Vertical and horizontal distribution of fluorescent dissolved organic matter in the Southern Ocean

The vertical and horizontal distribution of fluorescent dissolved organic matter (FDOM), determined by fluorescence intensity at 320 nm excitation and 420 nm emission, were clarified in nine stations on two transects at the Southern Ocean, including a subtropical, subantarctic, polar frontal and Antarctic zone. All vertical profiles of fluorescence intensity showed that levels were lowest in the surface waters, increased with increasing the depth in mid-depth waters ( 2000 m), and then stayed within a relatively narrow range from there to the bottom. Such vertical profiles of FDOM were similar to those of nutrients, but were adverse to dissolved oxygen. In water columns below the temperature-minimum subsurface water (dichothermal waters) in the Antarctic zone and below the winter mixed layer in the other zones, we determined the relationships of fluorescence intensity to concentrations of nutrients and apparent oxygen utilization (AOU) over the entire area of the present study, and found significant linear correlations between the levels of fluorescence intensity and nutrient concentrations (r =  0.70 and 0.71 for phosphate and nitrate + nitrite, respectively) and AOU (r = 0.91). From the strong correlation coefficient between fluorescence intensity and AOU, we concluded that FDOM in the Southern Ocean is formed in situ via the biological oxidation of organic matter. The regeneration of the nutrients/consumption of the oxygen/formation of FDOM was active in mid-depth waters. However, the correlations between fluorescence intensities and nutrients and AOU were different in the mid-depth water masses, Subantarctic Mode Water (SAMW), and Antarctic Intermediate Water (AAIW), indicating that the sources of organic matter responsible for FDOM formation were different. A considerable amount of FDOM in the SAMW is thought to be produced by the remineralization of DOM in addition to sinking particulate organic matter, while DOM is less responsible for FDOM formation in the AAIW.     

Limited nutritional benefit to the seagrass Halophila ovalis, in culture, following sediment organic matter enrichment

Essential nutrients for seagrass growth may be derived from benthic decomposition of organic matter. To test this idea, cores of Halophila ovalis (seagrass-vegetated) and unvegetated sediment (control) were amended with either particulate organic matter (POM) or dissolved organic matter (DOM) to test whether a positive feed-back loop exists, where increased organic matter results in increased seagrass nutrients. POM was added in the form of seagrass wrack (0, 1, 5, 12 g core⁻¹) and DOM was added with sucrose diffusion tubes at the root zone (0, 0.8, 2.4, 5.2 g core⁻¹). Cores were incubated under saturating light conditions (12 h light/12 h dark) at 18 °C, for 4 weeks. Results suggest a complex balance between positive and negative effects of organic matter enrichment. Whilst leaf molar concentrations of N and P of H. ovalis increased (by 15 and 30% respectively), plant growth declined (up to 50% relative to control) for both DOM and POM enrichments. Phosphate was removed from sediment porewater following POM addition and most likely translocated to the leaves. Stressors other than nutrient limitation (e.g. biogeochemical constraints) reduce growth and affect the nutrient dynamics of the seagrass and should be the focus of future work.     

Spring–summer cycling of DOC, DON and inorganic N in a highly seasonal system encompassing the Northeast Water Polynya, 1993

Dissolved organic nitrogen (DON), dissolved organic carbon (DOC) and inorganic nutrient concentrations were determined in samples from an area encompassing the Northeast Water Polynya from June to August 1993. In June, still ice-covered polynya area surface waters (PySW) had significantly higher (p<0.05) DOC concentrations (110 μM, n=68) than surface water outside the polynya area (96 μM, n=6). Melting ice and ice algae are suggested as DOC sources. DOC concentrations found in this study are consistent with other studies showing higher DOC concentrations in the Arctic than in other ocean areas. As the productive season progressed, DOC concentrations in Polynya surface water (PySW) decreased (p<0.05) from 110 to 105 μM, while DON concentrations increased (p<0.05) from 5.6 to 6.1 μM, causing a significant decrease (p<0.05) in the C : N ratios of DOM from spring (C : N ratio 20) to summer (C : N ratio 17). We found a significant (p<0.05) decrease in the DOM C : N ratio in all water masses within the polynya area as the productive season progressed. DON was the largest fraction of total dissolved nitrogen (TDN) in PySW and surface waters outside the polynya area. TDN was calculated as the sum of DON, nitrate, nitrite and ammonium concentrations. DON increased (p<0.05) from 62% to 73% of TDN in PySW from spring to summer, a result of increasing DON concentrations and decreasing inorganic nitrogen concentrations over the productive season. The seasonal accumulation of DON and the corresponding decrease in nitrate concentrations in waters with primary production indicate that it is important to take the DON pool into account when estimating export production from nitrate concentration decreases in surface waters. PySW TDN concentrations decreased (p<0.05) from 9.1 (n=61) to 8.6 μM (n=60) from spring (May 25 through June 19) to summer (July 1 through July 27). The seasonal decrease in surface water TDN concentrations corresponded to increases in TDN concentrations in deeper water masses within the Polynya. Most of the TDN increase in deep water was in the form of DON. A possible explanation is that PON was dissolved (partially remineralized) in the water column at mid depths, causing increases in the DON concentration. Transfer of N from PySW (with a short residence time in the polynya area) to Polynya Intermediate Water and deep waters of the Norske and Westwind Trough with multi-year residence times keeps N from leaving the polynya area. In spring, nutrients from degradation of OM in PyIW could support primary production. The role of PyIW as an OM trap could be important in supporting primary production in the polynya area.     

