Variability in inorganic and organic nitrogen uptake associated with riverine nutrient input in the Gulf of Riga, Baltic Sea

Concentrations and rates of uptake of dissolved organic nitrogen (DON, free amino acids, and urea) and inorganic nitrogen (DIN, nitrate, and ammonium) were measured along two transects in the Gulf of Riga, a sub-basin of the Baltic Sea, during May and July 1996. Concentrations of total dissolved nitrogen (TDN) were 23±3 μg-at N 1⁻¹ in the northern region (mouth) and 41±5 μg-at N 1⁻¹ in the southern region (head) of the Gulf. Rates of nitrogen uptake, determined with¹⁵N-labeled substrates, reflected differences in TDN concentration between the regions. In May, uptake of DIN+DON measured 0.17 and 0.43 μg-at N 1⁻¹ h⁻¹ in the northern and southern parts of the Gulf, respectively. In July, DIN+DON uptake measured 0.38 and 0.68 μg-at N 1⁻¹ h⁻¹ in the north and south, respectively. Most of the variability in total nitrogen flux between the northern and southern regions was due to heterogeneity of DON utilization. Uptake of urea and dissolved free amino acid were up to 6 and 3 times greater in the south compared to the north. As evidenced by size-fractionation, plankton size structure appeared to play a role in the uptake of DON. The community in the southern part was largely composed of cells <5 μm, while up to 67% of the community in the northern part was composed of cells >5 μm. Our results indicate that DON was a major source of nitrogen to phytoplankton, particularly in the southern part of the Gulf.     

Isotopic biogeochemistry of dissolved organic nitrogen: A new technique and application

We present a new technique for isolating and isotopically characterizing dissolved organic nitrogen (DON) for non-marine waters, δ¹⁵N values for DON from lacustrine samples and data suggesting that this technique will be applicable to marine samples. Our technique involves preconcentration of DON via rotary evaporation and removal of dissolved inorganic nitrogen (DIN) via dialysis using a membrane that retains material above 100 Da. Results demonstrate quantitative removal of DIN, complete recovery of DON (95% or greater) and retention of isotopic integrity (isotope effect less than 0.4‰) for a solution containing a DON standard (tripeptide) and DIN in deionized water. Reproducibility of carbon and nitrogen isotope values and elemental concentrations is demonstrated for DOM from Chefswet Basin, Lake Superior and Grand Traverse Bay, Lake Michigan. The applicability of this technique to marine samples is suggested by demonstrating 99% removal of DIN from a sample of Gulf Stream water amended with ammonium and nitrate.     

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

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

Algal activity of dissolved organic nitrogen (DON) in the sediments of Lake Taihu,Eastern China

Understanding the contents and reactivity of dissolved organic nitrogen (DON) is important for illustrating its productivity contribution in aquatic ecosystem. The primary objective of this study was to investigate the characteristics and algal activity of DON in the sediments of Lake Taihu. A series of experiments were carried out to evaluate the algal bioavailability of DON fractions in the sediments of Lake Taihu, Eastern China. DON extracted in the lake sediments was separated into hydrophilic and hydrophobic forms by DAX-8 resin, and ammonia nitrogen in raw sample and hydrophilic fraction was removed by cation exchange resin. 77.42–109.18% DON recovery rates were obtained after DON fractionation at ZSW and DPG stations. The hydrophilic DON was the main DON form contributing 62.74–76.33% of total DON concentrations. Selenastrum capricornutum was incubated for 15 days with different nitrogen forms (raw sample, hydrophilic and hydrophobic fractions). Approximately 33.69–79.23% DON of the three fractions was available for algal uptake in the incubation. The order of DON bioavailability was ranked as follows: raw sample > hydrophilic fraction > hydrophobic fraction, indicating that hydrophilic fractions and raw samples exhibited higher DON bioavailability for algae. Parallel factor analysis resulted in identification of tryptophan-like proteins, tyrosine-like proteins and humic acid (HA)-like substances during the incubation periods. During the growth phase, the relative fluorescent intensities of tryptophan-like proteins, tyrosine-like substance and HA-like substance accumulated greatly with 24.84–26.38, 27.82–62.73 and 0–28.92%, respectively.     

