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.     

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.     

In Situ Response of Phytoplankton to Nutrient Additions in a Tropical Coastal Lagoon, (La Mancha,Veracruz, Mexico)

An experimental in situ microcosm study was conducted in the tropical lagoon La Mancha (Gulf of Mexico) to determine whether or not nutrient limitation occurs and to examine the direct effect of an inorganic nutrient pulse on the phytoplankton community structure. The phytoplankton community response to the addition of four treatments with different combinations of nitrogen (N), phosphorus (P), and silica (Si) (+N-NH₄ ⁺, +P-PO₄ ^?, +Si-SO₃, and N:P16) showed that phytoplankton was N-limited as indicated by an increase in phytoplankton biomass (i.e., chlorophyll a) (range, 8–34 mg m^?3) during the dry season in two consecutive years (2006 and 2007). Picophytoplankton abundance significantly increased in the +N treatment (145.46 10³ cells L^?1), while microphytoplankton reached a maximum abundance (68.38 10³ cells L^?1) in the N:P16 treatment. Phytoplankton composition changed from a community initially dominated by dinoflagellates (e.g., Prorocentrum spp.) to another dominated by diatoms (Thalassiosira and Nitzschia longissima) in the N:P16 treatment. The +N treatment significantly increased Synechococcus sp. growth rates (1.3 divisions per day) (picocyanobacteria). Biomarker pigments measured in the experimental microcosms confirmed observed changes in phytoplankton groups. Our results reveal that La Mancha lagoon is a N-limited coastal system during the dry season and provides evidence of the temporal species successional patterns and mechanisms regulating the phytoplankton community response to nutrient enrichment pulses in this already eutrophic coastal lagoon.     

Kinetics of the (Fe2++OH−)mica→(Fe3++O2−)mica+H oxidation reaction in bulk single-crystal biotite studied by Mössbauer spectroscopy

We report the first kinetic study of iron oxidation in a mica. Large singly-crystal biotite wafers were heated in air to various temperatures and for various times. Room temperature ⁵⁷Fe Mössbauer spectroscopy was used to quantify the resulting Fe²⁺ and Fe³⁺ amounts. A simple activation model is consistent with the measurements and gives an activation energy of e _b = 2.36 eV and an attempt frequency of f ₀ = 2.9×10⁷ Hz. We are lead to propose that, iron oxidation and ordinary dehydroxylation have the same rate limiting step: local dissociation of an OH group as OH^?→O^2-+H⁺. In oxidation this is followed by Fe²⁺ +H⁺→Fe³+H whereas in dehydroxylation it is followed by OH^? +H⁺→H₂O.     

Sediment-water oxygen and nutrient exchanges along the longitudinal axis of Chesapeake Bay: Seasonal patterns,controlling factors and ecological significance

