Long-Term Changes in Water Quality and Productivity in the Patuxent River Estuary: 1985 to 2003

We conducted a quantitative assessment of estuarine ecosystem responses to reduced phosphorus and nitrogen loading from sewage treatment facilities and to variability in freshwater flow and nonpoint nutrient inputs to the Patuxent River estuary. We analyzed a 19-year dataset of water quality conditions, nutrient loading, and climatic forcing for three estuarine regions and also computed monthly rates of net production of dissolved O₂ and physical transport of dissolved inorganic nitrogen (DIN) and phosphorus (DIP) using a salt- and water-balance model. Point-source loading of DIN and DIP to the estuary declined by 40–60% following upgrades to sewage treatment plants and correlated with parallel decreases in DIN and DIP concentrations throughout the Patuxent. Reduced point-source nutrient loading and concentration resulted in declines in phytoplankton chlorophyll-a (chl-a) and light-saturated carbon fixation, as well as in bottom-layer O₂ consumption for upper regions of the estuary. Despite significant reductions in seaward N transport from the middle to lower estuary, chl-a, turbidity, and surface-layer net O₂ production increased in the lower estuary, especially during summer. This degradation of water quality in the lower estuary appears to be linked to a trend of increasing net inputs of DIN into the estuary from Chesapeake Bay and to above-average river flow during the mid-1990s. In addition, increased abundance of Mnemiopsis leidyi significantly reduced copepod abundance during summer from 1990 to 2002, which favored increases in chl-a and allowed a shift in total N partitioning from DIN to particulate organic nitrogen. These analyses illustrate (1) the value of long-term monitoring data, (2) the need for regional scale nutrient management that includes integrated estuarine systems, and (3) the potential water quality impacts of altered coastal food webs.     

Net Ecosystem Metabolism and Nonconservative Fluxes of Organic Matter in a Tropical Mangrove Estuary, Piauí River (NE of Brazil)

Net ecosystem metabolism (NEM) was measured in the Piauí River estuary, NE Brazil. A mass balance of C, N, and P was used to infer its sources and sinks. Dissolved inorganic carbon (DIC) concentrations and fluxes were measured over a year along this mangrove dominated estuary. DIC concentrations were high in all estuarine sections, particularly at the fluvial end member at the beginning of the rainy season. Carbon dioxide concentrations in the entire estuary were supersaturated throughout the year and highest in the upper estuarine compartment and freshwater, particularly at the rainy season, due to washout effects of carbonaceous soils and different organic anthropogenic effluents. The estuary served as a source of DIC to the atmosphere with an estimated flux of 13 mol CO₂ m^?2 year^?1. Input from the river was 46 mol CO₂ m^?2 year^?1. The metabolism of the system was heterotrophic, but short periods of autotrophy occurred in the lower more marine portions of the estuary. The pelagic system was more or less balanced between auto- and heterotrophy, whereas the benthic and intertidal mangrove region was heterotrophic. Estimated annual NEM yielded a total DIC production in the order of 18 mol CO₂ m^?2 year^?1. The anthropogenic inputs of particulate C, N, and P, dissolved inorganic P (DIP), and DIC were significant. The fluvial loading of particulate organic carbon and dissolved inorganic nitrogen (DIN) was largely retained in two flow regulation and hydroelectric reservoirs, promoting a reduction of C:N and C:P particulate ratios in the estuary. The net nonconservative fluxes obtained by a mass balance approach revealed that the estuary acts as a source of DIP, DIN, and DIC, the latter one being almost equivalent to the losses to the atmosphere. Mangrove forests and tidal mudflats were responsible for most of NEM rates and are the main sites of organic decomposition to sustain net heterotrophy. The main sources for this organic matter are the fluvial and anthropogenic inputs. The mangrove areas are the highest estuarine sources of DIP, DIC, and DIN.     

Atmospheric deposition of nitrogen: Implications for nutrient over-enrichment of coastal waters

