Development of lipids during a spring plankton bloom in the northern North Sea: I. Particulate fatty acids

The plankton spring bloom in the northern North Sea was extensively investigated during a period of three months in 1976 at a fixed station occupied by the R.V. “Meteor”. Samples of different depth-profiles, representative of the phytoplankton development, were collected eleven times to analyze the concentration of fatty acids of the particulate matter. The water column was divided into an upper and lower layer according to the thermocline depths, because different processes take place in these layers. During the exponential growth phase the fatty acid concentration rose only slightly due to increases in polyunsaturated fatty acids (18:4, 20:5, 22:6), which are typical for marine plankton. With the exhaustion of nutrients the biochemical composition changed and the fatty acid concentration increased sharply from about 3 to 20 μmol C dm^? finally to about 30% of the particulate carbon. The main proportion consisted of oleic acid (28.3%) and palmitic acid (24.2%). The first phytoplankton bloom, dominated by diatoms (Chaetoceros species), was characterized by the increase in fatty acids with 16 carbon atoms, whereas during the second smaller bloom, with dinoflagellates as the main species, more fatty acids with 18 carbon atoms occurred. After the stationary growth phase the phytoplankton biomass strongly decreased, resulting in an increase of particulate matter below the thermocline. The fatty acid pattern there was similar to that during the stationary phase of the phytoplankton bloom in the upper layer.     

Glucose fluxes and concentrations of dissolved combined neutral sugars (polysaccharides) in the Ross Sea and Polar Front Zone, Antarctica

We hypothesized that dissolved carbohydrates would be large components of the labile dissolved organic carbon (DOC) pool and would support much bacterial growth in Antarctic waters, especially the Ross Sea, since previous work had observed extensive phytoplankton blooms with potentially high production rates of carbohydrates in Antarctic seas. These hypotheses were tested on cruises in the Ross Sea and Antarctic Polar Front Zone as part of the US JGOFS program. Concentrations and fluxes of free glucose (the only free sugar detected) were very low, but dissolved polysaccharides appeared to be important components of the DOC pool. Concentrations of dissolved combined neutral sugars increased >3-fold during the phytoplankton bloom in the Ross Sea and were a large fraction (ca. 50%) of the semi-labile fraction of DOC. The relatively high concentrations of dissolved combined neutral sugars, which are thought to be quite labile, appear to explain why DOC accumulated during the phytoplankton bloom was degraded so quickly once the bloom ended. Some of the polysaccharides appeared to be more refractory, however, since dissolved combined neutral sugars were observed in deep waters (>550 m) and in early spring (October) in the Ross Sea, apparently having survived degradation for >8 months. The molecular composition of these refractory polysaccharides differed from that of polysaccharides sampled during the phytoplankton bloom. Fluxes of DOC were low in the Ross Sea compared to standing stocks and fluxes of particulate material, but the DOC that did accumulate during the phytoplankton bloom appeared to be sugar-rich and relatively labile.     

胶州湾海水痕量金属?溶解有机质分配特征及其影响因素探讨

采集胶州湾表层和底层海水样品，分析了Cu、Cr、Cd、Pb、Ni、Co等痕量金属在海水中的空间分布特征及其在不同分子量溶解有机质中的分配特征，并探讨了痕量金属?溶解有机质分配机理及浮游生物活动与盐度等环境因素对该分配过程的影响。结果表明，胶州湾海水中痕量金属呈近岸浓度较高的分布特征，在湾东北部出现高值区，Cd和Pb还分别在湾口与湾中部出现高值区。胶州湾海水中痕量金属平均有70.1%分配于低分子量(<1 kDa)组分中，其中Cu和Cd低分子量组分所占平均比例分别达79.0%与77.6%，Cr、Ni和Co稍低，分别为71.5%、67.3%及66.9%，Pb则仅为58.2%。海水中的溶解有机碳也以低分子量组分为主，所占比例平均达73.1%，且光谱特征显示低分子量溶解有机质中类腐殖质含量更高，含有丰富的羧基和羟基，金属配合能力较高，导致痕量金属多分配于低分子量溶解有机质中。高分子量溶解有机质(>1 kDa)所占比例与叶绿素a浓度呈显著正相关，表明浮游植物初级生产通过释放高分子量溶解有机质影响海水痕量金属?溶解有机质的分配过程。胶州湾湾顶盐度较低海域痕量金属高分子量组分略高，可能是生物活动及陆源输入(产生更多高分子量溶解有机质)与盐度(低盐有利于高分子量有机质的稳定性)共同作用的结果。     

