The contribution of agricultural and urban activities to inorganic carbon fluxes within temperate watersheds

The lateral transport of bicarbonate as dissolved inorganic carbon (DIC) to the oceans is an integral component of the global carbon budget and can represent the sequestration of CO₂ from the atmosphere. Recently studies have implicated land use change, in particular agricultural development, as an accelerator of bicarbonate export. However, due to the co-variation of land use, bedrock and surficial geologies, and the relationship between bicarbonate export and climate, the impact of anthropogenic activities on DIC export remains an important research question. In order to examine the land use controls on DIC export from small temperate watersheds we sampled 19 streams draining catchments of varying land uses with similar bedrock and surficial geologies. In addition to an agricultural effect, there was a strong correlation between the percent of watershed in urban development and DIC concentrations and DIC yields. Urban watersheds exported 7.8 times more DIC than their nearby forested counterparts and 2.0 times more DIC than nearby agricultural catchments. Isotopic data suggest that excess DIC export from altered systems results from increased chemical weathering, enhanced CO₂ production within urban green spaces, and as a result of organic matter loading from septic systems and leaky sewer lines. Furthermore, we found that nitrogen additions (e.g. fertilizers and manure) are aiding in the dissolution of lime, increasing the total export of DIC from agricultural watersheds. Calculated anthropogenic loading rates ranged from 0.43 to 0.86 mol C m^− 2 yr^− 1. These loading rates suggest that a significant portion of global DIC export might be attributable to human activities, although the impacts on CO₂ sequestration are difficult to determine.     

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.     

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.     

Variability of continental riverine freshwater and nutrient inputs into the North Sea for the years 1977–2000 and its consequences for the assessment of eutrophication

We determined the monthly and annual riverine freshwater, nitrogen (N) and phosphorus (P) loading into the North Sea from Belgium, The Netherlands, and Germany for the years 1977–2000. An average of 133 km³ yr⁻¹ of the 309 km³ yr⁻¹ precipitation into the watershed is carried by the rivers into the sea. Total freshwater discharge fluctuates with a strong 6–7 yr periodicity, is strongly correlated with precipitation, and exhibits a slight long-term decrease. The temporal changes of regional patterns of precipitation lead to changing ratios of annual discharge of the western rivers compared to the eastern rivers, varying between 2.2 and 3.5. The long-term oscillations in discharge were more pronounced as discharge increased. The annual means of total and dissolved inorganic N and P loads were estimated to be 722 and 582 kt N yr⁻¹ and 48 and 26 kt P yr⁻¹, respectively. The monthly N loads were much more strongly correlated with discharge, compared to the monthly P loads. Total N and P as well as dissolved inorganic N also demonstrated a 6–7 yr periodicity. The annual N loads decreased by about 17 kt N yr⁻¹ from 1977 to 2000. The total phosphorus and phosphate loads decreased from about 80 and 50 kt P yr⁻¹ in the 1980s to 25 and 12 kt P yr⁻¹, respectively, in the 1990s. The western rivers contributed the major part of the nutrient loads. The long-term oscillations in their nutrient loads were much more pronounced, compared to the eastern rivers. The area-specific loading rates estimated for all rivers are comparable to earlier estimates using shorter data records, smaller sample sizes, and a less complete watershed monitoring program. The monthly and annual average N:P ratios and their variability increased considerably for individual rivers during the study interval. These results confirm that the water quality of European continental rivers is strongly influenced by intense land use. They demonstrate the necessity for using long time series monitoring results to assess change and evaluate the effects of climate change on the North Sea coastal ecosystems, using ecosystem models on decadal time scales.     

