A preliminary methods comparison for measurement of dissolved organic nitrogen in seawater

Routine determination of dissolved organic nitrogen (DON) is performed in numerous laboratories around the world using one of three families of methods: UV oxidation (UV), persulfate oxidation (PO), or high temperature combustion (HTC). Essentially all routine methods measure total dissolved nitrogen (TDN) and calculate DON by subtracting the dissolved inorganic nitrogen (DIN). While there is currently no strong suggestion that any of these methods is inadequate, there are continuing suspicions of slight inaccuracy by UV methods.This is a report of a broad community methods comparison where 29 sets (7 UV, 13 PO, and 9 HTC) of TDN analyses were performed on five samples with varying TDN and DIN concentrations. Analyses were done in a “blind” procedure with results sent to the first author. With editing out one set of extreme outliers (representing 5 out of 145 ampoules analyzed), the community comparability for analyzing the TDN samples was in the 8–28% range (coefficient of variation representing one standard deviation for the five individual samples by 28 analyses). When DIN concentrations were subtracted uniformly (single DIN value for each sample), the comparability was obviously worse (19–46% cv). This comparison represents a larger and more diverse set of analyses, but the overall comparability is only marginally better than that of the Seattle workshop of a decade ago. Grouping methods, little difference was seen other than inconclusive evidence that the UV methods gave TDN values for several of the samples higher than HTC methods. Since there was much scatter for each of the groups of methods and for all analyses when grouped, it is thought that more uniformity in procedures is probably needed. An important unplanned observation is that variability in DIN analyses (used in determining the final analyte in most UV and PO methods) is essentially as large as the variability in the TDN analyses.This exercise should not be viewed as a qualification exercise for the analysts, but should instead be considered a broad preliminary test of the comparison of the families of methods being used in various laboratories around the world. Based on many independent analyses here, none of the routinely used methods appears to be grossly inaccurate, thus, most routine TDN analyses being reported in the literature are apparently accurate. However, it is not reassuring that the ability of the international community to determine DON in deep oceanic waters continues to be poor. It is suggested that as an outgrowth of this paper, analysts using UV and PO methods experiment and look more carefully at the completeness of DIN conversion to the final analyte and also at the accuracy of their analysis of the final analyte. HTC methods appear to be relatively easy and convenient and have potential for routine adoption. Several of the authors of this paper are currently working together on an interlaboratory comparison on HTC methodology.     

HPLC analysis of algal pigments: a comparison exercise among laboratories and recommendations for improved analytical performance

Pure individual and mixed pigment standards were distributed among Joint Global Ocean Flux Study (JGOFS) pigment analysts to estimate the variability of their spectrophotometric and chromatographic systems. To monitor the integrity of the pigments during the comparison exercise, chlorophyll and carotenoid standards were archived and periodically analyzed by high-performance liquid chromatography (HPLC). Pigment standards stored in the dark under nitrogen at − 20 °C were found to be stable for periods of at least one year. Results from three separate intercalibration exercises document a better agreement for spectrophotometric analyses than for HPLC. For the spectrophotometric comparisons, 90% of the pigments analyzed by participant laboratories were within ± 6% of the mean “consensus” values. By contrast, 65 and 85% of the laboratories agreed to within ± 10 and ± 20%, respectively, when chromatographic analyses were compared. Chlorophyll absorption measurements obtained with a diode array-type spectrophotometer were 6–9% lower than those obtained with monochromator-type spectrophotometers. These underestimates probably result from chlorophyll fluorescence contamination associated with the optical configuration of the diode array spectrophotometer. It was also determined that HPLC methods which are not capable of separating monovinyl chlorophyll a from divinyl chlorophyll a can produce 15–25% overestimates of total chlorophyll a concentration in Prochlorococcus-dominated oceanic waters. A simple dichromatic approach is described for eliminating this variable source of error caused by co-elution of these structurally-related pigments. The use of internal standards and periodic calibration checks with external standards is highly recommended for improving analytical performance.     