Atmospheric deposition of nitrogen (AD-N) is a significant source of nitrogen enrichment to nitrogen (N)-limited estuarine and coastal waters downwind of anthropogenic emissions. Along the eastern U.S. coast and eastern Gulf of Mexico, AD-N currently accounts for 10% to over 40% of new N loading to estuaries. Extension of the regional acid deposition model (RADM) to coastal shelf waters indicates that 11, 5.6, and 5.6 kg N ha⁻¹ may be deposited on the continental shelf areas of the northeastern U.S. coast, southeast U.S. coast, and eastern Gulf of Mexico, respectively. AD-N approximates or exceeds riverine N inputs in many coastal regions. From a spatial perspective, AD-N is a unique source of N enrichment to estuarine and coastal waters because, for a receiving water body, the airshed may exceed the watershed by 10–20 fold. AD-N may originate far outside of the currently managed watersheds. AD-N may increase in importance as a new N source by affecting waters downstream of the oligohaline and mesohaline estuarine nutrient filters where large amounts of terrestrially-supplied N are assimilated and denitrified. Regionally and globally, N deposition associated with urbanization (NO_x, peroxyacetyl nitrate, or PAN) and agricultural expansion (NH₄ ⁺ and possibly organic N) has increased in coastal airsheds. Recent growth and intensification of animal (poultry, swine, cattle) operations in the midwest and mid-Atlantic regions have led to increasing amounts of NH₄ ⁺ emission and deposition, according to a three decadal analysis of the National Acid Deposition Program network. In western Europe, where livestock operations have dominated agricultural production for the better part of this century, NH₄ ⁺ is the most abundant form of AD-N. AD-N deposition in the U.S. is still dominated by oxides of N (NO_x) emitted from fossil fuel combustion; annual NH₄ ⁺ deposition is increasing, and in some regions is approaching total NO₃ ⁻ deposition. In receiving estuarine and coastal waters, phytoplankton community structural and functional changes, associated water quality, and trophic and biogeochemical alterations (i.e, algal blooms, hypoxia, food web, and fisheries habitat disruption) are frequent consequences of N-driven eutrophication. Increases in and changing proportions of various new N sources regulate phytoplankton competitive interactions, dominance, and successional patterns. These quantitative and qualitative aspects of AD-N and other atmospheric nutrient sources (e.g., iron) may promote biotic changes now apparent in estuarine and coastal waters, including the proliferation of harmful algal blooms, with cascading impacts on water quality and fisheries.     

Prehistoric nutrient inputs and productivity in Narragansett Bay

Calculations by others of the preindustrial deposition of inorganic nitrogen from the atmosphere in the area of Narragansett Bay compared with recent measurements suggest that this flux has increased almost 15 times over natural background. On the basis of modern studies of the export of nitrogen and phosphorus from temperate forests, the prehistoric watershed also probably contributed very little reactive N or P to the bay. New information from undisturbed old-growth forests suggests that most of the N that was exported from the watershed was probably associated with refractory dissolved organic matter and thus contributed little to the fertility of the bay. The largest source of reactive dissolved inorganic nitrogen (DIN) and phosphorus (DIP) for Narragansett Bay under prehistoric conditions was the coastal ocean water entrained in the bay in estuarine circulation. The total input of DIN to this estuary has increased about five-fold and the input of total DIP has approximately doubled as a result of human activities. Recent ecosystem-level experiments using large (13 m³, 5 m deep) mesocosms designed as living models of Narragansett Bay showed that the primary production of phytoplankton in the bay is limited by the supply of DIN and that annual phytoplankton production is strongly correlated with the rate of input of DIN. The relationship between DIN input and annual phytoplankton production in the mesocosms is consistent with observations published by others working in 10 different natural marine systems, and a functional regression of the field and experimental data provides a tool to calculate the rate of prehistoric phytoplankton production that would have been associated with the prehistoric DIN input estimates. The result of this calculation suggests that phytoplankton production in the bay has approximately doubled (from about 130 g C m^?2 yr^?1 to 290 g C m^?2 yr^?1 for a baywide average) since the time of European contact. It also seems likely that seagrasses and macroalgae once made a much larger contribution to total system production than they do today.     