Global Nitrogen Cycle: Pre-Anthropocene Mass and Isotope Fluxes and the Effects of Human Perturbations

We present a nitrogen cycle model for pre-industrial times based on an extensive literature database. The model consists of 18 reservoirs in the domains of the atmosphere, land, and ocean. The biotic reservoirs on land and in the ocean (N-fixing plants, non-N-fixing plants, and marine biota) interact with atmospheric N₂ and dissolved inorganic nitrogen (DIN, consisting of N₂, NO₃ ^?, and NH₄ ⁺) in the ocean and soil waters. Marine DIN is taken up by marine biota and transformed from ocean particulate organic matter to dissolved organic nitrogen and the ocean sediment. The atmosphere, the largest nitrogen reservoir, supplies N₂ to the system by N fixation, deposition, and dissolution, and these input fluxes are balanced by denitrification and volatilization back to the atmosphere. The land and ocean domains are linked by river transport, which carries both dissolved and particulate nitrogen to the oceanic coastal zone. The isotope–mass balances of the N reservoirs are calculated from the isotopic composition of the reservoirs and the fractionation factors accompanying the fluxes between the reservoirs based on reported values from different natural conditions. The model sensitivity was tested for different biouptake rates and was run with various human perturbations, including fertilization, nitrous oxide emissions, population-related sewage disposal, land-use changes, and temperature-dependent rate kinetics. The new N mass–isotope cycle model provides the basis for assessment of the impact of artificial fertilization between 1700 and 2050. The perturbation experiments in this study suggest that land-use change is the key factor altering the N mass cycle since industrialization.     

The role of hydrology in annual organic carbon loads and terrestrial organic matter export from a midwestern agricultural watershed

Defining the control that hydrology exerts on organic carbon (OC) export at the watershed scale is important for understanding how the source and quantity of OC in streams and rivers is influenced by climate change or by landscape drainage. To this end, molecular (lignin phenol), stable carbon isotope, and dissolved organic carbon (DOC) data were collected over a range of flow conditions to examine the influence of hydrology on annual OC export from an 850 km² Midwestern United States agricultural watershed located in west central Indiana. In years 2002 and 2003, modeled annual DOC loads were 19.5 and 14.1 kg ha⁻¹yr⁻¹, while 71% and 85%, respectively, of the total annual OC was exported in flow events occurring during less than 20% of that time. These results highlight the importance of short-duration, high-discharge events (common in smaller watersheds) in controlling annual OC export. Based on reported increases in annual stream discharge coupled with current estimates of DOC export, annual DOC loads in this watershed may have increased by up to 40% over the past 50 years. Molecular (lignin phenol) characterization of quantity and relative degradation state of terrestrial OC shows as much temporal variability of lignin parameters (in high molecular weight dissolved organic carbon) in this one watershed as that demonstrated in previously published studies of dissolved organic matter in the Mississippi and Amazon Rivers. These results suggest that hydrologic variability is at least as important in determining the nature and extent of OC export as geographic variability. Moreover, molecular and bulk stable carbon isotope data from high molecular weight dissolved organic carbon and colloidal organic carbon showed that increased stream flow from the study watershed was responsible for increased export of agriculturally derived OC. When considered in the context of results from other studies that show the importance of flood events and in-stream processing of terrestrial organic carbon, our results show how hydrologic variability in smaller watersheds can reflect landscape-scale carbon dynamics in ways that cannot necessarily be measured at the outlets of large rivers due to multiple source signals and attenuated hydrology.     

Dynamics of NH4 + and NO3 − uptake in the water column of the Neuse River Estuary,North Carolina

