Short-term variability of fCO2 in seawater and air–sea CO2 fluxes in a coastal upwelling system (Ría de Vigo, NW Spain)

Coastal upwelling systems are regions with highly variable physical processes and very high rates of primary production and very little is known about the effect of these factors on the short-term variations of CO₂ fugacity in seawater (fCO₂^w). This paper presents the effect of short-term variability (<1 week) of upwelling–downwelling events on CO₂ fugacity in seawater (fCO₂^w), oxygen, temperature and salinity fields in the Ría de Vigo (a coastal upwelling ecosystem). The magnitude of fCO₂^w values is physically and biologically modulated and ranges from 285 μatm in July to 615 μatm in October. There is a sharp gradient in fCO₂^w between the inner and the outer zone of the Ría during almost all the sampling dates, with a landward increase in fCO₂^w.CO₂ fluxes calculated from local wind speed and air–sea fCO₂ differences indicate that the inner zone is a sink for atmospheric CO₂ in December only (−0.30 mmol m⁻² day⁻¹). The middle zone absorbs CO₂ in December and July (−0.05 and −0.27 mmol·m⁻² day⁻¹, respectively). The oceanic zone only emits CO₂ in October (0.36 mmol·m⁻² day⁻¹) and absorbs at the highest rate in December (−1.53 mmol·m⁻² day⁻¹).     

High-resolution measurement of Southern Ocean CO2 and O2/Ar by membrane inlet mass spectrometry

This paper evaluates the simultaneous measurement of dissolved gases (CO₂ and O₂/Ar ratios) by membrane inlet mass spectrometry (MIMS) along the 180° meridian in the Southern Ocean. The calibration of pCO₂ measurements by MIMS is reported for the first time using two independent methods of temperature correction. Multiple calibrations and method comparison exercises conducted in the Southern Ocean between New Zealand and the Ross Sea showed that the MIMS method provides pCO₂ measurements that are consistent with those obtained by standard techniques (i.e. headspace equilibrator equipped with a Li–Cor NDIR analyser). The overall MIMS accuracy compared to Li–Cor measurements was 0.8 μatm. The O₂/Ar ratio measurements were calibrated with air-equilibrated seawater standards stored at constant temperature (0 ± 1 °C). The reproducibility of the O₂/Ar standards was better than 0.07% during the 9 days of transect between New Zealand and the Ross Sea.The high frequency, real-time measurements of dissolved gases with MIMS revealed significant small-scale heterogeneity in the distribution of pCO₂ and biologically-induced O₂ supersaturation (ΔO₂/Ar). North of 65°S several prominent thermal fronts influenced CO₂ concentrations, with biological factors also contributing to local variability. In contrast, the spatial variation of pCO₂ in the Ross Sea gyre was almost entirely attributed to the biological utilization of CO_2, with only small temperature effects. This high productivity region showed a strong inverse relationship between pCO₂ and biologically-induced O₂ disequilibria (r² = 0.93). The daily sea air CO₂ flux ranged from − 0.2 mmol/m² in the Northern Sub-Antarctic Front to − 6.4 mmol/m² on the Ross Sea shelves where the maximum CO₂ influx reached values up to − 13.9 mmol/m². This suggests that the Southern Ocean water (south of 58°S) acts as a seasonal sink for atmospheric CO₂ at the time of our field study.     

Seasonal and interannual variability of the air–sea CO2 flux in the Atlantic sector of the Barents Sea

The seasonal and interannual variability of the air–sea CO₂ flux (F) in the Atlantic sector of the Barents Sea have been investigated. Data for seawater fugacity of CO₂ (fCO₂^sw) acquired during five cruises in the region were used to identify and validate an empirical procedure to compute fCO₂^sw from phosphate (PO₄), seawater temperature (T), and salinity (S). This procedure was then applied to time series data of T, S, and PO₄ collected in the Barents Sea Opening during the period 1990–1999, and the resulting fCO₂^sw estimates were combined with data for the atmospheric mole fraction of CO₂, sea level pressure, and wind speed to evaluate F.The results show that the Atlantic sector of the Barents Sea is an annual sink of atmospheric CO₂. The monthly mean uptake increases nearly monotonically from 0.101 mol C m^− 2 in midwinter to 0.656 mol C m^− 2 in midfall before it gradually decreases to the winter value. Interannual variability in the monthly mean flux was evaluated for the winter, summer, and fall seasons and was found to be ± 0.071 mol C m^− 2 month^− 1. The variability is controlled mainly through combined variation of fCO₂^sw and wind speed. The annual mean uptake of atmospheric CO₂ in the region was estimated to 4.27 ± 0.68 mol C m^− 2.     

