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.     

Sediment-water oxygen and nutrient fluxes in a river-dominated estuary

Sediment oxygen uptake and net sediment-water fluxes of dissolved inorganic and organic nitrogen and phosphorus were measured at two sites in Fourleague Bay, Louisiana, from August 1981, through May 1982. This estuary is an extension of Atchafalaya Bay which receives high discharge and nutrient loading from the Atchafalaya River. Sediment O₂ uptake averaged 49 mg m^?2 h^?1. On the average, ammonium (NH₄ ⁺) was released from the sediments (mean flux =+129 μmol m^?2 h^?1), and NO₃ ^? was taken up (mean flux =?19 μmol m^?2h^?1). However, very different NO₃ ^? fluxes were observed at the two sites, with sediment uptake at the upper, river-influenced, high NO₃ ^? site (mean flux =?112 μmol m^?2 h^?1) and release at the lower, marine-influenced low NO₃ ^? site (mean flux =+79 μmol m^?2 h^?1). PO₄ ^3? fluxes were low and often negative (mean flux =?8 μmol m^?2 h^?1), while dissolved organic phosphorus fluxes were high and positive (mean flux =+124 μmol m^?2 h^?1). Dissolved organic nitrogen fluxes varied greatly, ranging from a mean of +305 μmol m^?2 h^?1 at the lower bay, to ?710 μmol m^?2 h^?1 at the upper bay. Total dissolved nitrogen and phosphorus fluxes indicated the sediments were a nitrogen (mean flux =+543 μmol m^?2 h^?1) and phosphorus source (mean flux =+30 μmol m^?2 h^?1) at the lower bay, and a nitrogen sink (mean flux =?553 μmol m^?2 h^?1) and phosphorus source (mean flux =+17 μmol m^?2 h^?1) in the upper bay. Mean annual O∶N ration of the positive inorganic sediment fluxes were 27∶1 at the upper bay and 18∶1 at the lower bay. Based on these data we hypothesize that nitrification and denitrification are important sediment processes in the upper bay. We further hypothesize that Atchafalaya River discharge affects sediment-water fluxes through seasonally high nutrient loading which leads to net nutrient uptake by sediments in the upper bay and release in the lower bay, where there is less river influnces.     

Reciprocal influence of Kürtün Dam and wastewaters from the settlements on water quality in the stream Harşit,NE Turkey

This paper aims to reveal the reciprocal influence of Kürtün Dam and wastewaters from the settlements on the water quality in the stream Har?it, NE Turkey. Several key water-quality indicators were measured: water temperature (T), pH, dissolved oxygen (DO), electrical conductivity, water hardness, chemical oxygen demand (COD), ammonium nitrogen (NH₄ ⁺–N), nitrite nitrogen (NO₂ ^?–N), nitrate nitrogen (NO₃ ^?–N), total Kjeldahl nitrogen (TKN), total nitrogen (TN), orthophosphate phosphorus (PO₄ ^3?–P), and methylene blue active substances (MBAS). The monitoring and sampling studies were conducted every 15 days from March 2009 to February 2010 at two stations selected in the upstream and downstream of the Kürtün Dam. It was concluded that the Kürtün Dam Lake had a high-quality water in terms of T, pH, DO, COD, NH₄ ⁺–N, NO₂ ^?–N and NO₃ ^?–N values, but slightly polluted water with respect to TKN, PO₄ ^3?–P, and MBAS according to the Turkish Water Pollution Control Regulation. The dam improved the stream water quality by increasing the DO concentration, and decreasing the NO₂ ^?–N and PO₄ ^3?–P concentrations thanks to its hydraulic residence time despite the wastewater discharge by the nearby settlements. However, the wastewater discharge deteriorated the stream water quality increasing the COD, NH₄ ⁺–N, NO₃ ^––N, and TN concentrations.     