Dissolved organic matter (DOM) export to a temperate estuary: seasonal variations and implications of land use

Inputs of dissolved carbon, nitrogen, and phosphorus were assessed for an estuary and its catchment (Horsens, Denmark). Seasonal patterns in the concentrations of DOM in the freshwater supply to the estuary differed depending on the soil and drainage characteristics of the area. In streams draining more natural areas the, patterns observed were largely driven by seasonal temperature fluctuations. The material exported from agricultural areas was more variable and largely controlled by precipitation events. Positive exponential relationships were found between the nitrogen and phosphorus loading, and the percentage of catchment area used for agriculture. Colored DOM (CDOM) loading measurements were found to be a good predictor of dissolved organic carbon (DOC) loading across the different subcatchments, offering a rapid and inexpensive alternative of operationally monitoring DOC export. For all the dissolved nutrient inputs to the estuary, dissolved inorganic nitrogen (DIN) and dissolved organic phosphorus dominated the loadings. Although 81% of the nitrogen annually supplied to the estuary was DIN, 83% of the nitrogen exported from the estuary was dissolved organic nitrogen (DON). Results show that increasing the area of the catchment covered by forest and natural pastures would have a positive effect on the trophic status of the estuary, leading to a considerable decrease in the phosphorus loading and a shift in the nitrogen loading from DIN to DON. Such a change in land use would also increase the export of DOC and CDOM to the estuary having the potential to increase oxygen consumption and reduce the photic depth.     

Decadal Changes in Water Quality and Net Productivity of a Shallow Danish Estuary Following Significant Nutrient Reductions

We utilized an extensive data set (1977–2013) from a water quality monitoring program to investigate the recovery of a Danish estuary following large reductions in total phosphorus (TP) and total nitrogen (TN) loading. Monthly rates of net transport and biogeochemical transformation of dissolved inorganic nitrogen (DIN) and phosphorus (DIP) were computed in two basins of the estuary using a box model approach, and oxygen-based rates of net ecosystem production (NEP) were determined. Since 1990, nutrient loading was reduced by 58 % for nitrogen and 80 % for phosphorus, causing significant decreases in DIN (60 %) and DIP (85 %) concentrations. Reductions in nutrient loadings and concentrations reduced annual chlorophyll levels by 50 % in the inner estuary and improved Secchi depth by approximately 1 m during the same period, particularly in the summer period. In the outer, deeper region of the estuary trends in water quality was less evident. Improvements in the inner estuary were strongly coupled to declines in DIN. Thresholds of DIN and DIP concentrations limiting phytoplankton growth indicated that both regions of the estuary were nitrogen limited. NEP rates indicated the development of more net autotrophic conditions over time that were likely associated with higher benthic primary production stimulated by improved light conditions. Box model computations revealed a modest reduction in summer net production of DIP over time, despite the persistence of elevated fluxes for several years after external loads were reduced. Since the mid-1990s, nutrient loading and transformation were stable while nutrient concentrations continued to decline and water quality improved in the inner estuary. The oligotrophication trajectory involved an initial fast transformation and modest retention of nutrients followed by a gradual decline in the rate of improvement towards a new stable condition.     

Submarine Groundwater Discharge Estimates Using Radium Isotopes and Related Nutrient Inputs into Tauranga Harbour (New Zealand)

