Dissolved organic matter in the subterranean estuary of a volcanic island,Jeju: Importance of dissolved organic nitrogen fluxes to the ocean

We observed the origin, behavior, and flux of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), colored dissolved organic matter (CDOM), and dissolved inorganic nitrogen (DIN) in the subterranean estuary of a volcanic island, Jeju, Korea. The sampling of surface seawater and coastal groundwater was conducted in Hwasun Bay, Jeju, in three sampling campaigns (October 2010, January 2011, and June 2011). We observed conservative mixing of these components in this subterranean environment for a salinity range from 0 to 32. The fresh groundwater was characterized by relatively high DON, DIN, and CDOM, while the marine groundwater showed relatively high DOC. The DON and DIN fluxes through submarine groundwater discharge (SGD) in the groundwater of Hwasun Bay were estimated to be 1.3 × 10⁵ and 2.9 × 10⁵ mol d^− 1, respectively. In the seawater of Hwasun Bay, the groundwater-origin DON was almost conservative while about 91% of the groundwater-origin DIN was removed perhaps due to biological production. The DON flux from the entire Jeju was estimated to be 7.9 × 10⁸ mol yr^− 1, which is comparable to some of the world's large rivers. Thus, our study highlights that DON flux through SGD is potentially important for delivery of organic nitrogen to further offshore while DIN is readily utilized by marine plankton in near-shore waters under N-limited conditions.     

Hydrography of chromophoric dissolved organic matter in the North Atlantic

The distribution and optical absorption characteristics of chromophoric dissolved organic matter (CDOM) were systematically investigated along three meridional transects in the North Atlantic Ocean and Caribbean Sea conducted as part of the 2003 US CLIVAR/CO₂ Repeat Hydrography survey. Hydrographic transects covered in aggregate a latitudinal range of 5° to 62° north along longitudes 20°W (line A16N, Leg 1), 52°W (A20), and 66°W (A22). Absorption spectra of filtered seawater samples were collected and analyzed for depths ranging from the surface to ∼6000 m, sampling all the ocean water masses in the western basin of the subtropical North Atlantic and several stations on the North and South American continental slopes. The lowest surface abundances of CDOM (< 0.1 m⁻¹ absorption coefficient at 325 nm) were found in the central subtropical gyres while the highest surface abundances (∼0.7 m⁻¹) were found along the continental shelves and within the subpolar gyre, confirming recent satellite-based assessments of surface CDOM distribution. Within the ocean interior, CDOM abundances were relatively high (0.1–0.2 m⁻¹ absorption coefficient at 325 nm) except in the subtropical mode water, where a local minimum exists due to the subduction of low CDOM surface waters during mode water formation. In the subthermocline water masses of the western basin, changes in CDOM abundance are not correlated with increasing ventilation age as assessed using chlorofluorocarbon (CFC) concentrations and the atmospheric CFC history. But dissolved organic carbon (DOC) mass-specific absorption coefficients of CDOM increase with increasing ventilation age in the deep sea, indicating that CDOM is a refractory component of the DOC pool. The overall CDOM distribution in the North Atlantic reflects the rapid advection and mixing processes of the basin and demonstrates that remineralization in the ocean interior is not a significant sink for CDOM. This supports the potential of CDOM as a tracer of ocean circulation processes for subducted water masses.     

Chromophoric dissolved organic matter and dissolved organic carbon in Chesapeake Bay

Chromophoric dissolved organic matter (CDOM) is the light absorbing fraction of dissolved organic carbon (DOC). The optical properties of CDOM potentially permit remote sensing of DOC and CDOM, and correction for CDOM absorption is essential for remote sensing of chlorophyll a (chl a) in coastal and estuarine waters. To provide data for this purpose, we report the distributions of CDOM, DOC, and chl a from seven cruises in Chesapeake Bay in 1994–1997. We observed non-conservative distributions of chl a and DOC in half of the cruises, indicating net accumulations within the estuary; however, there were no net accumulations or losses of CDOM, measured as absorption at 355 nm or as fluorescence. Freshwater end member CDOM absorption varied from 2.2 to 4.1 m⁻¹. Coastal end member CDOM absorption was considerably lower, ranging over 0.4–1.1 m⁻¹. The fluorescence/absorption ratio was similar to those reported elsewhere for estuarine and coastal waters; however, in the lower salinity/high CDOM region of the Bay, the relationship was not constant, suggestive of the mixing of two or more CDOM sources. Chl a was not correlated with the absorption for most of the cruises nor for the data set as a whole; however, CDOM and DOC were significantly correlated, with two groups evident in the data. The first group had high CDOM concentrations per unit DOC and corresponded to the conservative DOC values observed in the transects. The second group had lower CDOM concentrations per unit DOC and corresponded to the non-conservative DOC values associated with net DOC accumulation near the chl a maximum on the salinity gradient. This indicates the production of non-chromophoric DOC in the region of the chl a maximum of Chesapeake Bay. In terms of remote sensing, these data show that (1) the retrieval of the absorption coefficient of CDOM from fluorescence measurements in the Bay must consider the variability of the fluorescence/absorption relationship, and (2) estimates of DOC acquired from CDOM absorption will underestimate DOC in regions with recent, net accumulations of DOC.     