Nutrient availability to marine macroalgae in siliciclastic versus carbonate-rich coastal waters

Abundant populations of frondose epilithic macroalgae from a variety of carbonate-rich tropical waters were significantly depleted in phosphorus relative to carbon and nitrogen when compared to macroalgae from temperate siliciclastic waters. Percent carbon (C) and percent nitrogen (N) dry weight contents were similar between tissues from the siliciclastic and carbonate environments (means of 22.6% vs. 20.1% and 1.0% vs. 1.2%, respectively), but phosphorus (P) levels were two-fold lower (0.15% vs. 0.07%) in the carbonate-rich systems. Accordingly, the molar C:N tissue ratios were comparable between macroalgae from the siliciclastic and carbonate sites (mean of 29.2 vs. 23.1), whereas large differences were observed for the C:P (mean of 430 vs. 976) and N:P ratios (mean of 14.9 vs. 43.4). In addition, alkaline phosphatase activity was low and often undetectable in the macroalgae from siliciclastic habitats (mean of 7.3 μM PO₄ ^3? released g dry wt^?1 h^?1) compared to seven-fold higher rates (52.5 μM PO₄ ^3? released g dry wt^?1 h^?1) observed in the macroalgae from carbonate systems. Seawater samples taken adjacent to benthic macroalgae from the carbonate-rich tropical waters contained relatively high levels of dissolved inorganic nitrogen with low concentrations of soluble reactive phosphorus (SRP), and showed elevated N:SRP ratios (mean=36) compared to siliciclastic environments (mean <3). These data support the precept that availability of N limits the productivity of macroalgae in temperate siliciclastic waters but, conversely, suggest that availability of P, rather than N, may be of paramount importance in limiting primary production of macroalgae in carbonate-rich tropical waters.     

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.     

Community Oxygen and Nutrient Fluxes in Seagrass Beds of Florida Bay, USA

We used clear, acrylic chambers to measure in situ community oxygen and nutrient fluxes under day and night conditions in seagrass beds at five sites across Florida Bay five times between September 1997 and March 1999. Underlying sediments are biogenic carbonate with porosities of 0.7–0.9 and with low organic content (<1.6%). The seagrass communities always removed oxygen from the water column during the night and produced oxygen during daylight, and sampling date and site significantly affected both night and daytime oxygen fluxes. Net daily average fluxes of oxygen (?4.9 to 49 mmol m^?2 day^?1) ranged from net autotrophy to heterotrophy across the bay and during the 18-month sampling period. However, the Rabbit Key Basin site, located in the west-central bay and covered with a dense Thalassia testudinum bed, was always autotrophic with net average oxygen production ranging from 4.8 to 49 mmol m^?2 day^?1. In November 1998, three of the five sites were strongly heterotrophic and oxygen production was least at Rabbit, suggesting the possibility of hypoxic conditions in fall. Average ammonium (NH₄) concentrations in the water column varied widely across the bay, ranging from a mean of 6.9 μmol l^?1 at Calusa in the eastern bay to a mean of 0.6 μmol l^?1 at Rabbit Key for the period of study. However, average NH₄ fluxes by site and date (?240 to 110 μmol m^?2 h^?1) were not correlated with water column concentrations and did not vary in a consistent diel, seasonal, or spatial pattern. Concentrations of dissolved organic nitrogen (DON) in the water column, averaged by site (15–25 μmol l^?1), were greater than mean NH₄ concentrations, and the range of day and night DON fluxes (?920 to 1,300 μmol m^?2 h^?1), averaged by site and date, was greater than the range of mean NH₄ fluxes. Average DON fluxes did not vary consistently from day to night, seasonally or spatially. Mean silicate fluxes ranged from ?590 to 860 μmol m^?2 h^?1 across all sites and dates, but mean net daily fluxes were less variable and most of the time contributed small amounts of silicate to the water column. Mean concentrations of filterable reactive phosphorus (FRP) in the water column across the bay were very low (0.021–0.075 μmol l^?1); but site average concentrations of dissolved organic phosphorus (DOP) were higher (0.04–0.15 μmol l^?1) and showed a gradient of increasing concentration from east to west in the bay. A pronounced gradient in average surficial sediment total phosphorus (1.1–12 μmol g DW^?1) along an east-to-west gradient was not reflected in fluxes of phosphorus. FRP fluxes, averaged by site and date, were low (?5.2 to 52 μmol m^?2 h^?1), highly variable, and did not vary consistently from day to night or across season or location. Mean DOP fluxes varied over a smaller range (?8.7 to 7.4 μmol m^?2 h^?1), but also showed no consistent spatial or temporal patterns. These small DOP fluxes were in sharp contrast to the predominately organic phosphorus pool in surficial sediments (site means?=?0.66–7.4 μmol g DW^?1). Significant correlations of nutrient fluxes with parameters related to seagrass abundance suggest that the seagrass community may play a major role in nutrient recycling. Integrated means of net daily fluxes over the area of Florida Bay, though highly variable, suggest that seagrass communities might be a source of DOP and NH₄ to Florida Bay and might remove small amounts of FRP and potentially large amounts of DON from the waters of the bay.     