Removal of trace metals from seawater during a phytoplankton bloom as studied with sediment traps in Funka Bay,Japan

To study biological effects on the particulate removal of chemical elements from seawater, sediment trap experiments were carried out successively ten times throughout the spring phytoplankton bloom in Funka Bay. Sediment traps were deployed every one to two weeks at 1, 40 and 80 m depths. The settling particles obtained were analyzed for trace metals, phosphate and silicate. The propagation of diatoms in spring results in larger particulate fluxes than that of dinoflagellates. The biogenic silicate concentration is higher in the earlier period, when diatoms are predominant, than in the subsequent period, when dinoflagellates are predominant. The concentrations of aluminum, iron, manganese and cobalt in the settling particles comprising largely biogenic particles are lower during phytoplankton bloom. The concentration of copper is not reduced by the addition of biogenic particles, and its vertical flux is approximately proportional to the total flux, indicating that its concentration in the biogenic particles is nearly equal to that in the non-biogenic particles. The results for nickel and lead show the same tendency as for copper. Cadmium is more concentrated in biogenic particles than in non-biogenic particles, and the concentration of cadmium in the settling particles decreases with depth, similarly to phosphate and organic matter. Thus, metals in seawater are segregated by biological affinities, and the degree of incorporation into biogenic particles is in the order Cd > Pb, Ni, Cu > Co > Mn, Fe, Al. Biogenic particles are the most important agent controlling the vertical distribution of metals in the ocean. They remove the metals from the surface water, transport them through the water column, and regenerate them in the deep.     

Trace metal concentrations in the Ross Sea and their relationship with nutrients and phytoplankton growth

Dissolved and particulate trace metal concentrations (dissolved Fe, Zn, Cd, Co, Cu and Ni; particulate Fe, Mn and Al) were measured along two transects in the Ross Sea during austral summer of 1990. Total Fe concentrations in southern Ross Sea and inshore waters were elevated >3.5 times that of northern waters. Dissolved Zn, Cd and Co concentrations were lower by factors of 4.5, 3.5 and 1.6 in southern surface waters relative to northern waters. Dissolved Cu and Ni concentrations were similar in both areas. Elevated Fe concentrations coincided with areas of increased productivity, phytoplankton biomass and nutrient drawdown, indicating that Fe is an important factor controlling the location of phytoplankton blooms in the Ross Sea. Particulate concentrations of Fe, Mn and Al indicate two possible sources of iron to the Ross Sea, resuspension of continental shelf sediments and iron incorporated in annual sea ice and released with meltwaters.     

Contribution of abiogenic and biogenic particles to trace-metal composition of phytoplankton assemblages in seawater of Shimizu Port, Japan

The contribution of abiogenic and biogenic particles to trace-metal (As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sb, Ti, V, and Zn) composition was investigated for phytoplankton (primarily diatoms) collected in Shimizu Port, a coastal seawater region. Except for Cd, the trace metals occurred predominantly in lithogenic or nonlithogenic abiogenic particles associated with plankton. In contrast, it is likely that Cd in seawater is taken up intracellularly, and not adsorbed extracellularly by phytoplankton. The lower P-normalized quotas of Cd in Shimizu Port than in offshore regions may be because plankton are dominated by diatoms.     

Metal sources to the Baltic clam Macoma balthica (Mollusca: Bivalvia) in the southern Baltic Sea (the Gulf of Gdansk)

