Distributions and seasonal variations of dissolved carbohydrates in the Jiaozhou Bay,China

Surface seawater samples were collected in the Jiaozhou Bay, a typical semi-closed basin located at the western part of the Shandong Peninsula, China, during four cruises. Concentrations of monosaccharides (MCHO), polysaccharides (PCHO) and total dissolved carbohydrates (TCHO) were measured with the 2,4,6-tripyridyl-s-triazine spectroscopic method. Concentrations of TCHO varied from 10.8 to 276.1 μM C for all samples and the ratios of TCHO to dissolved organic carbon (DOC) ranged from 1.1 to 67.9% with an average of 10.1%. This result indicated that dissolved carbohydrates were an important constituent of DOC in the surface seawater of the Jiaozhou Bay. In all samples, the concentrations of MCHO ranged from 2.9 to 65.9 μM C, comprising 46.1 ± 16.6% of TCHO on average, while PCHO ranged from 0.3 to 210.2 μM C, comprising 53.9 ± 16.6% of TCHO on average. As a major part of dissolved carbohydrates, the concentrations of PCHO were higher than those of MCHO. MCHO and PCHO accumulated in January and July, with minimum average concentration in April. The seasonal variation in the ratios of TCHO to DOC was related to water temperature, with high values in January and low values in July and October. The concentrations of dissolved carbohydrates displayed a decreasing trend from the coastal to the central areas. Negative correlations between concentrations of TCHO and salinity in July suggested that riverine input around the Jiaozhou Bay had an important effect on the concentrations of dissolved carbohydrates in surface seawater. The pattern of distributions of MCHO and PCHO reported in this study added to the global picture of dissolved carbohydrates distribution.     

Trace metal composition of colloidal organic material in marine environments

Marine colloidal material (1 kDa–0.2 μm) was isolated by cross-flow ultrafiltration followed by diafiltration and freeze-drying from surface waters of the Gulf of Mexico and the Middle Atlantic Bight (MAB), as well as from estuarine waters of Galveston Bay. Elemental characterization of isolated colloidal material included organic carbon (OC) and selected trace metal (Cu, Pb, Zn, Cd, Co, Ni, Cr, Be, Fe, Al, Mn, V, Ba, and Ti) determinations. It was found that levels of these metals in marine colloids ranged from <0.1 to 50 μg/g colloidal matter, except for Fe which generally had a concentration >120 μg/g. Most metals (Cu, Pb, Zn, Ni, Al, Mn, V, and Ti) had an average concentration >1 μg/g while concentrations of Cd, Co and Be were usually <1 μg/g. Metal concentrations (μg/g) in isolated colloids were, in general, higher in Galveston Bay than in the Gulf of Mexico, suggesting either high abundance of trace metals in estuarine waters or differences in organic matter composition. Higher colloidal metal concentrations in the MAB than in the Gulf of Mexico might be due to higher terrestrial inputs in the MAB. Colloidal metal concentrations (μg/g) were generally lower than those in average soils, continental crust and suspended particles. However, metal/aluminum ratios (Me/Al) in isolated marine colloids were significantly higher than those for average soils and continental crust. Most importantly, colloids had a metal composition and metal/OC ratio (Me/C) similar to humic substances and marine plankton, suggesting that marine colloids largely originate from planktonic sources and are composed of predominately organic components. The Me/C ratios of Galveston Bay colloids followed the sequence of Cu>Ni, Cr, Zn>Mn>Co>Pb, Cd, which is similar to the Irving–Williams order except for Mn, suggesting that the interaction of metals with marine colloids is determined by the affinity of metals for specific organic ligands.     