Phosphorus adsorption characteristics at the sediment–water interface and relationship with sediment properties in FUSHI reservoir, China

This study was designed to survey the reservoir sediment properties, assess the phosphorus (P) sorption isotherm, and analyze the relationship between sediment properties and sorption parameters. Physicochemical analysis indicated that sediment from the FUSHI reservoir in Zhejiang Province, China, has similar physical and chemical properties and has been contaminated by P. Sorption isotherm experiments showed that the sorption process could be described by Langmuir and Freundlich models. The parameters of Q _max (Phosphorus sorption maximum) and K (Freundlich adsorption isotherm constant) ranged from 618.98 to 825.70?mg?kg^?1 and 114.18 to 170.74?l?kg^?1, respectively. EPC₀ (zero P equilibrium concentration) ranged from 0.14 to 0.24?mg?l^?1, more than the total P concentration in the water of the reservoir. Thus, the reservoir sediment releases P into the water and acts as a ??P resource??. The clay, Fe_o, Al_t, and Fe_t?+?Al_t content were the main active components in P sorption. Q _max had a highly significant positive relationship with some properties and could be estimated by a combination of these.     

Synthesis and nutrient release patterns of a biochar-based N–P–K slow-release fertilizer

Biochar has excellent solute adsorption capacity, yet few studies have investigated its application as a nutrient carrier in the development of slow-release fertilizers. The current study developed a biochar-based N–P–K fertilizer (BSRF) and evaluated its nutrient release patterns relative to a conventional fertilizer. SEM and EDX analyses confirmed the coarse and highly porous microstructure of the biochar (SBC) that enabled it to effectively sorb NO₃ ^?, PO₄ ^3?, and K⁺ and form a nutrient-impregnated BSRF. BSRF had lower NO₃ ^?, PO₄ ^3?, and K⁺ release than the conventional chemical fertilizer, demonstrating its low release behavior. BSRF-amended sandy soil had higher water retention capacity than that amended with a conventional chemical fertilizer. BSRF has potential to reduce nutrient leaching, improve water retention, and hence increase crop nutrient and water use efficiencies. Future research should focus on understanding nutrient release mechanisms, synchronization of nutrient release with plant uptake, and applications of the BSRF in environmental remediation.     

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.     

Holtedahlite, a new magnesium phosphate from Modum, Norway

Holtedahlite occurs in a serpentine-magnesite deposit at Modum in association with althausite and (OH,F) apatite. It is colourless, transparent, has a vitreous lustre, occurs in massive form and shows no cleavage. The Mohs' hardness is $\text{4}\text{1}\text{2}\text{?5}$; specific gravity 2.94(2) (Berman balance), calculated density 2.936 g/cm³. It is uniaxial negative, ω = 1.599(1), ? = 1.597(1).Chemical analysis with the electron microprobe and separate determinations of CO₂ and H₂O give a formula close to Mg₂PO₄OH or more specifically (Mg,Na)₂(PO₄, CO₃OH)(OH,F). Holtedahlite is hexagonal, $\text{α = 11.188(2), c = 4.975(1)}\text{A}\text{?}\text{, V = 539.3(3)}\text{A}\text{?}{}^3\text{Z = 6}$, space group $\text{P321, P3m}\text{l}\text{or}\text{P}\text{3}\text{m}\text{l}$. The strongest lines in the X-ray powder pattern are (in Å, with intensities and indices): 3.722(90) ($\text{11}\text{2}\text{1}$), 3.475(50) ($\text{20}\text{2}\text{1}$), 3.234(30) ($\text{30}\text{3}\text{0}$), 2.796(30), 2.438(100) ($\text{22}\text{4}\text{1}$), 2.177(30) (2.177(30) ($\text{40}\text{4}\text{1}$), 1.859(30) ($\text{22}\text{4}\text{2}$). The infrared spectrum shows the presence of OH^?, CO₃^2?, and PO₄^3? and indicates an O-H… O distance of ca. 3.02 Å.     