Spatial and seasonal evolution of dissolved oxygen and nutrients in the Southern Levantine Basin (Eastern Mediterranean Sea): chemical characterization of the water masses and inferences on the N : P ratios

The spatial and seasonal variability of nutrients and dissolved oxygen concentrations as well as the chemical characterization of the different water masses of the Southern Levantine Basin were determined in detail. In summer, the upper 150 m of the water body was stratified and the cross basin distribution of dissolved oxygen and nutrients was fairly constant. Surficial waters were saturated with dissolved oxygen, and a shallow oxygen maximum (oversaturated) was present at about 80 m depth. Oversaturation was attributed mainly to the physical process of rapid capping and trapping of oxygen in the Atlantic water (AW) mass, with only 28% of the excess oxygen originating from biological production. Nutrient concentrations were very low and showed an increase in the intermediate levels, coupled with a decrease in oxygen. The winter cross-section distribution showed an upper mixed layer of 100 m, with dissolved oxygen and nutrient concentrations fairly constant across the basin. The concentration of nitrate was higher than in summer, while phosphate was slightly lower and silicic acid similar. In winter, the influence of the physical features (gyres) could be detected up to the surface, and in summer they were detected by the chemical properties in the 150–600 m layer. In the transition layer between the Levantine intermediate water (LIW) and the deep water (DW) (400–700 m) there was a gradual decrease in dissolved oxygen and an increase in nutrient concentrations eastwards. The DW showed no seasonal variation, only spatial variability: dissolved oxygen decreased and silicic acid increased eastwards. No differences were found in nitrate and phosphate concentrations between the DW in the western and eastern provinces, indicating the oxidation of organic matter poor in N and P.N : P ratios in the upper water masses were seasonally dependent. The largest variation was found in the Levantine surface water (LSW), from an average of 52 in winter to 5 in summer. It is hypothesized that the gradual decrease from winter to summer values was due mainly to preferential atmospheric input of N in winter and P in summer, together with biological consumption and differential regeneration of N and P. In the DW, the N : P ratios were constant throughout the year (25.2±2.7, n=567), and higher than Redfield's ratio. It was speculated that the high N : P ratio in the DW was a result of oxidation of particulate organic matter deficient in P.The winter wet atmospheric input of N provided 12% of new N to the LSW. Average new production for the Southern Levantine Basin was estimated from the new N as 4.75 g C m⁻² yr⁻¹. The dry atmospheric contribution of P was estimated to significantly increase the P pool in the LSW. Dry deposition is not evenly distributed and occurs in episodic and localized events, which may have a large effect on productivity in the short periods when deposition occurs.There have been recently reported changes in the deep thermohaline circulation of the Eastern Mediterranean, with main contribution of the Aegean Sea as a source of DW. The data presented here can serve as a reference for assessing future changes in the chemical composition of the water masses in the Southern Levantine.     

Control of domoic acid toxin expression in Pseudo-nitzschia multiseries by copper and silica: Relevance to mussel aquaculture in New England (USA)

The production of the toxin Domoic Acid (DA) by the diatoms Pseudo-nitzschia spp. is affected by several environmental factors, among them copper and silica. The effects of these nutrients upon DA production have been studied individually, but not in combination. There is evidence, however, that in diatoms copper can enter the cell via the silicic-acid transport site. The goal of this study was to analyze the effect of the interaction between copper and silicic-acid supply upon DA production in Pseudo-nitzschia multiseries. The study was motivated by concerns about the risk of toxigenic Pseudo-nitzschia spp. impacting mussel aquaculture in New England (USA). The results of the present study do not indicate that copper uses the silicic acid transport site to enter the cell; nevertheless, there is an interaction between these two nutrients that produces a synergistic affect upon toxin production. A small increase in copper, without a simultaneous increase in silicate, as well as an increase in both copper and silicate, leads to DA up-regulation. Furthermore, the field component of this study reports the presence of species of Pseudo-nitzschia on the New England coast that are capable of producing DA. Together these findings indicate that risk of DA impacting mussel aquaculture along the coast of New England would be increased by an unusual enrichment of copper in the vicinity of mussel farms.     