Seasonal variations and distributions of dissolved free and total carbohydrates at the İzmir Bay, Aegean Sea

Seasonal variations and distributions of dissolved carbohydrate concentrations at the İzmir Bay were investigated with salinity, chlorophyll a (Chl a), and dissolved organic carbon (DOC) levels to understand their relationships. Samples were collected from surface, subsurface and bottom depths at seven stations. DOC concentrations ranged from 32.2 to 244.2 μmol/L, and in general, DOC levels increased from winter to summer, then slightly decreased in autumn. Monosaccharide (MCHO), polysaccharide (PCHO) and total dissolved carbohydrate (TDCHO) levels were found between 0.7-8.3, 0.7-19.5, and 2.6-24.6 μmol/L. DOC, MCHO, PCHO and TDCHO levels were found higher in middle-inner bays, under the influence of anthropogenic inputs, compared to outer bay. Seasonal changes of MCHO/DOC, PCHO/DOC and TDCHO/DOC ratios were statistically significant (p<0.05) and the ratios showed decrease trends from winter to summer-autumn seasons. Distributions of TDCHO/DOC ratios at wide ranges (2.5%-42.3%) indicated the presence of newly forming and degrading fractions of DOM. According to results of factor analysis, Chl a, MCHO and TDCHO were explained in the same factor groups. In conclusion, the results showed that dissolved carbohydrate levels in the İzmir Bay might be influenced by biological processes and terrestrial/anthropogenic inputs.     

冬季中国东海中溶解碳水化合物浓度分布

采集了中国东海(2009-12~2010-01)35个站位的海水样品,其中包括6个站位的垂直断面。用TPTZ方法测定了溶解态的单糖(MCHO)、多糖(PCHO)和总糖(TCHO)的浓度,对其水平分布和PN断面分布进行了研究。结果表明,受到长江冲淡水和黑潮水的影响,表层海水中MCHO、PCHO和TCHO浓度的水平分布表现出由近岸向外海递减的分布趋势。PN断面由于受冬季东北季风的影响,水体混合强烈,使得MCHO、PCHO和TCHO浓度在垂直方向上分层无明显规律。对长江口外3个断面海水中TCHO浓度与环境因子做了相关性研究。结果表明,TCHO浓度与盐度和温度呈显著的线性负相关,与Chl-a浓度呈线性正相关。     

Isolation of colloidal monomethyl mercury in natural waters using cross-flow ultrafiltration techniques

A series of experiments was conducted to evaluate the appropriateness of cross-flow ultrafiltration (CFUF) techniques for the determination of the phase speciation of monomethyl mercury (MeHg) in natural waters. Spiral-wound cartridge (Amicon S1Y1) and Miniplate (Amicon) were evaluated for their nominal molecular weight cut-offs of 1 and 10 kDa, respectively. The ultrafiltration behavior of standard macromolecules showed that the permeation of high molecular weight (HMW) organic macromolecules was not significant when a concentration factor (CF)>15 was used. The retention of low molecular weight (LMW) molecules was significant, especially at a low CF<5, suggesting that the use of a high CF (15) will minimize the retention of LMW molecules. Sorptive losses of MeHg in the solution phase to the 1 kDa membrane were negligible, but MeHg bound to HMW macromolecules was still retained (20%), even with a preconditioned membrane. The mass balance recovery of MeHg during ultrafiltration averaged 101±15% (n=7) and 105±14% (n=5) for the 1 and 10 kDa membranes, respectively. Sample storage over 24 h caused significant coagulation (47%) of the <10 kDa MeHg into the 10 kDa–0.45 μm colloidal or the particulate MeHg pool. The 1 kDa–0.45 μm colloidal MeHg in Galveston Bay and the Trinity River water samples accounted for 40–48% of the filter-passing MeHg, although the most abundant fraction (52–60%) of MeHg was the truly dissolved fraction (<1 kDa). The partition coefficient between the colloidal (1 kDa–0.45 μm) and truly dissolved MeHg (average log K_C=5.2) was higher than the partition coefficient based on particle/filter-passing (average log K_D=4.6) or particle/truly dissolved MeHg (average log K_P=4.8), suggesting that MeHg has stronger affinity for natural colloids than macroparticulate materials (>0.45 μm).     