Nutrient transport in a riverine-influenced,tidal freshwater bayou in Louisiana

Transport of ammonium (NH₄ ⁺), nitrate + nitrite (NO₃ ^?), total Kjeldahl nitrogen (TKN), soluble reactive phosphate (SRP), and total suspended solids (TSS) was measured in a freshwater tidal bayou located in a marsh system near the mouth of the Atchafalaya River in Louisiana. Sampling was conducted six times over one year and was timed to assess effects of seasonal variation in river flow and mean sea level of the Gulf of Mexico on material fluxes. Net fluxes of all materials were large and ebb directed in all seasons except fall, when net transport was 2 to 3 orders-of-magnitude smaller than in any other season. These results demonstrate that riverine forcing was the primary influence on materials transport in all seasons except fall when tidal forcing was most important. The range of net fluxes (g s^?1) for each nutrient was as follows (a negative sign indicates a net export toward the Gulf): NO₃ ^?, ?0.006 to ?6.69; TKN, 0.09 to ?10.41; NH₄ ⁺, ?0.02 to ?1.36; SRP, ?0.001 to ?0.53; TSS, ?2 to ?81. Analysis of nutrient concentrations indicated the marsh/aquatic system removed NO₃ ^?, SRP, and TSS from the water column from late spring through early fall and released NH₄ ⁺ and TKN in summer. The results of this study show that net materials export per unit cross section channel area increased as riverine influence increased.     

The influence of upwelling and short-term changes in concentrations of nutrients in the water column on fluxes across the surface of a salt marsh

Oceanic upwelling results in the intermittent intrusion of cold ocean water enriched in nitrate, and to a lesser extent soluble reactive phosphorus (SRP), into the Kariega Estuary (South Africa). Laboratory measocosm experiments were conducted to determine the effects of such changes on fluxes of dissolved nutrients across the surface of a salt marsh within the estuary. When replicate mesocosms of the tidal creek and salt marsh were inundated with nonupwelled water (at 25°C and nitrate concentrations of 4.5 μmoll^?1), nitrate fluxes in both regions were small, and the tidal creek exhibited net uptake (negative value) of nitrate from the water column (?85 μmol m^?2 tide^?1), and the marsh, net release (positive values; 113 μmol m^?2 tide^?1). When the mesocosms were inundated with upwelled water, at 16°C and with nitrate concentrations of 24.2 μmol l^?1, both regions exhibited large net uptakes of nitrate (?514 μmol m^?2 tide^?1 and ?226 μmol m^?2 tide^?1 for the tidal creek and salt marsh, respectively). In contrast to nitrate, the fluxes of nitrite, ammonium, and SRP were not significantly different under upwelling and nonupwelling conditions, probably because initial concentrations in the two water types were similar. To determine the extent to which the nitrate uptakes were caused by decreased water temperatures or increased concentrations of nitrate, experiments were conducted in which mesocosms were inundated with water with a range of nitrate concentrations (1.8–25 μmol l^?1), at two temperatures representative of summer upwelling (16°C) and nonupwelling conditions (25°C). In both regions, the net fluxes of nitrate were positively correlated with initial concentrations of nitrate in the water column. For any given concentration, the fluxes at 16°C fell within the range of values at 25°C, indicating that the shifts in fluxes caused by upwelling occurred in response to increased concentrations in the water column and not reduced temperatures.     

Impact of Oyster Farming on Diagenetic Processes and the Phosphorus Cycle in Two Estuaries (Brittany,France)

This study aims to compare the impact of oyster cultures on diagenetic processes and the phosphorus cycle in the sediments of the Aber Benoît and the Rivière d’Auray, estuary of Brittany, France. Our results showed clear evidence of the seasonal impact of oyster cultures on sediment characteristics (grain size and organic matter parameters) and the phosphorus cycle, especially in the Aber Benoît. At this site, seasonal variations in sulfide and Fe concentrations in pore waters, as well as Fe–P concentrations in the solid phase, highlighted a shift from a system governed by iron reduction (Reference) to a system governed by sulfate reduction (beneath oyster). This could be partly explained by the increase in labile organic matter (i.e., biodeposits) beneath oysters, whose mineralization by sulfate led to high sulfide concentrations in pore waters (up to 4,475 µmol l^?1). In turn, sulfide caused an enhanced release of phosphate in the summer, as adsorption sites for phosphate decreased through the formation of iron–sulfide compounds (FeS and FeS₂). In the Aber Benoît, dissolved Fe/PO₄ ratios could be used as an indicator of phosphate release into oxic water. Low Fe/PO₄ ratios in the summer indicated higher effluxes of phosphate toward the water column (up to 47 µmol m^?2 h^?1). At other periods, Fe/PO₄ ratios higher than 2 mol/mol indicated very low phosphate fluxes. In contrast, in the Rivière d’Auray, the occurrence of macroalgae, stranding regularly all over the site, clearly masked the impact of oyster cultures on sediment properties and the phosphorus cycle and made the use of Fe/PO₄ ratios more difficult in terms of indicators of phosphate release.     