Compositions and transport of lipid biomarkers through the water column and surficial sediments of the equatorial Pacific Ocean

A systematic investigation of fluxes and compositions of lipids through the water column and into sediments was conducted along the U.S. JGOFS EgPac transect from l2°N to l5°S at 140°W. Fluxes of lipids out of the euphotic zone varied spatially and temporally, ranging from ≈0.20 – 0.6 mmol lipid-C m⁻² day⁻¹. Lipid fluxes were greatly attenuated with increasing water column depth, dropping to 0.002-0.06 mmol lipid-C m⁻² day⁻¹ in deep-water sediment traps. Sediment accumulation rates for lipids were ≈ 0.0002 – 0.00003 mmol lipid-C m⁻² day⁻¹. Lipids comprised ≈ 11–23% of C_org in net-plankton, 10–30% in particles exiting the euphotic zone, 2–4% particles in the deep EgPac, and 0.1-1 % in sediments. Lipids were, in general, selectively lost due to their greater reactivity relative to bulk organic matter toward biogeochemical degradation in the water column and sediment. Qualitative changes in lipid compositions through the water column and into sediments are consistent with the reactive nature of lipids. Fatty acids were the most labile compounds, with polyunsaturated fatty acids (PUFAs) being quickly lost from particles. Branchedchain C₁₅ and C₁₇ fatty acids increased in relative abundance as particulate matter sank and was incorporated into the sediment, indicating inputs of organic matter from bacteria. Long-chain C₃₉ alkenones of marine origin and long-chain C₂₀-C₃₀ fatty acids, alcohols and hydrocarbons derived from land plants were selectively preserved in sediments. Compositional changes over time and space demonstrate the dynamic range of reactivities among individual biomarker compounds, and hence of organic matter as a whole. A thorough understanding of biogeochemical reprocessing of organic matter in the oceanic water column and sediments is, thus, essential for using the sediment record for reconstructing past oceanic environments.     

Uptake of atmospheric carbon dioxide in Arctic shelf seas: evaluation of the relative importance of processes that influence pCO2 in water transported over the Bering–Chukchi Sea shelf

The uptake of atmospheric carbon dioxide in the water transported over the Bering–Chukchi shelves has been assessed from the change in carbon-related chemical constituents. The calculated uptake of atmospheric CO₂ from the time that the water enters the Bering Sea shelf until it reaches the northern Chukchi Sea shelf slope (1 year) was estimated to be 86±22 g C m⁻² in the upper 100 m. Combining the average uptake per m³ with a volume flow of 0.83×10⁶ m³ s⁻¹ through the Bering Strait yields a flux of 22×10¹² g C year⁻¹. We have also estimated the relative contribution from cooling, biology, freshening, CaCO₃ dissolution, and denitrification for the modification of the seawater pCO₂ over the shelf. The latter three had negligible impact on pCO₂ compared to biology and cooling. Biology was found to be almost twice as important as cooling for lowering the pCO₂ in the water on the Bering–Chukchi shelves. Those results were compared with earlier surveys made in the Barents Sea, where the uptake of atmospheric CO₂ was about half that estimated in the Bering–Chukchi Seas. Cooling and biology were of nearly equal significance in the Barents Sea in driving the flux of CO₂ into the ocean. The differences between the two regions are discussed. The loss of inorganic carbon due to primary production was estimated from the change in phosphate concentration in the water column. A larger loss of nitrate relative to phosphate compared to the classical ΔN/ΔP ratio of 16 was found. This excess loss was about 30% of the initial nitrate concentration and could possibly be explained by denitrification in the sediment of the Bering and Chukchi Seas.     

Spectrophotometric pH measurement in estuaries using thymol blue and m-cresol purple

The conditional acid dissociation constants (pK_a′) of two sulfonephthalein dyes, thymol blue (TB) and m-cresol purple (mCP), were assessed throughout the estuarine salinity range (0<S<40) using a tris/tris–HCl buffer and spectrophotometric measurement. The salinity dependence of the pK_a′ of both dyes was fitted to the equations (25 °C, total proton pH scale, mol kg soln⁻¹):

The estimated accuracy of pH measurements using these calculated pK_a′ values is considered to be comparable to that possible with careful use of a glass electrode (±0.01 pH unit) but spectrophotometric measurements in an estuary have the significant advantage that it is not necessary to calibrate an electrode at different salinities. pH was measured in an estuary over a tidal cycle with a precision of ±0.0005 pH unit at high (S>30) salinity, and ±0.002 pH unit at low (S<5) salinity. The pH increased rapidly in the lower salinity ranges (0<S<15) but less rapidly at higher salinities.     