Characterization of dissolved organic matter fluorescence in the South Atlantic Bight with use of PARAFAC model: Relationships between fluorescence and its components,absorption coefficients and organic carbon concentrations

In this study, the CDOM absorption coefficient at 350 nm [a_CDOM(350)] and CDOM excitation emission matrix (EEM) fluorescence were used to estimate annual fluxes of dissolved organic carbon (DOC) from the Cape Fear River to Long Bay in the South Atlantic Bight. Water samples were collected during a 3.5 year period, from October 2001 through March 2005, in the vicinity of the Cape Fear River (CFR) outlet and adjacent Onslow Bay (OB). Parallel factor analysis (PARAFAC) of CDOM EEM spectra identified six components: three terrestrial humic-like, one marine humic-like and two protein-like. Empirical relationships were derived from the PARAFAC model between DOC concentration and a_CDOM(350), total fluorescence intensity and the intensities of respective EEM components. DOC concentration and CDOM optical parameters were very well correlated and R² values ranged from 0.77 to 0.90. Regression analyses revealed that the non-absorbing DOC fraction, in DOC concentration estimated from CDOM optical parameters, varied with the qualitative composition of the CDOM. DOC concentration and intensity of the humic-like CDOM components characterized by excitation maxima at longer wavelengths have significantly higher estimated non-absorbing DOC compared to the analogous relationships between DOC and intensity of the humic-like CDOM components characterized by excitation maxima at shorter wavelengths. The relationships between DOC concentration and intensity of one of the protein-like components resulted in significantly reduced non-absorbing DOC fraction in DOC concentration estimation. Results of regression analyses between fluorescence intensities of specific EEM components and CDOM-specific absorption coefficients suggest that the relative proportion of humic-like CDOM components (characterized by excitation maximum at longer wavelengths) and the main protein-like component have the most impact on the values of a?_CDOM(350). Based on the relationships between a_CDOM(350), Cape Fear River flow, and DOC concentrations, DOC fluxes were estimated for 2002, 2003 and 2004. DOC fluxes varied from 1.5 to 6.2 × 10¹⁰ g C yr^? 1, depending on river flow.     

Ectoenzymatic activity in surface waters: A transect from the Mediterranean Sea across the Indian Ocean to Australia

The activities of two hydrolytic enzymes (leucine aminopeptidase and β glucosidase), belonging to the particle-bound enzymatic fraction, were measured in open-sea surface waters. Samples were collected along a transect crossing the Indian Ocean during the early NW monsoon period (November and December 2001). The latitudinal pattern of the ectoenzymatic activities highlighted a generally increasing trend of glycolysis approaching the equator, with significantly higher β glucosidase activity (0.79–3.00 nmol l⁻¹ h⁻¹) within the latitudinal range from 12°N to 16°S. In this area, the surface waters coming from the Indonesian Throughflow and the Bay of Bengal carry a considerable quantity of carbohydrates (38.9–41.9 μg l⁻¹), which stimulated glycolytic activity and its cell-specific rates scaled to bacterial abundance. On the other hand, in the Central Indian Ocean, the proteolytic activity was considerable (0.91–2.03 nmol l⁻¹ h⁻¹), although the particulate proteins did not show significant increases and the dissolved proteinlike signal was one of the lowest of the entire transect (0.7 mg l⁻¹ on average compared to the 1.4–1.6 mg l⁻¹ of the adjacent areas). Therefore, in this area, the two ectoenzymes studied did not respond to the same stimulatory effect (namely the specific substrate concentrations). The time needed for the hydrolysis of macromolecules within the particulate and dissolved organic substrate fractions, although these measures are affected by a number of assumptions starting with the potential nature of the ectoenzymatic determinations, confirms these observations. The Central Indian Ocean displayed the lowest values, from 8 to 26 days for particulate and dissolved organic carbon, respectively. As observed in the equatorial areas of the Atlantic Ocean, the relevant degradation activity of the central area of the Indian Ocean Basin suggests a notable heterotrophy based on a faster turnover of organic substrates.     