Metal concentrations of Cu, Fe, Mn, Ni, Pb and Zn in an infaunal facultative deposit-feeding bivalve, the Baltic clam Macoma balthica, in the Gulf of Gdansk (southern Baltic Sea) were assessed and compared to selected concentrations of metals in the environment. Between October 1996 and September 1997, dissolved and easy extractable (by 1M HCl) metal fractions of total suspended particulate matter (TPM) in the overlying water and of surficial sediments (<63 microm) were measured monthly at five sublittoral sites in the Gulf of Gdansk, and accumulated tissue metal concentrations in M. balthica were determined simultaneously. The study highlights the importance of sediment geochemistry as a factor modifying ambient trace metal bioavailabilities. Surficial sediments appeared to contribute most to the accumulation of Cu and Pb in M. balthica, reflecting the high metal availability in the Gulf. Assimilation of Cu from sediments is controlled by Mn components possibly through an inhibitory effect of Mn oxyhydroxides, while Pb accumulation from sediments depends on the organic content of the sediment. A dual metal uptake pathway, with a suspended particulate-bound fraction and surficial sediments, was apparent for Mn and Zn. Partitioning of Mn in sediments was related to the concentration of labile Fe, with increased levels of Fe tending to inhibit the accumulation of Mn by the clam. Tissue accumulated Zn might have been altered by the clam's internal regulation, making Zn tissue concentrations, to some degree, independent of its environmental level. The principal source of Ni accumulated by the clams exists in the soluble phase.     

The distribution of Mn,Fe, Zn,Cd and Cu in Baltic seawater; a study on the basis of one anchor station

A total of 150 samples were collected at a 10-days' anchor station in the Bornholm basin (55° 31.1′N, 15° 32.1′E) and analyzed for dissolved (< 0.4 μm) and particulate trace metals. For dissolved Mn, large gradients have been found in the vertical distribution with minimum concentrations (< 0.2 μgl^?1) in the halocline zone and considerably higher values in the deep waters (up to 50 μgl^?1). Ultrafiltration studies indicate that dissolved Mn is probably present as Mn²⁺ in the oxygenated bottom layer. The primary production process was not evident in the particulate Mn profile; the suspended particulate material (SPM), however, shows a considerable enrichment with depth, apparently due to Mn-oxide precipitation.The distribution of dissolved Fe was rather homogeneous, with average concentrations throughout the water column between 0.86 and 1.1 μgl^?1, indicating that the oxidation of Fe²⁺ ions released from the sediments must already be complete in the very near oxidation boundary layer. Relatively high concentrations of particulate Fe were actually measured in the bottom layer, with the maximum mean of 11.2 μgl^?1 at 72 m. Similarly to Mn, the profile of particulate Fe does not reflect the SPM curve of the eutrophic layer. On average, about 70% of the total Fe in surface waters was found to be particulate.The average concentrations of dissolved Zn, Cd and Cu were found to be rather homogeneous in the water column but showed a relatively high variability with time. A simplified model on trace-metal uptake by phytoplankton indicates no significant change in dissolved metal concentrations during the period of investigation. On average, only 1.7% Zn, 3.3% Cd and 9.8% Cu of the total metal concentrations were found in particulate form. SPM analyses showed significant correlations of Zn, Cd and Cu with Fe, indicating that particulate iron is an important carrier for particulate trace metals in Baltic waters.     

The influence of organic matter and atmospheric deposition on the particulate trace metal concentration of northwest Atlantic surface seawater

Particulate trace metals (PTM), organic carbon (POC), and organic nitrogen (PON) were measured in a series of surface bucket samples collected between the New England coast of the United States and Bermuda. PTM concentrations were lower or equivalent to the lowest PTM concentrations reported in the literature. Examination of the relative variations in PTM with respect to particulate aluminum and carbon led to the conclusion that organic matter was the probable regulator of PTM abundance in open-ocean surface waters and was important in this respect for continental shelf and slope waters as well.Enrichment factors of trace metals relative to their crustal abundances were found to be similar in the atmosphere sampled in Bermuda and in Sargasso Sea surface water particulate matter. A simplistic vertical flux model was constructed which showed atmospheric input of trace metals to the Sargasso Sea to be of the same approximate magnitude as the rate of removal of PTM from the mixed layer by sinking in association with POC. Essentially all of the particulate Al, Fe, and Mn in the Sargasso Sea mixed layer was attributed to aeolian sources. The fate of other atmospherically derived trace metals in the Sargasso Sea mixed layer was suggested to be a function of their solubility in seawater.     

