Dissolved carbohydrates in seawater. I,A precise spectrophotometric analysis for monosaccharides

A relatively precise and rapid method for the analysis of total dissolved monosaccharides at the concentrations that occur in seawater is described which uses 1-ml quantities for each analytical and control replicate. The alditols remain unchanged while the pentoses and hexoses are reduced to the alditol form by borohydride. The total alditols are then oxidized with periodate to form two moles of formaldehyde per mole of monosaccharide and the formaldehyde is determined spectrophotometrically with 3-methyl-2-benzothiazolinone hydrazone hydrochloride (MBTH). Unlike other spectrophotometric methods, similar curves are obtained for equimolar concentrations of different carbohydrates while the differences on a weight basis are only due to the small difference in molecular weight between pentoses and hexoses. Winter—Spring samples from surface waters of lower Narragansett Bay ranged from 122 to 226 μg l^?1 with a mean of 159 μg l^?1.     

Concentrations of suspended matter and particulate cadmium,copper, lead and zinc in the Indian sector of the antarctic ocean

The concentrations of suspended matter and particulate Cd, Cu, Pb and Zn were determined for 36 samples collected at 6 stations in the Antarctic Ocean during December, 1970 and January, 1971 using membrane filters. The concentration of suspended matter was determined gravimetrically and trace metal levels were determined using anodic stripping voltammetry. For waters deeper than 100 m the concentration of suspended matter was < 100 μg l^?1. Concentrations up to 542 μg l^?1 were recorded between surface and 100 m. Individual concentrations of the metals were scattered with depth. Average concentrations of particulate metals were: Cd, 3.5 ng l^?1; Cu, 100 ng l^?1; Pb, 35 ng l^?1; and Zn, 230 ng ;l^?1 These measurements represent non-steady state conditions of early Antarctic summer as the ice pack disintegrates and biological activity increases.     

Chemical determination of particulate nitrogen in San Francisco Bay. Nitrogen: chlorophyll a ratios in plankton

Particulate nitrogen (PN) and chlorophyll a (Chla) were measured in the northern reach of San Francisco Bay throughout 1980. The PN values were calculated as the differences between unfiltered and filtered (0·4 μm) samples analyzed using the UV-catalyzed peroxide digestion method. The Chla values were measured spectrophotometrically, with corrections made for phaeopigments. The plot of all $\text{PN}\text{Chl}\text{a}$ data was found to be non-linear, and the concentration of suspended particulate matter (SPM) was found to be the best selector for linear subsets of the data. The best-fit slopes of $\text{PN}\text{Chl}\text{a}$ plots, as determined by linear regression (model II), were interpreted to be the N: Chla ratios of phytoplankton. The Y-intercepts of the regression lines were considered to represent easily-oxidizable detrital nitrogen (EDN). In clear water ( < 10 mg l^?1 SPM), the N: Chla ratio was 1·07 μg-at N per μg Chla. It decreased to 0·60 in the 10–18 mg l^?1 range and averaged 0·31 in the remaining four ranges (18–35, 35–65, 65–155, and 155–470 mg l^?1). The EDN values were less than 1 μg-at N l^?1 in the clear water and increased monotonically to almost 12 μg-at N l^?1 in the highest SPM range. The N: Chla ratios for the four highest SPM ranges agree well with data for phytoplankton in light-limited cultures. In these ranges, phytoplankton-N averaged only 20% of the PN, while EDN averaged 39% and refractory-N 41%.     

Dissolved carbohydrates in seawater. II,A spectrophotometric procedure for total carbohydrate analysis and polysaccharide estimation

A procedure is described which adds a hydrolysis step to the Johnson and Sieburth 3-methyl-2-benzothiazolinone hydrazone hydrochloride (MBTH) assay for total dissolved monosaccharides. The advantages of the monosaccharide test are retained in the total carbohydrate test, giving nearly equivalent responses for a variety of combined carbohydrates. A total sample of 50 ml is adequate for both total carbohydrate and monosaccharide assays which permit the estimation of polysaccharide by difference. Values for Narragansett Bay and adjacent waters ranged from 452 to 2023 μg l^?1 for total dissolved carbohydrate, 272 to 1353 μg l^?1 for polysaccharide, and 153 to 814 μg l^?1 for monosaccharide, which accounted for 6–18%, 4–13%, and 2–5% of the total dissolved carbon, respectively. We suggest that this is a sensitive and precise procedure which will be useful for investigating the distribution of dissolved carbohydrates in seawater and factors which affect its production, distribution and utilization.     