Behaviour of colloidal trace metals (Cu, Pb and Cd) in estuarine waters: An approach using frontal ultrafiltration (UF) and stripping chronopotentiometric methods (SCP)

The frontal cascade ultrafiltration (UF) technique in conjunction with stripping chronopotentiometry (SCP) has been evaluated for determining the colloidal distribution of Cu, Pb and Cd in estuarine waters. Metallic concentrations in seven size fractions (0.45 μm–0.22 μm; 0.22 μm–300 kDa; 300–50 kDa; 50–30 kDa; 30–10 kDa; 10–5 kDa; <5 kDa) were determined with the aim to investigate their changes along the salinity gradient of the Penzé system (NW France). These data, completed by analysis of the total dissolved metals at 10 stations over the whole freshwater–seawater mixing zone, provided some insights in the removal and addition processes that affect Cu, Pb and Cd in estuaries.     

Particulate carbohydrates and uronic acids in the northern East China Sea

Carbohydrate species, such as uronic acids, play an important role in oceanic carbon cycling, coagulation and adsorption processes. Concentrations of particulate carbohydrates (PCHO) and uronic acids (PURA) were measured in the northern East China Sea (ECS) during June and November, 2006. In June, maximum concentrations of PCHO and PURA were observed in the surface layer of coastal waters. Their concentrations rapidly decreased with depth, suggesting that they are both bio-reactive. Moreover, phytoplankton abundance and bacterial biomass seem to be associated with observed PCHO and PURA concentrations in the ECS during June, suggesting that production of carbohydrate species in the ECS is regulated by phytoplankton assemblages, bacterial assimilation or degradation. In November, however, PCHO and PURA concentrations were homogenous within the water column due to strong vertical mixing. No strong correlations were observed between carbohydrate species (PCHO and PURA) and phytoplankton or bacterial biomass, suggesting that production of these compounds in November might be caused by the physiological difference between nutrient limited and non-nutrient limited phytoplankton. Furthermore, strong negative correlations between nutrients and PCHO species suggest that nutrient levels may be one of the driving forces behind the production of these compounds in the ECS.     

Determination of dissolved nucleic acids in seawater by the fluorescence dye, ethidium bromide

A new method for the determination of dissolved double-stranded deoxyribonucleic acid (DNA) and ribonucleic acid (RNA) in seawater was developed, evaluated and used to study the fates of these nucleic acids in marine ecosystems. These nucleic acids, which were pre-concentrated on a hydroxyapatite column, were determined fluorometrically by the use of ethidium bromide dye, which binds specifically to the double-stranded polynucleotide. No dissolved organic matter coexisting in the pre-concentrated sample solution interfered in the analysis of DNA and RNA. Column recoveries of DNA and RNA in a sample volume of up to 11 were 93% and 97%, respectively, and 90% of both at 51. The detection limits of DNA and RNA concentrated from a 51 sample by this fluorometric method were 0.6 and 1.1 μg l⁻¹, respectively. The concentration of dissolved nucleic acids in the waters from Tokyo Bay and Sagami Bay showed great variation in space and time. DNA ranged from 1 to 32 μg l⁻¹, and RNA from below the detection limit to 34 μg l⁻¹. The total amount of phosphorus in nucleic acids was an important fraction (12.9 ± 8.2%) of the dissolved organic phosphorus (DOP) and showed a good correlation with DOP.     

Complexation of mercury by dissolved organic matter in surface waters of Galveston Bay, Texas

The chemical speciation of dissolved mercury in surface waters of Galveston Bay was determined using the concentrations of mercury-complexing ligands and conditional stability constants of mercury-ligand complexes. Two classes of natural ligands associated with dissolved organic matter were determined by a competitive ligand exchange-solvent solvent extraction (CLE-SSE) method: a strong class (L_s), ranging from 19 to 93 pM with an average conditional stability constant (K_HgLs) of 10²⁸, and a weak class (L_w) ranging from 1.4 to 9.8 nM with an average K_HgLs of 10²³. The range of conditional stability constants between mercury and natural ligands suggested that sulfides and thiolates are important binding sites for dissolved mercury in estuarine waters. A positive correlation between the estuarine distribution of dissolved glutathione and that of mercury-complexing ligands supported this suggestion. Thermodynamic equilibrium modeling using stability constants for HgL, HgCl_x, Hg(OH)_x, and HgCl(OH) and concentrations of each ligand demonstrated that almost all of the dissolved mercury (> 99%) in Galveston Bay was complexed by natural ligands associated with dissolved organic matter. The importance of low concentrations of high-affinity ligands that may originate in the biological system (i.e., glutathione and phytochelatin) suggests that the greater portion of bulk dissolved organic matter may not be important for mercury complexation in estuarine surface waters.     