Sediment-water oxygen and nutrient (NH₄ ⁺, NO₃ ^?+NO₂ ^?, DON, PO₄ ^3?, and DSi) fluxes were measured in three distinct regions of Chesapeake Bay at monthly intervals during 1 yr and for portions of several additional years. Examination of these data revealed strong spatial and temporal patterns. Most fluxes were greatest in the central bay (station MB), moderate in the high salinity lower bay (station SB) and reduced in the oligohaline upper bay (station NB). Sediment oxygen consumption (SOC) rates generally increased with increasing temperature until bottom water concentrations of dissolved oxygen (DO) fell below 2.5 mg l^?1, apparently limiting SOC rates. Fluxes of NH₄ ⁺ were elevated at temperatures >15°C and, when coupled with low bottom water DO concentrations (<5 mg l^?1), very large releases (>500 μmol N m^?2 h^?1) were observed. Nitrate + nitrite (NO₃ ^?+NO₂ ^?) exchanges were directed into sediments in areas where bottom water NO₃ ^?+NO₂ ^? concentrations were high (>18 μM N); sediment efflux of NO₃ ^?+NO₂ ^? occurred only in areas where bottom water NO₃ ^?+NO₂ ^? concentrations were relatively low (<11 μM N) and bottom waters well oxygenated. Phosphate fluxes were small except in areas of hypoxic and anoxic bottom waters; in those cases releases were high (50–150 μmol P m^?2 h^?1) but of short duration (2 mo). Dissolved silicate (DSi) fluxes were directed out of the sediments at all stations and appeared to be proportional to primary production in overlying waters. Dissolved organic nitrogen (DON) was released from the sediments at stations NB and SB and taken up by the sediments at station MB in summer months; DON fluxes were either small or noninterpretable during cooler months of the year. It appears that the amount and quality of organic matter reaching the sediments is of primary importance in determining the spatial variability and interannual differences in sediment nutrient fluxes along the axis of the bay. Surficial sediment chlorophyll-a, used as an indicator of labile sediment organic matter, was highly correlated with NH₄ ^?, PO₄ ^3?, and DSi fluxes but only after a temporal lag of about 1 mo was added between deposition events and sediment nutrient releases. Sediment O:N flux ratios indicated that substantial sediment nitrification-denitrification probably occurred at all sites during winter-spring but not summer-fall; N:P flux ratios were high in spring but much less than expected during summer, particularly at hypoxic and anoxic sites. Finally, a comparison of seasonal N and P demand by phytoplankton with sediment nutrient releases indicated that the sediments provide a substantial fraction of nutrients required by phytoplankton in summer, but not winter, especially in the mid bay region.     

Mechanism of efficient nutrient removal and microbial analysis of a combined anaerobic baffled reactor–membrane bioreactor process

A combined ABR–MBR process consisting of an anaerobic baffled reactor (ABR) combined with an aerobic membrane bioreactor (MBR) treating municipal wastewater was investigated at controlled pH range 6.5–8.5 and at constant temperature 25 ± 1 °C. Total nitrogen (TN), ammonia (NH₄ ⁺–N), total phosphorus (TP), and chemical oxygen demand (COD) removal performances were evaluated by analyzing the mechanism for efficient nutrient removal. The results showed that the average removal rates of COD, NH₄ ⁺–N, TN, and TP reached 93, 99, 79, and 92 %, respectively, corresponding with the COD, NH₄ ⁺–N, TN, and TP effluent of 24 (18–31), 0.4 (0–0.8), 10.6 (8.8–12.9), and 0.31 (0.1–0.5) mg/L under the operational condition of hydraulic retention time (HRT) 7.5 h, recycle ratio 200 %, and dissolved oxygen 3 mg/L. The MBR enhanced NH₄ ⁺–N, TN, and TP removal rates of 13, 10, and 18 %, respectively, and the membrane retention reduced TP 0.17 mg/L. The process was able to maintain a stable performance with high-quality effluent. Analysis of the results by fluorescence in situ hybridization showed that the abundance of ammonia-oxidizing bacteria, nitrite-oxidizing bacteria, and phosphorus accumulating organisms as percentages of all bacteria in each compartment was stable. The enriched microorganisms in the system appear to be the main drivers of the process efficient for nutrient removal.     

Effects of stormwater nutrient discharges on eutrophication processes in nearshore waters of the Florida keys