In an attempt to more fully understand the dissolved inorganic nitrogen dynamics of the Neuse River estuary, ¹⁵NH₄ ⁺ and ¹⁵NO₃ ^? uptake rates were measured and daily depth-integrated rates calculated for seven stations distributed along the salinity gradient. Measurements were made at 2–3-wk intervals from March 1985 to February 1989. Significant dark NH₄ ⁺ uptake occurred and varied both spatially and seasonally, accounting for as much as 95% of light uptake with the median being 33%. Apparent NH₄ ⁺ uptake ranged from 0.001 μmol N 1^?1 h^?1 to 4.2 μmol N 1^?1 h^?1, with highest rates occurring during late summer-fall in the oligohaline estuary. Apparent NH₄ ⁺ uptake was significantly related to NH₄ ⁺ concentration (p<0.01); however, the regression explained <3% of the variation. Daily-integrated NH₄ ⁺ uptake ranged from 0.1 mmol N m^?2 d^?1 to 133 mmol N m^?2 d^?1 and followed the trend of apparent uptake. Annual NH₄ ⁺ uptake of the estuary was significantly lower in 1988 than for any other year. Dark uptake of NO₃ ^? was only 14% of maximum light uptake. Apparent NO₃ ^? uptake rates ranged from 0.001 μmol N 1^?1 h^?1 to 1.84 μmol N 1^?1 h^?1 with highest rates occurring in the oligohaline estuary. Apparent NO₃ ^? uptake was significantly related to NO₃ ^? concentration (p<0.01); however, the regression explained <5% of the variation. In general, NO₃ ^? uptake was only 20% of total dissolved inorganic nitrogen (DIN) uptake. Daily-integrated NO₃ ^? uptake ranged from 0.1 mmol N m^?2 d^?1 to 53 mmol N m^?2 d^?1 and followed similar patterns of apparent uptake. Annual NH₄ ⁺ uptake was 11.39 mol N m^?2 yr^?1, 10.28 mol N m^?2 Yr^?1, 10.93 mol N m^?2 yr^?1, and 7.38 mol N m^?2 yr^?1, and 1.84 mol N m^?2 yr^?1, with the 4-yr mean being 10.0. Annual NO₃ ^? uptake was 3.12 mol N m^?2 yr^?1, 3.40 mol N m^?2 yr^?1, 1.96 mol N m^?2 yr^?1, and 1.84 mol N m^?2 yr^?1, with the 4-yr mean being 2.6. The total annual DIN uptake was more than twice published estimates of phytoplankton DIN demand, indicating that there is an important heterotrophic component of DIN uptake occurring in the water column. The extrapolation of nitrogen demand from primary productivity results in serious underestimates of estuarine nitrogen demand for the Neuse River estuary and may be true for other estuaries as well.     

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.     

Atmospheric input of inorganic nitrogen to Delaware Bay

The coastal waters of the mid-Atlantic region of the United States receive inputs of atmospheric pollutants as a consequence of being located downwind from major industrial and urban emissions. These inputs are potentially the largest received by any marine area of the country. Of current interest is the atmospheric input of dissolved inorganic nitrogen (DIN = NO₃ ^?+NH₄ ⁺). We have conducted a first-order examination of the magnitude of atmospheric DIN deposition relative to other large-scale inputs for Delaware Bay, a partially urbanized mid-Atlantic coastal plain estuary. The following loading terms: direct atmospheric deposition, indirect atmospheric loading, urban point discharges, fluvial input, benthic flux, and salt marsh export were evaluated. On an annual basis, municipal-industrial effluents provide a dominant source (ca. 40%) of the DIN inputs to the estuary. Total (wet plus dry) atmospheric deposition accounts for about 15% of the total annual DIN inputs. However, during summer, which is characterized by low river-flow and seasonally maximum atmospheric loading, this figure increases to around 25%. Although atmospheric input can satisfy only a fraction of the primary production demands, this summer flux may represent an ecologically important source of external DIN, half of which is directly deposited to surface photic zones where it is readily available for biological uptake.     

Nitrogen flow and the interaction of Boston harbor with Massachusetts Bay

This paper summarizes evidence that most of the considerable nitrogen loading (～8, 470 mmol total N m^?2 yr^?1) to Boston Harbor (Massachusetts, USA) is expelled to shallow shelf waters of Massachusetts Bay, where it strongly influences ecological dynamics. Examination of nitrogen concentrations in the harbor, compared with loading, indicated that removal processes are active in the harbor. Comparison to other estuarine systems showed that the harbor’s nitrogen concentrations are consistent with its loading, if they are corrected for tidal flushing effects on the water residence time. Furthermore, extensive measurements of sediment denitrification confirmed that rates of N₂ gas loss are high in an absolute sense (～600–800 mmol N m^?2 yr^?1) but nonetheless remove only a small portion (<10%) of the annual land-derived nitrogen loading. Burial in sediments apparently removes only about 2% of the N input, implying export to offshore environments as the major removal process (～88–90% of N input). Western Massachusetts Bay receiving waters were examined for a signature of export from the harbor. Data consistently show a gradient of decreasing nitrogen concentrations from the harbor to about 10–20 km into the bay. In many cases, plots of nitrogen concentrations versus salinity show nearly conservative mixing character, which implies virtual export. Seasonally, the data suggest most of the export from the harbor in winter is as dissolved inorganic forms (NH₄ ⁺, NO₃ ^?, NO₂ ^?). In summer, export is dominated by the outflow of organic nitrogen forms. Chlorophyll export is evident as well, suggesting that the nutritional coupling of the harbor and bay in summer involves organic fertilization of the bay’s surface water. Finally, high-resolution studies over different stages of the tidal cycle help refine understanding of the advection of chlorophyll and stimulation of in situ chlorophyll growth at the seaward edge of the tidal excursion into the bay.     