Nutrient uptake in a highly turbid estuary (the Humber, United Kingdom) and adjacent coastal waters

Surveys were conducted in April and June 1995 to quantify the uptake of dissolved nutrients in a highly turbid estuary (the Humber, United Kingdom) and to determine the factors controlling nutrient uptake rates. A combination of isotope labelling methods were used in conjunction with on-deck incubation techniques to estimate the uptake of dissolved nutrients (PO₄ ^3?, NH₄ ⁺, NO₃ ^?, and urea) in surface samples collected from coastal waters. Similarly, isotope labelling and laboratory incubgation techniques were employed to estimate dissolved nitrogen uptake (NH₄ ⁺, NO₃ ^?, and urea) in surface samples collected from the estuary mouth. Nutrient uptake rates were at the low end of ranges for coastal and estuarine environments reported in the literature. Concentrations of chlorophyll and the availability of photosynthetically active radiation were identified as potentially important factors controlling the uptake rates of nutrients. Uptake rates of dissolved nitrogen in the Humber mouth appeared to be related to the location of smapling sites. Depletion rates of dissolved nutrients in situ were estimated on the basis of integrated water column nutrient uptake rates and indicated assimilation of up to 16% of nutrients in the entire water column. Estimated depletion rates did not indicate preferential loss of any of the nutrient species investigated.     

The Contribution of Groundwater Discharge to Nutrient Exports from a Coastal Catchment: Post-Flood Seepage Increases Estuarine N/P Ratios

Four months of daily nutrient and radon (a natural groundwater tracer) observations at the outlet of a heavily drained coastal wetland illustrated how episodic floods and diffuse groundwater seepage influence the biogeochemistry of a sub-tropical estuary (Richmond River, New South Wales, Australia). Our observations downstream of the Tuckean Swamp (an acid sulphate soil floodplain) covered a dry stage, a flood triggered by a 213-mm rain event and a post-flood stage when surface water chemistry was dominated by groundwater discharge. Significant correlations were found between radon and ammonium and N/P ratios and between radon and dissolved organic nitrogen (DON) during the post-flood stage. While the flood lasted for 14?% of the time of the surface water time series, it accounted for 18?% of NH₄, 32?% of NO _x , 66?% of DON, 58?% of PO₄ and 55?% of dissolved organic phosphorus (DOP) catchment exports. Over the 4-month study period, groundwater fluxes of 35.0, 3.6, 36.3, 0.5 and 0.7?mmol?m^?2?day^?1 for NH₄, NO _x , DON, PO₄ and DOP, respectively, were estimated. The groundwater contribution to the total surface water catchment exports was nearly 100?% for ammonium, and <20?% for the other nutrients. Post-flood groundwater seepage shifted the system from a DON to a dissolved inorganic N-dominated system and doubled N/P ratios in surface waters. We hypothesise that the Richmond River Estuary N/P ratios may reflect a widespread trend of tidal rivers and estuaries becoming more groundwater-dominated and phosphorus-limited as coastal wetlands are drained for agriculture, grazing and development.     

In situ observation of crystal growth in a basalt melt and the development of crystal size distribution in igneous rocks