Some peculiarities of the trace-metal distribution in Baltic waters and sediments

Between 1980 and 1984 extensive studies were carried out in the Baltic Sea on trace metals (Cd, Co, Cu, Fe, Hg, Mn, Ni, Pb and Zn) in water, suspended matter and sediments. The results enabled the influence of different factors on metal distribution patterns to be considered. The vertical profiles of dissolved and particulate metals in waters of the central deep basins reflect influences caused by oxygen deficiency and anoxic conditions in near-bottom water layers. Peculiarities at Station BY15 in the Gotland Deep included high dissolved Fe, Mn and Co concentrations and remarkable enrichment of Zn (0.64%), Cd (51 μg g⁻¹) and Cu (0.15%) in particulate matter from the anoxic zone. Manganese-rich particles were accumulated above this layer.In fine-grained soft sediments below anoxic deep waters, maximum contents of Cd, Cu and Zn were observed, relative to other coring sites, between Bothnian Bay and Lübeck Bight. The Hg content in sediments probably reflects the joint flocculation with organic matter. Land-based sources seem to play the leading part for maximum lead contents.     

Development of lipids during a spring plankton bloom in the northern North Sea: II. Dissolved lipids and fatty acids

During the spring plankton bloom (1976) in the northern North Sea the fatty acid and lipid distribution of the chloroform extractable fraction of seawater was analyzed by gas chromatography and thin-layer chromatography. The fatty acids in the seawater made up about 3% of the total dissolved organic matter. Maximum concentrations during the first phytoplankton bloom were in the range of 5 μmol C dm^?3. Palmitic acid (30.4%) and oleic acid (21.4%) as well as myristic, stearic and palmitoleic acids were the main fatty acids. The concentrations of fatty acids were higher below the thermocline in the deeper layers of the water column. The oleic acid showed large fluctuations, especially below the thermocline and seemed to be bound in a polar fraction. Different lipid classes containing fatty acids were determined by thin-layer chromatography. An estimation showed that the free fatty acid fraction made up the main portion (47.9%), followed by the triacylglycerol fraction (22.8%) and a more polar fraction with 25.1%. The triacylglycerol fraction appears to be more stable than the other fraction in the water column.     

Neutral aldoses as source indicators for marine snow

The chemical characteristics of aggregating material in the marine environment are largely unknown. We investigated neutral aldose (NA) abundance and composition in aggregation of marine snow and other organic matter (OM) size fractions in the field. Four sample sets were fractionated using membrane filtration and ultrafiltration into the following size fractions: particulate material, high-molecular-weight (HMW) material, and low-molecular-weight (LMW) material. We also collected three sample sets of marine-snow aggregates. Each sample set contained small, medium, and large aggregate size fractions and each size fraction consisted of 25–50 aggregates. For 7 marine-snow samples and for each water-sample size fraction, we determined monomeric and polymeric NA concentration, NA yield (amount of NA-C normalized to organic carbon), and composition; total organic carbon (TOC) concentration; transparent exopolymer particles (TEP) concentration, and TEP propensity (TEP concentration after inducing TEP formation in filtered samples). This is the first study to include compound-specific NA determinations on these four marine OM size fractions.The mass balances of organic carbon and NA indicated that there were no serious contamination or loss problems. Concentrations, yields, and NA mol fractions in water samples were similar to results from other studies. Glucose and galactose had the highest relative abundance in all size fractions. The NA yield increased with increasing molecular weight or particle size for all fractions except marine snow. The NA yield increased in the order: LMW< marine snow< HMW< particles. Marine snow had a higher average NA yield than the LMW fraction, but lower than particle and HMW-fractions. This indicates that OM in marine snow could have been diagenetically derived from particulate and HMW-fractions, that is, marine snow may include material from the particulate and the colloidal phase.TEP concentration or TEP propensity was positively correlated with concentrations of all individual NAs as well as the sum NA concentrations, indicating that TEP contains neutral sugars in addition to the acidic polysaccharides stained in the determination of TEP concentrations.Despite the relatively low NA yield in marine snow, marine snow was enriched in NA when compared with seawater, with enrichment factors of 34–225 (average 125). By combining data from this study with data from other studies, we estimate that < 10% of carbohydrates in marine snow comprise NAs.There was no clear correlation between marine-snow aggregate size and NA yield, that is, there appears to be no general age difference between small and large marine-snow aggregates. NA composition was similar among different marine-snow size fracions collected during the same day, indicating that aggregation/disaggregation reactions resulted in homogenizing NA composition in marine-snow aggregates of all sizes. The NA composition of marine snow was different from that of other OM size fractions, indicating either that bacterial degradation has modified the composition of marine snow to a larger extent than other OM size fractions or that marine snow is formed through the aggregation of selected subcomponents of OM.     