Microbial biogeochemistry and bioturbation in the sediments of Great Bay, New Hampshire

The influence of bioturbation on certain aspects of the biogeochemistry of sulfur and iron was examined in shallow-water sediments of Great Bay Estuary, New Hampshire. A bioturbated (JEL) and non-bioturbated (SQUAM) site were compared. Annual sulfate reduction measured with ³⁵S, was 4·5 times more rapid at JEL. A significant portion of this difference was attributed to rapid rates which occurred throughout the upper 12 cm of sediment at JEL due to infaunal reworking activities. Sulfate reduction decreased rapidly with depth at SQUAM. FeS in the upper 2 cm at JEL increased in concentration from 3 to 45 μmol ml⁻¹ from early May to late July while only increasing from 3 to 8 μmol ml⁻¹ at SQUAM. Infaunal irrigation and reworking activities caused rapid and continous subsurface cycling of iron and sulfur at JEL. This maintained dissolved iron concentrations at 160–170 μM throughout the summer despite rapid sulfide production. Therefore, dissolved sulfide never accumulated in JEL pore waters. Although dissolved organic carbon (DOC) was generated during sulfate reduction, bioturbation during summer caused a net removal of DOC from JEL pore waters. Sulfate reduction rates, decomposition stoichiometry and nutrient concentrations were used to calculate turnover times of nutrients in pore waters. Nutrient turnover varied temporally and increased three-to five-fold during bioturbation. A secondary maximum in the abundance of recoverable sulfate-reducing bacteria occurred at 10 cm in JEL sediments only during periods of active bioturbation, demonstrating the influence of macrofaunal activities on bacterial distributions.     

Organic chemistry of seawater particulates - concepts and developments

Organic chemistry of particulates has recently been developed with the increasing quality of analytical methods. Because of the low organic content in deep sea, most of the studies were dealing with the euphotic layer. So we have very little information about the purely detrital material. Particulate organic carbon range from about 100 μg/1 in the surface layer, to 5–30 μg/1 in deep sea. Total particulate organic carbon in the world ocean must be about 2 · 10¹⁶g.It is important to obtain more detailed information about this enormous quantity of organic matter, the relative stability of which suggests that it could be used as a geochemical tracer. The distribution of particulate organic carbon exhibits regional variations, especially in surface waters, and a sharp vertical gradient of limited extent down to 200–300 m.At this depth, the deep water situation is reached with a quite constant carbon concentration disrupted only by pronounced increases associated with particular water masses. Though particles are generally recovered by filtration on 0.45 μ pore size filters, many smaller particles are present in sea water. The dialysis of seawater demonstrated a recovery of non dialysable material of about six times the amount recovered by filtration. While we have to take into account the existence of soluble high molecular substances, it seems possible for a great part of them to be in the colloidal state. If we except the biological processes, most of the chemical reactions occurring in the sea must concern this fraction. The detritus are for the most part too inert to play an important role in chemical reactions, while the strictly dissolved compounds are rapidly degraded by organisms. This colloidal fraction is thus responsible for the metals fixation, aggregation and sedimentation processes. It has been proved that it plays a very important role in the fixation of pesticides and hydrocarbons and must be considered in all the studies dealing with pollution.Some works on the origin of suspensions, showed that they can be formed by bubbling. Large organic active molecules adsorb to bubbles and produce monomolecular film which may be aggregated into insoluble organic particles; the agitation results in a semi-stable colloidal suspension of organic materials.It is highly probable that most of the organic matter in the deep sea is in the form of heteropolycondensed molecules, containing important carbohydrates and protein chains. These molecules are in a colloidal state in the supposedly dissolved material, which can be adsorbed on, or aggregated with particles by physical or biological processes.     