Rainfall events cause episodic discharges of groundwaters contaminated with septic tank effluent into nearshore waters of the Florida keys, enhancing eutrophication in sensitive coral reef communities. Our study characterized the effects of stormwater discharges by continuously (30-min intervals) measuring salinity, temperature, tidal stage, and dissolved oxygen (DO) along an offshore eutrophication gradient prior to and following heavy rainfall at the beginning of the 1992 rainy season. The gradient included stations at a developed canal system (PP) on Big Pine Key, a seagrass meadow in a tidal channel (PC), a nearshore patch reef (PR), a bank reef at Looe Key National Marine Sanctuary (LK), and a blue water station (BW) approximately 9 km off of Big PIne Key. Water samples were collected at weekly intervals during this period to determine concentrations of total nitrogen (TN), ammonium (NH₄ ⁺), nitrate plus nitrite NO₃ ^? plus NO₂ ^?), total phosphorus (TP), total dissolved phosphorus (TDP), soluble reactive phosphorus (SRP), and chlorophyll a (chl a). Decreased salinity immediately followed the first major rainfall at Big Pine Key, which was followed by anoxia (DO <0.1 mg I^?1), high concentrations of NH₄ ⁺ (≈24 μM), TDP (≈1.5 μM), and chl a (≈20 μg I^?1). Maximum concentration of TDP (≈0.30 μM) also followed the initial rainfall at the PC, PR, and LK stations. In contrast, NH₄ ⁺ (≈4.0 μM) and chl a (0.45 μg I^?1) lagged the rain event by 1–3 wk, depending on distance from shore. The highest and most variable concentrations of NH₄ ⁺, TDP, and chl a occurred at PP, and all nutrient parameters correlated positively with rainfall. DO at all stations was positively correlated with tide and salinity and the lowest values occurred during low tide and low salinity (high rainfall) periods. Hypoxia (DO <2.5 mg I^?1) was observed at all stations follwing the stormwater discharges, including the offshore bank reef station LK. Our study demonstrated that high frequency (daily) sampling is necessary to track the effects of episodic rainfall events on water quality and that such effects can be detected at considerable distances (12 km) from shore. The low levels of DO and high levels of nutrients and chl a in coastal waters of the Florida Keys demand that special precautions be exercised in the treatment and discharge of wastewaters and land-based runoff in order to preserve sensitive coral reef communities.     

Nitrogen isotope chemostratigraphy of the Ediacaran and Early Cambrian platform sequence at Three Gorges,South China

The appearance of multicellular animals and subsequent radiation during the Ediacaran/Cambrian transition may have significantly changed the oceanic ecosystem. Nitrogen cycling is essential for primary productivity and thus its connection to animal evolution is important for understanding the co-evolution of the Earth's environment and life. Here, we first report on coupled organic carbon and nitrogen isotope chemostratigraphy from the entire Ediacaran to Early Cambrian period by using drill core samples from the Yangtze Platform, South China. The results show that δ¹⁵N_TN values were high (~ + 6‰) until middle Ediacaran, gradually dropping down to − 1‰ at the earliest Cambrian, then rising back to + 4‰ in the end of the Early Cambrian. Organic carbon and nitrogen contents widely varied with a relatively constant C/N ratio in each stratigraphic unit, and do not apparently control the carbon and nitrogen isotopic trends. These observations suggest that the δ¹⁵N_TN and C/N trends mainly reflect secular changes in nitrogen cycling in the Yangtze Platform. Onset of the observed negative N isotope excursion coincided with a global carbon isotope excursion event (Shuram excursion). Before the Shuram event, the high δ¹⁵N probably reflects denitrification in a nitrate-limited oceanic condition. Also, degradation of dissolved and particulate organic matter could be an additional mechanism for the ¹⁵N-enrichment, and may have been significant when the ocean was rich in organic matter. At the time of the Shuram event, both δ¹³C_carb and δ¹⁵N_TN values were dropped probably due to massive re-mineralization of organic matter. This scenario is supported by an anomalously low C/N ratio, implying that enhanced respiration resulted in selective loss of carbon as CO₂ with recycled organic nitrogen. After the Shuram event, the δ¹⁵N value continued to decrease despite that δ¹³C_carb rose back to + 4‰. The continued δ¹⁵N drop appears to have coincided with a decreasing phosphorus content in carbonate. This suggests that ocean oxygenation may have generated a more nitrate-rich condition with respect to phosphorus as a limiting nutrient. Similar to the Shuram event, another negative δ¹³C_carb event in the Canglanpuan stage of the Early Cambrian is also characterized by carbon isotopic decoupling as well as the low C/N ratio. The results strongly support that the two stages of the decoupled negative δ¹³C_carb excursions reflect a disappearance of a large organic carbon pool in the ocean. The two events appear to relate with the appearance of new metazoan taxa with novel feeding strategies, suggesting a link between ocean oxygenation, nutrient cycling and the appearance and adaptation of metazoans. The nitrogen isotope geochemistry is very useful to understand the link between the environmental, ecological and biological evolutions.     