Chlorophyll distributions in the Delaware estuary: Regulation by light-limitation

Phytoplankton chlorophyll concentrations in the Delaware estuary range over two orders of magnitude and display several maxima over the seasonal cycle. These maxima were found to be regulated both spatially and temporally by light availability. Both the spring chlorophyll maximum, which reaches 50–60 μg chlorophyll l^?1 during a Skeletonema costatum dominated bloom, and transient fall blooms (15–20 μg l^?1) are focused in mid-estuary. These blooms are regulated spatially by settling out of suspended sediment below the turbidity maximum and both spatially and temporally by physical factors (e.g. river flow) that cause vertical stratification in mid-estuary. In freshwater regions, chlorophyll concentrations display seasonal periodicity correlated with solar irradiance; summer chlorophyll concentrations average 30 μg l^?1. These freshwater and mid-estuarine biomass maxima may be correctly predicted using a steady-state light-limitation model. In contrast, summer chlorophyll concentrations in the lower estuary remain below 10 μg l^?1 and are not correctly modeled, despite minimum turbidity, and non-nutrient limiting conditions. These chlorophyll concentrations appear to be regulated by a combination of light availability and grazing.Although extremely high anthropogenic nutrient inputs in the freshwater region of the Delaware River provide non-limiting nutrient concentrations throughout the estuary, regulation of phytoplankton growth by light-limitation restricts chlorophyll concentrations below the nuisance levels found in many eutrophic systems.     

Accumulation of Zn,Cu and Cd by crabs and barnacles

The crab Carcinus maenas (L.) and the barnacle Elminius modestus Darwin were exposed to a range of dissolved concentrations of Zn, Cu and Cd for 21 days in artificial seawater. Accumulation of Zn and Cu by crabs has been interpreted in terms of the presence of a regulation mechanism to maintain constant body concentrations (83·2 ± 19·4 μg Zn g^?1 dry wt.; 39·8 ± 9·8 μg Cu g^?1 dry wt.) under varying external dissolved metal levels, until a threshold dissolved metal concentration (c. 400 μg Zn l^?1; c. 170 μg Cu l^?1) beyond which net accumulation of metal begins. Cadium appears to be accumulated by C. maenas at all exposures with no evidence for regulation of body cadmium concentrations. Exposure of E. modestus to Zn, Cu or Cd caused net accumulation of the respective metal in the bodies of the barnacles, with no evidence for regulation of body metal concentrations.     

Accumulation and Export of Dissolved Organic Carbon in Surface Waters of Subtropical and Tropical Pacific Ocean

Dissolved organic carbon (DOC) concentrations in surface waters of the Pacific Ocean during October–November, 1995, were determined using a high-temperature combustion method. The DOC in the surface mixed-layer was approximately homogeneous with a concentration between 55 and 89 μmol C l⁻¹. This homogeneity indicates that there is a strong control of the vertical distribution of DOC by mixing processes. The DOC concentrations in the mixed-layer in the subtropical region were up to 27 μmol C l⁻¹ higher than in the tropical region. This difference reflects the subtropical accumulation and the tropical export of DOC. There is a significant positive correlation between DOC and chlorophyll a concentrations in the mixed-layer of the North Pacific subtropical region, suggesting that phytoplankton is the primary source of DOC accumulated in this region. Calculations using simple box models suggest that DOC export in the tropical region (0–50 m depth, 10°N-10°S, along 160°W) occurs primarily by poleward advection at a rate of 0.5–3 mmol C m⁻²day⁻¹. A comparison with estimates of the export rate of particulate organic carbon published in previous studies leads us to conclude that DOC export may contribute less to the carbon budget in the tropical region than has recently been supposed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Flux of dissolved organic carbon and pore water through the substrate of a Spartina alterniflora marsh in North Carolina

The export of dissolved organic carbon (DOC) from a sandy substrate Spartina alterniflora marsh in North Carolina was studied from August 1982 to July 1983. DOC of the pore water was determined using a total organic carbon analyzer and was reliably estimated by measuring the absorbance of the pore water. DOC ranged between 1 and 6 mg l⁻¹ and was highest during summer and lowest in winter. Based on hydraulic conductivity calculations, over 34 000 1 year⁻¹ of pore water was exported through the 1×25 m transect perpendicular to a tidal creek. Most of this flux (over 90%) occurred within 2 m of the creek bank. Based on this pore water flux, belowground DOC export was only 1·52 g Cm⁻² year⁻¹.     

Particulate protein measurement in oceanographic samples by dye binding

A modified version of the Coomassie Brilliant Blue dye binding protein assay has been developed for oceanographic samples and intercalibrated with the widely used Lowry assay. Particulate protein measurements were made at seven stations in the Gulf of Maine using the method. Measurements were made on cell-free homogenates. Protein concentration ranged from 2 to 212 μg l^?1 (0.02–0.68 μg at N l^?1) and averaged 58 μg l^?1. ETS activity, chlorophyll and particulate nitrogen were significantly correlated with protein concentrations.     