Distribution, condition, and growth of newly settled southern flounder (Paralichthys lethostigma) in the Galveston Bay Estuary, TX

Several flatfish species, including southern flounder (Paralichthys lethostigma) recruit to estuaries during early life. Therefore, evaluation of estuarine sites and habitats that serve as nurseries is critical to conservation and management. The present study used density data in conjunction with biochemical condition and growth measurements to evaluate settlement sites used by southern flounder in the Galveston Bay Estuary (GBE). In 2005, beam-trawl collections were made in three major sections of the GBE (East Bay, Galveston Bay, West Bay). Three sites were sampled in each bay. Within each sampling site, replicate collections were taken from three habitats: 1) marsh edge (< 1 m depth), 2) intermediate zone (10–20 m from marsh interface;  1 m depth), and 3) bay zone (typically > 100 m from marsh interface; depth > 1 m). Average size of southern flounder collected was 12–19 mm standard length, and peak densities occurred in January and February. Catch data indicated that densities of southern flounder were significantly greater in East Bay (2.75 per 100 m²) than in Galveston Bay (0.91 per 100 m²) or in West Bay (0.45 per 100 m²). Densities were statistically similar among habitats. Otolith-based estimates of age indicated that the majority of southern flounder collected were 35–45 days old and derived from early December to early January hatch-dates. Growth rates were similar among bays and among habitats, with the average growth rate being 0.40 mm day^− 1 (range: 0.21–0.76 mm day^− 1). RNA:DNA was above the established baseline value for nutritional stress, indicating that newly settled southern flounder in the GBE were in relatively high condition. Habitat-specific differences in RNA:DNA ratios were not observed; however, ratios were significantly lower in West Bay (average 8.0) than in East Bay (average 9.5) or in Galveston Bay (average 9.8), suggesting the condition of new recruits may vary spatially within the GBE. Findings from the current study suggest density and condition of newly settled southern flounder vary at the bay scale, suggesting that parts of GBE do not function equally as nurseries.     

Distribution and seasonal variation of concentrations of particulate carbohydrates and uronic acids in the northern Indian Ocean

Suspended particulate matter (SPM) samples were collected from the surface seawaters at 31 stations, and from various depths (2 to 1000 m) at 9 locations in the northern Indian Ocean during various seasons. SPM samples were analyzed for total particulate carbohydrate (TPCHO), total particulate uronic acid (TPURA) and total particulate neutral carbohydrate (TPNCHO) concentrations and composition. Strong spatial, temporal and depth related variations were evident in the distribution of these compounds. In surface waters, concentrations of TPCHO, TPNCHO, and TPURA varied from 0.57 to 3.58 μM C, 0.11 to 2.34 μM C, and from 0.01 to 0.31 μM C, respectively, and accounted for 2.6 to 34.6%, 2 to 24.5%, and 0.2 to 6.3% of POC, respectively, whereas the TPURA accounted for 4.7 to 22.7% of TPCHO. Concentrations and yields of both TPNCHO and TPURA decreased rapidly in the upper 100 m of the water column suggesting their utilization by heterotrophic organisms. Glucose was the most abundant constituent of the TPNCHO. Glucose mole fraction decreased while that of other monosaccharides, especially galactose, arabinose, mannose, rhamnose and fucose increased in the upper 100 m water. Below this depth, mole fraction of glucose increased while that of other sugars decreased with the increasing water depth. Generally, high C:N ratios were associated with low yields of carbohydrates and uronic acids. Inverse correlation between the mole fractions of arabinose plus xylose and rhamnose plus fucose indicates the importance of biogenic and terrestrial organic matter input to the Bay of Bengal. TPURA are surface-active in nature and thus may play an important role in coagulation of particles and macromolecules. The observed spatial and seasonal variations of these compounds may be due to differences in phytoplankton biomass, nutrient status, and the influence of terrestrial material.     