Sources of nutrient inputs to the Patuxent River estuary

We quantified annual nutrient inputs to the Patuxent River estuary from point and nonpoint sources and from direct atmospheric deposition. We also compared nonpoint source (NPS) discharges from Piedmont and Coastal Plain regions and from agricultural and developed lands. Using continuous automated-sampling, we measured discharges of water, nitrogen, phosphorus, organic carbon (C), and suspended solids from a total of 23 watersheds selected to represent various proportions of developed land and cropland in the Patuxent River basin and the neighboring Rhode River basin. The sampling period spanned two years that differed in annual precipitation by a factor of 1.7. Water discharge from the watershed to the Patuxent River estuary was 3.4 times higher in the wet year than in the dry year. Annual water discharges from the study watersheds increased as the proportion of developed land increased. As the proportion of cropland increased, there were increases in the annual flow-weighted mean concentrations of nitrate (NO₃ ^?), total nitrogen (TN), dissolved silicate (Si), total phosphate (TPO₄ ^3?), total organic phosphorus (TOP), total P (TP), and total suspended solids (TSS) in NPS discharges. The effect of cropland on the concentrations of NO₃ ^? and TN was stronger for Piedmont watersheds than for Coastal Plain watersheds. As the proportion of developed land increased, there were increases in annual mean concentrations of NO₃ ^?, total ammonium (TNH₄ ⁺), total organic N (TON), TN, total organic C (TOC), TPO₄ ^3?, TOP, TP, and TSS and decreases in concentrations of Si. Annual mean concentrations of TON, TOC, forms of P, and TSS were highest in the wet year. Annual mean concentrations of NO₃ ^?, TNH₄ ⁺, TN, and Si did not differ significantly between years. We directly measured NPS discharges from about half of the Patuxent River basin and estimated discharges from the other half of the basin using statistical models that related annual water flow and material concentrations to land cover and physiographic province. We compared NPS discharges to public data on point source (PS) discharges. We estimated direct atmospheric deposition of forms of N, P, and organic C to the Patuxent River estuary based on analysis of bulk deposition near the Rhode River. During the wet year, most of the total terrestrial and atmospheric inputs of forms of N and P came from NPS discharges. During the dry year, 53% of the TNH₄ ⁺ input was from atmospheric deposition and 58% of the NO₃ ^? input was from PS discharges; NPS and PS discharges were about equally important in the total inputs of TN and TPO₄ ^3?. During the entire 2-yr period, the Coastal Plain portion of the Patuxent basin delivered about 80% of the NPS water discharges to the estuary and delivered similar proportions of the NPS TNH₄ ⁺, TN, TOP, and TSS. The Coastal Plain delivered greater proportions of the NPS TON, TOC, Si, and TP (89%, 90%, 93%, and 95%, respectively) than of water, and supplied nearly all of the NPS TPO₄ ^3? (99%). The Piedmont delivered 33% of the NPS NO₃ ^? while delivering only 20% of the NPS water to the stuary. We used statistical models to infer the percentages of NPS discharges supplied by croplands, developed lands, and other lands. Although cropland covers only 10% of the Patuxent River basin, it was the most important source of most materials in NPS discharge, supplying about 84% of the total NPS discharge of NO₃ ^?; about three quarters of the TPO₄ ^3?, TOP, TP, and TSS; and about half of the TNH₄ ⁺ and TN. Compared to developed land, cropland supplied a significantly higher percentage of the NPS discharges of NO₃ ^?, TN, TPO₄ ^3?, TOP, TP, and TSS, despite the fact development land covered 12% of the basin.     

Nitrogen concentration of rainfall in Dalian, China

Wet atmospheric deposition samples were collected in rainy days from 2004 to 2008 in Dalian of Liaoning Province, Northeast of China, which were measured by rain gauge and analyzed for total inorganic nitrogen (TIN) concentration. The mean annual volume of rainfall was from 438.25 to 850.94 mm, and the concentration of TIN was 3.47 mg/L, which showed negative correlation with the volume of rainfall. The order of TIN concentration among seasons was: winter > spring > autumn > summer. Increased use of fertilizers in agricultural areas or widespread use of private transportation led to the increase of TIN fluxes. Variations of TIN concentration among years were significantly different; the annual precipitation TIN inputs were positively related to the volume of rainfall and were surprisingly high with the deposition flux ranging from 10.24 to 25.17 kg N/(hm²·a). The maximum mean annual flux was 25.17 kg N/(hm²·a) which is equal to 53.94 kg N/(hm²·a) usage of CO(NH)₂ (an amount that could have caused changes in terrestrial life). The fluxes of TIN also showed a different seasonal fluctuation during the course of our study, and we found that majority of TIN deposition occurred in summer (from June to August), which accounted for 56.44% of total annual precipitation and 40.06% of total annual deposition flux. Annual TIN fluxes decreased considerably after the rainy season and reached the lowest level (1.39 kg N/(hm²·a)) in winter.     