Microbial degradation rates of small peptides and amino acids in the oxygen minimum zone of Chilean coastal waters

We found similar microbial degradation rates of labile dissolved organic matter in oxic and suboxic waters off northern Chile. Rates of peptide hydrolysis and amino acid uptake in unconcentrated water samples were not low in the water column where oxygen concentration was depleted. Hydrolysis rates ranged from 65 to 160 nmol peptide L⁻¹ h⁻¹ in the top 20 m, 8–28 nmol peptide L⁻¹ h⁻¹ between 100 and 300 m (O₂-depleted zone), and 14–19 nmol peptide L⁻¹ h⁻¹ between 600 and 800 m. Dissolved free amino acid uptake rates were 9–26, 3–17, and 6 nmol L⁻¹ h⁻¹ at similar depth intervals. Since these findings are consistent with a model of comparable potential activity of microbes in degrading labile substrates of planktonic origin, we suggest, as do other authors, that differences in decomposition rates with high and low oxygen concentrations may be a matter of substrate lability. The comparison between hydrolysis and uptake rates indicates that microbial peptide hydrolysis occurs at similar or faster rates than amino acid uptake in the water column, and that the hydrolysis of peptides is not a rate-limiting step for the complete remineralization of labile macromolecules. Low O₂ waters process about 10 tons of peptide carbon per h, double the amount processed in surface-oxygenated water. In the oxygen minimum zone, we suggest that the C balance may be affected by the low lability of the dissolved organic matter when this is upwelled to the surface. An important fraction of dissolved organic matter is processed in the oxygen minimum layer, a prominent feature of the coastal ocean in the highly productive Humboldt Current System.     

High 226Ra and 228Ra activities in Nueces Bay,Texas indicate large submarine saline discharges

We have investigated submarine groundwater discharge to Nueces Bay (Texas) using naturally occurring Ra isotopes. Dissolved Ra activities in Nueces Bay are among the highest observed in coastal estuaries; as great as 2600 dpm m^− 3 for ²²⁸Ra and 1000 dpm m^− 3 for ²²⁶Ra. Using a combination of salt and Ra mass balances, we demonstrate that river discharge and bay bottom sediments cannot supply the Ra needed to balance tidal export. In the case of ²²⁶Ra there is an additional source of 218 × 10⁶ ± 105% dpm day^− 1 which is 9 times the maximum supply from bay bottom sediments and 50 times the Ra supplied by the Nueces River. A groundwater flux of 310,000 m³ day^− 1 is required to supply the needed ²²⁶Ra, based on the measured maximum Ra activity of local groundwater. Though as little as 10% of this flux may be advecting terrestrial groundwater this would still represent 160% of the Nueces River discharge. This makes it unlikely that groundwater discharge alone is supplying all of the additional ²²⁶Ra. Oil-field brine could potentially account for the remainder. Leakage of 6290 m³ day^− 1 of oil-field brine from the submerged petroleum wells and pipelines within the bay could supply all of the needed ²²⁶Ra. Such large fluxes of brackish groundwater and oil-field brine could significantly affect bay nitrogen budgets, salinities, and dissolved oxygen concentrations and should be considered when determining the freshwater inflow requirements for Nueces Bay and similar estuaries.     

Nutrient and phytoplankton dynamics off the west coast of Vancouver Island during the 1997/98 ENSO event