Variations in the chemical lability of iron in estuarine, coastal and shelf waters and its implications for phytoplankton

The relationship between total and chemically labile Fe has been studied in estuarine, coastal and shelf waters of the Gulf of Maine, U.S.A. Measurements of the labile fraction of total Fe, defined by complexation with 8-hydroxyquinoline in 1 h, correlate with the availability of Fe to marine phytoplankton and therefore can be used to estimate Fe availability in seawater. The results show that the relative lability (=labile/total) of Fe in seawater varied both spatially and temporally from near-zero to 100%. Although particulate Fe (>0.45 μm) was generally less labile than dissolved Fe (<0.45 μm), the particulate fraction often contributed substantially to labile Fe concentrations overall. Conversely, as much as 75% of ‘dissolved’ Fe was non-labile, and therefore was probably not available to phytoplankton. In seawater/river-water mixing experiments, aggregation diminished the relative lability of Fe by 30%, even though much of it remained in the ‘dissolved’ fraction. Considering phytoplankton nutrition, these results demonstrate that equating dissolved Fe concentrations with ‘available’ metal can be misleading. Furthermore, the large variability observed in the labile proportion of total Fe in seawater indicates that Fe availability to phytoplankton cannot be estimated by applying fixed lability-ratios to total Fe concentrations.     

Distributions of carbohydrate species in the Gulf of Mexico

In order to study the role of polysaccharides in the cycling of marine organic matter and transparent exopolymeric particles (TEP), the concentrations of total carbohydrates (p-TCHO), total uronic acids (URA) and total acid polysaccharides (APS) in suspended and sinking particles, as well as carbohydrates in the filter-passing “dissolved” phase (d-TCHO), were measured in vertical profiles along a N–S transect in the Gulf of Mexico, across a cold core (CCR) and a warm core (WCR) ring (eddy) during both July 2000 and May 2001. The concentrations of d-TCHO in 2000 ranged from 4 to 22 μM C, with a subsurface maximum, which was located slightly above the depth of chl a maximum, amounting to, on average, 34% of DOC in the CCR, and 13% in the WCR. The concentration of particulate carbohydrates (p-TCHO) in different size fractions (0.7–10, 10–53, and >53 μm) ranged from 0.04 to 1.1, 0.005 to 0.40, and 0.006 to 0.26 μM C, respectively, indicating that carbohydrates are mostly concentrated in small particles (0.7–10 μm). URA and APS were similarly concentrated in small particles, in which, on average, URA accounted for 87% and 57% of total URA, and APS for 92% and 88% of total APS in 2000 and 2001, respectively. URA accounted for 3–9% of carbohydrates in suspended particles, suggesting that URA are a minor component of the p-TCHO pool. Due to its surface-reactive nature, URA could play a major role in the coagulation of particles and macromolecules despite its relatively low abundance. While, on average, p-TCHO and total APS were more enriched in suspended particles than in sinking particles in both 2000 and 2001, the opposite was true for URA in both years. The greater contents of URA that are present in settling particles compared to suspended particles could indicate a mass flow in the direction of sinking particles, either caused by coagulation, by bacterial reworking of particulate and colloidal organic matter, or by their more refractory nature.     

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.     

A sensitive and rapid method for analysis of dissolved mono- and polysaccharides in seawater

A spectrophotometric method is described for the determination of dissolved mono- and polysaccharides in seawater. It is based upon the well known alkaline ferricyanide reaction, but uses the reagent 2,4,6-tripyridyl-s-triazine (TPTZ) to give a strongly colored complex with the reduced iron. The method has been tested on model carbohydrates and other compounds, and also on natural samples of coastal and oceanic waters. Total carbohydrate content of the natural samples ranged from 5.2 to 25.1 μmol glucose-Cl⁻¹. The coefficient of variation was typically below 6% for values near 17 μmol Cl⁻¹ and approximately 10% for values near 3.5 μmol Cl⁻¹.     