Land-based pollutants such as fertilizers and wastewater can infiltrate into aquifers and discharge into surrounding coastal water bodies as submarine groundwater discharge (SGD). Oceanic islands, with a large coast length to land area ratio, may be hot spots of SGD into the global ocean. Although SGD may be a major pathway of dissolved nutrients, carbon and metals to coastal waters, studies have been limited due to the difficulties in measuring this often diffuse process. This study used radium isotopes (²²³Ra, ²²⁴Ra, ²²⁶Ra) to investigate SGD and the associated fluxes of nutrients into Tauranga Harbour, New Zealand. We calculated the apparent water mass ages of the harbour to be between ~4.1 and 7.8 days, which was similar to a previous numerical model of ~2–8 days. A ²²⁶Ra mass balance was constructed to quantify SGD fluxes at the harbour scale. A minimum SGD flux rate of 0.53 cm day^?1 was calculated by using the maximum groundwater end-member value from 22 sample sites. However, using the geometric mean from these samples as a representative end-member, a final value of 2.83 cm day^?1 or a flux of 3.09 × 10⁶ m³ day^?1 was calculated. These values were between ~1 and 2.8 times greater than all the major river and creeks discharging into the harbour during the sampling period. Due to the higher observed nutrient concentrations in groundwater, the SGD-derived dissolved inorganic nitrogen (DIN), dissolved organic nitrogen (DON) and total dissolved phosphorus (TDP) fluxes were calculated to be 1.07, 0.87 and 0.05 mmol m² day^?1, respectively. These SGD inputs were ~5 times (for nitrogen) and ~8 times (for phosphorus) greater than the input from surrounding rivers and streams. The average N:P ratio in groundwater samples was 36:1 (which was greatly in excess of the Redfield ratio of 16). The harbour water had a N:P ratio of ~17:1. A positive relationship between radium isotopes and N:P ratios in the harbour further supported the hypothesis that SGD can have major implications for primary production, including recurrent algal bloom events which occur in the harbour. We suggest SGD as a major driver of nutrient dynamics in Tauranga Harbour and potentially other similar coastal lagoon systems and estuaries on oceanic islands.     

Inorganic and Organic Nitrogen Use by Phytoplankton Along Chesapeake Bay,Measured Using a Flow Cytometric Sorting Approach

Two different approaches to measuring phytoplankton nitrogen (N) use were compared in late summer 2004 along the main axis of Chesapeake Bay. Uptake of ¹⁵N-labeled ammonium and nitrate and dual-labeled (¹⁵N and ¹³C) urea and dissolved free amino acids (DFAA) were measured in surface water samples from upper, mid, and lower bay stations. Two distinct methods were used to assess the relative uptake of N substrates by phytoplankton and correct for bacterial artifacts: (1) traditional filtration using Whatman glass fiber (GF/F) filters and (2) flow cytometric (FCM) sorting of chlorophyll-containing cells. The concentration of dissolved inorganic N (DIN) decreased with distance south along the bay, whereas dissolved organic N (DON) concentrations were relatively constant. Absolute N uptake rates measured using the traditional approach exceeded those of FCM-sorted phytoplankton, thereby suggesting the possibility of bacterial “contamination.” Ammonium was the dominant N form used throughout the transect, although FCM-sorted phytoplankton relied more on urea and DFAA as the ratio of DON/DIN increased toward the bay mouth. Overall, ammonium comprised 74 ± 17%, urea 10 ± 9%, DFAA 9 ± 7%, and nitrate 7 ± 12% of total measured N uptake by phytoplankton. Results suggest that bacteria relied primarily on DFAA and ammonium for N nutrition but also used N from urea at a rate similar to that of phytoplankton, whereas bacterial nitrate uptake was insignificant. On average, phytoplankton uptake of ammonium, urea, and DFAA was overestimated by 61%, 53%, and 135%, respectively, as a result of bacterial retention on GF/F filters.     

Marine Macrophyte Wrack Inputs and Dissolved Nutrients in Beach Sands

We investigated the role of sandy beaches in nearshore nutrient cycling by quantifying macrophyte wrack inputs and examining relationships between wrack accumulation and pore water nutrients during the summer dry season. Macrophyte inputs, primarily giant kelp Macrocystis pyrifera, exceeded 2.3 kg m⁻¹ day⁻¹. Mean wrack biomass varied 100-fold among beaches (range = 0.41 to 46.43 kg m⁻¹). Mean concentrations of dissolved inorganic nitrogen (DIN), primarily NO_x⁻-N, and dissolved organic nitrogen (DON) in intertidal pore water varied significantly among beaches (ranges = 1 to 6,553 μM and 7 to 2,006 μM, respectively). Intertidal DIN and DON concentrations were significantly correlated with wrack biomass. Surf zone concentrations of DIN were also strongly correlated with wrack biomass and with intertidal DIN, suggesting export of nutrients from re-mineralized wrack. Our results suggest beach ecosystems can process and re-mineralize substantial organic inputs and accumulate dissolved nutrients, which are subsequently available to nearshore waters and primary producers.     