Photochemical production of ammonium and transformation of dissolved organic matter in the Baltic Sea

The release of ammonium from the photochemical degradation of dissolved organic matter (DOM) has been proposed by earlier studies as a potentially important remineralisation pathway for refractory organic nitrogen. In this study the photochemical production of ammonium from Baltic Sea DOM was assessed in the laboratory. Filtered samples from the Bothnian Bay, the Gulf of Finland and the Arkona Sea were exposed to UVA light at environmentally relevant levels, and the developments in ammonium concentrations, light absorption, fluorescence and molecular size distribution were followed. The exposures resulted in a decrease in DOM absorption and loss of the larger sized fraction of DOM. Analysis of the fluorescence properties of DOM using parallel factor analysis (PARAFAC) identified 6 independent components. Five components decreased in intensity as a result of the UVA exposures. One component was produced as a result of the exposures and represents labile photoproducts derived from terrestrial DOM. The characteristics of DOM in samples from the Bothnian Bay and Gulf of Finland were similar and dominated by terrestrially derived material. The DOM from the Arkona Sea was more autochthonous in character. Photoammonification differed depending on the composition of DOM. Calculated photoammonification rates in surface waters varied between 121 and 382 μmol NH₄⁺ L^− 1 d^− 1. Estimated areal daily production rates ranged between 37 and 237 μmol NH₄⁺ m^− 2 d^− 1, which are comparable to atmospheric deposition rates and suggest that photochemical remineralisation of organic nitrogen may be a significant source of bioavailable nitrogen to surface waters during summer months with high irradiance and low inorganic nitrogen concentrations.     

Response of early Ruppia cirrhosa litter breakdown to nutrient addition in a coastal lagoon affected by agricultural runoff

The response of early Ruppia cirrhosa Petagna (Grande) litter decomposition to external nitrogen and phosphorus availability in La Tancada (Ebro River, NE Spain), a coastal lagoon that receives agricultural freshwater runoff from rice fields has been examined. Recently abscised dead R. cirrhosa stems were collected and 25 g of fresh weight was placed in litter bags with a mesh size of 100 μm and 1 mm. These bags were fertilised by adding nitrogen (N), a mixture of nitrogen plus phosphorus (N + P), or phosphorus (P), or were left untreated (CT). Macroinvertebrates were retrieved from the bags and the ash-free dry weight, and carbon, and N and P content of the remaining plant material were measured after 0, 3, 7, 14, 22 and 32 days. Litter decomposition rates, k (day⁻¹), were estimated using a simple exponential model. Litter decay was clearly accelerated by the addition of P in the fine (100 μm) litter bags (0.042), but when N was added alone (0.0099) the decomposition rate was lower than in the CT treatments (0.022). No significant difference was observed between the N (0.0099–0.018) and N + P (0.0091–0.015) treatments in either the fine or the coarse (1 mm) litter bags. These results could be attributed to the relatively high availability of external (environmental) and internal (detritus contents) N. No significant effect of macro invertebrates was observed in the CT treatment or under N or P or N + P addition. The ratio between the decomposition rates in coarse and fine litter bags (k_c/k_f) was lower in disturbed Tancada lagoon (0.82) than in Cesine lagoon (2.11), a similar Mediterranean coastal water body with almost pristine conditions. These results indicate that, in addition to data on macroinvertebrate community structure, decomposition rates could also be used to assess water quality in coastal lagoons.     

Variations of the Nutrients Loads to the Mainland U.K. Estuaries: Correlation with Catchment Areas, Urbanization and Coastal Eutrophication