Biological components of Ross Sea short-term particle fluxes in the austral summer of 1995–1996

The Ross Sea, a region of high seasonal production in the Southern Ocean, is characterized by blooms of the haptophyte Phaeocystis antarctica and of diatoms. The different morphology, structural composition and consumption of these two phytoplankton by grazing zooplankton may result in different carbon cycling dynamics and carbon flux from the euphotic zone. We sampled short-term (2 days) particle flux at 5 sites from 177.6°W to 165°E along a transect at 76.5°S with traps placed below the euphotic zone at 200 m during December 1995–January 1996. We estimated carbon flux of as many eucaryotic organisms and fecal pellets as possible using microscopy for counts and measurements and applying volume:carbon conversions from the literature. Eucaryotic organisms contributed about 20–40% of the total organic carbon flux in both the central Ross Sea polynya and in the western polynya, and groups of organisms differed in contribution to the carbon flux at the different sites. Algal carbon flux ranged from 4.5 to 21.1 mg C m⁻² day⁻¹ and consisted primarily of P. antarctica (cell plus mucus) and diatom carbon at all sites. Different diatom species dominated the diatom flux at different sites. Carbon fluxes of small pennate diatoms may have been enhanced by scavenging, by sinking senescent P. antarctica colonies. Heterotrophic carbon flux ranged from 9.2 to 37.6 mg C m⁻² day⁻¹ and was dominated by athecate heterotrophic dinoflagellate carbon in general and by carbon flux of a particular large athecate dinoflagellate at two sites. Fecal pellet carbon flux ranged from 4.6 to 54.5 mg C m⁻² day⁻¹ and was dominated by carbon from ovoid/angular pellets at most sites. Analysis of fecal pellet contents suggested that large protozoans identified by light microscopy contributed to ovoid/angular fecal pellet fluxes. Carbon flux as a percentage of daily primary production was lowest at sites where P. antarctica predominated in the water column and was highest at sites where fecal pellet flux was highest. This indicates the importance of grazers in carbon export.     

Anomalously low alkenone temperatures caused by lateral particle and sediment transport in the Malvinas Current region, western Argentine Basin

We analysed the alkenone unsaturation ratio (U^K′₃₇) in 87 surface sediment samples from the western South Atlantic (5°N–50°S) in order to evaluate its applicability as a paleotemperature tool for this part of the ocean. The measured U^K′₃₇ ratios were converted into temperature using the global core-top calibration of Müller et al. (1998) and compared with annual mean atlas sea-surface temperatures (SSTs) of overlying surface waters. The results reveal a close correspondence (<1.5°C) between atlas and alkenone temperatures for the Western Tropical Atlantic and the Brazil Current region north of 32°S, but deviating low alkenone temperatures by −2° to −6°C are found in the regions of the Brazil–Malvinas Confluence (35–39°S) and the Malvinas Current (41–48°S). From the oceanographic evidence these low U^K′₃₇ values cannot be explained by preferential alkenone production below the mixed layer or during the cold season. Higher nutrient availability and algal growth rates are also unlikely causes. Instead, our results imply that lateral displacement of suspended particles and sediments, caused by strong surface and bottom currents, benthic storms, and downslope processes is responsible for the deviating U^K′₃₇ temperatures. In this way, particles and sediments carrying a cold water U^K′₃₇ signal of coastal or southern origin are transported northward and offshore into areas with warmer surface waters. In the northern Argentine Basin the depth between displaced and unaffected sediments appears to coincide with the boundary between the northward flowing Lower Circumpolar Deep Water (LCDW) and the southward flowing North Atlantic Deep Water (NADW) at about 4000 m.     