Specific affinity for phosphate uptake and specific alkaline phosphatase activity as diagnostic tools for detecting phosphorus-limited phytoplankton and bacteria

We analyzed responses of soluble reactive phosphorus (SRP), bioavailable phosphate (PO₄), particulate phosphorus, turnover time of orthophosphate (T_t), and alkaline phosphatase activity (APA) to varying degrees of nutrient stress. The nutrient stress was evoked by different treatments in concentration and combination of inorganic nitrogen (N) and phosphorus (P), and labile organic carbon (glucose) to mesocosms in experiments carried out in eutrophic southern (Odense Fjord, Denmark) and northern (Tvärminne Archipelago, Finland) coastal zones of the Baltic Sea. Despite seasonal and geographical differences, similar responses were observed in both experiments. Low SRP (<100 nmol l^?1), shortT _t (<10 h), and increased levels of APA were observed in both N+P balanced and P deficient treatments, while the opposite trend was observed in P replete treatments. The shortestT _t and the highest APA were found when glucose was combined with N treatment. Bioavailable PO₄ was estimated usingT _t and P uptake rates as derived from stoichiometric conversion of carbon based primary and bacterial production. With shorterT _t, the PO₄ pool declined to <1 nmol-P l^?1, whereas the SRP background pool (difference between SRP and PO₄) remained relatively constant (c. 50 nmol l^?1). APA was inversely related to PO₄ but not to SRP. Responses of specific APA and specific affinity for PO₄ uptake, which are APA and PO₄ uptake rates (inverse ofT _t), respectively, normalized to the summed P biomass of phytoplankton and bacteria, responded consistently to the pattern and magnitude of nutrient limitation evoked in our experiments. Our results, together with a literature survey, suggest that both parameters can be useful in examining PO₄ availability for the natural phytoplankton and bacteria community in P starved aquatic systems.     

Nutrient dynamics in pore water of tidal marshes near the Yangtze Estuary and Hangzhou Bay, China

Tidal marshes act as a buffer system for nutrients in the pore water and play important roles in controlling the budget of nutrients and pollutants that reach the sea. Spatial and seasonal dynamics of pore water nutrients were surveyed in three tidal marshes (Chongming Island, Hengsha Island, and Fengxian tidal flat) near the Yangtze Estuary and Hangzhou Bay from August 2007 to May 2008. Nutrient variations in pore water closely followed seawater quality in the estuaries, while the average concentration of NH₄ ⁺–N, the main form of inorganic nitrogen in pore water, was over two orders of magnitude higher than that in seawater which was dominated by nitrate. NH₄ ⁺–N export (13.81 μmol m^?2 h^?1) was lower than the import of (NO₃ ^?+NO₂ ^?)–N (?24.17 μmol m^?2 h^?1) into sediment over the 1-year period, hence reducing N-eutrophication in coastal waters. The export of SiO₃ ^2?–Si and PO₄ ^3?–P from tidal marshes regulated nutrient level and composition and lifted the ratio beyond potentidal element limitation in the coastal system. Moreover, macrophyte plants (Spartina alterniflora and Phragmites australis) played significant roles in controlling nutrient concentration in pore water and its exchange between marshes and estuaries. Fengxian marsh was characterized by higher nutrient concentrations and fluxes than other marshes in response to the more serious eutrophication in Hangzhou Bay than in the Yangtze Estuary.     