The annual loads of nutrients (TO_xN equal to nitrate+nitrite; ammonium, phosphate, silicate) to all the estuaries on the mainland of the United Kingdom were estimated from data on water flow through gauging stations at the tidal limits of estuaries, and from concentration measurements under the Harmonised Monitoring Scheme of nutrient concentrations in water samples from these stations. The annual loads of nutrients showed distinct regional variations, with estuaries along the west coast of Wales and northern Scotland having much smaller loads than those along the east coast of England. The largest nitrogen loads were of TO_xN, and ammonium loads were usually small in comparison. The Severn, Mersey, Humber and Thames had the highest loads, although these were small in relation to the larger continental European estuaries. Loads of TO_xN per unit of catchment area were surprisingly constant (about 10⁵ moles N km⁻² y⁻¹). The nutrient loads showed that most U.K. catchments were influenced by human activity, the majority being in the ‘ moderately influenced ’ category. Nutrient loads were also normalized for the area of each estuary, as a measure of the relative influence of nutrients on the receiving estuaries. The ratios of N:P, N:Si and P:Si in the annual loads suggested that most estuaries were likely to be, if anything, P limited rather than N or Si limited. However, crude annual loads may conceal significant seasonal variations.The spring maximum chlorophylla concentrations in coastal waters adjacent to each estuary were significantly correlated with the log total annual loads of TO_xN, ammonium and phosphate (but not silicate) for each estuary, providing a direct link between a measure of the degree of biological response in coastal waters and the nutrient load through the estuaries. There were no significant correlations between spring maximum chlorophyll a concentrations and either catchment-normalized or estuary-normalized nutrient loads. There was significant correlation between catchment area-normalized loads of phosphate and an urbanization index for the catchments, but not with the catchment area-normalized loads of the other nutrients.     

Abundance, size distribution, and stable carbon and nitrogen isotopic compositions of marine organic matter isolated by tangential-flow ultrafiltration

Tangential-flow ultrafiltration was used to isolate particulate and high-molecular-weight dissolved material from seawater collected at various depths and geographic regions of the Pacific and Atlantic Oceans. Ultrafiltration proved to be a relatively fast and efficient method for the isolation of hundreds of milligrams of material. Optical and electron microscopy of the isolated materials revealed that relatively fragile materials were recovered intact. Depth-weighted results of the size distribution of organic matter in seawater indicated that ˜ 75% of marine organic carbon was low-molecular-weight (LMW) dissolved organic carbon (< 1 nm), ˜ 24% was high-molecular-weight (HMW) dissolved organic carbon (1–100 nm), and ˜ 1% was particulate organic carbon (> 100 nm). The distribution of carbon in surface water was shifted to greater relative abundances of larger size fractions, suggesting a diagenetic sequence from macromolecular material to small refractory molecules. The average C:N ratios of particulate organic matter (POM) and HMW dissolved organic matter (DOM) were 7.7 and 16.7, respectively. Differences in C:N ratios between POM and HMW DOM were large and invariant with depth and geographic region, indicating that the aggregation of HMW DOM to form POM must be of minor significance to overall carbon dynamics. The stable carbon isotope composition (δ¹³C) of POM averaged −22.7%. in surface water and −25.2%. in subsurface water. Several possible explanations for the observed isotopic shift with depth were explored, but we were unable to discern the cause. The δ¹³C of HMW DOM samples was relatively constant and averaged −21.7%., indicating a predominantly marine origin for this material. The δ¹⁵N values of POM were highly variable (5.8–15.4%.), and the availability of nitrate in surface waters appeared to be the major factor influencing δ¹⁵N values in the equatorial Pacific. In the upwelling region nitrate concentrations were relatively high and δ¹⁵N values of POM were low, whereas to the north and south of the upwelling nitrate concentrations were low and δ¹⁵N values were high. The δ¹⁵N values of HMW DOM reflected the same trends observed in the POM fraction and provided the first such evidence for biological cycling of dissolved organic nitrogen (DON). Using the observed δ¹⁵N values and an estimate of meridional advection velocity, we estimated a turnover time of 0.3 to 0.5% day⁻¹ for HMW DON. These results suggest a major role for DON in the upper ocean nitrogen cycle.     

Photochemical production of the hydroxyl radical in Antarctic waters

Photochemical production rates and steady-state concentrations of the highly reactive OH radical were determined in Antarctic seawater in the Weddell-Scotia Confluence during the austral spring of 1993 and along the Antarctic Peninsula during the austral summer of 1994. OH radical photoproduction rates were 30±2 nM/day and 46±2 nM/day in surface open oceanic and coastal waters, respectively. Corresponding steady-state concentrations were 2.6×10⁻¹⁹ and 4.3×10⁻¹⁹ M which are similar to those found in tropical latitudes. In-situ irradiation experiments (drifter deployments) at different depths in the upper water column indicated that multiple sources for the OH radical existed at three Antarctic stations. Ultrafiltration studies and model calculations based on wavelength-dependent OH radical quantum yields indicated that the main sources were photochemical reactions of low molecular weight dissolved organic matter (DOM), nitrate, and nitrite. Production of the OH radical from nitrate photolysis was almost exclusively UV-B dependent, while OH radical production from nitrite photolysis was mainly UV-A dependent. OH production from DOM photolysis was both UV-A and UV-B dependent. In the upper few meters at open oceanic sites, nitrate and DOM were the dominant OH radical sources, while deeper in the water column DOM and nitrite were important because of the greater importance of UV-A with depth. During non-ozone hole conditions, nitrate contributed about 33%, while DOM plus nitrite contributed about 67% of the predicted OH radical production in open oceanic surface waters. During an ozone hole (151 Dobson units), the corresponding percentages changed to about 40 and 60% for nitrate and DOM due to the higher UV-B irradiance. Model calculations predict that during an ozone hole (151 Dobson units), OH radical production in surface waters will be enhanced by at least 20%, mostly from nitrate photolysis and to a lesser extent from DOM photochemical reactions. This study indicates that ozone hole events significantly increase OH radical production, as well as the photolysis of DOM, in Antarctic waters, and that rates can be as high or higher than those at lower latitudes, especially if differences in temperature and solar irradiance are taken into account.     