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.     

Do we have enough pieces of the jigsaw to integrate CO2 fluxes in the coastal ocean?

Annually integrated air-water CO₂ flux data in 44 coastal environments were compiled from literature. Data were gathered in 8 major ecosystems (inner estuaries, outer estuaries, whole estuarine systems, mangroves, salt marshes, coral reefs, upwelling systems, and open continental shelves), and up-scaled in the first attempt to integrate air-water CO₂ fluxes over the coastal ocean (26×10⁶ km²), taking into account its geographical and ecological diversity. Air-water CO₂ fluxes were then up-scaled in global ocean (362×10⁶ km²) using the present estimates for the coastal ocean and those from Takahashi et al. (2002) for the open ocean (336×10⁶ km²). If estuaries and salt marshes are not taken into consideration in the up-scaling, the coastal ocean behaves as a sink for atmospheric CO₂(−1.17 mol C m⁻² yr⁻¹) and the uptake of atmospheric CO₂ by the global ocean increases by 24% (−1.93 versus −1.56 Pg C yr⁻¹). The inclusion of the coastal ocean increases the estimates of CO₂ uptake by the global ocean by 57% for high latitude areas (−0.44 versus −0.28 Pg C yr⁻¹) and by 15% for temperate latitude areas (−2.36 versus −2.06 Pg C yr⁻¹) At subtropical and tropical latitudes, the contribution from the coastal ocean increases the CO₂ emission to the atmosphere from the global oceam by 13% (0.87 versus 0.77 Pg C yr⁻¹). If estuaries and salt marshes are taken into consideration in the upscaling, the coastal ocean behaves as a source for atmospheric CO₂ (0.38 mol C m⁻² yr⁻¹) and the uptake of atmospheric CO₂ from the global ocean decreases by 12% (−1.44 versus −1.56 Pg C yr⁻¹) At high and subtropical and tropical latitudes, the coastal ocean behaves as a source for atmospheric CO₂ but at temperate latitudes, it still behaves as a moderate CO₂ sink. A rigorous up-scaling of air-water CO₂ fluxes in the coastal ocean is hampered by the poorly constrained estimate of the surface area of inner estuaries. The present estimates clearly indicate the significance of this biogeochemically, highly active region of the biosphere in the global CO₂ cycle.     

Scales of nutrient-limited phytoplankton productivity in Chesapeake Bay

The scales on which phytoplankton biomass vary in response to variable nutrient inputs depend on the nutrient status of the plankton community and on the capacity of consumers to respond to increases in phytoplankton productivity. Overenrichment and associated declines in water quality occur when phytoplankton growth rate becomes nutrient-saturated, the production and consumption of phytoplankton biomass become uncoupled in time and space, and phytoplankton biomass becomes high and varies on scales longer than phytoplankton generation times. In Chesapeake Bay, phytoplankton growth rates appear to be limited by dissolved inorganic phosphorus (DIP) during spring when biomass reaches its annual maximum and by dissolved inorganic nitrogen (DIN) during summer when phytoplankton growth rates are highest. However, despite high inputs of DIN and dissolved silicate (DSi) relative to DIP (molar ratios of N∶P and Si∶P>100), seasonal accumulations of phytoplankton biomass within the salt-intruded-reach of the bay appear to be limited by riverine DIN supply while the magnitude of the spring diatom bloom is governed by DSi supply. Seasonal imbalances between biomass production and consumption lead to massive accumulations of phytoplankton biomass (often>1,000 mg Chl-a m^?2) during spring, to spring-summer oxygen depletion (summer bottom water <20% saturation), and to exceptionally high levels of annual phytoplankton production (>400 g m^?2 yr^?1). Nitrogen-dependent seasonal accumulations of phytoplankton biomass and annual production occur as a consequence of differences in the rates and pathways of nitrogen and phosphorus cycling within the bay and underscore the importance of controlling nitrogen inputs to the mesohaline and lower reaches of the bay.     