Analytical intercomparison results from the 1990 Intergovernmental Oceanographic Commission open-ocean baseline survey for trace metals: Atlantic Ocean

“Dissolved” (< 0.4 μm filtered) and “total dissolvable” (unfiltered) trace element samples were collected using “clean” sampling techniques from four vertical profiles in the eastern Atlantic Ocean on the first IOC Trace Metals Baseline expedition. The analytical results obtained by 9 participating laboratories for Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, and Se on samples from station 4 in the northeast Atlantic have been evaluated with respect to accuracy and precision (intercomparability). The data variability among the reporting laboratories was expressed as 2 × SD for a given element and depth, and was comparable to the 95% confidence interval reported for the NASS seawater reference standards (representing analytical variability only). The discrepancies between reporting laboratories appear to be due to inaccuracies in standardization (analytical calibration), blank correction, and/or extraction efficiency corrections.Several of the sampling bottles used at this station were not adequately pre-cleaned (anomalous Pb results). The sample filtration process did not appear to have been a source of contamination for either dissolved or particulate trace elements. The trace metal profiles agree in general with previously reported profiles from the Atlantic Ocean. We conclude that the sampling and analytical methods we have employed for this effort, while still in need of improvement, are sufficient for obtaining accurate concentration data on most trace metals in the major water masses of the oceans, and to enable some evaluation of the biogeochemical cycling of the metals.     

A method to measure the isotopic (C) composition of dissolved organic carbon using a high temperature combustion instrument

The stable isotopes of dissolved organic carbon (DOC) are a powerful tool for distinguishing sources and inputs of organic matter in aquatic systems. While several methods exist to perform these analyses, no labs routinely utilize a high temperature combustion (HTC) instrument. Advantages of HTC instruments include rapid analysis, small sample volumes and minimal sample preparation, making them the favored devices for most routine oceanic DOC concentration measurements. We developed a stable carbon DOC method based around an HTC system. This method has the benefit of a simple setup, requiring neither vacuum nor high pressures. The main drawback of the method is a significant blank, requiring careful accounting of all blank sources for accurate isotopic and concentration values. We present here a series of experiments to determine the magnitude, source and isotopic composition of the HTC blank. Over time, the blank is very stable at  20 ng of carbon with a δ¹³C of − 18.1‰ vs. VPDB. The similarity of the isotopic composition of the blank and seawater samples makes corrections relatively minor. The precision of the method was determined by oxidizing organic standards with a wide isotopic and concentration range (− 9‰ to − 39‰; 18 μM to 124 μM). Analysis of seawater samples demonstrates the accuracy for low concentration, high salinity samples. The overall error on the measurement is approximately ± 0.8‰.     

A mechanistic study of the high-temperature oxidation of organic matter in a carbon analyzer

This study examines the mechanism of oxidation of dissolved organic matter (DOM) in a high-temperature combustion (HTC) carbon analyzer. The HTC analyzer, which is commonly used to measure the concentration of dissolved organic carbon (DOC) in seawater, is still largely empirical in its operation, and little information is yet available on the chemical and physical mechanisms responsible for oxidation of DOM. To examine the role of water, which has been hypothesized to be a source of reactive oxidants in HTC analyzers, several experiments were conducted using gaseous hexane samples and several wet/dry carrier gases. Because the quantity of O₂(g) needed to oxidize an injected sample of DOM is quite small, a substantial effort has been made to exclude O₂(g) from the combustion furnace of the HTC instrument. In this modified, “air-tight” instrument, the efficiency of conversion of hexane into CO₂ was greatest in dry O₂ and slightly lower in moist O₂. Hexane was only slightly oxidized in dry N₂, but it was largely converted into CO₂ when moist N₂ was used as the carrier gas. These experiments confirm that water provides reactive oxidizing species (perhaps hydroxyl radical) that rapidly convert hexane into CO₂ in the combustion tube of a carbon analyzer. Additional experiments with aqueous solutions of potassium hydrogen phthalate and a variety of carrier gases support this basic hypothesis.     

Seasonal variations in dissolved organic carbon concentrations and characteristics in a shallow coastal bay