南海北部陆丰凹陷中新世底栖有孔虫组合与古环境演化研究

The Miocene epoch marks the most crucial period during the Cenozoic cooling trend, characterized by the Middle Miocene Climatic Optimum(MMCO) and a series of short–lived cooling events(Miocene isotope events).To understand the paleoenvironmental evolution along the shallow water shelf in the South China Sea during the Miocene, the benthic foraminiferal assemblage and total organic carbon content(TOC) were analyzed at Hole LF14 located in the Lufeng Sag, northern South China Sea. Three benthic foraminiferal assemblages(e.g., the Uvigerina spp. assemblage, the Cibicides spp. assemblage, and the Cibicidoides spp. assemblage), corresponding to different watermass conditions, were recognized based on Q–mode factor analysis. Early studies suggested that Hole LF14 was deposited under semienclosed bay, middle to outer shelf or even upper bathyal environment during ～18.7–4.53 Ma. The dominant Uvigerina spp. assemblage was characterized by low diversity and shallow infaunal to infaunal species, indicating a warm, low–oxygenation and eutrophic conditions since the Early Miocene to MMCO(～18.7–14.24 Ma). An abrupt sea level drop and significant faunal changes were recorded during 14.24–13.41 Ma, suggesting development of the East Antarctic Ice Sheets, which resulted in a drop of sea level and change in benthic foraminiferal assemblages along the shallow water shelf. Beyond the Uvigerina spp.assemblage, the Cibicides spp. assemblage became important during the middle–late Middle Miocene(14.24–11.54 Ma). This assemblage was dominated by epifaunal species with relative high diversity, suggesting high–energy, high–oxygenation and oligotrophic conditions with episodic supply of organic food. The dominant Cibicidoides spp. assemblage with high diversity, indicates a mesotrophic conditions with relative high–oxygen content during the Late Miocene to Pliocene(11.54–4.53 Ma). The appearance and continuous occurrence of Ammonia spp. and Pseudorotalia spp. since 10.02 Ma, may reflect the influence of the Kuroshio Current.     

Effects of simulated benthic fluxes on phytoplankton dynamic and photosynthetic parameters in a mesocosm experiment (Bay of Brest,France)

Benthic faunal activity and density play an important role in determining the rates of benthic nutrient fluxes, which enrich the water column and contribute to phytoplankton growth. The intensity of nutrient fluxes in the Bay of Brest depends on the density of the invasive gastropod, Crepidula fornicata. In order to study the impact of benthic fluxes on phytoplankton dynamics, realistic daily nutrient inputs simulating various densities of C. fornicata were added to six enclosures during three weeks. The increase in fertilization intensity influenced the phytoplankton biomass. A succession from Chaetoceros spp. to Pseudo-nitzschia spp. and Leptocylindrus danicus was observed in all enclosures, but the dynamics of successions were different. Pseudo-nitzschia spp. was favored in the three more fertilized enclosures, while Chaetoceros spp. persisted longer in less enriched enclosures. Despite an apparent nitrogen limitation, the quantum efficiency of PSII (F_v/F_m) was high (>0.5) and stable in all enclosures. The maximal photosynthetic capacity (P^Bmax) was also invariable and oscillated around an average value of 2.23 mg C (mg Chl a)⁻¹ h⁻¹. The stability of F_v/F_m and P^Bmax observed at different nutrient input intensities demonstrates that the daily inputs maintained the physiological balance of the microalgae. The maximal light utilization efficiency (α) and the light saturation parameter (E_k) were also quite stable after day 8, which reveals that photosynthetic parameters were driven by growth constraints due to nutrient availability and not by incident light or species successions. We suggest that our results correspond to an “E_k independent variation” regulation. We propose that such regulation of photosynthetic parameters appears when there are frequent nutrient additions which do not allow replete nutrient conditions to be reached but lead to physiological equilibrium.     