Organic matter distribution in the modern sediments of the Pearl River Estuary

We determined biomarker concentrations and distributions for surface sediments from 54 sites in the Pearl River Estuary, China. We focus on a suite of four biomarker-based indicators for relative terrestrial to marine organic matter (OM) source: the branched-isoprenoid tetraether (BIT) index, the ratio of high/low molecular weight n-alcohols [(ΣC_26–34/(ΣC₁₆₊₁₈ + ΣC_26–34)], an analogous ratio for n-fatty acids and the ΣC₂₉-steroids/(ΣC₂₉-steroids + brassicasterol) ratio. All four exhibit the same terrestrial to marine transition seen in previous bulk δ¹³C studies, but with an abrupt decrease in the relative terrestrial contribution across the delta front to pro-delta transition. Concentrations of terrestrially-derived biomarkers show no systematic decrease across the transition. Instead, the decrease in the proportion of terrestrial OM is due to a decrease in the sedimentation rate and associated terrestrial OM burial across the delta toe. This suggests that diagenetic controls on the fate of terrestrial OM, such as increased biodegradation where sedimentation rate is low, are subordinate to sedimentological processes. Biomarker-derived temperature values are cooler than expected for the lower Pearl River catchment, suggesting that the dominant component of the terrestrial OM is derived from the cooler upland regions of the catchment. The dominance of input from more distal terrain with greater topographic relief is evidence for the importance of geomorphological control on terrigenous OM transport. Collectively, the results demonstrate the importance of sedimentological processes in the supply, deposition and transport of terrestrial OM.     

Nitrogen,phosphorus and sulfur mineralization as affected by soil depth in rangeland ecosystems

The potential mineralization and immobilization of soil nitrogen (N), phosphorus (P) and sulfur (S) are relatively high in natural ecosystems. This study was conducted to investigate the changes in essential plant macronutrients; N, P, and S status in response to different soil depth in rangeland ecosystems in vitro. The net nutrient mineralization was measured during 90 days at different depths (0–15, 15–30, 30–45 and 45–60 cm), using kinetic models to estimate the release rate. The net ammonification and mineralization of P and S were described using parabolic diffusion equation, while the power function equation was used to describe the net nitrification. The results indicated that the amount of released ammonium (NH₄ ⁺) decreased with time and depth and the rates of net ammonification were negative in all samples. Conversely, nitrification increased with time and depth and the rates were all positive. The net mineralization for both P and S reduced with time. The concentration of mineralized SO₄ ^2? increased with depth like nitrate (NO₃ ^?). Accumulation of SO₄ ^2? and NO₃ ^? in subsurface soils and NH₄ ⁺ and P at surface horizons can increase the potential of their loss by leaching or volatilization.     

Nitrogen Sources and Rates of Phytoplankton Uptake in Different Regions of Hong Kong Waters in Summer

Phytoplankton uptake rates of ammonium (NH₄ ⁺), nitrate (NO₃ ⁻), and urea were measured at various depths (light levels) in Hong Kong waters during the summer of 2008 using ¹⁵N tracer techniques in order to determine which form of nitrogen (N) supported algal growth. Four regions were sampled, two differentially impacted by Pearl River discharge, one impacted by Hong Kong sewage discharge, and a site beyond these influences. Spatial differences in nutrient concentrations, ratios, and phytoplankton biomass were large. Dissolved nutrient ratios suggested phosphorus (P) limitation throughout the region, largely driven by high N loading from the Pearl River in summer. NH₄ ⁺ and urea made up generally ≥50% of the total N taken up and the f ratio averaged 0.26. Even at the river-impacted site where concentrations of NO₃ ⁻ were >20 μM N, NH₄ ⁺ comprised >60% of the total N uptake. Inhibition experiments demonstrated that NO₃ ⁻ uptake rates were reduced by 40% when NH₄ ⁺ was >5 μM N. The relationship between the total specific uptake rates of N (sum of all measured substrates, V, per hour) and the chlorophyll a-specific rates (micromolars of N per microgram of Chl a per hour) varied spatially with phytoplankton biomass. Highest uptake rates and biomass were observed in southern waters, suggesting that P limitation and other factors (i.e., flushing rate) controlled production inshore and that the unincorporated N (mainly NO₃ ⁻) was transported offshore. These results suggest that, at the beginning of summer, inshore algal blooms are fueled primarily by NH₄ ⁺ and urea, rather than NO₃ ⁻, from the Pearl River discharge. When NH₄ ⁺ and urea are depleted, then NO₃ ⁻ is taken up and can increase the magnitude of the bloom.     