Dissolved organic matter (DOM) composition and dynamics in temperate shallow coastal bays are not well described although these bays may be important as local sources of organic carbon to ocean waters and are often sites of economically-important fisheries and aquaculture. In this study surface water samples were collected on a monthly to bi-monthly basis over two years from a mid-Atlantic coastal bay (Chincoteague Bay, Virginia and Maryland, USA). Dissolved organic carbon (DOC) concentrations and light absorbance characteristics were measured on sterile-filtered water, and high-molecular weight (> 1 kDa) dissolved OM (DOM) was isolated to determine stable isotope composition and molecular-level characteristics. Our time series encompassed both a drought year (2002) and a year of above-average rainfall (2003). During the dry year, one of our sites developed a very intense bloom of the brown tide organism Aureococcus anophagefferens while during the wet year there were brown tide bloom events at both of our sampling sites. During early spring of the wet year, there were higher concentrations of > 1 kDa DOC; this fraction represented a larger proportion of overall DOC and appeared considerably more allochthonous. Based upon colored dissolved organic matter (CDOM) and high-molecular weight DOM analyses, the development of extensive phytoplankton blooms during our sampling period significantly altered the quality of the DOM. Throughout both years Chincoteague Bay had high DOC concentrations relative to values reported for the coastal ocean. This observation, in conjunction with the observed effects of phytoplankton blooms on DOM composition, indicates that Chincoteague Bay may be a significant local source of “recently-fixed” organic carbon to shelf waters. Estimating inputs of DOC from Chincoteague Bay to the Mid-Atlantic Bight suggests that shallow productive bays should be considered in studies of organic carbon on continental shelves.     

Analysis of marine DOC using a dry combustion method

As part of a continuing effort to verify and improve measurements of marine dissolved organic carbon (DOC), we combusted dried sea salts + adhered organic matter to assay DOC concentrations in representative samples from the Atlantic and Pacific oceans. Combustions were performed overnight at 580 °C in sealed tubes, and oxidation of organic materials occurred via a novel mechanism, thermal sulfate reduction: 2H₂SO₄ + CH₂O → 2SO₂ + 3H₂O + CO₂Measured DOC concentrations ranged from 43 to 114 μM C, with highest values observed in inshore surface samples from Woods Hole Harbor, and lowest values observed in twelve deep offshore Atlantic and Pacific waters. Stable carbon isotope values determined for all samples were near − 22%., consistent with a predominantly marine phytoplankton origin for DOC. A seasonal study in Woods Hole Harbor showed no significant temporal trend in nearshore DOC concentrations. Problems associated with sample storage and contamination during drying steps prevented highly precise (± 1 μM) DOC concentration determinations; however, an improved drying and measurement system is outlined (Appendix A) for possible future dry-combustion studies of DOC concentrations.     

Seasonal Investigations of Dissolved Organic Carbon Dynamics in the Tamar Estuary, U.K.

A high temperature catalytic oxidation (HTCO) technique was used to measure dissolved organic carbon (DOC) during seasonal surveys of the Tamar Estuary, U.K. At the time of the programme, the field of DOC analysis had been plagued by numerous analytical difficulties. However, using thorough calibration of the analytical systems and the systematic analysis of an internal reference material, a valuable estuarine DOC data set was produced. The range of DOC concentrations observed (478–110 μM C) is consistent with the published data for riverine and coastal sea waters respectively. The Tamar Estuary is a freshwater DOC-dominated system, with strong correlation between lateral DOC distribution and salinity. However, mixing behaviour was not strictly conservative. During tidal cycle studies at a fixed station, DOC concentrations appeared to be uncoupled from salinity, and were inversely related to turbidity. It is concluded that tidally-induced resuspension of bottom sediments provided the dominant control mechanism for DOC concentration. The Tamar Estuary shows contrasting behaviour to the larger, more heavily impacted, Severn Estuary. Hence it is likely that the behaviour of DOC in estuaries cannot be classified as typical per se, but is a function of the natural and anthropogenic characteristics of the catchment and hydrology.     

Stocks and dynamics of dissolved and particulate organic matter in the southern Ross Sea, Antarctica

Dissolved and particulate organic matter was measured during six cruises to the southern Ross Sea. The cruises were conducted during late austral winter to autumn from 1994 to 1997 and included coverage of various stages of the seasonal phytoplankton bloom. The data from the various years are compiled into a representative seasonal cycle in order to assess general patterns of dissolved organic matter (DOM) and particulate organic matter (POM) dynamics in the southern Ross Sea. Dissolved organic carbon (DOC) and particulate organic carbon (POC) were at background concentrations of approximately 42 and 3 μM C, respectively, during the late winter conditions in October. As the spring phytoplankton bloom progressed, organic matter increased, and by January DOC and POC reached as high as 30 and 107 μM C, respectively, in excess of initial wintertime conditions. Stocks and concentrations of DOC and POC returned to near background values by autumn (April). Approximately 90% of the accumulated organic matter was partitioned into POM, with modest net accumulation of DOM stocks despite large net organic matter production and the dominance of Phaeocystis antarctica. Changes in NO₃ concentration from wintertime values were used to calculate the equivalent biological drawdown of dissolved inorganic carbon (DIC_equiv). The fraction of DIC_equiv drawdown resulting in net DOC production was relatively constant (ca. 11%), despite large temporal and spatial variability in DIC_equiv drawdown. The C : N (molar ratio) of the seasonally produced DOM had a geometric mean of 6.2 and was nitrogen-rich compared to background DOM. The DOM stocks that accumulate in excess of deep refractory background stocks are often referred to as “semi-labile” DOM. The “semi-labile” pool in the Ross Sea turns over on timescales of about 6 months. As a result of the modest net DOM production and its lability, the role DOM plays in export to the deep sea is small in this region.     