Six research cruises were conducted off the west coast of Vancouver Island between April and October of 1997 and 1998 as part of the Canadian GLOBEC project to compare nutrient and phytoplankton dynamics between ENSO (1997) and non-ENSO (1998) years. Limited sampling also was conducted during three cruises in 1999. During the 1997 ENSO period, there was a shallow thermocline (∼10 m) that resulted in a shallower mixed layer, lower salinity and density, and stronger summer stratification. In general on the shelf, the 1997 growing season was characterized by higher nitrate (7.5 μM) and silicic acid (17 μM) concentrations, lower total chlorophyll (∼76 mg m⁻²), lower phytoplankton carbon biomass (0.2 mg C L⁻¹), and lower diatom abundance and biomass than in 1998. Phytoplankton assemblages were dominated by nanoplankton in 1997 and by diatoms in 1998. These results suggest that the 1997 ENSO was responsible for a reduction in the growth and biomass of larger phytoplankton cells. In mid-1998, the hydrographic characteristics off the west coast of Vancouver Island changed suddenly. The 1997 poleward transport of warm water reversed to an equatorward transport of coastal water in July 1998, which was accompanied by normal summer upwelling. During 1998, a large diatom bloom (mainly dominated by Chaetoceros debilis, Leptocylindrus danicus and to a lesser extent by Skeletomema and Pseudo-nitzschia sp.) was observed in July over the continental shelf. This large bloom resulted in chlorophyll concentrations of up to 400 mg m⁻², primary productivity of up to 11 g C m⁻² d⁻¹, and near undetectable dissolved nitrogen concentrations at some of the shelf stations in 1998. In contrast, during 1997, the sub-tropical waters that were advected over the slope, resulted in low chlorophyll a and primary productivity (generally <1 g C m⁻² d⁻¹). Therefore, there was a sharp contrast between the very high primary productivity on the shelf in July 1998, due to normal nutrient replenishment from summer upwelling and outflow from the Strait of Juan de Fuca, and the lower primary productivity during the 1997 ENSO year. During 1998, non-ENSO conditions resulted in phytoplankton biomass that was twice as high on the shelf as that measured in regions beyond the continental shelf of the west coast of Vancouver Island.     

On-line determination of silver in natural waters by inductively-coupled plasma mass spectrometry: Influence of organic matter

We investigated interference effects on the analysis of silver in estuarine and oceanic waters using on-line high resolution inductively coupled plasma mass spectrometry (ICP-MS). A mini-column packed with a strong anion exchange resin (Dowex 1-X8) was used in a flow-injection system to separate and concentrate silver from the saline samples prior to on-line determination by ICP-MS. A series of analyses showed the concentrations of silver measured in San Francisco Bay estuary and the North Pacific that had been acidified (pH < 2) and stored for periods of 1–2 years were 10–70% lower than those measured in aliquots of those samples after ultraviolet (UV) irradiation. Additional silver released after UV irradiation of the estuarine waters, but not the ocean waters, was positively correlated (r = 0.77, simple linear correlation) with chlorophyll-a concentrations, but not with dissolved organic carbon (DOC) concentrations. Spatial distributions of chlorophyll-a and UV-released silver also exhibited similar patterns along a salinity gradient in the San Francisco Bay estuary, suggesting an in situ biogenic source of the interferent for the silver measurements.     

Rhenium in rivers and estuaries of India: Sources,transport and behaviour

The concentration of dissolved and particulate Re have been measured in the Narmada, Tapi and the Mandovi estuaries in the Arabian Sea and the Hooghly estuary in the Bay of Bengal. Re concentration in water and particulate matter of these estuaries is highly variable. Re in river waters analysed varies from 1 to 41 pmol/kg, the lowest in the Mandovi and the highest in the Mahi river. Re concentrations in the rivers analysed except in the Mandovi river are higher than the average global riverine Re concentration of 2.1 pmol/kg. Based on this study and the available data, the contemporary global annual flux of dissolved riverine Re is estimated to be ~ 350 × 10³ mol with an average concentration of ~ 9.2 pmol/kg, much higher than the earlier estimates. Residence time of Re in the oceans based on this estimate is 175,000 years, ~ 4 times lower compared to earlier estimates. Re behaves conservatively in all the estuaries studied. Re concentrations of seawater in the Bay of Bengal and in the Arabian Sea, estimated from the data of the Hooghly and the Mandovi estuaries respectively are ~ 40 pmol/kg, similar to the open ocean Re values of the Arabian Sea measured in this study and the values reported for in other oceanic regions. However, the dissolved Re in the Gulf of Cambay is 2 to 5 times higher, consistent with the high Re measured in the Mahi estuary and in the coastal waters of the Gulf of Cambay. The source of high Re in the Gulf of Cambay seems to be anthropogenic, measurements of Re in rivers and industrial waste waters draining into the Gulf supply amount to ~ 2300 mol of Re annually. This anthropogenic supply coupled with high residence time of water in the Gulf contribute to its high Re. Re concentration in suspended sediments of the Narmada estuary varies from 1 to 2 pmol/g, and does not show any discernible trend with salinity.The contemporary global riverine Re supply to the oceans estimated in this study is ~ 2–4 times higher compared to its removal in the reducing (anoxic/suboxic) sediments, indicating non-steady state of Re in the ocean. High dissolved riverine Re flux coupled with high Re content in the Gulf of Cambay highlights the need of a detailed study of Re in the various global rivers and in oceans including coastal regions and semi enclosed basins of the world to understand its behaviour in various reservoirs and to constrain the residence time of Re in the ocean.     