Remineralization and accumulation of organic carbon and nitrogen in marine sediments of eutrophic bays: the case of the Bay of Concepcion, Chile

The Bay of Concepcion (36°40′S; 73°02′W) is a semi-enclosed and shallow embayment in which biogeochemical processes are seasonally coupled to coastal upwelling during the austral spring and summer. The nutrient cycle in the bay is complex due to the combined effects of a pronounced O₂ minimum layer and high nutrient concentrations both originating from subsurface equatorial water during coastal upwelling and a rapid rate of sediment nutrient recycling. The sediments are characterized by a high content of organic matter mainly due to the extremely high rates of phytoplankton production and deposition. During the upwelling period, a black flocculent layer frequently covers the sediment–water interface in the inner part of the bay where an extensive mat of Beggiatoa spp. develops. Three approaches are used to analyse the extent to which the benthic system recycles or retains nutrients at two stations, located at the centre (station C, St. C) and mouth (station B, St. B) of the bay for a 1-year period (March 1996–1997): (1) estimation of C and N remineralization rates based on SO₄²⁻ reduction measurements, (2) calculation of C and N turnover rates using a diagenetic model applied to total organic carbon and total nitrogen vertical distributions and, (3) construction of C and N budgets from direct measurements of sedimentation (from a sediment trap) and estimates of the C and N burial rates. Depth-integrated SO₄²⁻ reduction rates varied between 3.4 (winter) and 25.5 (summer) mmol m⁻² d⁻¹. Estimated C and N oxidation rates ranged between 7.9 and 87.8 mol C m⁻² yr⁻¹ and between 0.9 and 6.9 mol N m⁻² yr⁻¹, respectively. Each approach yielded minor differences in the C and N remineralization rates (and also minor differences between both studied stations), except when the kinetic model was applied to C and N distribution without including the presence of the flocculent layer. The rates of carbon oxidation and sulphate reduction were considerably higher than in other coastal sediments with similar depositional regime. The C and N burial rates were 2.23 and 0.21 (St. C) and 1.30 and 0.09 (St. B) mol m⁻² yr⁻¹, respectively. The C/N ratio of the buried fraction was ca. 10.6 at St. C and 14.4 at St. B. Because the observed differences in burial rates could not be ascribed to distinctive depositional (both stations have similar sediment accumulation rates) and oceanographic (similar O₂ concentration and hydrography) conditions, differences may be due to in part spatial heterogeneity in the supply of organic matter. The degree of preservation of organic matter as plankton detritus and nitrogen accumulating bacterial biomass associated with Beggiatoa spp. at St. C may also be involved.     

Interannual variations of the Antarctic Ocean CO2 uptake from 1986 to 1994

The interannual variations of CO₂ sources and sinks in the surface waters of the Antarctic Ocean (south of 50°S) were studied between 1986 and 1994. An existing, slightly modified one-dimensional model describing the mixed-layer carbon cycle was used for this study and forced by available satellite-derived and climatological data. Between 1986 and 1994, the mean Antarctic Ocean CO₂ uptake was 0.53 Pg C year⁻¹ with an interannual variability of 0.15 Pg C year⁻¹.Interannual variation of the Antarctic Ocean CO₂ uptake is related to the Antarctic Circumpolar Wave (ACW), which affects sea surface temperature (SST), wind-speed and sea-ice extent. The CO₂ uptake in the Antarctic Ocean has increased from 1986 to 1994 by 0.32 Pg C. It was found that over the 9 years, the surface ocean carbon dioxide fugacity (fCO₂) increase was half that of the atmospheric CO₂ increase inducing an increase of the air–sea fCO₂ gradient. This effect is responsible for 60% of the Antarctic Ocean CO₂ uptake increase between 1986 and 1994, as the ACW effect cancels out over the 9 years investigated.     

N2O Production, Nitrification and Denitrification in an Estuarine Sediment

The mechanisms regulating N₂O production in an estuarine sediment (Tama Estuary, Japan) were studied by comparing the change in N₂O production with those in nitrification and denitrification using an experimental continuous-flow sediment–water system with¹⁵N tracer (¹⁵N-NO−3 addition). From Feburary to May, both nitrification and denitrification in the sediment increased (246 to 716 μmol N m⁻² h⁻¹and 214 to 1260 μmol N m⁻² h⁻¹, respectively), while benthic N₂O evolution decreased slightly (1560 to 1250 nmol N m⁻² h⁻¹). Apparent diffusion coefficients of inorganic nitrogen compounds and O₂at the sediment–water interface, calculated from the respective concentration gradients and benthic fluxes, were close to the molecular diffusion coefficients (0·68–2·0 times) in February. However, they increased to 8·8–52 times in May except for that of NO−2, suggesting that the enhanced NO−3 and O₂supply from the overlying water by benthic irrigation likely stimulated nitrification and denitrification. Since the progress of anoxic condition by the rise of temperature from February to May (9 to 16 °C) presumably accelerated N₂O production through nitrification, the observed decrease in sedimentary N₂O production seems to be attributed to the decrease in N₂O production/occurrence of its consumption by denitrification. In addition to the activities of both nitrification and denitrification, the change in N₂O metabolism during denitrification by the balance between total demand of the electron acceptor and supply of NO−3+NO−2 can be an important factor regulating N₂O production in nearshore sediments.     