Nutrient-Replete Benthic Microalgae as a Source of Dissolved Organic Carbon to Coastal Waters

Dissolved organic carbon (DOC) flux dynamics were examined in the context of other biogeochemical cycles in intertidal sediments inhabited by benthic microalgae. In August 2003, gross oxygenic photosynthetic (GOP) rates, oxygen penetration depths, and benthic flux rates were quantified at seven sites along the Duplin River, GA, USA. Sediments contained abundant benthic microalgal (BMA) biomass with a maximum chlorophyll a concentration of 201 mg chl a m^?2. Oxygen microelectrodes were used to determine GOP rates and O₂ penetration depth, which were tightly correlated with light intensity. Baseline and ¹⁵N-nitrate amended benthic flux core incubations were employed to quantify benthic fluxes and to investigate the impact of BMA on sediment water exchange under nitrogen (N)-limited and N-replete conditions. Unamended sediments exhibited tight coupling between GOP and respiration and served as a sink for water column dissolved inorganic nitrogen (DIN) and a source of silicate and dissolved inorganic carbon (DIC). The BMA response to the N addition indicated sequential nutrient limitation, with N limitation followed by silicate limitation. In diel (light–dark) incubations, biological assimilation accounted for 83% to 150% of the nitrate uptake, while denitrification (DNF) and dissimilatory nitrate reduction to ammonium (DNRA) accounted for <7%; in contrast, under dark conditions, DNF and DNRA accounted for >40% of the NO₃ ^? uptake. The N addition shifted the metabolic status of the sediments from a balance of autotrophy and heterotrophy to net autotrophy under diel conditions, and the sediments served as a sink for water column DIN, silicate, and DIC but became a source of DOC, suggesting that the increased BMA production was decoupled from sediment bacterial consumption of DOC.     

Nutrient and Phytoplankton Dynamics in Harima-Nada, Eastern Seto Inland Sea, Japan During a 35-Year Period from 1973 to 2007

Long-term monitoring of water quality and phytoplankton was conducted at 19 sampling stations in Harima-Nada, eastern Seto Inland Sea, Japan for 35 years from 1973 to 2007. There were two significant long-term changes, an increase in winter water temperatures of 0.042°C year^?1, and a decrease in dissolved inorganic nitrogen (DIN) from about 10 μM in the 1970s to ~5 μM in the late 1990s due to the reduction in nutrient inputs. DIN concentrations and total phytoplankton cell density were both higher during the 1970s to the early 1980s and then exhibited a significant decrease in the mid 1980s and remained relatively constant thereafter. Diatoms were the dominant phytoplankton group (>90%) over the 35-year period, and there was a dramatic shift from Skeletonema dominance (~70%) to Chaetoceros in the mid 1980s. This shift in diatom species may be attributed to differences in the life cycle of Skeletonema and Chaetoceros and the response to the decrease in DIN concentration.     

A preliminary study on the distribution characteristics of nutrients （N, P, Si, C） in the Wujiang River Basin

