradation were low relative to rates reported for other freshwater and marine environments. This was particularly true for the coastal plain (“blackwater”) rivers that contribute about 35% of the riverine DOC exported to coastal marine environments in this region; extrapolation of biodegradation rates to the adjacent continental shelf predict biodegradation of a maximum of 11% of exported blackwater DOC within the estuary-shelf system (with transit times of up to 140 d). DOC from Piedmont rivers was more biologically labile, with maximum losses of 30% predicted within the estuary and adjacent shelf. Short exposures to natural sunlight increased the lability of the riverine DOC and enhanced biodegradation rates by over 3-fold in some cases, although significant inter-estuary differences in susceptibility of riverine DOC to photolysis were also evident. *** DIRECT SUPPORT *** A01BY085 00007     

Marsh-water column interactions in two Louisiana estuaries. II. Nutrient dynamics

The exchange of dissolved nutrients between marshes and the inundating water column was measured using throughflow marsh flumes built, in two microtidal Louisiana estuaries: the Barataria Basin estuary and Fourleague Bay. The flumes were sampled between September 1986 and April 1988, coincident with an extended period of low sea level on the Louisiana coast. The Barataria Basin estuary is in the later, deteriorating stage of the deltaic cycle, characterized by low freshwater inputs and subsiding marshes. Both brackish and saline marshes supplied dissolved organic nitrogen (DON), inorganic nitrogen (ammonium + nitrate + nitrite = DIN), dissolved organic carbon (DOC), and total nitrogen (as total Kjeldahl nitrogen = TKN) to the water column. The export of DIN is probably related to the N accumulated in earlier stages of deltaic development and released as these marshes deteriorate. Coastal brackish marshes of Fourleague, Bay, part of an accreting marsh system in an early, developmental stage of the deltaic cycle, exported TKN to the open water estuary in all samplings. This marsh apparently acted as a short-term buffer of DIN by taking up NH₄ ⁺ in spring, when baywide concentrations were high, and supplying DIN to the estuary in summer and fall, when concentrations, in the bay were lower. Differences in phosphorus (P), DOC, and DON fluxes between these two estuaries were also observed. The Fourleague Bay site exported soluble reactive phosphorus (SRP) and total phosphorus (TP) and imported DOC. This P export may be related to remobilization of sediment-bound riverine P by the reducing, soils of the marshes. Fluxes of SRP at the Barataria Basin sites were variable and low while DOC was imported. Most imports of dissolved nutrients were correlated with higher upstream [source] concentrations, and flux rates were fairly consistent throughout the tide. Dissolved nutrient exports, did not correlate with upstream concentrations, though, and in many cases the flux was dominated by early, flood tide nutrient release. This pulsed behavior may be caused by rapid diffusion from the sediments early in the tidal cycle, when the sediment-water concentration gradient is largest. Interestuary differences were also seen in particulate organic matter fluxes, as the Fourleague Bay marsh exported POC and PON during all samplings while Barataria Basin imported these nutrients. In general, the magnitude and direction of nutrient exchanges in Louisiana marshes, seem to reflect the deltaic successional stage of the estuary.