A chemical survey of the Mississippi estuary

A “snap shot” survey of the Mississippi estuary was made during a period of low river discharge, when the estuarine mixing zone was within the deltaic channels. Concentrations of H⁺, Ca²⁺, inorganic phosphorus and inorganic carbon suggest that the waters of the river and the low salinity (<5‰) portion of the estuary are near saturation with respect to calcite and sedimentary calcium phosphate. An input of oxidized nitrogen species and N₂O was observed in the estuary between 0 and 4‰ salinity. The concentrations of dissolved NH₄ ⁺ and O₂, over most of the estuary, appeared to be influenced by decomposition of terrestrial organic matter in bottom sediments. The estuarine bottom also appears to be a source of CH₄ which has been suggested to originate from petroleum shipping and refining operations. Estuarine mixing with offshore Gulf waters was the dominant influence on distributions of dissolved species over most of the estuary (i.e., from salinities >5‰). The phytoplankton abundance (measured as chlorophylla) increased as the depth of the mixed layer decreased in a manner consistent with that expected for a light-limited ecosystem. Fluxes of NO₃ ^?+NO₂ ^? and soluble inorganic phosphorus to the Gulf of Mexico were estimated to be 3.4±0.2×10³ g N s^?1 and 1.9±0.2 g P s^?1 respectively, at the time of this study.     

Distribution and isotope composition of nitrogen in Bay of Quinte (Lake Ontario) sediments

The concentrations and isotopic compositions of the various forms of nitrogen in silty clay sediments from the Bay of Quinte (Lake Ontario) have been determined. The total organic-N content is high throughout the sediment profiles and generally decreases with depth. On the contrary, exchangeable NH⁺₄-N concentration is quite low and tends to increase with depth in two out of three sediment cores examined. The concentration of non-exchangeable NH⁺₄-N and the 6 N HCl hydrolyzable NH⁺₄-N are relatively constant with depth. Among the N fractions analyzed, the exchangeable NH⁺₄-is most enriched in ¹⁵N. In most cases, the δ ¹⁵ N values of the N fractions remain relatively constant with sediment depth. There is no apparent correlation of δ ¹⁵ N values with the N concentration for any of the individual N fractions. The observed ranges in the δ ¹⁵ N values are: exchangeable NH⁺₄, + 5–+10‰; 6 N HCl hydrolyzable total N and 6 N HCl hydrolyzable NH⁺₄-N, + 3.5–+5.5‰.     

The role of phosphorus in rhyolitic liquids as determined from the homogeneous iron redox equilibrium