The distribution of nutrients (N, P, Si, C) in the Wujiang River surface water was studied during the high-flow and low-flow periods in 2002. The results showed that nitrate nitrogen (NO3-N) is the main form of dissolved inorganic nitrogen (DIN) in the Wujiang River Basin. It accounts for about 90% of DIN. The average NO3-N concentrations in the mainstream are 147.5 μM in the high-flow period and 158.0 μM in the low-flow period, respectively. The average concentrations of total phosphorus (TP) are 6.43 μM in the high-flow period and 4.18 μM in the low-flow period, respectively. Of the various forms of phosphorus, particulate phosphorus (PP) has the highest percentage ( 62.9%) of TP in the high-flow period. In the low-flow period, however, phosphate is the main form of phosphorus, which accounts for 49% of TP. With the Wujiangdu Reservoir as the boundary, the concentrations of DIN and phosphorus in the upper reaches are different from those in the lower reaches of the Wujiang River. As a whole, the concentrations of DIN and phosphorus are both higher in the low-flow period than in the high-flow period. The spatial and temporal variations of DIN and phosphorus concentrations suggested that DIN and phosphorus come from agricultural and domestic wastewaters and groundwaters and that the Wujiangdu Reservoir has an important impact on the concentrations and distribution of DIN and phosphorus in the Wujiang River. The distribution patterns of dissolved silica (DSi) and dissolved organic carbon (DOC) are similar. Both of them maintain no change in the whole course of the river and their concentrations (with the exception of the reservoir itself) are higher in the high-flow period than in the low-flow period. The average DSi and DOC concentrations in the mainstream are 85.4, 84.6 μM in the high-flow period and 60.8, 53.9 μM in the low-flow period, respectively. The concentrations of nutrients in most of the major tributaries are lower than in the mainstream. This suggested that the contributions of most tributaries are relatively small but importance should be attached to the influence of some individual tributaries such as the Qingshuijiang River and the Weng'an River on the mainstream.     

Fluxes of dissolved combined neutral sugars (polysaccharides) in the Delaware estuary

This project examined concentrations, composition and turnover neutral sugars in the Delaware estuary to gain insights into dissolved inorganic nitrogen (DIN) use by heterotrophic bacteria and into the lability and diagenetic state of dissolved organic material (DOM) during passage through the estuary. Dissolved free monosaccharides were not measurable (<5 nM) in the estuary whereas concentrations of dissolved combined neutral sugars (DCNS) were high, much higher than observed in oceanic waters. DCNS made up a similar fraction of dissolved organic carbon (DOC) as in the oceanic waters examined to date, and the monosaccharide composition of the DCNS pool was similar to that of oceanic waters. The composition did not vary substantially within the estuary or seasonally, but it did vary among three size fractions of the organic matter pool. Glucose was enriched in the low molecular weight fraction of DOC and in particulate material, whereas the high molecular weight DOC fraction was slightly depleted in glucose. Depletion experiments indicated that DCNS is not used extensively on the day time scale in the Delaware estuary, although freshly-produced polysaccharides may still be important carbon sources for heterotrophic bacteria. The very low concentrations of free monosaccharides in the Delaware estuary help to explain why DIN use by heterotrophic bacteria is relatively low in this estuary. Although DOC-DIN interactions in the Delaware apparently differ from oceanic waters, the portion of DOM traced by DCNS, which is thought to be the labile fraction, appears to be similar to that of oceanic DOM, suggesting that organic material in the estuary is degraded extensively before being exported to the coastal ocean.     

太湖水体氮、磷赋存量的逐月变化规律研究

基于中国科学院太湖湖泊生态系统研究站2005~2009年对太湖逐月叶绿素a、氮、磷各形态因子及水深的监测,结合太湖大浦水文站的逐日水位数据,估算出2005~2009年太湖的逐日水量,并运用泰森多边形法,估算出太湖水体总氮（TN）、总磷（TP）、溶解性总氮（TDN）、溶解性总磷（TDP）、硝态氮（NO3）、铵态氮（NH4）、亚硝态氮（NO2）、反应性活性磷（PO₄）、颗粒态总氮（TPN）、颗粒态总磷（TPP）、浮游藻类叶绿素a（Chla）的逐月动态变化过程。结果表明:（1）太湖2005~2009年TN、TDN、NO₂、NO₃、NH₄、TP、TDP、PO₄、TPN、TPP、Chla的平均赋存量分别为1.36×104t、1.02×104t、0.02×104t、0.37×104t、0.25×104t、514.34 t、147.30 t、51.44 t、0.34×104t、367.04 t、7.92 t,不同月份、年际之间变化剧烈,变幅分别为106%、142%、657%、252%、233%、95%、196%、276%、236%、131%、276%;（2）2007年6月无锡贡湖水厂"饮用水危机"事件之后,截止到2009年12月,太湖水体各形态氮及总磷赋存量的下降趋势不明显,溶解性总磷、反应性活性磷的赋存量反而增高,反映出营养盐控制任务的艰巨性。本研究表明,对于年水量变幅巨大的大型湖泊,全湖水体营养盐赋存量在评估水体营养盐污染状况中是一个有价值的指标;对于太湖流域的污染控制效果,仅从浓度角度评价具有一定的缺陷,有必要从水体营养盐赋存量的变化规律上探讨其治理效果。     

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.     