The speciation of CO₂ in dacite, phonolite, basaltic andesite, and alkali silicate melt was studied by synchrotron infrared spectroscopy in diamond anvil cells to 1,000 °C and more than 200 kbar. Upon compression to 110 kbar at room temperature, a conversion of molecular CO₂ into a metastable carbonate species was observed for dacite and phonolite glass. Upon heating under high pressure, molecular CO₂ re-appeared. Infrared extinction coefficients of both carbonate and molecular CO₂ decrease with temperature. This effect can be quantitatively modeled as the result of a reduced occupancy of the vibrational ground state. In alkali silicate (NBO/t = 0.98) and basaltic andesite (NBO/t = 0.42) melt, only carbonate was detected up to the highest temperatures studied. For dacite (NBO/t = 0.09) and phonolite melts (NBO/t = 0.14), the equilibrium CO₂ + O^2? = CO₃ ^2? in the melt shifts toward CO₂ with increasing temperature, with ln K = ?4.57 (±1.68) + 5.05 (±1.44) 10³ T ^?1 for dacite melt (ΔH = ?42 kJ mol^?1) and ln K = ?6.13 (±2.41) + 7.82 (±2.41) 10³ T ^?1 for phonolite melt (ΔH = ?65 kJ mol^?1), where K is the molar ratio of carbonate over molecular CO₂ and T is temperature in Kelvin. Together with published data from annealing experiments, these results suggest that ΔS and ΔH are linear functions of NBO/t. Based on this relationship, a general model for CO₂ speciation in silicate melts is developed, with ln K = a + b/T, where T is temperature in Kelvin and a = ?2.69 ? 21.38 (NBO/t), b = 1,480 + 38,810 (NBO/t). The model shows that at temperatures around 1,500 °C, even depolymerized melts such as basalt contain appreciable amounts of molecular CO₂, and therefore, the diffusion coefficient of CO₂ is only slightly dependent on composition at such high temperatures. However, at temperatures close to 1,000 °C, the model predicts a much stronger dependence of CO₂ solubility and speciation on melt composition, in accordance with available solubility data.     

Structural states of natural potassium feldspar: An infrared spectroscopic study

Natural samples of K-feldspar representing various states of Al, Si order were characterised using X-ray methods, transmission electron microscopy, and Fourier transform infrared spectroscopy. Line profiles of infrared absorption bands were observed to show strong correlation with the degree of Al, Si order present. In particular, the absorption frequencies of the 540 cm^?1 and 640 cm^?1 bands were seen to vary by ca. 10 cm^?1 between sanidine and microcline, with modulated samples respresenting intermediate behaviour. Linewidths of these modes also decrease by ca. 50% in this series. The experimental results are discussed within the framework of Hard Mode Infrared Spectroscopy (HMIS), and it is shown that the absorption frequencies vary with the short range order parameter τ = (4t₁-1)² and the symmetry breaking order parameter describing Al, Si order, Q _od=(t₁ 0?t₁ m)/Q _od=(t₁ 0+t₁ m), where t₁ is the average Al occupancy on the T₁ sites and t₁ o and t₁ m are the individual site occupancies of the T₁ o and T₁ m sites, respectively. The structural state of orthoclase is characterised by strain-induced modulations with large spatial variations of the modulation wavelength. No such modulations were observed in the degree of local Al, Si order. Sanidine shows mode hardening in excess of the extrapolated effect of symmetry breaking Al, Si order, which is presumably related to nonsymmetry breaking ordering between T₁ and T₂ sites and/or as yet unobserved short range order of the symmetry breaking ordering scheme. The possibility of an additional phase transition in K-feldspar at temperatures above 1300 K is discussed.     

Functional Performance of Three Invasive <Emphasis Type="Italic">Marenzelleria</Emphasis> Species Under Contrasting Ecological Conditions Within the Baltic Sea

A 4-week laboratory experiment investigated the behaviour (survival and bioirrigation) and impact of the invasive polychaetes Marenzelleria viridis, M. neglecta and M. arctia on sediment-water solutes exchange, porewater chemistry, and Fe and P interactions in high-salinity sandy sediment (HSS) and low-salinity muddy sediment (LSM) from the Baltic Sea. M. viridis showed deep burrowing with efficient bioirrigation (11 L m^?2 day^?1) and high survival (71%) in HSS, while M. arctia exhibited shallow burrowing with high bioirrigation (12 L m^?2 day^?1) and survival (88%) in LSM. M. neglecta behaved poorly in both ecological settings (bioirrigation, 5–6 L m^?2 day^?1; survival, 21–44%). The deep M. viridis bioirrigation enhanced total microbial CO₂ (TCO₂) production in HSS by 175% with a net efflux of NH₄⁺ and PO₄^3?, at rates 3- to 27-fold higher than for the other species. Although the shallow and intense bioirrigation of M. arctia in LSM stimulated microbial TCO₂ production to some extent (61% enhancement), the nutrient fluxes close to zero indicate that it effectively prevented the P release. Porewater Fe:PO₄^3? ratios revealed that the oxidizing effect of M. arctia bioirrigation increased the PO₄^3? adsorption capacity of LSM twofold relative to defaunated controls while no buffering of PO₄^3? was detected in M. viridis HSS treatment. Therefore, the different behaviour of the three species in various environments and the sharp contrast between M. viridis and M. arctia effects on C, N and P cycling must be considered carefully when the ecological role of Marenzelleria species in the Baltic Sea is evaluated.     