Dissolved inorganic and organic iodine in the Chesapeake Bay and adjacent Atlantic waters: Speciation changes through an estuarine system

The distributions of iodate, iodide and dissolved organic iodine (DOI) were determined in two deep sub-basins in the Chesapeake Bay, the shallow waters at the mouth of the Bay and the adjacent North Atlantic between the late spring and the early fall along the net flow-path of the water entering and exiting the Chesapeake Bay by using an improved analytical scheme designed for the quantitative recovery of DOI. The concentration of R-DOI found in the surface mixed layer in the upper Bay was about twice of those found at the same location in previous studies. (R-X was the concentration of a dissolved iodine species X that had been normalized to a constant salinity of 35.) Thus, DOI in estuarine waters might have been underestimated significantly in the earlier studies. Following the water along its net flow-path, iodate initially constituted more than 60% of total iodine (TI) in the source water in the Middle Atlantic Bight off the Delmarva Peninsula. As this water entered the Chesapeake Bay through the northern part of its mouth, the concentration of R-iodate decreased while that of R-iodide increased progressively until the former became undetectable in the surface mixed layer while the latter reached a maximum of 0.42 μM in the deep water in the upper Bay. Then, the concentration of R-iodate rebounded while that of R-iodide decreased in the outflowing water that exited through the southern part of the mouth of the Bay and was later entrained by the Gulf Stream. The concentration of R-DOI in the surface waters followed the same pattern as R-iodide and reached a maximum of 0.20 μM in the upper Bay. However, R-DOI was depleted in the deep water in the sub-basins. Its concentration dropped to around the detection limit in the suboxic waters in the upper Bay. R-TI in the Bay far exceeded that in the incoming Middle Atlantic Bight water and reached 0.55 μM in the upper Bay. These distributions of the iodine species suggest that, as water from the Middle Atlantic Bight intruded into the Chesapeake Bay, in the well oxygenated surface mixed layer, iodate was reduced to iodide, and the inorganic iodine species could also be converted to DOI. In the deep water, iodate and DOI were converted to iodide. Superimposed on these inter-conversions among the iodine species, dissolved iodine, possibly in the form of iodide, was also added to the water column from the underlying sediments and the process was especially significant in the suboxic deep water in the upper Bay. Mixing between the surface mixed layer and the deep water could also have increased the concentrations of iodide and total iodine in the former.     

Investigation of Cd, Cu, Ni and Th in the colloidal size range in the Gulf of Maine

Size-fractionated seawater samples were collected from the Gulf of Maine to determine the fraction (f_c/d) of total dissolved (< 1 μm) Cd, Cu, Ni and ²³⁴Th in the colloidal size range (1,000 nominal molecular weight, NMW, to 1 μm) using cross-flow filtration. Colloidal Cd, Cu and Ni represents < 1–7% of the total dissolved concentration in these shelf waters and increases with an increase in particle concentration. By comparison, results obtained for particle-reactive ²³⁴Th indicate that < 1–47% of total dissolved is associated with the colloidal size fraction. A revised relationship between the concentration of colloids (C_c) and suspended particles (C_p) is reported (log C_c = 0.66 log C_p −2.01 kg L⁻¹) and used to examine the dependence of f_c/d for these metals on the concentration of suspended particles for C_p = 0.01–100 mg L⁻¹. Results indicate that a significant fraction (˜ 10–30%) of Cd, Cu, Ni and ²³⁴Th in the traditionally defined ‘dissolved’ fraction may exist in the colloidal size range in regions characterized by high particle concentrations (C_p > 1–10 mg L⁻¹), such as in near-shore and estuarine waters.     

Dissolved titanium distributions in the Mid-Atlantic Bight

Although titanium is abundant in Earth's crust, its sources and distribution in the ocean are poorly understood. To elucidate its behavior, distributions of dissolved (< 0.2 μm) Ti were determined in surface waters and vertical profiles from the Mid-Atlantic Bight (MAB). Concentrations of Ti decreased from 390 pM at the Delaware Bay mouth to < 100 pM across the Delaware continental shelf. In vertical profiles, small increases in bottom waters suggest a possible flux of Ti from shelf sediments, consistent with previous reports of pore water enrichments of dissolved Ti in MAB sediments. Concentrations in surface waters of the outer shelf and slope ranged between 30 and 140 pM, with most values below 90 pM. Concentrations in a 1000 m vertical profile in the eastern Gulf Stream ranged between 110 and 280 pM, and showed a variable distribution attributed to the mixing of water masses in the outer MAB. A simple model of Ti sources to the MAB suggests that atmospheric deposition of dissolved Ti is comparable to net riverine contributions and therefore must be considered in applications of Ti as a tracer of oceanographic processes.