Chemistry of the heavily urbanized Bagmati River system in Kathmandu Valley, Nepal: export of organic matter, nutrients, major ions, silica, and metals

Water quality in less-developed countries is often subject to substantial degradation, but is rarely studied in a systematic way. The concentration and flux of major ions, carbon, nitrogen, silicon, and trace metals in the heavily urbanized Bagmati River within Kathmandu Valley, Nepal, are reported. The concentrations of all chemical species increased with distance downstream with the exceptions of protons and nitrate, and showed strong relationships with population density adjacent to the river. Total dissolved nitrogen (TDN), dominated by NH₄, was found in high concentrations along the Bagmati drainage system. The export of dissolved organic carbon (DOC) and TDN were 23 and 33 tons km^?2 year^?1, respectively, at the outlet point of the Kathmandu Valley, much higher than in relatively undeveloped watersheds. The cationic and silica fluxes were 106 and 18 tons km^?2 year^?1 at the outlet of the Bagmati within Kathmandu Valley, and 36 and 32 tons km^?2 year^?1 from the relatively pristine headwater area. The difference between headwaters and the urban site suggests that the apparent weathering flux is three times higher than the actual weathering rate in the heavily urbanized Bagmati basin. Fluxes of cations and silica are above the world average, as well as fluxes from densely populated North American and European watersheds. End-member composition of anthropogenic sources like sewage or agricultural runoff is needed to understand the drivers of this high rate of apparent weathering.     

Tidal pumping drives nutrient and dissolved organic matter dynamics in a Gulf of Mexico subterranean estuary

We hypothesize that nutrient cycling in a Gulf of Mexico subterranean estuary (STE) is fueled by oxygen and labile organic matter supplied by tidal pumping of seawater into the coastal aquifer. We estimate nutrient production rates using the standard estuarine model and a non-steady-state box model, separate nutrient fluxes associated with fresh and saline submarine groundwater discharge (SGD), and estimate offshore fluxes from radium isotope distributions. The results indicate a large variability in nutrient concentrations over tidal and seasonal time scales. At high tide, nutrient concentrations in shallow beach groundwater were low as a result of dilution caused by seawater recirculation. During ebb tide, the concentrations increased until they reached a maximum just before the next high tide. The dominant form of nitrogen was dissolved organic nitrogen (DON) in freshwater, nitrate in brackish waters, and ammonium in saline waters. Dissolved organic carbon (DOC) production was two-fold higher in the summer than in the winter, while nitrate and DON production were one order of magnitude higher. Oxic remineralization and denitrification most likely explain these patterns. Even though fresh SGD accounted for only ∼5% of total volumetric additions, it was an important pathway of nutrients as a result of biogeochemical inputs in the mixing zone. Fresh SGD transported ∼25% of DOC and ∼50% of total dissolved nitrogen inputs into the coastal ocean, with the remainder associated with a one-dimensional vertical seawater exchange process. While SGD volumetric inputs are similar seasonally, changes in the biogeochemical conditions of this coastal plain STE led to higher summertime SGD nutrient fluxes (40% higher for DOC and 60% higher for nitrogen in the summer compared to the winter). We suggest that coastal primary production and nutrient dynamics in the STE are linked.     