Vertical distribution of zooplankton and active flux across an anticyclonic eddy in the Canary Island waters

The vertical distribution (0–900 m) of zooplankton biomass and indices of feeding (gut fluorescence, GF) and metabolism (electron transfer system, ETS) were studied across an anticyclonic eddy south of Gran Canaria Island (Canary Islands). Two dense layers of organisms were clearly observed during the day, one above 200 m and the other at about 500 m, coincident with the deep scattering layer (DSL). The biomass displacement due to interzonal migrants in the euphotic zone was more than 2-fold higher than that previously reported for the southern area of this archipelago. The gut flux estimated (0.14–0.44 mgC m⁻² d⁻¹) was similar to the values previously found in the Canaries. The respiratory flux outside the eddy (1.85 mgC m⁻² d⁻¹) was in the lower range of values reported for this area. Inside the eddy, migrant biomass and respiration rates were 2- and 4- fold higher than in the surrounding waters. Active flux mediated by diel vertical migrants inside the eddy (8.28 mgC m⁻² d⁻¹) was up to 53% of the passive carbon flux to the mesopelagic zone (15.8 mgC m⁻² d⁻¹). It is, therefore, suggested that the anticyclonic eddy enhanced both migration from deep waters and active flux.     

Vertical distribution of zooplankton in Canary Island waters: implications for export flux

Zooplankton biomass, gut fluorescence and electron transfer system (ETS) activity were measured in vertical profiles (0–900 m) in two different size classes (<1 and >1 mm) in Canary Island waters. Both size fractions displayed a typical pattern of distribution with higher biomass, gut fluorescence and ETS in the shallower layers at night. By day, however, the vertical distribution varied between the size fractions, with higher biomass of the small fraction in the 0–200 m and a layer of large organisms at depth (∼500 m). For both size fractions, average ETS activity was higher by day than at night at depths between 200 and 600 m. Similarly, gut fluorescence was slightly higher by day below 200 m. The downward export of respiratory carbon was 1.92 and 4.29 mg C m⁻² d⁻¹ for samples obtained southwest of Gran Canaria Island and west of Tenerife Island respectively, being 2.68 mg C m⁻² d⁻¹ for the whole area. These values represented 16–45% (22–28% for the area) of the calculated passive particulate export production resulting from primary production. The estimated “gut flux” accounted for 0.35 (western zone) and 2.37 mg C m⁻² d⁻¹ (southwest of Gran Canaria), being 1.28 mg C m⁻² d⁻¹ for the whole area and represented between 3 and 25% (11–14% for the whole area) of the estimated passive particle export flux. These results agree with previous estimates and suggest that diel-migrant zooplankton can play an important role in the downward flux of carbon.     

Phytoplankton dynamics in the NE subarctic Pacific

Ocean Station Papa (OSP, 50°N 145°W) in the NE subarctic Pacific is characterised as high nitrate low chlorophyll (HNLC). However, little is known about the spatial extent of these HNLC waters or the phytoplankton dynamics on the basin scale. Algal biomass, production and size-structure data are presented from winter, spring and summer between 1992 and 1997 for five stations ranging from coastal to open-ocean conditions. The inshore stations (P04–P16) are characterised by the classical seasonal cycle of spring and late summer blooms (production >3 g C m⁻² d⁻¹), diatoms are not Fe-stressed, and growth rate is probably controlled by macronutrient supply. The fate of the phytoplankton is likely sedimentation by diatom-dominated spring blooms, with a pelagic recycling system predominating at other times. The offshore stations (P20/OSP) display low seasonality in biomass and production (OSP, mean winter production 0.3 g C m⁻² d⁻¹, mean spring/summer production 0.85 g C m⁻² d⁻¹), and are dominated by small algal cells. Low Fe availability prevents the occurrence of diatom blooms observed inshore. The main fate of phytoplankton is probably recycling through the microbial food web, with relatively low sedimentation compared to inshore. However, the supply of macro- and micro-nutrients to the coastal and open ocean, respectively, may vary between years. Variability in macro-nutrient supply to the coastal ocean may result in decreased winter reserve nitrate, summer nitrate limitation, subsequent floristic shifts towards small cells, and reduced primary production. Offshore, higher diatom abundances are occasionally observed, perhaps indicating episodic Fe supply. The two distinct oceanic regimes have different phytoplankton dynamics resulting in different seasonality, community structure and fate of algal carbon. These differences will strongly influence the biogeochemical signatures of the coastal and open-oceanic NE subarctic Pacific.     