Sources and transport of dissolved and particulate organic carbon in the Mississippi River estuary and adjacent coastal waters of the northern Gulf of Mexico

Dissolved organic carbon (DOC), stable carbon isotopic (δ¹³C) compositions of DOC and particulate organic carbon (POC), and elemental C/N ratios of POC were measured for samples collected from the lower Mississippi and Atchafalaya rivers and adjacent coastal waters in the northern Gulf of Mexico during the low flow season in June 2000 and high flow season in April 2001. These isotopic and C/N results combined with DOC measurements were used to assess the sources and transport of terrestrial organic matter from the Mississippi and Atchafalaya rivers to the coastal region in the northern Gulf of Mexico. δ¹³C values of both POC (−23.8‰ to −26.8‰) and DOC (−25.0‰ to −29.0‰) carried by the two rivers were more depleted than the values measured for the samples collected in the offshore waters. Strong seasonal variations in δ¹³C distributions were observed for both POC and DOC in the surface waters of the region. Fresh water discharge and horizontal mixing played important roles in the distribution and transport of terrestrial POC and DOC offshore. Our results indicate that both POC and DOC exhibited non-conservative behavior during the mixing especially in the mid-salinity range. Based on a simple two end-member mixing model, the comparison of the measured DOC-δ¹³C with the calculated conservative isotopic mixing curve indicated that there was a significant in situ production of marine-derived DOC in the mid- to high-salinity waters consistent with our in situ chlorophyll-a measurements. Our DOC-δ¹³C data suggest that a removal of terrestrial DOC mainly occurred in the high-salinity (>25) waters during the mixing. Our study indicates that the mid- to high- (10–30) salinity range was the most dynamic zone for organic carbon transport and cycling in the Mississippi River estuary. Variability in isotopic and elemental compositions along with variability in DOC and POC concentrations suggest that autochthonous production, bacterial utilization, and photo-oxidation could all play important roles in regulating and removing terrestrial DOC in the northern Gulf of Mexico and further study of these individual processes is warranted.     

Resistance to UV and persulphate oxidation of dissolved organic carbon produced by selected marine phytoplankton

We describe an investigation into the reactivity of dissolved organic carbon (DOC), produced from marine algae, to conventional persulphate and ultraviolet (UV) oxidation methods. Marine algae were grown in batch culture in the presence of ¹⁴C bicarbonate and filtered samples of the phytoplankton dissolved organic carbon (PDOC) were oxidized with persulphate and UV techniques. The amount of fixed label found in solution after the oxidation procedures was compared with the initial amount of labelled DOC. Marine algae examined in this way included: the diatoms, Chaetoceros gracilis, Skeletonema costatum, Phaeodactylum tricornutum; the flagellate, Isochrysis galbana; and the cyanobacterium, Synechococcus strain DC2. It was found that 5–18% of the DOC produced by these phytoplankton resisted persulphate oxidation. Samples were also measured for their resistance to UV oxidation by an autoanalyzer method. It was found that 15–27% of these samples resisted UV oxidation. However, 95% of PDOC was oxidized after exposure for 6 h to high intensity UV irradiation using a variable exposure time system. P. tricornutum and Synechococcus PDOC samples were ultrafiltered into low molecular weight (< 10 000 Da) and colloidal (> 10 000 Da) size fractions. Both species produced mainly (> 68%) low molecular weight material. Slightly greater resistance to persulphate oxidation was generally found for the colloidal Synechococcus PDOC (15–22%) than for the low molecular weight material (14–17%). However, the opposite was found for the P. tricornutum PDOC which generally showed less resistance for the colloidal fraction (5–12%) than for the low molecular weight fraction (10–15%).Experiments were also conducted to determine the effects of short-term (days) and long-term (months) ageing of PDOC solutions in the presence of microbial populations from coastal seawater. Long-term ageing decreased the amount of PDOC that resisted oxidation in all cases. However, the fraction of PDOC resisting persulphate oxidation increased by small amounts over a short-term experiment. Increased resistance was attributed to preferential degradation of biologically and chemically labile components of PDOC by bacteria.The percentages of phytoplankton-produced (and microbially aged) DOC found in this study to resist UV or persulphate oxidation were low (5–27%), compared with those values (50–65%) reported for DOC in surface seawater on the basis of recent high temperature catalytic oxidation analyses.     