CO2 Input Dynamics and Air–Sea Exchange in a Large New England Estuary

Repeated surveys of the Kennebec estuary, a macrotidal river estuary in Maine, USA, between 2004 and 2008 found spatial and temporal variability both in sources of carbon dioxide (CO₂) to the estuary and the air–sea flux of estuary CO₂. On an annual basis, the surveyed area of the Kennebec estuary had an area-weighted average partial pressure of CO₂ (pCO₂) of 559 μatm. The area-weighted average CO₂ flux to the atmosphere was 3.54 mol C m^?2 year^?1. Overall, the Kennebec estuary was an annual source of 7.2?×?10⁷ mol CO₂ to the atmosphere. Distinct seasonality in estuarine pCO₂ was observed, with shifts in the seasonal pattern evident between lower and higher salinities. Fluxes of CO₂ from the estuary were elevated following two summertime storms, and inputs of riverine CO₂ outweighed internal estuarine CO₂ inputs in nearly all months. River and estuarine inputs of CO₂ represented 68 and 32 % of the total CO₂ contributions to the estuary, respectively. This study examines the variability of CO₂ in a large New England estuary, and highlights the comparatively high contribution of CO₂ from riverine sources.     

Seasonal distributions of suspended particulate material and dissolved nutrients in a coastal plain estuary

The temporal and spatial distributions of salinity, dissolved oxygen, suspended particulate material (SPM), and dissolved nutrients were determined during 1983 in the Choptank River, an estuarine tributary of Chesapeake Bay. During winter and spring freshets, the middle estuary was strongly stratified with changes in salinity of up to 5‰ occurring over 1 m depth intervals. Periodically, the lower estuary was stratified due to the intrusion of higher salinity water from the main channel of Chesapeake Bay. During summer this intrusion caused minimum oxygen and maximum NH₄ ⁺ concentrations at the mouth of the Choptank River estuary. Highest concentrations of SPM, particulate carbon (PC), particulate nitrogen (PN), total nitrogen (TN), total phosphorous (TP) and dissolved inorganic nitrogen (DIN) occurred in the upper estuary during the early spring freshet. In contrast, minimum soluble reactive phosphate (SRP) concentrations were highest in the upper estuary in summer when freshwater discharge was low. In spring, PC:PN ratios were >13, indicating a strong influence by allochthonous plant detritus on PC and PN concentrations. However, high concentrations of PC and PN in fall coincided with maximum chlorophyll a concentrations and PC:PN ratios were <8, indicating in situ productivity controlled PC and PN levels. During late spring and summer, DIN concentrations decreased from >100 to <10 μg-at l^?1, resulting mainly from the nonconservative behavior of NO₃ ^?, which dominated the DIN pool. Atomic ratios of both the inorganic and total forms of N and P exceeded 100 in spring, but by summer, ratios decreased to <5 and <15, respectively. The seasonal and spatial changes in both absolute concentrations and ratios of N and P reflect the strong influence of allochthonous inputs on nutrient distributions in spring, followed by the effects of internal processes in summer and fall.     

Chesapeake Bay nutrient and plankton dynamics: III. The annual cycle of dissolved silicon

Silicic acid (H₄SiO₄) flux from the sediment, H₄SiO₄ concentration and river flow were used to obtain an annual dissolved silicon budget for Chesapeake Bay. H₄SiO₄ concentrations vary seasonally in the estuary: for a 12-year period, mean H₄SiO₄ concentrations in the mesohaline region were high both in spring and in late summer to early fall, and were low in late spring—occasionally approaching levels potentially limiting to diatom growth. Most of the annual allochthonous H₄SiO₄ supply to the estuary derives from the three major rivers, but regenerative H₄SiO₄ flux from the sediment to the water column exceeds the total riverine input by a factor of at least five. Sediment H₄SiO₄ efflux exhibits seasonality and averages approximately 2–3 mol Si m^?2 yr^?1. The high rates of sediment dissolution and efflux appear to maintain high levels of H₄SiO₄ in the mesohaline region, and Si-limitation of diatom growth there seems unlikely. The relative rates of biogenic silica formation and dissolution do not vary synchronously: seasonal variations in diatom productivity, sedimentary release of H₄SiO₄ and river flow all contribute to the observed late winter and late summer seasonal maxima and late spring minimum in water column H₄SiO₄ concentrations. If the only source of Si to support sedimentary H₄SiO₄ efflux is biogenic particulate silica recently deposited from the water column and this silica in turn was produced by diatoms in a ratio of 8C:1 Si, the minimum annual primary production by diatoms is at least 260 g C m^?2, approximately half of annual total plankton primary production. This estimate would be revised upwards according to the amount of particulate biogenic silica dissolving in the water column. Burial of biogenic silica amounts to from 2 to 84% of the sediment efflux of H₄SiO₄, depending on location in the bay. On an annual basis, burial represents from 60 to 100% of fluvial H₄SiO₄-Si inputs.     