Silver in the subarctic northeast Pacific Ocean: Explaining the basin scale distribution of silver

Five vertical profiles of silver (Ag) in the subarctic northeast Pacific are presented. Dissolved (< 0.2 μm) Ag concentrations within the surface mixed layer range from 6–25 pM, with the highest observed values at the most coastal site. Elevated Ag concentrations at this station are most likely attributable to the estuarine circulation in the Juan de Fuca Strait. One open-ocean station (P20) exhibited a strong surface Ag maximum. The station was located at the edge of a Haida eddy which raises the possibility that such eddies transport Ag seaward from the coastal zone. Ag concentrations in the deep waters ranged from 60–80 pM. These measurements are consistent with other recent Ag data collected in the Pacific. Ag profiles throughout the Pacific Ocean yield a strong positive correlation between Ag concentration and dissolved silicic acid concentration. However, Ag is depleted relative to silicic acid at intermediate depths where dissolved O₂ concentrations are low, implying a possible removal of Ag from oxygen-depleted waters by scavenging and/or precipitation.     

Modelling phytoplankton deposition to Chesapeake Bay sediments during winter–spring: interannual variability in relation to river flow

The often-rapid deposition of phytoplankton to sediments at the end of the spring phytoplankton bloom is an important component of benthic–pelagic coupling in temperate and high latitude estuaries and other aquatic systems. However, quantifying the flux is difficult, particularly in spatially heterogeneous environments. Surficial sediment chlorophyll-a, which can be measured quickly at many locations, has been used effectively by previous studies as an indicator of phytoplankton deposition to estuarine sediments. In this study, surficial sediment chlorophyll-a was quantified in late spring at 20–50 locations throughout Chesapeake Bay for 8 years (1993–2000). A model was developed to estimate chlorophyll-a deposition to sediments using these measurements, while accounting for chlorophyll-a degradation during the time between deposition and sampling. Carbon flux was derived from these estimates via C:chl-a = 75.Bay-wide, the accumulation of chlorophyll-a on sediments by late spring averaged 171 mg m⁻², from which the chlorophyll-a and carbon sinking fluxes, respectively, were estimated to be 353 mg m⁻² and 26.5 gC m⁻². These deposition estimates were ∼50% of estimates based on a sediment trap study in the mid-Bay. During 1993–2000, the highest average chlorophyll-a flux was in the mid-Bay (248 mg m⁻²), while the lowest was in the lower Bay (191 mg m⁻²). Winter–spring average river flow was positively correlated with phytoplankton biomass in the lower Bay water column, while phytoplankton biomass in that same region of the Bay was correlated with increased chlorophyll-a deposition to sediments. Responses in other regions of the Bay were less clear and suggested that the concept that nutrient enrichment in high flow years leads to greater phytoplankton deposition to sediments may be an oversimplification. A comparison of the carbon flux associated with the deposition of the spring bloom with annual benthic carbon budgets indicated that the spring bloom did not contribute a disproportionately large fraction of annual carbon inputs to Chesapeake Bay sediments. Regional patterns in chlorophyll-a deposition did not correspond with the strong regional patterns that have been found for plankton net community metabolism during spring.     