Trace metals in the Göta river estuary

The concentrations of the trace metals Cd, Cu, Fe, Ni, Pb and Zn in the Göta River estuary have been investigated. The following metal fractions have been determined: acid-leachable, dissolved, labile and particulate.The estuary represents a salt wedge type estuary and is situated in a densely populated region of Sweden. The metal concentrations found for the dissolved fraction is in the range of what can be considered as background levels for freshwater. It is difficult to evaluate any estuarine processes other than conservative mixing for Cd, Cu, Ni and Zn. The dissolved levels in the freshwater end member are Cd, 9–25 ngl^?1; Cu, 1·1–1·4 μgl^?1; Fe, 20–75 μg l^?1: Ni, 0·7–0·9 μg l^?1: Pb 0·09–0·2 μg l^?1; and Zn, 6–7 μg l^?1:The results from the acid-leachable fraction show that at high suspended load the particles sediment in the river mouth. The trace metal levels in this fraction are subject to large variations.     

Water and organic carbon fluxes from an irregularly flooded brackish marsh on the upper Texas coast,U.S.A.

Water flows, concentrations of total (TOC), dissolved (DOC), and particulate (POC) organic carbon and seston were monitored for 52 diel periods in the single creek draining a 270-ha Spartina patens-Distichlis spicata marsh on the upper Texas coast. Rainfall, creek water flows, and water levels in the creek and on the marsh were measured by recording instruments.Rainfall accounted for most marsh flooding, and water outflow was significantly correlated with both rainfall and marsh water level. Creek flows were predominantly outward because microtopographic features and dense vegetation restricted overmarsh water flows and thereby reduced tidal flooding while extending the time of precipitation runoff. Concentrations of organic carbon in water leaving the marsh were highest in spring and summer and averaged 25·62, 21·41 and 3·35 mg l^?1 of TOC, DOC and POC, respectively. These were 9·34, 9·93 and 0·04 mg l^?1, respectively, higher than bay water. Most POC was 0·3–28 μm in diameter. Seston > 28μ leaving the marsh was 95% amorphous material; the rest was plankton, grass particles and fecal pellets. Loss of organic carbon was directly correlated with net water flux, and thus rainfall accounted for most carbon loss. Net carbon loss averaged 196 kg TOC, 150 kg DOC and 32 kg POC per day. Net annual loss was 2·4–5·5% of net aerial primary productivity (NAPP), or 21·55-30·09 g TOC m^?2 year^?1.Export from this marsh falls within the range found for other marshes and the data collectively indicate that coastal marshes are not losing as much organic carbon as has been suggested by indirect measurements. The discrepancy between potential and realized export is explained by the fact that export is not a simple removal of excess detritus by tidal action but is a more complicated process mediated by the interaction of additional factors such as rainfall, vegetation structure, microtopographic variation and decomposition, which can serve to reduce the amount and quality of NAPP exported.     

Distribution and Seasonal Variability of Organic Matter in a Small Eutrophicated Salt Lake

Distribution and seasonal variability of dissolved organic carbon (DOC) and surface active substances (SAS) were studied along the depth profile (15 m) in a small eutrophicated and periodically anoxic sea lake (Rogoznica Lake, Eastern Adriatic coast) in 1996 and 1997. The range of DOC concentrations was characteristic for productive coastal marine ecosystems (60% of samples in the range of 1–2 mg l⁻¹and 40% between 2 and 3 mg l⁻¹). Distribution of SAS concentrations was uniform and shifted toward higher concentrations in comparison to other coastal areas in the Adriatic Sea. Eutrophication in the lake is generated by nutrient recycling under anaerobic conditions. Systematically higher concentrations of chlorophyll a, DOC and SAS were determined at the chemocline in the bottom layer (10–12 m) than in the upper water layer (0·5–2 m). Seasonal variability of organic matter was discussed regarding distributions of microphytoplankton (cells >20 μm) and photosynthetic pigments as well as oxygen and salinity changes along the depth profile. The dissolved oxygen saturation reaching up to 300% in the water layer between 8 m and 10 m depths in May and June 1996, was correlated with enhanced concentrations of phytoplankton biomass (reflected as chl a and b, fucoxanthin, peridinin, zeaxanthin) and increased concentrations of DOC and SAS.     