Global patterns of dissolved inorganic and particulate nitrogen inputs to coastal systems: Recent conditions and future projections

We examine the global distribution of dissolved inorganic nitrogen (DIN) and particulate nitrogen (PN) export to coastal systems and the effect of human activities and natural processes on that export. The analysis is based on DIN and PN models that were combined with spatially explicit global databases. The model results indicate the widely uneven geographic distribution of human activities and rates of nitrogen input to coastal systems at the watershed, latitudinal, and regional-continental scales. Future projections in a business-as-usual scenario indicate that DIN export rates increase from approximately 21 Tg N yr⁻¹ in 1990 to 47 Tg N yr⁻¹ by 2050. Increased DIN inputs to coastal systems in most world regions are predicted by 2050. The largest increases are predicted for Southern and Eastern Asia, associated with predicted large increases in population, increased fertilizer use to grow food to meet the dietary demands of that population, and increased industrialization. Results of an alternative scenario for North America and Europe in 2050 indicate that reductions in the human consumption of animal protein could reduce fertilizer use and result in substantial decreases in DIN export rates by rivers. In another scenario for 2050, future air pollution control in Europe that would reduce atmospheric deposition of nitrogen oxides in watersheds is predicted to decrease DIN export by rivers, particularly from Baltic and North Atlantic watersheds. Results of a newly developed global PN river export model indicate that total global PN and DIN export by rivers in 1990 are similar, even though the global distribution of the two differ considerably.     

Temporal and spatial patterns of trace elements in the Patuxent River: A whole watershed approach

Trace element distributions, partitioning, and speciation were examined at 15 sites in the Patuxent River watershed from May 1995 through October 1997 to determine possible sources of trace elements to the river and estuary, to examine the relationship of the trace element discharges to freshwater discharges as well as to land use and geographic region, to validate previous estimates of loadings to the river, and to provide baseline data for trace elements in the Patuxent River watershed and estuary. Six freshwater sites were examined, representing different basins and geographic provinces, and nine sites along the estuarine salinity gradient. Subregions within the watershed varied considerably in concentrations and areal yields for some elements. Concentrations of As, Cd, Ni, Pb, and Zn were elevated in the Coastal Plain sites compared to the Piedmont sites, while Cu and Hg were more evenly distributed. Cadmium, Cu, Hg, Ni, Pb, and Zn showed overall positive correlations with river flow while As and methylHg (meHg) showed negative correlations with river flow. Concentrations of trace elements in the estuarine portion of the river were generally low, and consistent with mixing between Patuxent River water with elevated concentrations and the lower concentrations of the Chesapeake Bay. Interesting features included a local Cd maximum in the low salinity region of the estuary, probably caused by desorption from suspended sediments, and a significant input of water containing high As concentrations from the Chesapeake Bay and from As being released from bottom sediments in summer. Comparisons between the estimated annual flux of trace elements and the estimates of suspected source terms (atmospheric deposition, urban runoff, and known point sources) suggest that, except for Hg, direct atmospheric deposition is small compared to fluvial loads. Current estimates of trace element inputs from point sources or from urban runoff are inadequate for comparison with other sources, because of inappropriate techniques and/or unacceptably high detection limits. A complete examination of trace element dynamics in the Patuxent River (and in other coastal systems) will require better data for these potential sources.     

Spatial and Temporal Variability of the CO2 Fluxes in a Tropical, Highly Urbanized Estuary

The spatial and temporal variations of the flux of CO₂ were determined during 2007 in the Recife estuarine system (RES), a tropical estuary that receives anthropogenic loads from one of the most populated and industrialized areas of the Brazilian coast. The RES acts as a source of nutrients (N and P) for coastal waters. The calculated CO₂ fluxes indicate that the upstream inputs of CO₂ from the rivers are largely responsible for the net annual CO₂ emission to the atmosphere of +30 to +48 mmol m^?2 day^?1, depending on the CO₂ exchange calculation used, which mainly occurs during the late austral winter and early summer. The observed inverse relationship between the CO₂ flux and the net ecosystem production (NEP) indicates the high heterotrophy of the system (except for the months of November and December). The NEP varies between ?33 mmol m^?2 day^?1 in summer and ?246 mmol m^?2 day^?1 in winter. The pCO₂ values were permanently high during the study period (average ~4,700 μatm) showing a gradient between the inner (12,900 μatm) and lower (389 μatm) sections on a path of approximately 30 km. This reflects a state of permanent pollution in the basin due to the upstream loading of untreated domestic effluents (N/P?=?1,367:6 μmol kg^?1 and pH?=?6.9 in the inner section), resulting in the continuous mineralization of organic material by heterotrophic organisms and thereby increasing the dissolved CO₂ in estuarine waters.     