Population structure, density and food sources of Terebralia palustris (Potamididae: Gastropoda) in a low intertidal Avicennia marina mangrove stand (Inhaca Island, Mozambique)

Population structure and distribution of Terebralia palustris were compared with the environmental parameters within microhabitats in a monospecific stand of Avicennia marina in southern Mozambique. Stable carbon and nitrogen isotope analyses of T. palustris and potential food sources (leaves, pneumatophore epiphytes, and surface sediments) were examined to establish the feeding preferences of T. palustris. Stable isotope signatures of individuals of different size classes and from different microhabitats were compared with local food sources. Samples of surface sediments 2.5–10 m apart showed some variation (−21.2‰ to −23.0‰) in δ¹³C, probably due to different contributions from seagrasses, microalgae and mangrove leaves, while δ¹⁵N values varied between 8.7‰ and 15.8‰, indicating that there is a very high variability within a small-scale microcosm. Stable isotope signatures differed significantly between the T. palustris size classes and between individuals of the same size class, collected in different microhabitats. Results also suggested that smaller individuals feed on sediment, selecting mainly benthic microalgae, while larger individuals feed on sediment, epiphytes and mangrove leaves. Correlations were found between environmental parameters and gastropod population structure and distribution vs. the feeding preferences of individuals of different size classes and in different microhabitats. While organic content and the abundance of leaves were parameters that correlated best with the total density of gastropods (>85%), the abundance of pneumatophores and leaves, as well as grain size, correlated better with the gastropod size distribution (>65%). Young individuals (height < 3 cm) occur predominantly in microhabitats characterized by a low density of leaf litter and pneumatophores, reduced organic matter and larger grain size, these being characteristic of lower intertidal open areas that favour benthic microalgal growth. With increasing shell height, T. palustris individuals start occupying microhabitats nearer the mangrove trees characterized by large densities of pneumatophores and litter, as well as sediments of smaller grain size, leading to higher organic matter availability in the sediment.     

Molecular masses and chromophoric properties of dissolved organic ligands for copper(II) in oceanic water

The distribution of molecular masses of organic ligands for copper(II) in oceanic water was investigated. The bulk dissolved organic matter (DOM) was fractionated by ultrafiltration and organic ligands were extracted from the resultant fractions by using immobilized metal ion affinity chromatography (IMAC). Contributions of total organic ligands were 2.0–4.4% of the bulk DOM in surface waters, as determined by the UV absorbance. In the distribution of molecular masses of organic ligands, relative contribution of the fraction with low molecular masses (<1000 Da) was dominant (49–62%), while 26–33% of the total organic ligands was in the 1000–10,000 Da fraction, leaving 10–19% in the >10,000 Da fraction. The distribution of molecular masses of organic ligands shifted to higher molecular masses, as compared with that of the bulk DOM. The fluorescence intensities of organic ligands were shown to be associated with carboxyl contents, based on peak excitation/emission wavelengths and the pH-dependence of fluorescence. Two ligand classes with different conditional stability constants (log K_CuL′≈7 and 9) were determined from fluorescence quenching of ligand fractions during copper(II) titration. Organic ligands in low molecular mass fractions were relatively weak and strong ligands occurred in higher molecular mass fractions. It is suggested that the weaker ligand sites would consist of two or more carboxyl groups (log K_HL′=4), whereas carboxyl groups (log =2), which are protonated at lower pH, and primary amine may additionally contribute to the formation of more stable copper(II) complexes of the stronger ligand.     

Benthic nitrate biogeochemistry affected by tidal modulation of Submarine Groundwater Discharge (SGD) through a sandy beach face, Ria Formosa, Southwestern Iberia

To investigate both the role of tides on the timing and magnitude of Submarine Groundwater Discharge (SGD), and the effect on benthic nitrogen biogeochemistry of nitrate-enriched brackish water percolating upwards at the seepage face, we conducted a study of SGD rates measured simultaneously with seepage meters and mini-piezometers, combined with sets (n = 39) of high resolution in-situ porewater profiles describing NH₄⁺, NO₃⁻, Si(OH)₄ and salinity distribution with depth (0–20 cm). Sampling took place during two consecutive spring tidal cycles in four different months (November 2005, March, April and August 2006) at a backbarrier beach face in the Ria Formosa lagoon, southern Portugal. Our results show that the tide is one of the major agents controlling the timing and magnitude of SGD into the Ria Formosa. Intermittent pumping of brackish, nitrate-bearing water at the beach face through surface sediments changed both the magnitudes and depth distributions of porewater NH₄⁺ and NO₃⁻ concentrations. The most significant changes in nitrate and ammonium concentrations were observed in near-surface sediment horizons coinciding with increased fraction of N in benthic organic matter, as shown by the organic C:N ratio. On the basis of mass balance calculations executed on available benthic profiles, providing ratios of net Ammonium Production Rate (APR) to Nitrate Reduction Rate (NRR), coupled to stoichiometric calculations based on the composition of organic matter, potential pathways of nitrogen transformation were speculated upon. Although the seepage face occasionally contributes to reduce the groundwater-borne DIN loading of the lagoon, mass balance analysis suggests that a relatively high proportion of the SGD-borne nitrogen flowing into the lagoon may be enhanced by nitrification at the shallow (1–3 cm) subsurface and modulated by dissimilatory nitrate reduction to ammonium (DNRA).     