Methane in the Sevastopol coastal area, Black Sea

Concentrations of dissolved methane in seawater and bottom sediments, as well as of methane emanating from gas seeps were measured at 18 stations including several small bays in the Sevastopol coastal area (Black Sea) during 2007–2008. Methane concentrations in surface waters ranged from 10 to 2,970 nmol l^?1, and correlated well with values recorded for sediments. Methane concentrations in the water column were influenced by water depth, as well as by air and water temperatures. In the spring and summer of 2008, in situ CH₄ saturation relative to air was in the range of 970–71,900%. Maximum saturation was in summer. CH₄ fluxes to the atmosphere from the Sevastopol coastal area were estimated to vary from 190 to 1,550 μmol m^?2 day^?1. Gas bubbles escaping from the seepages contained about 57 vol% methane. Radiocarbon dating of the methane revealed an age not exceeding 150 years, implying a biogenic origin.     

Determination of volatile fatty acid turnover rates in organic-rich marine sediments

Volatile fatty acid (VFA) apparent turnover rates in organic-rich marine sediments were determined by measuring whole sediment VFA concentration and the corresponding first-order reaction rate constants. In order to measure VFA concentrations, bulk wet sediment samples were basified, freeze-dried, extracted with methanol, derivatized to form methyl esters of the VFAs, and analyzed by packed-column gas chromatography using hexanoic acid as an internal standard. The detection limits for acetate, propionate, iso-butyrate and butyrate were 1.0, 0.4, 0.2 and 0.2 μmol l^?1_s, respectively, for 600 ml samples. Rate constants for acetate and propionate were determined by anaerobically incubating samples at in-situ temperatures with tracer levels of ¹⁴C-labelled VFAs. Metabolized label was recovered as CO₂, CH₄, cellular material, water-soluble material, and VFA (ether-soluble) fractions. Apparent turnover rates measured during summer and winter in anoxic Cape Lookout Bight, North Carolina (U.S.A.) sediments were in the range of 19–330 μmol l^?1_s h^?1 for acetate and 0.7–7.0 μmol l^?1_s h^?1 for propionate.     

Effects of some representative petroleum refinery effluent compounds on photosynthesis and growth of natural marine phytoplankton assemblages: Part 1—cresols

The effects of cresols on the photosynthesis and growth of natural marine phytoplankton assemblages from the Scripps Pier at La Jolla, California, USA were measured. In two experiments, in which dinoflagellates were the dominant algae, photosynthesis (measured by ¹⁴C uptake) was inhibited at concentrations > 100 μg litre^?1 and the concentration giving half-maximal photosynthesis was 10,000 μg litre^?1. In a third experiment, in which diatoms were dominant, photosynthesis was not inhibited until levels > 10,000 μg litre^?1 were reached and the half-maximal concentration was 20,000 μg litre^?1. These experiments suggested that dinoflagellates were more sensitive to cresols than diatoms. However, the reverse was true in an experiment using cultures. In a long-term growth experiment (natural assemblages from the Scripps Pier), only a level of 88,000 μg litre^?1 completely inhibited growth. There was a two-day lag in growth at 8500 μg litre^?1, but the algae recovered and grew as well as the controls which contained no cresols. This experiment was started with a mixed diatom-dinoflagellate-microflagellate population but only the diatoms grew. High concentrations of cresols (> 900 μg litre^?1) resulted in a decrease in the diatom Skeletonema costatum, compared with the controls. Otherwise there was no selection for resistant species. In these experiments, cresols were measured by extraction with methylene chloride from seawater followed by measurement by UV absorption. In all experiments cresol levels decreased with time. This was attributed to uptake by phytoplankton and bacterial degradation.     

Dissolved organic carbon in the freshwater tidal reaches of the Schelde estuary

To unravel the factors that regulate DOC dynamics in the freshwater tidal reaches of the Schelde estuary, DOC concentration and biodegradability were monitored in the upper Schelde estuary and its major tributaries. Although the Schelde estuary possesses a densely populated and industrialized catchment, our data suggest that the bulk of DOC in the freshwater tidal reaches is not derived from waste water. This was concluded from the low biodegradability of DOC (on average 9%), DOC concentrations that are close to the mean for European rivers (4.61 mg l⁻¹) and the absence of an inverse relationship between DOC and discharge. Most DOC originating from waste water being discharged in tributaries of the estuary appears to be remineralised before these tributaries reach the main estuary. Although dense phytoplankton blooms were observed in the upper estuary during summer (up to 700 μg chl a l⁻¹), these blooms did not appear to produce large quantities of DOC in the freshwater tidal reaches as DOC concentrations were low when phytoplankton biomass was high. The fact that DOC concentrations were high in winter and decreased in summer suggests a predominantly terrestrial source of DOC in the freshwater tidal reaches of the Schelde estuary.     