The PAH composition of surface sediments from Stagnone coastal lagoon, Marsala (Italy)

This paper examines the presence, distribution, nature and sources of 22 Aromatic Hydrocarbons (PAHs), which are important environmentally and toxicologically, in sediments from the Stagnone coastal lagoon at Marsala (Italy). Analysis was performed by gas chromatography/mass spectrometry (GC/MS) with selected ion monitoring (SIM). The total concentration of polycyclic aromatic hydrocarbons ranged from 72 to 18381 μg/kg of dry matrix. The relative standard deviation (RSD) of the replicates on the concentrations of individual compounds ranged from 5% to 20%. The accuracy of method was estimated by analyzing “blank” samples added of known quantities of analytes and the recover percentage was 88 ± 9%. The detection limit (LOD) of analytical procedure was less than 0.2 μg/kg d.w. for all analytes. The quantification limit (LOQ) of analytical procedure was less than 0.7 μg/kg d.w.The resulting distributions and weight ratios of specific compounds are discussed in terms of sampling location and origin of organic matter. A comparison with other studies of total PAHs suggests that the levels are within the concentration ranges already reported by other authors. From an eco-toxicological point of view, total PAH concentrations at seven out of the eight sites studied represent a relatively clean environment when compared to other sites.Organic matter content and PAH concentrations were found to be correlated and the compounds present in Stagnone sediments were shown to be mainly of pyrolitic origin, while a negligible quantity of PAHs may derive from biogenic sources since all the sediments contain perylene traces. There is no evidence of coal-tar contamination.Cluster analysis was carried out in order to discriminate between different PAH origins.     

A laser-based fluorometry system for investigations of seawater and porewater fluorescence

A highly sensitive laser-induced fluorescence (LIF) system has been developed to study the fluorescence of dissolved organic carbon (DOC) in the marine environment. The LIF detector has a detection limit of 10 attomoles (10 × 10⁻¹⁸ moles) of pterin and eliminates internal quenching in highly fluorescent samples such as anoxic porewaters encountered when using conventional fluorometry. LIF analysis is rapid, reproducible, and uses only 100 μl of a sample. This small size requirement permits fluorescence analyses of samples often available only in limited amounts, such as porewaters, hydrothermal vent waters, and rainwaters. In addition, the LIF detection system may greatly simplify extraction and separation procedures required to characterize the fluorescent components of DOC.     

The reliability of analytical data for tributyltin (TBT) in sea water and its implications on water quality criteria

To investigate the reliability of analytical data for tributyltin (TBT) in sea water, split water samples were distributed to ten laboratories in six countries. The sub-surface samples comprised: (i) an offshore (0·5 km) water sample, (ii) the same sample but spiked with an undisclosed quantity of TBT standard compound (175 ng TBT⁺ liter⁻¹), and (iii) a sample taken from a yacht marina. The seven acceptable data sets were in good agreement for the spiked sample (178 ± 26 ng TBT⁺ liter⁻¹) but showed a greater variation in concentrations reported for the yacht marina sample (366 ± 93 ng TBT⁺ liter⁻¹). Atomic absorption and gas chromatographic-flame photometric detection techniques produced results of similar accuracy and precision. Samples acidified with 1 ml of 10% (v/v) acetic acid appeared stable for more than 2 weeks when stored refrigerated and in darkness. Analyses of the offshore seawater sample revealed TBT contamination (9 ± 7 ng TBT⁺ liter⁻¹) indicating dispersion of the compound to the shelf waters off Monaco. The spread in values reported by the laboratories demonstrates inherent difficulties in obtaining good precision below approximately 20 ng TBT⁺ liter⁻¹. This observation is discussed with respect to the setting and enforcing of water quality standards.     