Erosion balance in the watersheds of the western Paris Basin by high-frequency monitoring of discharge and suspended sediment in surface water

An accurate quantification of erosion, based on high-frequency monitoring of river discharge and suspended sediment fluxes is proposed for two watersheds in the western Paris Basin, a sensitive area with respect to erosion phenomena. This continuous monitoring makes it possible to include flood events of short duration, but significant erosion potential. The obtained erosion rate (16 and 21 t?km^?2?yr^?1) is among the weakest of the planet (3.5 to 18?000 t?km^?2?yr^?1). However, this annual balance does not reflect the behaviour of these rivers which can be torrential in certain cases. To cite this article: B. Laignel et al., C. R. Geoscience 338 (2006).     

Inorganic nitrogen dynamics in intertidal rocky biofilms and sediments of the Douro River estuary (Portugal)

In this study rates of oxygen, ammonium (NH₄ ⁺), nitrate (NO₃ ⁻), nitrite (NO₂ ⁻), and nitrous oxide (N₂O) fluxes, nitrogen (N) fixation, nitrification, and denitrification were compared between two intertidal sites for which there is an abundant global literature, muddy and sandy sediments, and two sites representing the rocky intertidal zone where biogeochemical processes have scarcely been investigated. In almost all sites oxygen production rates greatly exceeded oxygen consumption rates. During daylight, NH₄ ⁺ and NO₃ ⁻ uptake rates together with ammonification could supply the different N requirements of the primary producer communities at all four sites; N assimilation by benthic or epilithic primary producers was the major process of dissolved inorganic nitrogen (DIN) removal; N fixation, nitrification, and denitrification were minor processes in the overall light DIN cycle. At night, distinct DIN cycling processes took place in the four environments, denitrification rates ranged from 9 ± 2 to 360 ± 30 μmol N₂ m⁻² h⁻¹, accounting for 10–48% of the water column NO₃ ⁻ uptake; nitrification rates varied from 0 to 1712 ± 666 μmol NH₄ ⁺ m⁻² h⁻¹. A conceptual model of N cycle dynamics showed major differences between intertidal sediment and rocky sites in terms of the mean rates of DIN net fluxes and the processes involved, with rocky biofilm showing generally higher fluxes. Of particular significance, the intertidal rocky biofilms released 10 times the amount of N₂O produced in intertidal sediments (up to 17 ± 6 μmol N₂O m⁻² h⁻¹), representing the highest N₂O release rates ever recorded for marine systems. The biogeochemical contributions of intertidal rocky substrata to estuarine and coastal processes warrant future detailed investigation.     

Non-conservative P and N fluxes and net ecosystem production in San Quintin Bay,México