Groundwater Discharge as a Source of Dissolved Carbon and Greenhouse Gases in a Subtropical Estuary

Groundwater may be highly enriched in dissolved carbon species, but its role as a source of carbon to coastal waters is still poorly constrained. Exports of deep and shallow groundwater-derived dissolved carbon species from a small subtropical estuary (Korogoro Creek, Australia, latitude ?31.0478°, longitude 153.0649°) were quantified using a radium isotope mass balance model (²³³Ra and ²²⁴Ra, natural groundwater tracers) under two hydrological conditions. In addition, air-water exchange of carbon dioxide and methane in the estuary was estimated. The highest carbon inputs to the estuary were from deep fresh groundwater in the wet season. Most of the dissolved carbon delivered by groundwater and exported from the estuary to the coastal ocean was in the form of dissolved inorganic carbon (DIC; 687 mmol m^?2 estuary day^?1; 20 mmol m^?2 catchment day^?1, respectively), with a large export of alkalinity (23 mmol m^?2 catchment day^?1). Average water to air flux of CO₂ (869 mmol m^?2 day^?1) and CH₄ (26 mmol m^?2 day^?1) were 5- and 43-fold higher, respectively, than the average global evasion in estuaries due to the large input of CO₂- and CH₄-enriched groundwater. The groundwater discharge contribution to carbon exports from the estuary for DIC, dissolved organic carbon (DOC), alkalinity, CO₂, and CH₄ was 22, 41, 3, 75, and 100 %, respectively. The results show that CO₂ and CH₄ evasion rates from small subtropical estuaries surrounded by wetlands can be extremely high and that groundwater discharge had a major role in carbon export and evasion from the estuary and therefore should be accounted for in coastal carbon budgets.     

Dissolved Inorganic Nitrogen,Soluble Reactive Phosphorous,and Microbial Pollutant Loading from Tropical Rural Watersheds in Hawai'i to the Coastal Ocean During Non-Storm Conditions

This study quantifies dissolved inorganic nitrogen (DIN), soluble reactive phosphorous (SRP), and microbial pollutant inputs to a tropical embayment, Hanalei Bay, Kaua'i, Hawai'i from rural watersheds during two field excursions during non-storm conditions. We employ land cover analysis and a suite of nucleic acid fecal source tracking markers (host-specific Bacteroidales and human enterovirus) to identify sources of pollutants to the bay. The highest concentrations of DIN and SRP are in streams draining watersheds with large areas of cultivated land, suggesting fertilizer is a source of these nutrients to the streams and coastal waters. Pollutant areal loading correlates with the fractions of urban and cultivated land cover. Microbial source tracking indicates the presence of human, pig, and ruminant feces in the streams. This work provides preliminary evidence that human development affects loading of DIN, SRP, and microbial pollutants to tropical coastal waters; further study is needed to confirm this. Additionally, results point to a mix of microbial pollutant sources.     

Effect of water residence time on annual export and denitrification of nitrogen in estuaries: A model analysis

A simple model of annual average response of an estuary to mean nitrogen loading rate and freshwater residence time was developed and tested. It uses nitrogen inputs from land, deposition from the atmosphere, and first-order calculations of internal loss rate and net export to perform a steady-state analysis over a yearly cycle. The model calculates the fraction of total nitrogen input from land and the atmosphere that is exported and the fraction that is denitrified or lost to other processes within the estuary. The model was tested against data from the literature for 11 North American and European estuaries having a wide range of physical characteristics, nitrogen loading rates, and geographical and climatic settings. The model shows that the fraction of nitrogen entering an estuary that is exported or denitrified can be predicted from the freshwater residence time. The first-order rate constant for nitrogen loss within an estuary, as a fraction of total nitrogen in the water column, is 0.30 mo⁻¹. Denitrification typically accounts for 69–75% of the total annual net nitrogen removal from the water column by processes within the estuary. The model makes explicit the dependence of nitrogen concentration in the water column on the loading rate of nitrogen, water residence time, estuary volume, and the rate constant for loss within the estuary.     