The redox ratio of iron is used as an indicator of solution properties of silicate liquids in the system (SiO–Al₂O₃–K₂O–FeO–Fe₂O₃–P₂O₅). Glasses containing 80–85 mol% SiO₂ with 1 mol% Fe₂O₃ and compositions covering a range of K₂O/Al₂O₃ were synthesized at 1400°C in air (fixed fO₂). Variations in the ratio FeO/FeO_1.5 resulting from the addition of P₂O₅ are used to determine the solution behavior of phosphorus and its interactions with other cations in the silicate melt. In 80 mol% SiO₂ peralkaline melts the redox ratio, expressed as FeO/FeO_1.5, is unchanged relative to the reference curve with the addition of 3 mol% P₂O₅. Yet, the iron redox ratio in the 85 mol% SiO₂ potassium aluminosilicate melts is decreased relative to phosphorus-free liquids even for small amounts of P₂O₅ (0.5 mol%). The redox ratio in peraluminous melts is decreased relative to phosphorus- free liquids at P₂O₅ concentrations of 3 mol%. In peraluminous liquids, complexing of both Fe⁺³–O–P⁺⁵ and Al⁺³–O–P⁺⁵ occur. The activity coefficient of Fe⁺³ is decreased because more ferric iron can be accommodated than in phosphorus-free liquids. In peralkaline melts, there is no evidence that P⁺⁵ is removing K⁺ from either Al⁺³ or Fe⁺³ species. In chargebalanced melts with 3 mol% Fe₂O₃ and very high P₂O₅ concentrations, phosphorus removes K⁺ from K–O–Fe⁺³ complexes resulting in a redox increase. P₂O₅ should be accommodated easily in peraluminous rhyolitic liquids and phosphate saturation may be suppressed relative to metaluminous rhyolites. In peralkaline melts, phosphate solubility may increase as a result of phosphorus complexing with alkalis. The complexing stoichiometry may be variable, however, and the relative influence of peralkalinity versus temperature on phosphate solubility in rhyolitic melts deserves greater attention.     

Effect of soil-applied calcium carbide and plant derivatives on nitrification inhibition and plant growth promotion

The aim of this study was to evaluate the relative performance of three nitrification inhibitors (NIs) viz. calcium carbide (CaC₂), and plant derivatives of Pongamia glabra Vent. (karanj) and Melia azedarach (dharek) in regulating N transformations, inhibiting nitrification and improving N recovery in soil–plant systems. In the first experiment under laboratory incubation, soil was amended with N fertilizer diammonium phosphate [(NH₄)₂HPO₄] at a rate of 200 mg N kg^?1, N + CaC₂, N + karanjin, and N + M. azedarach and incubated at 22 °C for 56 days period. Changes in total mineral N (TMN), NH₄ ⁺–N and NO₃ ^?–N were examined during the study. A second experiment was conducted in a glasshouse using pots to evaluate the response of wheat to these amendments. Results indicated that more than 92 % of the NH₄ ⁺ initially present had disappeared from the mineral N pool by the end of incubation. Application of NIs i.e., CaC₂, karanjin, and M. azedarach resulted in a significant reduction in the extent of NH₄ ⁺ disappearance by 49, 32, and 13 %, respectively. Accumulation of NO₃ ^?–N was much higher in N amended soil 57 % compared to 11 % in N + CaC₂, 13 % in N + karanjin, and 18 % in N + M. azedarach. Application of NIs significantly increased growth, yield, and N uptake of wheat. The apparent N recovery in N-treated plants was 20 % that was significantly increased to 38, 34, and 37 % with N + CaC₂, N + karanjin, and N + M. azedarach, respectively. Among the three NIs tested, CaC₂ and karanjin proved highly effective in inhibiting nitrification and retaining NH₄ ⁺–N in the mineral pool for a longer period.     

Effect of fish and mesozooplankton manipulation on the phytoplankton community in the Patos Lagoon estuary,Southern Brazil

An enclosure experiment in the Patos Lagoon estuary, southern Brazil (32°S, 52°W) investigated the response of phytoplankton to the enhancement of mesozooplankton and fish abundance. Addition of nutrients (NO₃ ^? and PO₄ ^?) stimulated the growth of 3–20 μm diameter phytoplankton, especially the diatomCylindrotheca closterium, which, in turn, was heavily grazed by the dominant mesozooplankter, the copepodAcartia tonsa. Acartia did not consume small (2–3 μm) autotrophic flagellates and the cyanobacteriaAnabaena sp., despite their high cell number. Largest grazing ofC. closterium by the copepod occurred only after a decrease of ciliate abundance. The addition of mesozooplankton did not change the levels of primary production, but it significantly increased the phytoplankton assimilation number. Highest chlorophylla concentrations were measured in enclosures stocked with juveniles of the fishXenomelaniris brasiliensis. The large phytoplankton biomass and low mesozooplankton abundance found in this treatment indicates an, effective predator-mediated action on the phytoplankton community.     