Primary productivity in the German Bight (1994–1996)

Within the KUSTOS program (Coastal Mass and Energy Fluxes-the Land-Sea Transition in the Southeastern North Sea) 28 to 36 German Bight stations were seasonally surveyed (summer 1994, spring 1995, winter 1995–1996) for light conditions, dissolved inorganic nutrient concentrations, chlorophylla (chla), and photosynthesis versus light intensity (P:E) parameters. Combining P:E curve characteristics with irradiance, attenuation, and chlorophyll data resulted in seasonal estimates of the spatial distribution of total primary production. These data were used for an annual estimate of the total primary production in the Bight. In winter 1996 the water throughout the German Bight was well mixed. Dissolved inorganic nutrient concentrations were relatively high (nitrogen [DIN], soluble reactive phosphorus [SRP], and silicate [Si]: 23, 1, and 10 μM, respectively). Chla levels generally were low (< 2 μg l⁻¹) with higher concentrations (4–16 μg l⁻¹) in North Frisian coastal waters. Phytoplankton was limited by light. Total primary production averaged 0.2 g C m⁻² d⁻¹. Two surveys in April and May 1995 captured the buildup of a strong seasonal thermo-cline accompained by the development of a typical spring diatom bloom. High nutrient levels in the mixed layer during the first survey (DIN, SRP, and Si: 46, 0.45, and 11 μM, respectively) decreased towards the second survey (DIN, SRP, and Si: 30.5, 0.12, and 1.5 μM, respectively) and average nutrient ratios shifted further towards highly imbalanced values (DIN:SRP: 136 in survey 1, 580 in survey 2; DIN:Si: 13.5 in survey 1, 96 in survey 2). Chla ranged from 2 to 16 μg l⁻¹ for the first survey and rose to 12–50 μg l⁻¹ in the second survey. Phytoplankton in nearshore areas continued to be light limited during the second survey, while data from the stratified regions in the open German Bight indicates SRP and Si limitation. Total primary production ranged from 4.0 to 6.3 g C m⁻² d⁻¹. During summer 1994 a strong thermal stratification was present in the German Bight proper and shallow coastal areas showed unusually warm (up to 22°C), mixed waters. Chla concentrations ranged from 2 to 18 μg l⁻¹. P:E characteristics were relatively high despite the low nutrient regime (DIN, SRP, and Si: 2, 0.2, and 1.5 μM, respectively), resulting in overall high total primary production values with an average of 7.7 g C m⁻² d⁻¹. Based on the seasonal primary production estimates of the described surveys a budget calculation yielded a total annual production of 430 g C m⁻² yr⁻¹ for the German Bight.     

Gamma-ray bursts as a result of the interaction of a shock from a supernova and a neutron-star companion

A supernova explosion in a close binary system in which one of the components is a compact magnetized object (neutron star or white dwarf) can form a narrow “tail” with length l _t ～10⁹ cm, width h _t ～10⁸ cm, and magnetic field B _t ～10⁶, due to the resulting shock wave flowing around the magnetosphere of the compact object. The energy released by the reconnection of magnetic field lines in this tail can accelerate electrons to relativistic speeds (γ≈10⁴), creating the conditions required for powerful synchrotron radiation at energies from hundreds of keV to several MeV, i.e., for a gamma-ray burst (GRB). The duration of this radiation will depend on the power of the shock that forms during the supernova. If the shock is not sufficiently powerful to tear off the magnetosphere tail from the compact object, the duration of the GRB will not exceed l _t /V _A ≤1 s, and the conditions necessary for an “afterglow” at softer energies will not arise. If the shock is more powerful, the tail can be torn from the magnetosphere, forming a narrow ejection, which is perceived in its relativistic motion toward the observer(Γ～10⁴) as an afterglow whose duration grows from tens of seconds at gamma-ray energies to tens of days in the optical. This may explain why afterglows are observed only in association with long GRBs (T ₉₀>10 s). Very short GRBs (T ₉₀<0.1 s) may be local, i.e., low-power, phenomena occurring in close pairs containing compact, magnetized objects, in which there is again an interaction between the magnetosphere of the compact object and a shock wave, but the shock is initiated by a flare on the companion, which is a red-dwarf cataclysmic variable, rather than by a supernova.