Photochemical production of hydrogen peroxide in Antarctic Waters

Photochemical production rates of hydrogen peroxide (H₂O₂) were determined in Antarctic waters during two research cruises. The first cruise was from mid-October to mid-November, 1993, in the confluence of the Weddell and Scotia Seas, and the second cruise was in December, 1994, along the coast of the Antarctic Peninsula. During these cruises, midday sea-surface production rates ranged from 2.1 to 9.6 nM h⁻¹, with an average rate of 4.5 nM h⁻¹. Production rates were consistently smaller than rates determined at lower latitudes (>9 nM h⁻¹), primarily due to the colder temperatures and lower ultraviolet irradiances in polar waters. In situ production rates were determined with a free-floating drifter that was deployed for 12–14 h. Production rates, averaged over the deployment time, were highest at or near the surface (ca. 2.4–3.5 nM h⁻¹) and decreased rapidly with depth to 0.1–0.7 nM h⁻¹ at 10–20 m. The decrease in production rates with depth generally paralleled the decrease in ultraviolet irradiance in the water column. Production rates of hydrogen peroxide in Antarctic seawater were largely controlled by the ultraviolet irradiance in the water column, although there was some evidence for production in the blue region of the solar spectrum. A laboratory study was conducted to determine the wavelength dependence of the apparent quantum yield for the photochemical formation of hydrogen peroxide in Antarctic waters. Apparent quantum yields determined at 0°C decreased from 0.74×10⁻³ mol einstein⁻¹ at 290 nm to 1.0×10⁻⁵ mol einstein⁻¹ 410 nm. At 20°C, apparent quantum yields for the photochemical production of hydrogen peroxide were within a factor of two of apparent quantum yields determined in temperate waters at 20–25°C. Sunlight-normalized H₂O₂ production rates were determined as a function of wavelength using noontime irradiance data from Palmer Station, Antarctica. A decrease in stratospheric ozone from 336 to 151 Dobson units resulted in a predicted 19–42% increase in the photoproduction of H₂O₂ at the sea surface in Antarctic waters. The magnitude of this increase depends on the concentration and absorbance characteristics of dissolved organic matter in the photic zone, as well as on other factors such as cloudiness and decreasing solar zenith angle that tend to lower photochemical rates offsetting increases due to stratospheric ozone depletion.     

Spatial and temporal variability of POC in the northeast Subarctic Pacific

Particulate organic carbon (POC) concentrations from 0 to 1000 m were quantified in size-fractionated particulate matter samples obtained by the multiple unit large volume in situ filtration system (MULVFS) in 1996 and 1997 along the 1600 km long “line P” transect from continental slope waters near southern Vancouver Island to Ocean Station PAPA (OSP, 50°N, 145°W). Regression of in situ POC vs. beam attenuation coefficient, c, from a simultaneously deployed 1-m pathlength SeaTech transmissometer gave slope, intercept and r² values of 6.15±0.19×10⁻⁵ m⁻¹ (nmol C l⁻¹)⁻¹, 0.363±0.003 m⁻¹, and 0.951 (n=145), respectively. This result agreed within several percent of calibrations obtained from two 2600-km-long transects of the equatorial Pacific in 1992 (Bishop, 1999). Data from other, more frequently deployed transmissometers were standardized against the 1-m instrument, and the combined optical data set was used to document POC variability at finer spatial and temporal scales than could be sampled directly using either conventional water bottle casts or MULVFS. Published bottle POC vs. c relationships show much more variability and remain problematic. Along the line P transect in the salinity-stratified upper 100 m, POC isolines shoaled from winter to summer in concert with seasonal stratification. At the same time, POC was progressively enriched in subeuphotic zone waters to depths greater than 500 m. Near-surface POC fields sampled in the winter time showed strong temporal POC variability over time scales of days as well as between years. POC concentrations at OSP in February 1996 were higher than those found at any other time of year. Less variability was found along line P in other seasons. In May 1996, kilometer-scale spatial variability of POC at OSP was small; dawn vs. dusk variations of c were used to calculate 0–100 m POC turnover times shorter than 6 d. Calculations also suggest that 25–50% of primary productivity was expressed as dissolved organic carbon at OSP in May 1996.     

Atmospheric nitrogen deposition to the Mullica River-Great Bay Estuary

Measurements of nitrate and ammonium in precipitation and associated with aerosols were conducted at Rutgers University Marine Field Station in Tuckerton, New Jersey from March 2004 to March 2005 to characterize atmospheric nitrogen deposition to the Mullica River-Great Bay Estuary. The arithmetic means of nitrate and ammonium concentrations for precipitation samples were 2.3 mg L⁻¹ and 0.42 mg L⁻¹, respectively. Nitrate and ammonium concentrations in aerosol samples averaged 3.7 μg m⁻³ and 1.6 μg m⁻³, respectively. Wet deposition rates appeared to vary with season; the highest rate of inorganic nitrogen deposition (nitrate + ammonium) occurred in the spring with an average value of 1.33 kg-N ha⁻² month⁻¹. On an annual basis, the total (wet and dry) direct atmospheric deposition fluxes into the Mullica River-Great Bay Estuary were 7.08 kg-N ha⁻² year⁻¹ for nitrate and 4.44 kg-N ha⁻² year⁻¹ for ammonium. The total atmospheric inorganic nitrogen directly deposited to the Mullica River-Great Bay Estuary was estimated to be 4.79 × 10⁴ kg-N year⁻¹, and the total atmospheric inorganic nitrogen deposited to the Mullica River watershed was estimated to be 1.69 × 10⁶ kg-N year⁻¹. Only a fraction of the nitrogen deposited on the watershed will actually reach the estuary; most of the nitrogen will be retained in the watershed due to utilization and denitrification during transport. The amount of N reaching the Mullica River-Great Bay Estuary indirectly is estimated to be 5.07 × 10⁴ kg-N year⁻¹, approximately 97% is retained within the watershed. This atmospheric nitrogen deposition may stimulate phytoplankton productivity in the Mullica River-Great Bay ecosystem.     