Behaviors of dissolved and particulate Co,Ni, Cu,Zn, Cd and Pb during a mesoscale Fe-enrichment experiment (SEEDS II) in the western North Pacific

During mesoscale Fe enrichment (SEEDS II) in the western North Pacific ocean, we investigated dissolved and particulate Co, Ni, Cu, Zn, Cd and Pb in seawater from both field observation and shipboard bottle incubation of a natural phytoplankton assemblage with Fe addition. Before the Fe enrichment, strong correlations between dissolved trace metals (Ni, Zn and Cd) and PO₄³⁻, and between particulate trace metals (Ni, Zn and Cd) and chlorophyll-a were obtained, suggesting that biogeochemical cycles mainly control the distributions of Ni, Zn and Cd in the study area. Average concentrations of dissolved Co, Ni, Cu, Zn, Cd and Pb in the surface mixed layer (0–20 m) were 70 pM, 4.9, 2.1, 1.6, 0.48 nM and 52 pM, respectively, and those for the particulate species were 1.7 pM, 0.052, 0.094, 0.46, 0.037 nM and 5.2 pM, respectively. After Fe enrichment, chlorophyll-a increased 3 fold (up to 3 μg L⁻¹) during developing phases of the bloom (<12 days). Mesozooplankton biomass also increased. Particulate Co, Ni, Cu and Cd inside the patch hinted at an increase in the concentrations, but there were no analytically significant differences between concentrations inside and outside the patch. The bottle incubation with Fe addition (1 nM) showed an increase in chlorophyll-a (8.9 μg L⁻¹) and raised the particulate fraction up to 3–45% for all the metals, accompanying changes in Si/P, Zn/P and Cd/P. These results suggest that Fe addition lead to changes in biogeochemical cycling of trace metals. The comparison between the mesoscale Fe enrichment and the bottle incubation experiment suggests that although Fe was a limiting factor for the growth of phytoplankton, the enhanced biomass of mesozooplankton also limited the growth of phytoplankton and the transformation of trace metal speciation during the mesoscale Fe enrichment. Sediment trap data and the elemental ratios taken up by phytoplankton suggest that export loss was another reason that no detectable change in the concentrations of particulate trace metals was observed during the mesoscale Fe enrichment.     

Seasonal distribution of primary production,phytoplankton biomass and size distribution in the Greenland Sea

The study establishes an annual estimate for annual primary production of 81 g C m⁻² for the open Greenland Sea based on data from five cruises and literature data. This estimate agrees well with a model estimate based on nutrient utilisation but is a factor of 2–5 less than published primary production estimates made by remote sensing of this area. The seasonal distribution of particulate primary production in open Greenland Sea waters followed the seasonal distribution of surface irradiance with a peak in June, indicating that light is the primary factor governing primary production in the area. At stations along the ice edge, blooms were recorded in both June and August, suggesting a pattern of repeated blooms during the summer season at the ice edge. Subsurface phytoplankton peaks were a persistent feature in the open Greenland Sea from May to August. These peaks were consisted of actively photosynthesising phytoplankton and up to 90% of total water column particulate primary production was estimated to occur in association with these peaks. Diatoms dominated the phytoplankton community during the spring bloom and in the Polar Water during August. Size distribution analyses of the phytoplankton communities indicated that the relative abundance of large cells compared to small cells was greatest in May as compared to June and August. No significant differences were noted between June and August in the slope of the phytoplankton size distribution spectra. Inorganic nitrogen and phosphorus nutrients were measurable in surface waters on all cruises. Only in August were there some indications (altered Redfield ratios and higher nutrient concentrations in subsurface chlorophyll peaks than at the surface) of nutrient depletion of surface waters. Implications for food web structure and carbon flux of these patterns in phytoplankton activity and distribution are discussed.     