Uptake of nitrogenous nutrients by phytoplankton in a barrier Island estuary: Great South Bay,New York

The uptake of urea, nitrate and ammonium by phytoplankton was measured using ¹⁵N isotopes over a one-year period in Great South Bay, a shallow coastal lagoon. The bay is a unique environment for the study of nutrient uptake since ambient concentrations of $\text{NO}{}_3{}^{\mathrm{?}}\text{NH}{}_4{}^{\mathrm{+}}$ and urea remain relatively high through the year, and phytoplankton are probably never nutrient limited. Urea nitrogen averaged 52% of the total assimilated, while ammonium represented 33% and nitrate 13%. High rates of ammonium uptake occurred only at low urea concentrations (ca< 1-μg-atom urea l^?1). Over the sampling period urea was present in relatively high concentrations, averaging 5·35 μg-atom N l^?1, while means for ammonium and nitrate averaged 1·94 and 0·65 μg-atom N l^?1, respectively. Total N uptake measured with ¹⁵N averaged about 3·3 times the calculated (from elemental ratios and ¹⁴C productivity measurements) N needs of the phytoplankton population. Highest nitrogen uptake occurred in the summer and coincided with the primary production maximum.     

Direct determination of barium in Sea water by inductively coupled plasma emission spectrometry

A method for the determination of barium in sea water was investigated using inductively coupled plasma emission spectrometry, and sea water samples from the Japan Sea and the Pacific Ocean were directly analyzed by this method. Artificial sea water was used to prepare matrix matched standard solutions to overcome the problem of physical interference. The detection limit (signal/noise ratio=2) for barium in deionized and distilled water was 0.08µg l^?1 and in sea water, 0.12µg l^?1. The reproducibilities in the purified water and in the sea water at the 10µg l^?1 level were 0.7% a#FFFFFFnd 0.5%, respectively. The barium concentration in both the Japan Sea and the Pacific Ocean increased with depth and ranged between 5.5–10.0µg l^?1 and 4.1–18.4µg l^?1, respectively.     

Particulate organic matter in the coastal and estuarine waters of Goa and its relationship with phytoplankton production

In the coastal and estuarine waters of Goa, particulate organic carbon (POC) varied from 0.52 to 2.51 mg l^?1 and from 0.28 to 5.24 mg l^?1 and particulate phosphorus (PP) varied from 0.71 to 5.18 μg l^?1 and from 0.78 to 20.34 μg l^?1, respectively. The mean values of chlorophyll and primary productivity were 1.94 mg m^?3 and 938.1 mg C m^?2 day^?1 in the coastal waters and 4.3 mg m^?3 and 636.5 mg C m^?1 day^?1 in the estuarine waters, respectively.$\text{POC}\text{chl}$ ratios were low in June and October even when POC values were quite high. The POC in surface waters was linearly correlated with the chlorophyll content. Also PP increased when chlorophyll and primary productivity remained high. The results suggest that the phytoplankton was sharply increasing and contributed to POC and PP content. The percentage of detritus calculated from the intercept values of chlorophyll on POC varied from 46 to 76% depending on season. Results indicate that the major portion of POC and PP during postmonsoon (October–January) is derived from phytoplankton production while the allochthonous matter predominate during monsoon (June–September).     

Sensitivity of estuarine phytoplankton to hexavalent chromium

Experiments were conducted in which we tested the effects of hexavalent chromium on both natural assemblages of phytoplankton and cultures of Thalassiosira pseudonana clone 3H. Water was collected from various locations in Yaquina Bay, Oregon, with salinities ranging from 32·5‰ to 0·03‰. A variety of nutrient regimes were tested by adding major nutrients and micro-nutrients, and/or stripping micro-nutrients with activated carbon. In one high salinity experiment, chromium was stimulatory, as were micro-nutrient additions. In other high and medium salinity experiments, chromium was neither stimulatory nor inhibitory, at levels up to 1·9 μ mole l^?1 Cr. There was, however, slight inhibition of growth at 19·0 μ mole l^?1 Cr, due specifically to inhibition of Skeletonema costatum. In our freshwater experiments, chromium was very inhibitory at 1·9 μ mole l^?1 Cr, and slightly inhibitory at 0·19 μ mole l^?1 Cr. Species inhibited by chromium were Surirella ovata, Detonula confervacea, and Cyclotella sp. Experiments were conducted with T. pseudonana grown over a wide range of salinities. Chromium was found to be very inhibitory in freshwater and became progressively less toxic as the salinity increased. Most inhibition was neutralized by a salinity of 2·1‰.