Nutrient limitation of the macroalgaEnteromorpha intestinalis collected along a resource gradient in a highly eutrophic estuary

We conducted a laboratory experiment to quantify nutrient (nitrogen and phosphorus) limitation of macroalgae collected along a gradient in water column nutrient availability in Upper Newport Bay estuary, a relatively nutrient-rich system in southern California, United States. We collectedEnteromorpha intestinalis and water for use in the experiment from five sites ranging from the lower end of the estuary to the head. Initial algal tissue N and P concentrations and molar N∶P ratios—as well as water column NO₃ and total Kjeldahl nitrogen (TKN)—increased along a spatial gradient from the lower end toward the head. Water column soluble reactive phosphorus (SRP) varied among sites as well but did not follow a pattem of increasing from the seaward end toward the head. Algae from each site were assigned to one of four experimental treatments: control (C), nitrogen enrichment (+N), phosphorus enrichment (+P), and nitrogen and phosphorus enrichment (+N+P). Each week for 3 wk we replaced the water in each unit with the appropriate treatment water to mimic a poorly flushed estuary. After 3 wk, the degree of nutrient limitation ofE. intestinalis varied spatially with distance from the head of the estuary. Growth ofE. intestinalis collected from several sites increased with N enrichment alone and increased further when P was added in combination with N This indicated that N was limiting and that when N was sufficient, P became limiting. Sites from whichE. intestinalis exhibited nutrient limitation spanned the range of background water column NO₃ (12.9±0.4 to 55.2±2.1 μM) and SRP (0.8±0.0 to 2.9±0.2 μM) concentrations. Algae that were N limited had initial tissue N levels ranging from 1.18±0.03 to 2.81±0.08% dry weight and molar N∶P ratios ranging from 16.75±0.39 to 26.40±1.98.     

Mapping Phytoplankton Community Physiology on a River Impacted Continental Shelf: Testing a Multifaceted Approach

Seasonal phosphorus limitation occurs on the Louisiana continental shelf as a result of high nitrogen loads in the spring and early summer. Prior studies have assessed such nutrient limitation by laborious and time-consuming nutrient analyses, enzyme assays, and nutrient addition bioassays. We undertook surface (0.5–1 m) mapping of fast repetition rate fluorescence (FRRF) parameters to assess nutrient limitation in real time on the Louisiana continental shelf and Mississippi River plume from 29 June to 08 July, 2002 in an effort to further understand phytoplankton productivity in this region, as well as to better inform effective nutrient management strategies. Surface nutrient concentrations (NO₃⁻, NO₂⁻, NH₄⁺, PO₄³⁻), chlorophyll a biomass, alkaline phosphatase (AP) activity, and four FRRF parameters: the maximum quantum yield of photochemistry (F _v /F _m ), the functional absorption cross section for PSII, the time constant for Q _A reoxidation, and the connectivity factor, were measured during continuous underway mapping. Results from traditional methods to assess phytoplankton nutrient stress indicated widespread phosphorus limitation from the Mississippi River plume to the Atchafalaya River, manifested as high inorganic N/P ratios and elevated AP activities associated with phytoplankton biomass. The FRRF data indicated complex patterns of phytoplankton physiology that were likely driven by the rapidly changing conditions in local surface waters and heterogeneous phytoplankton community structure. Correlations of nutrient data and enzyme assays with FRRF parameters were significant but low, potentially due to differences in the manner and time scale with which nutrient limitation affects the different techniques used, indicating that further work is needed to interpret FRRF parameters in large, heterogeneous environments such as estuaries and continental shelves.