San Quintin Bay, Mexico, is a hypersaline coastal lagoon where the main external forcing of physical and biogeochemical processes is oceanic. Non-conservative fluxes of inorganic N (ΔDIN) and P (ΔDIP), and aspects of net ecosystem metabolism were studied in this lagoon during August 1995, August 1996, and February 1996, by following the LOICZ budgetary modeling approach. The whole-system water exchange time during summer (≈13 d) was shorter than in winter (≈26 d) as northwesterly winds enhancing mixing with the ocean are more intense during the spring-summer upwelling season. Whole-bay ΔDIP values of +0.2 to +0.3 mmol m^?2 d^?1 in August, and <+0.01 mmol m^?2 d^?1 in February indicate that the system is a net source of dissolved inorganic phosphorus (DIP). DIP fluxes from the Bay to the ocean during August are probably balanced by a net import of particulate organic matter between 1,000–1,300 × 10³ mol C d^?1, equivalent to a net ecosystem production (NEP) between ?24 and ?31 mmol C m^?2 d^?1. ΔDIN showed opposite trends in August 1995 and August 1996, with a net import of 13×10³ mol N d^?1 and a net export of 30× 10³ mol N d^?1, respectively. However, N fixation minus denitrification (“apparent denitrification”) estimates of ≈?4 mmol N m^?2 d^?1 in both periods indicate that San Quintin Bay is a net sink of nitrogen. Results from a 3-box model indicate that during summer Box C, adjacent to the ocean, contributed 70–80% of the excess DIP produced in the whole-system. This observation and high apparent denitrification values of ≈?7 mmol N m^?2 d^?1 at the entrance of the Bay, suggest that the net heterotrophic condition of San Quintin Bay in summer is largely determined by imports of labile phytoplanktonic carbon generated in the adjacent ocean during upwelling.A net flux of organic carbon of 30×10⁶ mol C yr^?1 was estimated from Box C, adjacent to the ocean, to Box B, locally known as Bahia Falsa, which is the area designated for oyster aquaculture in the lagoon. It is estimated that this net organic carbon supply is almost equivalent to the annual oyster food demand; our estimate is that oyster aquaculture in San Quintin Bay accounts for the vast majority of the net heterotrophy of Bahia Falsa.     

Iron and other transition metals in Patagonian riverborne and windborne materials: geochemical control and transport to the southern South Atlantic Ocean

The bulk of particulate transition metals transported by Patagonian rivers shows an upper crustal composition. Riverine particulate 0.5 N HCl leachable trace metal concentrations are mainly controlled by Fe-oxides. Complexation of Fe by dissolved organic carbon (DOC) appears to be an important determinant of the phases transporting trace metals in Patagonian rivers. In contrast, aeolian trace elements have a combined crustal and anthropogenic origin. Aeolian materials have Fe, Mn, and Al contents similar to that found in regional topsoils. However, seasonal concentrations of some metals (e.g., Co, Pb, Cu, and Zn) are much higher than expected from normal crustal weathering and are likely pollutant derived.We estimate that Patagonian sediments are supplied to the South Atlantic shelf in approximately equivalent amounts from the atmosphere (∼30 × 10⁶ T yr⁻¹) and coastal erosion (∼40 × 10⁶ T yr⁻¹) with much less coming from the rivers (∼2.0 × 10⁶ T yr⁻¹). Low trace metal riverine fluxes are linked to the low suspended particulate load of Patagonian rivers, inasmuch most of it is retained in pro-glacial lakes as well as in downstream reservoirs. Based on our estimation of aeolian dust fluxes at the Patagonian coastline, the high nutrient-low chlorophyll sub Antarctic South Atlantic could receive 1.0 to 4.0 mg m⁻² yr⁻¹ of leachable (0.5 N HCl) Fe. Past and present volcanic activity in the southern Andes—through the ejection of tephra—must be highlighted as another important source of Fe to the South Atlantic Ocean. Based on the 1991 Hudson volcano eruption, it appears that volcanic events can contribute several thousand-fold the mass of “leachable” Fe to the ocean as is introduced by annual Patagonian dust fallout.     

Bioavailable iron in the Southern Ocean: the significance of the iceberg conveyor belt

Productivity in the Southern Oceans is iron-limited, and the supply of iron dissolved from aeolian dust is believed to be the main source from outside the marine reservoir. Glacial sediment sources of iron have rarely been considered, as the iron has been assumed to be inert and non-bioavailable. This study demonstrates the presence of potentially bioavailable Fe as ferrihydrite and goethite in nanoparticulate clusters, in sediments collected from icebergs in the Southern Ocean and glaciers on the Antarctic landmass. Nanoparticles in ice can be transported by icebergs away from coastal regions in the Southern Ocean, enabling melting to release bioavailable Fe to the open ocean. The abundance of nanoparticulate iron has been measured by an ascorbate extraction. This data indicates that the fluxes of bioavailable iron supplied to the Southern Ocean from aeolian dust (0.01–0.13 Tg yr^-1) and icebergs (0.06–0.12 Tg yr^-1) are comparable. Increases in iceberg production thus have the capacity to increase productivity and this newly identified negative feedback may help to mitigate fossil fuel emissions.     