Toward a geochemical mass balance of major elements in Lake Qinghai,NE Tibetan Plateau: A significant role of atmospheric deposition

Sediments in Lake Qinghai archive important information about past environmental changes. In order to faithfully interpret the sediment records and constrain the elemental cycles, it is critical to trace various sources of sediments in the lake. The results show that the elemental input–output budgets are imbalanced for most major elements between riverine fluxes and mass accumulation rate (MAR) of Lake Qinghai sediments. A realistic model must include contributions of dry/wet atmospheric deposition that allow the major element mass balance for the lake to be defined. The budget estimation is based on mass balances of Si and Al, which are relatively immobile and carried to the lake via particulate forms. Estimated annual budget of dry atmospheric deposition is ∼1.3 ± 0.3 × 10³ kt/a (accounting for ∼65% of the total inputs) to the lake sediments, assuming local loess within the catchment as a candidate for dry atmospheric deposition to the lake. The resultant flux of 300 ± 45 g/m²/a falls within the flux average of the desert area (400 g/m²/a) and the loess plateau (250 g/m²/a), consistent with the geographical setting of Lake Qinghai. The role of atmospheric deposition would be more significant if wet deposition via rainfall and snow were taken into account. This highlights the potential importance of dust as a significant source for sediment preservation flux for other catchments worldwide. The results also indicate that nearly all Ca input was preserved in the lake sediments under modern conditions, consistent with Ca²⁺ supersaturation of the lake water.     

The influence of subsurface hydrology on nutrient supply and smooth cordgrass (Spartina alterniflora) production in a developing barrier island marsh

The supply of nutrients from surface and subsurface water flow into the root zone was measured in a developing barrier island marsh in Virginia. We hypothesize that high production of tall-formSpartina alterniflora in the lower intertidal zone is due to a greater nitrogen input supplied by a larger subsurface flux. Individual nitrogen inputs to the tall-form and short-formS. alterniflora root zones were calculated from water flow rates into the root zone and the nutrient concentration corresponding to the source of the flow. Total dissolved inorganic nitrogen (DIN) input (as ammonium and nitrate) was then calculated using a summation of the hourly nutrient inputs to the root zone over the entire tidal cycle based on hydrologic and nutrient data collected throughout the growing season (April–August) of 1993 and 1994. Additionally, horizontal water flow into the lower intertidal marsh was reduced experimentally to determine its effects on nutrient input and plant growth. Total ammonium (NH₄ ⁺) input to the tall-formS. alterniflora root zone (168 μmoles 6 h^?1) was significantly greater relative to the short-form (45 μmoles 6 h^?1) during flood tide. Total NH₄ ⁺ input was not significantly different between growth forms during ebb tide, and total nitrate (NO₃ ^?) and total DIN input were not significantly different between growth forms during either tidal stage. During tidal flooding, vertical flow from below the root zone accounted for 71% and horizontal flow from the adjacent mudflat accounted for 19% of the total NH₄ ⁺ input to the tall-formS. alterniflora root zone. Infiltration of flooding water accounted for 15% more of the total NO₃ ^? input relative to the total NH₄ ⁺ input at both zones on flood tide. During ebb tide, vertical flow from below the root zone still accounted for the majority of NH₄ ⁺ and NO₃ ^? input to both growth forms. After vertical flow, horizontal subsurface flow from upgradient accounted for the next largest percentages of NH₄ ⁺ and NO₃ ^? input to both growth forms during ebb tide. After 2 yr of interrupted subsurface horizontal flow to the tall-formS. alterniflora root zone, height and nitrogen content of leaf tissue of treatment plants were only slightly, but significantly, lower than control plants. The results suggest that a dynamic supply of DIN (as influenced by subsurface water flows) is a more accurate depiction of nutrient supply to macrophytes in this developing marsh, relative to standing stock nutrient concentrations. The dynamic subsurface supply of DIN may play a role in spatial patterns of abovegroundS. alterniflora production, but determination of additional nitrogen inputs and the role of belowground production on nitrogen demand need to also be considered.     

Retention of phosphorus and nitrogen in the Ems estuary

From February 1992 until June 1993, the distribution of dissolved and particulate phosphorus and nitrogen was investigated in the Ems estuary at approximately monthly intervals. Nutrient import was quantified from the river load. Nutrient export to sea was quantified from river discharge and from the salinity-nutrient gradient in the outer estuary. In addition, sediment cores were taken from four sites along the main axis of the estuary in October 1992. On the basis of these data a nitrogen and phosphorus budget was made. On an annual basis, 45 × 10⁶ mol P and 2,360 × 10⁶ mol N are imported into the Ems estuary. Freshwater runoff is the main source of input, accounting for about 92% of the nitrogen input and 71% of the phosphorus input. Import of particulate phosphorus from the sea is important in the phosphorus budget (27%). Seventy-five percent of the nitrogen input is transported to the North Sea. Denitrification is the major loss factor (19% of the nitrogen input), and burial explains 6%. Of the phosphorus input, 60% is transported to the North Sea and 40% accumulates in the sediment. Nitrogen import during summer explains about one third of the annual primary production, indicating that nitrogen turn over is about three times. Phosphorus import during summer explains less than 16% of the annual primary production. We suggest that trapping of particulate P and adsorption onto Fe(oxy)hydroxides during the entire year and the release of Fe-bound P during summer after reduction of Fe(oxy)hydroxides is instrumental in sustaining high primary production, which could not be sustained if it depended only on P imported during the growing season.     