Seasonal dynamics of primary and new production in the northern South China Sea: The significance of river discharge and nutrient advection

Biochemical and productivity measurements and nutrient enrichment experiments were conducted on three cruises in summer and two cruises in winter on the shelf and the basin of the northern South China Sea (SCS) between 2001 and 2004. Phytoplankton production, in terms of depth-integrated new production (INP) or depth-integrated primary production (IPP), was higher in winter than in summer and on the shelf than in the basin. In winter, with deepening of the mixed layer, nitrate from the shallow nitracline that characterized the SCS waters was made available in the surface and supported the highest production of the year. Averaged INP measured in winter (0.25 g C m⁻² d⁻¹) was about twice the summer average (0.12 g C m⁻² d⁻¹) and was 0.19 g C m⁻² d⁻¹ on the shelf compared with 0.15 g C m⁻² d⁻¹ in the basin. In winter, average INP on the shelf was higher than the basin (0.34 versus 0.21 g C m⁻² d⁻¹); whereas in summer, averaged INP on the shelf (0.13 g C m⁻² d⁻¹) and the basin (0.11 g C m⁻² d⁻¹) were similar. While averaged IPP measured in the basin was higher in winter than in summer (0.53 versus 0.35 g C m⁻² d⁻¹), IPP on the shelf showed little temporal variation (0.82 in winter versus 0.84 g C m⁻² d⁻¹ in summer). Considerable spatial and inter-annual variation in production was measured in the shelf waters during summer, which could be linked to discharge volume and plume flow direction of the Zhujiang River. While the shelf waters in summer were mostly nitrogen starved or nitrogen and phosphorus co-limited, excessive river runoff may cause the nutritive state to shift to phosphorus deficiency. Waters with low surface salinities and high fluorescence from riverine mixing could be found extending from the Zhujiang mouth to as far as offshore southern Taiwan after a typhoon passed the northern SCS and brought heavy rainfall. Overall, both nutrient advection in winter and river discharge from the China coast in summer made new nitrogen available and shaped the dynamics of phytoplankton production in these oligotrophic waters.     

Oxygen distribution and aerobic respiration in the north and south eastern tropical Pacific oxygen minimum zones

Highly sensitive STOX O₂ sensors were used for determination of in situ O₂ distribution in the eastern tropical north and south Pacific oxygen minimum zones (ETN/SP OMZs), as well as for laboratory determination of O₂ uptake rates of water masses at various depths within these OMZs. Oxygen was generally below the detection limit (few nmol L⁻¹) in the core of both OMZs, suggesting the presence of vast volumes of functionally anoxic waters in the eastern Pacific Ocean. Oxygen was often not detectable in the deep secondary chlorophyll maximum found at some locations, but other secondary maxima contained up to ~0.4 µmol L⁻¹. Directly measured respiration rates were high in surface and subsurface oxic layers of the coastal waters, reaching values up to 85 nmol L⁻¹ O₂ h⁻¹. Substantially lower values were found at the depths of the upper oxycline, where values varied from 2 to 33 nmol L⁻¹ O₂ h⁻¹. Where secondary chlorophyll maxima were found the rates were higher than in the oxic water just above. Incubation times longer than 20 h, in the all-glass containers, resulted in highly increased respiration rates. Addition of amino acids to the water from the upper oxycline did not lead to a significant initial rise in respiration rate within the first 20 h, indicating that the measurement of respiration rates in oligotrophic Ocean water may not be severely affected by low levels of organic contamination during sampling. Our measurements indicate that aerobic metabolism proceeds efficiently at extremely low oxygen concentrations with apparent half-saturation concentrations (K_m values) ranging from about 10 to about 200 nmol L⁻¹.