Lipid biomarkers and bacterial lipase activities as indicators of organic matter and bacterial dynamics in contrasted regimes at the DYFAMED site, NW Mediterranean

This study investigated the relationships between dissolved organic matter (DOM) composition and bacterial dynamics on short time scale during spring mesotrophic (March 2003) and summer oligotrophic (June 2003) regimes, in a 0–500 m depth water column with almost no advection, at the DYFAMED site, NW Mediterranean. DOM was characterized by analyzing dissolved organic carbon (DOC), colored dissolved organic matter (CDOM) and lipid class biotracers. Bacterial dynamic was assessed through the measurement of in situ bacterial lipase activity, abundance, production and bacterial community structure. We made the assumption that by coupling the ambient concentration of hydrolysable acyl-lipids with the measurement of their in situ bacterial hydrolysis rates (i.e. the free fatty acids release rate) would provide new insights about bacterial response to change in environmental conditions. The seasonal transition from spring to summer was accompanied by a significant accumulation of excess DOC (+5 μM) (ANOVA, p<0.05, n=8) in the upper layer (0–50 m). In this layer, the free fatty acids release rate to the bacterial carbon demand (BCD) ratio increased from 0.6±0.3 in March to 1.3±1.0 in June (ANOVA, p<0.05, n=8) showing that more uncoupling between the hydrolysis of the acyl-lipids and the BCD occurred during the evolution of the season, and that free fatty acids contributed to the excess DOC. The increase of lipolysis index and CDOM absorbance (from 0.24±0.17 to 0.39±0.13 and from 0.076±0.039 to 0.144±0.068; ANOVA, p<0.05, n=8, respectively), and the higher contribution of triglycerides, wax esters and phospholipids (from <5% to 12–31%) to the lipid pool reflected the change in the DOM quality. In addition to a strong increase of bacterial lipase activity per cell (51.4±29.4–418.3±290.6 Ag C cell⁻¹ h⁻¹), a significant percentage of ribotypes (39%) was different between spring and summer in the deep chlorophyll maximum (DCM) layer in particular, suggesting a shift in the bacterial community structure due to the different trophic conditions. At both seasons, in the chlorophyll layers, diel variations of DOM and bacterial parameters reflected a better bioavailability and/or DOM utilization by bacteria at night (the ratio of free fatty acids release rate to bacterial carbon demand decreased), most likely related to the zooplankton trophic behaviour. In mesotrophic conditions, such day/night pattern was driving changes in the bacterial community structure. In more oligotrophic period, diel variations in bacterial community structure were depth dependent in relation to the strong summer stratification.     

Effect on marine sediment nitrogen fluxes caused by organic matter enrichment with varying organic carbon structure and nitrogen content

Enrichments with five types of organic carbon, differing in nitrogen content and type of organic carbon, were made to a marine sediment in order to study effects on nitrogen fluxes. The enrichments used were Ulva lactuca, Ascophyllum nodosum, Zostera marina, Ceratium spp., lignin, and mixtures of U. lactuca and A. nodosum. Fluxes of ammonium, nitrate, and phosphate were measured in short-term (48 h) microcosm experiments, using a carbon enrichment loading similar to that at the sampling site. Changes in microbial community growth and structure due to three types enrichments were also detected using molecular methods in a microcosm experiment run for 4 days to allow for detection at DNA-level.Ammonium fluxes changed from an efflux in the control to an influx for all enrichments apart from U. lactuca. The change was significantly related to the added material's C:N ratio when Ceratium spp. was excluded. All enrichments induced an influx of nitrate suggesting the formation of anoxic micro zones, but there was no relationship with C:N ratio. Instead, the magnitude of the nitrate influx is suggested to be related to the structure of the organic carbon, where enrichments containing a large pool of cellulose and lignin (Z. marina and lignin) gave rise to a lower influx, compared to algal material with more easily degraded organic matter like lipids and starch, which induced the highest influx of nitrate (Ceratium spp., U. lactuca, and A. nodosum). The occurrence of an ammonium influx together with increased nitrate influx and a lower efflux of phosphate in the enrichments suggests a growth of heterotrophic bacteria. This was also confirmed using molecular methods (PCR-DGGE) where the relative abundance of bacterial species in the enrichments increased.The sum of ammonium and nitrate fluxes showed that total nitrogen removal was enhanced in all enrichments compared to the nonenriched control sediment, but in different ways. Ceratium spp. induced the highest removal followed by A. nodosum, U. lactuca, Z. marina, and lastly, by lignin. The same pattern was observed also in a second experiment. These results indicate that easily degradable organic carbon, together with a lower C:N ratio of the added material, will remove nitrogen from the water phase, making the recycling of nitrogen to the overlying water mass smaller.     