Determination of the distribution of dissolved organic carbon in the Indian sector of the Southern Ocean

During France JGOFS campaign ANTARES 2 (R.V. Marion Dufresne), samples were taken along a section of the 62°E meridian from 49° to 66°S. The high temperature catalytic oxidation (HTCO) method was used to determine the concentration of dissolved organic carbon (DOC). The analyses were conducted both on-board ship and after the cruise in the laboratory. Collecting and storing acidified samples for post-cruise analysis induced no significant differences. The use of two separate but identical channels on the carbon analyzer increased the number of samples analysed per day and allowed independent monitoring of the instrument blank and the calibration of the detector response. The mixed layer concentrations of organic carbon varied from about 52 μM C in the Antarctic Divergence (64°S) to about 63 μM C in the Polar Frontal Zone (49°S). Vertical profiles showed a slight, but significant, decrease in organic carbon below the mixed layer, to about 42 μM C below 2000 m across the transect. The homogeneity and low concentration of organic carbon in deep water is consistent with values recently reported for the equatorial Atlantic and Pacific Ocean and supports the evidence for a constant deep water DOC concentration. In addition, this provides a verification of the instrument performance, thus validating observed DOC data trends and allowing a comparison with the ‘modern' DOC literature. In general, the organic carbon concentration in the mixed layer was lower than previously published data of the main ocean basins, which might -reflect the low chlorophyll a concentration (<0.5 μg/l) encountered in this region. Along the 62°E meridian section, organic carbon showed a trend with corresponding measurements of phytoplankton biomass and bacterial production, underlining the dependence of bacterial growth on a pool of ‘freshly' produced DOC. Organic carbon was found to exhibit a weak inverse trend versus apparent oxygen utilization (AOU). This suggests that only a small part of the oxygen consumption is due to the mineralisation of DOC.     

高温燃烧法测定海水中的溶解有机碳

１９９７年５月在莱州湾,１９９７年７月在东海,１９９７年１１月在胶州湾采集了海水样品,高温燃烧法测定了这些水样中的溶解有机碳浓度,了系统空白和标准曲线的选择对高温燃烧法测定结果的影响,并与紫外／硫酸钾法的测定进行了比较。     

Advanced characterization of marine dissolved organic matter by combining reversed-phase liquid chromatography and FT-ICR-MS

Marine dissolved organic matter (DOM) was separated by reversed-phase (RP) liquid chromatography method and analyzed with fluorescence/absorption detection and Fourier transform ion cyclotron mass spectrometry (FT-ICR-MS). The three key characteristics of the RP method are: (a) The C18-RP column chosen provides enhanced separation when the aqueous phase is 100% buffer-free water, and it does not degrade over time; (b) the water eluent adjusted to pH 7 significantly improves the resolution of water soluble compounds; (c) the initial flow maintained at low levels improves the separation of polar compounds. In samples, containing “fresh” DOM, specific peaks were detected, which were absent in “old” DOM samples. The combination with size exclusion chromatography (SEC) also demonstrated the relation between polarity and molecular size of DOM. FT-ICR-MS was applied to evaluate the quality of separation on a molecular scale demonstrating that physico-chemical characteristics of DOM can be related to molecular formulas. Sample extracts were separated into 4 preparative fractions, and a large suite of the identified molecular formulas only occurred in specific fractions. This is an important basis for the application of further analytical techniques in order to perform a more target-oriented analysis aiming at the determination of source and process biomarkers for DOM.     

Dynamics of carbohydrates in the Norwegian Sea inferred from monthly profiles collected during 3 years at 66°N, 2°E

Water samples were collected monthly for 3 years at 66°N, 2°E in the Norwegian Sea, 250 nautical miles off the Norwegian coast. Concentrations of mono- and polysaccharides were measured with the 2,4,6-tripyridyl-s-triazine (TPTZ) spectroscopic method. Total dissolved carbohydrates varied from 3.4 to 28.2 μM C of all samples and the ratio of carbohydrate to dissolved organic C (DOC) varied from an average of 14% at 0–25 m depth to 11% at 800–2000 m depth. This indicates that dissolved carbohydrates were a significant constituent of DOC in the Norwegian Sea. Polysaccharides varied from 0.4 to 21.5 μM C and monosaccharides from 0.7 to 11.7 μM C at all depths. The level of monosaccharides was relatively constant at 2.8–3.2 μM C below the euphotic zone, whereas polysaccharides showed more varying concentrations. Dissolved carbohydrates accumulated during the productive season, reaching maximum concentrations during summer although interannual differences were observed. A significant positive correlation between Chl a and soluble carbohydrate was found in one growing season with nutrient analyses. Average values for total carbohydrates were highest in the surface – 0 to 25 m – with 13.3 μM C and decreased to 8.4 μM C at 800–2000 m depth. The ratio of monosaccharides to polysaccharides exhibited a marked seasonal variation, increased from January to a maximum in June of 1.1, and declined to 0.5 in July.     