Alkalinity changes in the Sargasso Sea: geochemical evidence of calcification?

Strong seasonal patterns in upper ocean total carbon dioxide (TCO₂), alkalinity (TA) and calculated pCO₂ were observed in a time series of water column measurements collected at the US Joint Global Ocean Flux Study (JGOFS) BATS site (31 °50′N, 64 °10′W) in the Sargasso Sea. TA distribution was a conservative function of salinity. However, in February 1992, a non-conservative decrease in TA was observed, with maximum depletion of 25–30 μmoles kg⁻¹ occuring in the surface layer and at the depth of the chlorophyll maximum (˜ 80–100 m). Mixed-layer TCO₂ also decreased, while surface pCO₂ increased by 25–30 μatm. We suggest these changes in carbon dioxide species resulted from open-ocean calcification by carbonate-secreting organisms rather than physical processes. Coccolithophore calcification is the most likely cause of this event although calcification by foraminifera or pteropods cannot be ruled out. Due to the transient increase in surface pCO₂, the net annual transfer of CO₂ into the ocean at BATS was reduced. These observations demonstrate the potential importance of open-ocean calcification and biological community structure in the biogeochemical cycling of carbon.     

Inorganic carbon in the central California upwelling system during the 1997–1999 El Niño–La Niña event

Sea surface pCO₂ was monitored during 49 cruises from February 1997 to December 1999 along a section perpendicular to the central California Coast. Continuous measurements of the ocean–atmosphere difference of pCO₂ were made on a mooring in the same region from July 1997 to December 1999. The El Niño/La Niña cycle of 1997–1999 had a significant influence on local ocean–atmosphere CO₂ transfer. During the warm anomaly associated with El Niño, upwelling was suppressed and average sea surface pCO₂ was below atmospheric level. High rainfall and river runoff in the late winter and early spring of 1998 produced areas where pCO₂ was depressed by as much as 100 μatm. A flux ranging from 0.3 to 0.7 mol C m⁻² y⁻¹ from the atmosphere into the ocean was estimated for the El Niño period from wind and ΔpCO₂ data. Temperatures and upwelling returned to near normal in the summer of 1998, but a cold anomaly developed during autumn of that year. Temperature and pCO₂ data indicate that upwelling continued throughout much of the 1998–1999 winter and intensified significantly in the spring of 1999. During strong upwelling events, the estimate of ocean to atmosphere flux approached rates of 50 mol C m⁻² y⁻¹. The estimate for the average CO₂ flux from July 1998 to July 1999 was 1.5–2.2 mol C m⁻² y⁻¹ from the ocean to the atmosphere. While the flux estimate for the El Niño time period may be applicable to a larger area, the high ocean to atmosphere fluxes during La Niña might be the result of sampling near a zone of intense upwelling.     

The carbonic system distribution and fluxes in the NE Atlantic during Spring 1991

The potential of the North Atlantic as a sink for atmospheric CO₂ was investigated by studying the carbonic system using data obtained during the spring of 1991. The air-sea flux of CO₂ was related to chlorophyll and other environmental variables, and the regeneration of carbon in the mid-ocean studied by examining vertical sections representative of the study area.Poor correlations were found between pCO₂ and chlorophyll throughout much of the study area, although a good correlation was found along 16°W. The highest air-sea fluxes of CO₂ were calculated for areas where chlorophyll was highest (45°13′N, 16°04′W), and where the greatest wind speeds occurred (47°51′N, 28°18′W). The mean CO₂ flux from the atmosphere to the ocean during the study period (May) was calculated as 0.65mmol m⁻²d⁻¹, which compares well with other studies. Regression equations were developed to predict total inorganic carbon from nutrients; errors were typically less than 1 μmol kg⁻¹. Regeneration of carbon in the mid-ocean occurred in two principal stages: 0–1000m and>2300m. Regeneration in the upper zone was dominated by soft tissue carbon (86%), with skeletal carbon (calcite) contributing only 14%. The fraction of regenerated carbon of skeletal origin increased to 51% in the>2300m zone.     