Ecohydrographic constraints on biodiversity and distribution of phytoplankton and zooplankton in coral reefs of the Red Sea,Saudi Arabia

An integral concept of ecological research is the constraint of biodiversity along latitudinal and environmental gradients. The Red Sea features a natural example of a latitudinal gradient of salinity, temperature and nutrient richness. Coral reefs along the Red Sea coasts are supported with allochthonous resources such as oceanic and neritic phytoplankton and zooplankton; however, relatively little is known about how the ecohydrography correlates with plankton biodiversity and abundance. In this article we present the biodiversity of phytoplankton and zooplankton in Red Sea coral reefs. Oceanographic data (temperature, salinity), water samples for nutrient analysis, particulate organic matter, phytoplankton and zooplankton, the latter with special reference to Copepoda (Crustacea), were collected at nine coral reefs over ~1500 km distance along the Red Sea coast of Saudi Arabia. The trophic state of ambient waters [as indicated by chlorophyll a (Chl a)] changed from strong oligotrophy in the north to mesotrophy in the south and was associated with increasing biomasses of Bacillariophyceae, picoeukaryotes and Synechococcus as indicated by pigment fingerprinting (CHEMTAX) and flow cytometry. Net‐phytoplankton microscopy revealed a Trichodesmium erythraeum (Cyanobacteria) bloom north of the Farasan Islands. Several potentially harmful algae, including Dinophysis miles and Gonyaulax spinifera (Dinophyceae), were encountered in larger numbers in the vicinity of the aquaculture facilities at Al Lith. Changes in zooplankton abundance were mainly correlated to the phytoplankton biomass following the latitudinal gradient. The largest zooplankton abundance was observed at the Farasan Archipelago, despite high abundances of copepodites, veligers (Gastropoda larvae) and Chaetognatha at Al Lith. Although the community composition changed over latitude, biodiversity indices of phytoplankton and zooplankton did not exhibit a systematic pattern. As this study constitutes the first current account of the plankton biodiversity in Red Sea coral reefs at a large spatial scale, the results will be informative for ecosystem‐based management along the coastline of Saudi Arabia.     

Biooptical characteristics of the surface layer of the Baltic,Norwegian, and Barents seas in summer 2014–2016 from shipboard and satellite data

The article presents the results of shipboard and satellite measurements in the surface layer of the Baltic, Norwegian, and Barents seas during legs from the Baltic to the White Sea in June–August 2014–2016. Special attention is paid to marine phytoplankton blooms of cyanobacteria in the Baltic Sea and coccolithophores in the Barents Sea. No blooms were found in the Norwegian Sea. The efficiency of combined application of in situ and satellite optical methods for studying the parameters of phytoplankton blooms is shown.     

Plankton community diversity from bacteria to copepods in bloom and non-bloom conditions in the Celtic Sea in spring

The plankton community composition comprising heterotrophic bacteria, pro-/eukaryotes, heterotrophic nanoflagellates, microzooplankton and mesozooplankton was assessed during the spring bloom and at non-bloom stations in the English Channel and Celtic Sea between 6 and 12 April 2002. Non-bloom sites were characterised by a dominance of pro-/eukaryotic phytoplankton <20 μm, higher abundance of heterotrophic nanoflagellates, microzooplankton standing stocks ranging between 60 and 380 mg C m⁻², lower mesozooplankton diversity and copepod abundance of between 760 and 2600 ind m⁻³. Within the bloom, the phytoplankton community was typically dominated by larger cells with low abundance of pro-/eukaryotes. Heterotrophic nanoflagellate cell bio-volume decreased leading to a reduction in biomass whereas microzooplankton biomass increased (360–1500 mg C m⁻²) due to an increase in cell bio-volume and copepod abundance ranged between 1400 and 3800 ind m⁻³. Mesozooplankton diversity increased with an increase in productivity. Relationships between the plankton community and environmental data were examined using multivariate statistics and these highlighted significant differences in the abiotic variables, the pro-/eukaryotic phytoplankton communities, heterotrophic nanoflagellate, microzooplankton and total zooplankton communities between the bloom and non-bloom sites. The variables which best described variation in the microzooplankton community were temperature and silicate. The spatial variation in zooplankton diversity was best explained by temperature. This study provides an insight into the changes that occur between trophic levels within the plankton in response to the spring bloom in this area.     