Removal of organic matter from reservoir water: mechanisms underpinning surface chemistry of natural adsorbents

One of the key challenges in water treatment industry is the removal of organic compounds by cost-effective methods. This study evaluated the adsorptive removal of dissolved organic carbon (DOC) from reservoir water using fuller’s earth (FE) in comparison with natural (SQ) and modified quartz (MSQ) sands. The removal capacities of FE at different contact times, pH levels, adsorbent dosages and initial DOC concentrations were compared with both the quartz sands. The optimum DOC removals by FE and SQs were achieved at contact time of 60 and 30 min, pH level of 6 and 4, and at adsorbent dose of 1.5 g/150 mL and 10 g/100 mL, respectively. The adsorption capacity of FE (1.05 mg/g) was much higher compared to the MSQ (0.04 mg/g) and SQ (0.01 mg/g). Adsorption equilibrium data better fitted to the Freundlich model than to the Langmuir model, suggesting that adsorption occurred primarily through multilayer formation onto the surfaces of FE and SQ. The pseudo-second-order model described the uptake kinetics more effectively than the pseudo-first-order and intra-particle diffusion models, indicating that the mechanism was primarily governed by chemisorption. These observations were well supported by the physiochemical characteristics and charge behaviour of the adsorbents. In mass-transfer study, the results of liquid film diffusion model showed that the adsorption of DOC on FE was not controlled by film diffusion, but other mechanisms also played an essential role. This study demonstrates that FE is an effective adsorbent for the removal of DOC in surface water treatment.     

Effects of Local Watershed Land Use on Water Quality in Mid-Atlantic Coastal Bays and Subestuaries of the Chesapeake Bay

Nutrient inputs have degraded estuaries worldwide. We investigated the sources and effects of nutrient inputs by comparing water quality at shallow (< 2m deep) nearshore (within 200 m) locations in a total of 49 Chesapeake subestuaries and Mid-Atlantic coastal bays with differing local watershed land use. During July–October, concentrations of total nitrogen (TN), dissolved ammonium, dissolved inorganic N (DIN), and chlorophyll a were positively correlated with the percentages of cropland and developed land in the local watersheds. TN, DIN, and nitrate were positively correlated with the ratio of watershed area to subestuary area. Total phosphorus (TP) and dissolved phosphate increased with cropland but were not affected by developed land. The relationships among N, P, chlorophyll a, and land use suggest N limitation of chlorophyll a production from July–October. We compared our measurements inside the subestuaries to measurements by the Chesapeake Bay Program in adjacent estuarine waters outside the subestuaries. TP and dissolved inorganic P concentrations inside the subestuaries correlated with concentrations outside the subestuaries. However, water quality inside the subestuaries generally differed from that in adjacent estuarine waters. The concentration of nitrate was lower inside the subestuaries, while the concentrations of other forms of N, TP, and chlorophyll a were higher. This suggests that shallow nearshore waters inside the subestuaries import nitrate while exporting other forms of N as well as TP and chlorophyll a. The importance of local land use and the distinct biogeochemistry of shallow waters should be considered in managing coastal systems.     

Biogeochemical characteristics of the lower Mississippi River, USA, during June 2003

During June 2003, a period of mid level discharge (17,400 m⁻³ s⁻¹), a parcel of water in the lower Mississippi River was sampled every 2 h during its 4-d transit from river km 362 near Baton Rouge to km 0 at Head of Passes, Louisiana, United States. Properties measured at the surface during each of the 48 stations were temperature, salinity, dissolved organic carbon (DOC), total dissolved nitrogen, dissolved macronutrients (NO₃+NO₂, PO₄, Si(OH)₄), chlorophylla (chla; three size fractions: < 5 μm, 5–20 μm, and > 20 μm) pigment composition by HPLC, total suspended matter (TSM), particulate organic carbon (POC), and particulate nitrogen (PN). Air-water CO₂ flux was calculated from surface water dissolved inorganic carbon and pH. During the 4 d transit, large particles appeared to be settling out of the surface water. Concentrations of chla containing particles > 20 μm declined 37%, TSM declined 43%, POC declined 42% and PN declined 57%. Concentrations of the smaller chla containing particles did not change suggesting only large particulate materials were settling. There was no measurable loss of dissolved NO₃, PO₄, or Si(OH)₄, consistent with the observation that chla did not increase during the 4-d transit. DOC declined slightly (3%). These data indicate there was little autotrophic or heterotrophic activity in the lower Mississippi River at this time, but the system was slightly net heterotrophic.