Profiles of DMSP,algal pigments,nutrients and salinity in pack ice from eastern Antarctica

Concentrations of dimethylsulphoniopropionate (DMSP) were measured in seven pack ice cores from three sites in eastern Antarctica to determine their relation to algal pigments, nutrients (nitrate, silicate and phosphate) and bulk salinity. The algal groups haptophytes, dinoflagellates and diatoms were identified in surface, interior and bottom assemblages in the pack ice cores using the photosynthetic marker pigments 19′-hexanoyloxyfucoxanthin (HEX), peridinin (PER) and fucoxanthin (FUC), respectively. DMSP concentrations were significantly correlated (P<0.01, Pearson) with chlorophyll-a (r=0.58), HEX (r=0.75), PER (r=0.79) and FUC (r=0.63) concentrations. The pool of DMSP within the pack ice (mean 107 nM) was contributed mainly by interior and bottom algal assemblages (mean 94 and 268 nM, respectively), whilst the surface algal assemblages were minor contributors (mean 18 nM). DMSP production and/or accumulation appears to differ between surface, interior and bottom pack ice algal assemblages due to differences in biomass, class composition, and possibly the unique environmental conditions experienced by each assemblage. In pack ice, diatoms appear to be important producers of DMSP, due to their dominance of algal assemblages.     

Spatial variation of nutrients and primary productivity in the Rufiji Delta mangroves,Tanzania

Determinations of spatial and temporal variations in organic matter and nutrient dynamics in water and sediments are crucial for understanding changes in aquatic bodies. In this study, we (i) determine the spatial dynamics of dissolved inorganic nutrients, during the transition from the dry to the rainy season, and (ii) provide future productivity predictions for the Rufiji Delta mangroves, Tanzania, based on the input of various nutrients. Water samples were collected from six locations, three times per year between April 2012 and January 2014, and analysed for dissolved nutrients, total organic and inorganic carbon, chlorophyll a, chlorophyll b and total carotenoids. The prediction of future net primary productivity in the Rufiji mangroves was undertaken using the software STELLA. The mean nutrient concentrations were of the order: nitrate > phosphate > ammonium > silica > dissolved organic carbon. The study revealed that high nutrient concentrations occurred in the northern part of the Rufiji Delta as a result of anthropogenic influence in the watershed. Modelling of nutrient inputs into the delta indicated enhanced primary productivity, which is expected to increase the vulnerability of water quality in the near future due to eutrophication.     

Harpacticoid copepod response to epiphyte load variations in Posidonia oceanica (L.) Delile meadows

We conducted a field experiment to assess the response of phytal harpacticoids to nutrient‐driven increases of epiphyte load in Posidonia oceanica meadows. First, we evaluated differences in species richness, diversity and assemblage structure of phytal harpacticoids in P. oceanica meadows with differing epiphyte loads. Secondly, we conducted a field experiment where epiphyte load was increased through an in situ addition of nutrients to the water column and evaluated the responses of the harpacticoid assemblages. We predicted that there would be changes in the harpacticoid assemblages as a result of nutrient‐driven increases of epiphyte load, and that these changes would be of a larger magnitude in meadows of low epiphyte load. Our results show that the harpacticoid fauna (>500 μm) present in P. oceanica meadows in the Bay of Palma comprised taxa which are considered phytal and other less abundant ones previously described as sediment dwellers or commensal on other invertebrate species. Nutrient addition had an overall significant effect on epiphyte biomass and on harpacticoid abundance, diversity and assemblage structure, possibly as a response to the increased resources and habitat complexity provided by epiphytes. The abundance of dominant species at each location was favoured by nutrient addition and in some cases correlated with epiphytic biomass, although never strongly. This may indicate that structural complexity or diversity of the epiphytic cover might be more important than the actual epiphytic biomass for the harpacticoid species investigated. More species‐specific studies are necessary to ascertain this and clarify the relationships between harpacticoids and epiphytes in seagrass meadows. To our knowledge, this is the first account of harpacticoid species associated with P. oceanica leaves and the epiphytic community they harbour in the Mediterranean Sea.