Development and carbon sequestration of tropical peat domes in south-east Asia: links to post-glacial sea-level changes and Holocene climate variability

Tropical peatlands of SE-Asia represent a significant terrestrial carbon reservoir of an estimated 65 Gt C. In this paper we present a comprehensive data synthesis of radiocarbon dated peat profiles and 31 basal dates of ombrogenous peat domes from the lowlands of Peninsular Malaysia, Sumatra and Borneo and integrate our peatland data with records of past sea-level and climate change in the region. Based on their developmental features three peat dome regions were distinguished: inland Central Kalimantan (Borneo), Kutai basin (Borneo) and coastal areas across the entire region. With the onset of the Holocene the first peat domes developed in Central Kalimantan as a response to rapid post-glacial sea-level rise over the Sunda Shelf and intensification of the Asian monsoon. Peat accumulation rates in Central Kalimantan strongly declined after 8500 cal BP in close relation to the lowering rate of the sea-level rise and possibly influenced by the regional impact of the 8.2 ka event. Peat growth in Central Kalimantan apparently ceased during the Late Holocene in association with amplified El Niño activity as exemplified by several truncated peat profiles. Peat domes from the Kutai basin are all younger than ～8300 cal BP. Peat formation and rates of peat accumulation were driven by accretion rates of the Mahakam River and seemingly independent of climate. Most coastal peat domes, the largest expanse of SE-Asian peatlands, initiated between 7000 and 4000 cal BP as a consequence of a Holocene maximum in regional rainfall and the stabilisation and subsequent regression of the sea-level. These boundary conditions induced the highest rates of peat accumulation of coastal peat domes. The Late Holocene sea-level regression led to extensive new land availability that allowed for continued coastal peat dome formation until the present. The time weighted mean Holocene peat accumulation rate is 0.54 mm yr^?1 for Central Kalimantan, 1.89 mm yr^?1 for Kutai and 1.77 mm yr^?1 for coastal domes of Sumatra and Borneo. The mean Holocene carbon sequestration rates amount to 31.3 g C m^?2 yr^?1 for Central Kalimantan and 77.0 g C m^?2 yr^?1 for coastal sites, which makes coastal peat domes of south-east Asia the spatially most efficient terrestrial ecosystem in terms of long term carbon sequestration.     

Strontium isotope geochemistry of groundwaters and streams affected by agriculture,Locust Grove,MD

The effects of agriculture on the isotope geochemistry of Sr were investigated in two small watersheds in the Atlantic coastal plain of Maryland. Stratified shallow oxic groundwaters in both watersheds contained a retrievable record of increasing recharge rates of chemicals including NO₃⁻, Cl, Mg, Ca and Sr that were correlated with increasing fertilizer use between about 1940 and 1990. The component of Sr associated with recent agricultural recharge was relatively radiogenic (⁸⁷Sr/⁸⁶Sr=0.715) and it was overwhelming with respect to Sr acquired naturally by water–rock interactions in the oxidized, non-calcareous portion of the saturated zone. Agricultural groundwaters that penetrated relatively unoxidized calcareous glauconitic sediments at depth acquired an additional component of Sr from dissolution of early Tertiary marine CaCO₃ (⁸⁷Sr/⁸⁶Sr=0.708) while undergoing O₂ reduction and denitrification. Ground-water discharge contained mixtures of waters of various ages and redox states. Two streams draining the area are considered to have higher ⁸⁷Sr/⁸⁶Sr ratios and NO₃⁻ concentrations than they would in the absence of agriculture; however, the streams have consistently different ⁸⁷Sr/⁸⁶Sr ratios and NO₃⁻ concentrations because the average depth to calcareous reducing (denitrifying) sediments in the local groundwater flow system was different in the two watersheds. The results of this study indicate that agriculture can alter significantly the isotope geochemistry of Sr in aquifers and streams and that the effects could vary depending on the types, sources and amounts of fertilizers added, the history of fertilizer use and groundwater residence times.