Metal partitioning between colloidal and dissolved phases and its relation with bioavailability to American oysters

Kinetics and the extent of metal partitioning between colloidal and dissolved phases and coagulation of metals associated with colloids were examined to determine their effects on the bioavailability of selected metals (Cd, Co, Hg, Ag, Fe, and Zn) to American oysters (Crassostrea virginica) using radiotracer and short term exposure experiments. After dispersion of radiolabeled colloids into low molecular weight (LMW, < 1 kDa) seawater, metal partitioning between dissolved (<1 kDa) and colloidal (1 kDa-0.2 microm) phases resulted in a consistent pattern, with a relatively constant percentage in the colloidal phase for each metal. On average, about 90% of Hg and Fe, approximately 60% of Ag and approximately 40% of Zn, Co, and Cd were measured in the colloidal fraction during a short term exposure experiment, consistent with their partitioning in natural waters. Controlled laboratory experiments carried out in parallel using radioactively tagged colloids showed that coagulation of colloidal species, quantified as the fraction retained by a 0.2 microm filter, was insignificant for most metals under the conditions and time periods of the uptake experiments. The bioavailability of colloidally complexed metals, measured in terms of dry weight concentration factor (DCF, ml g(-1)) and uptake rate constant (ml g(-1) h(-1)), was somewhat depressed compared with their counterpart in the LMW treatment, but could be well predicted from the results of the LMW treatment and metal partitioning. Both DCF values and uptake rate constants were higher in the LMW treatment than in the colloidal treatment. In addition, B-type metals, such as Ag, Hg, and Zn, all had higher values of DCF and uptake rate constants, regardless of treatments, except for Cd which had a lower DCF and uptake rate constant. In contrast, Co and Fe had significantly lower DCF values and uptake rate constants. Most of Hg and Ag (60-80%) were measured in the soft tissue of oysters in both LMW and colloidal treatments. In contrast, 80% of Fe, 75% of Co, and approximately 60% of Cd were observed on the shell, while Zn was found evenly distributed between shell and soft tissue of oysters. These results agree well with the variation pattern of both DCF value and uptake rate constant for these two groups of metals.     

High frequency measurements of dissolved inorganic and organic nutrients using instrumented moorings in the southern and central North Sea

The aim of this study was to investigate the cycling of dissolved inorganic and organic nutrients using moored instrumented buoys (SmartBuoys) during the spring bloom in the North Sea. The instrumentation on the buoys enabled high frequency measurements of water-column integrated irradiance and in situ chlorophyll to be made, and also preserved water sample collection which were used for dissolved inorganic and organic nutrient analyses. The SmartBuoys were located in the year-round well-mixed plume zone associated with the River Thames and in the summer stratified central North Sea. These site locations allowed comparison of nutrient concentrations and cycling, and spring bloom development at two contrasting sites. The spring bloom was expected to be initiated at both stations due to increasing insolation and decreasing suspended load leading to higher water-column integrated irradiance. Due to differences in suspended load between the sites, the spring bloom started ∼2 months earlier in the central North Sea. The spring bloom in the Thames plume also resulted in higher maximum phytoplankton biomass due to the higher pre-bloom nutrient concentrations associated with riverine input. The use of SmartBuoys is also shown to allow the cycling of dissolved organic nutrients to be examined over the critical, and often undersampled, spring bloom period. Dissolved Organic Nitrogen (DON) clearly increased during the spring bloom in the central North Sea compared to winter concentrations. DON also increased in the Thames plume although showing greater winter variability related to higher riverine and sedimentary dissolved organic matter input at this shallow (∼18 m) coastal site. DON increase during the spring bloom was therefore related to primary production at both sites probably due to active release by phytoplankton. At both stations DON decreased to pre-bloom concentrations as the bloom declined suggesting the released DON was bioavailable and removed due to heterotrophic uptake and production. The preserved nutrient samples from the central North Sea site were also suitable for Dissolved Organic Phosphorus (DOP) analysis due to their low suspended load with similar trends and cycling to DON, albeit at lower concentrations. This suggested similar processes controlling both DON and DOP. The variable timing of short term events such as the spring bloom makes sampling away from coastal regions difficult without the use of autonomous technology. This study demonstrates for the first time the applicability of using preserved samples from automated buoys for the measurement of dissolved organic nutrients.