The distribution and δC of dissolved organic carbon and its humic fraction in estuaries of southeastern USA

In this study, we examine the distribution and carbon stable isotope signature of dissolved organic carbon (DOC) and humic substances (HS) along a salinity gradient in the Altamaha and Satilla River estuaries. The maximum DOC concentrations in the Altamaha and Satilla were 10 and 29 mg C l⁻¹, respectively, though concentrations were similar at the mouth of both estuaries. There was a decrease in HS content of DOC from 50 to 80% at the head of the estuaries to 10% at salinities higher than 30‰. The δ¹³C DOC varied between −25.5 and −19‰ and between −27 and −21‰ in the Altamaha and Satilla estuaries, respectively. The tendency towards more depleted δ¹³C DOC in the Satilla, especially in the lower salinity portion of this estuary, suggests greater terrestrial inputs in the Satilla than in the Altamaha. Seasonal fluctuations were observed in the form of increased (two to three times) range in DOC concentration, heavier δ¹³C DOC and increased proportion of estuarine–marine-derived DOC (average enrichment of δ¹³C DOC from +1 to +2) during low river flow (July–October). The δ¹³C HS in both rivers showed a similar trend, but was consistently more depleted than DOC, with an average range from −28 to −24.5‰. This suggests that HS have larger proportions of terrestrial components (a maximum of >60% at the mouth of the estuary) than DOC. The less depleted δ¹³C values of DOC in comparison with HS indicate a different source for the non-humic (non-HS) component of DOC (range in δ¹³C non-HS, −22 to −16‰). That source could either be the decomposition of detrital material derived from saltmarsh environments or microalgal-derived DOC of estuarine or marine origins.     

Modelling trace metal concentration distributions in estuarine waters

The concentration of dissolved organic carbon (DOC) was measured every few months from September 2000 through October 2001 at a coastal location in the center of Suruga Bay, Japan (34°51′N, 138°38′E). Water samples were collected three times per day (midday, night and predawn). DOC concentrations ranged from 91.3 to 45.2 μM C on the surface to 100 m depth. Diel variation in DOC concentrations, among the three sampling times, was greater in the upper 20 m, with a maximum difference of 21.7 μM C in July 2001, and reflected in diel DOC inventory variations from the surface to 50 m. Diel variations were controlled by both physical and biological factors. DOC concentrations were significantly correlated with potential density in the deeper layers (100–1000 m), indicating that the distribution of DOC concentrations in the deeper layer was mainly due to mixing. Most DOC concentrations in the upper layer (0–50 m) did not display the same relationship as in the deeper layer. Using the relationship with potential density at 100–1000 m, the DOC concentration in the upper layer, due simply to mixing, was calculated. The difference between the calculated and observed DOC was used to estimate biological contribution. The biological contributions to the DOC inventory in the upper layer (0–50 m) were found greatly in November 2000 and April 2001. This indicates that excess DOC accumulated, by biological processes, in the upper layer during these periods. In November 2000, the excess DOC in the inventory was constant throughout the sampling days (0.36–0.37 mol C m⁻²), whereas diel variations of DOC in the vertical profile were large and contrary to the variation between 10 and 20 m. This suggests that the excess DOC was contributed biologically during daytime in the uppermost layer and reached to the 50 m depth by deeper mixing. As a result, the inventory appeared to be stable over a day because of the compensating effects of DOC production and consumption throughout 50 m. In contrast, in spring and summer, there was a distinct diel inventory decrease in the nighttime, with apparent rates ranging from −0.61 to −0.35 μM C h⁻¹. It is probable that the DOC, which accumulated during the daytime, was mostly labile, with a turnover time of a few hours. The results indicate that the dynamics of diel DOC variations varied seasonally, and suggest that these variations need to be considered when estimating seasonal DOC pools in the coastal ocean.