Rates of nitrification along an estuarine gradient in Narragansett Bay

Rates of pelagic nitrification, measured using N-Serve-sensitive [¹⁴C]bicarbonate uptake, varied by as much as an order-of-magnitude among three sites along the salinity gradient of Narragansett Bay (Rhode Island, United States). Rates were always higher at the Providence River estuary site (0.04–11.2 μmol N I^?1 d^?1) than at either the lower Narragansett Bay site (0.02–0.98 μmol N I^?1d^?1) or the freshwater Blackstone River site (0.04–1.7 μmol N I^?1d^?1). Although temperature was the most important variable regulating the annual cycle of nitrification, ammonium concentrations were most likely responsible for the large differences in rates among the three sites in summer. At the levels found in this estuarine system, salinity and concentrations of oxygen or total suspended matter did not appear to have a direct measurable effect on nitrification and pH did only occasionally. Nitrification played an important role in the nitrogen cycle at all three sites. In Narragansett Bay, nitrification contributed 55% of the NO₂ ^? and NO₃ ^? entering annually, and was the major source during spring and summer. Water from offshore was the only other large source of NO₂ ^? and NO₃ ^?, contributing 34%. High summer rates of nitrification could support much of the phytoplankton uptake of NO₂ ^? and NO₃ ^?. In the Providence River estuary, the largest annual input of NO₂ ^? and NO₃ ^? was from rivers (54%), although nitrification (28%) and water from lower portions of the bay (11%) also made large contributions. Again, nitrification was most important in the summer. The high rates of nitrification in the Providence River estuary during summer were also likely to be important in terms of oxygen demand, and the production of nitric and nitrous oxides. In the Blackstone River, NO₂ ^? and NO₃ ^? concentrations increased as the river flowed through Rhode Island, and nitrification was a possible source.     

Nutrient inputs from the watershed and coastal eutrophication in the Florida keys

Widespread use of septic tanks in the Florida Keys increase the nutrient concentrations of limestone groundwaters that discharge into shallow nearshore waters, resulting in coastal eutrophication. This study characterizes watershed nutrient inputs, transformations, and effects along a land-sea gradient stratified into four ecosystems that occur with increasing distance from land: manmade canal systems (receiving waters of nutrient inputs), seagrass meadows, patch reefs, and offshore bank reefs. Soluble reactive phosphorus (SRP), the primary limiting nutrient, was significantly elevated in canal systems compared to the other ecosystems, while dissolved inorganic nitrogen (DIN; NH₄ ⁺ and NO₃ ^?) a secondary limiting nutrient, was elevated both in canal systems and seagrass meadows. SRP and NH₄ ⁺ concentrations decreased to low concentrations within approximately 1 km and 3 km from land, respectively. DIN and SRP accounted for their greatest contribution (up to 30%) of total N and P pools in canals, compared to dissolved organic nitrogen (DON) and dissolved organic phosphorus (DOP) that dominated (up to 68%) the total N and P pools at the offshore bank reefs. Particulate N and P fractions were also elevated (up to 48%) in canals and nearshore seagrass meadows, indicating rapid biological uptake of DIN and SRP into organic particles. Chlorophylla and turbidity were also elevated in canal systems and seagrass meadows; chlorophylla was maximal during summer when maximum watershed nutrient input occurs, whereas turbidity was maximal during winter due to seasonally maximum wind conditions and sediment resuspension. DO was negatively correlated with NH₄ ⁺ and SRP; hypoxia (DO<2.5 mg l^?1) frequently occurred in nutrient-enriched canal systems and seagrass meadows, especially during the warm summer months. These findings correlate with recent (<5 years) observations of increasing algal blooms, seagrass epiphytization and die-off, and loss of coral cover on patch and bank reef ecosystems, suggesting that nearshore waters of the Florida Keys have entered a stage of critical eutrophication.