The solubility of CaCO3 in seawater at 2°C based upon in-situ sampled pore water composition

Analyses of the concentration product (Ca²⁺) × (CO₃²⁻) in the pore waters of marine sediments have been used to estimate the apparent solubility products of sedimentary calcite (K′_SPc) and aragonite (K′_SPa) in seawater. Regression of the data gives the relation In K′^P_SPc = 1.94 × 10⁻³ δP − 14.59 The 2°C, 1 atm value of K′_SPc is, then, 4.61 × 10⁻⁷ mol² l⁻². The pressure coefficient yields a at 2°C of −43.8 cm³ atm⁻¹. A single station where aragonite is present in the sediments gives a value of K′_SPa = 9.2 × 10⁻⁷ (4°C, 81 atm). The calcite data are very similar to those determined experimentally by Ingle et al. (1973) for K′_SPc at 2°C and 1 atm. The calculated is also indistinguishable from the experimental results of Ingle (1975) if is assumed to be independent of pressure.     

The contribution of atmospheric acid deposition to ocean acidification in the subtropical North Atlantic Ocean

The absorption of anthropogenic CO₂ and atmospheric deposition of acidity can both contribute to the acidification of the global ocean. Rainfall pH measurements and chemical compositions monitored on the island of Bermuda since 1980, and a long-term seawater CO₂ time-series (1983–2005) in the subtropical North Atlantic Ocean near Bermuda were used to evaluate the influence of acidic deposition on the acidification of oligotrophic waters of the North Atlantic Ocean and coastal waters of the coral reef ecosystem of Bermuda. Since the early 1980's, the average annual wet deposition of acidity at Bermuda was 15 ± 14 mmol m^− 2 year^− 1, while surface seawater pH decreased by 0.0017 ± 0.0001 pH units each year. The gradual acidification of subtropical gyre waters was primarily due to uptake of anthropogenic CO₂. We estimate that direct atmospheric acid deposition contributed 2% to the acidification of surface waters in the subtropical North Atlantic Ocean, although this value likely represents an upper limit. Acidifying deposition had negligible influence on seawater CO₂ chemistry of the Bermuda coral reef, with no evident impact on hard coral calcification.     

Variability in duration and intensity of euphausiid spawning off central Oregon, 1996–2001

We tracked the duration and intensity of the euphausiid spawning season through biweekly sampling along a transect off Newport, OR (latitude 44°40′N) over a six year period from 1996 to 2001. Our sampling consisted of vertical plankton tows, CTD casts, and collection of water for determination of chlorophyll a. Here, we report on data collected from two stations, 5 and 15 nautical miles (9.3 and 27.8 km) offshore. The density of euphausiid eggs in our samples was highly variable spatially and temporally; we saw the most striking differences in egg densities and length of the spawning season, when we compared spawning before and after 1999. This year corresponded to the time when the Pacific Decadal Oscillation switched from warm phase (pre-1999) to cool phase (1999–present). The years 1996 and 1997 were characterized by one large, late summer peak in egg density at our inshore station. 1998, an El Niño year, followed this pattern for our offshore station, but eggs were nearly absent at our inshore station. Starting in 1999, we saw multiple peaks in egg density and found that the spawning season extended from spring through early fall. For example, in spring (March–May) at the inshore station, the abundance of eggs increased from an average of 0.4 m⁻³ (1996–1998) to 51.3 m⁻³ (1999–2001), and for summer (July–September), 27.8 m⁻³ to 132.6 m⁻³ for the same time period. At the offshore station, egg abundances doubled over the same two time periods: 7 m⁻³ versus 11 m⁻³ (spring) and 55 m⁻³ versus 186 m⁻³ (summer). Peaks in egg densities were often associated with phytoplankton blooms, but not in a predictable way. Peaks in egg densities often followed cold-water upwelling events, especially at the inshore station. It is not yet clear whether this connection is due to changes in advection or changes in upwelling-induced productivity.     

Seasonal variations of alkenones and U37 in the Chesapeake Bay water column

Alkenone unsaturation indices (U^K₃₇ and U^K′₃₇) have long been used as proxies for surface water temperature in the open ocean. Recent studies have suggested that in other marine environments, variables other than temperature may affect both the production of alkenones and the values of the indices. Here, we present the results of a reconnaissance field study in which alkenones were extracted from particulate matter filtered from the water column in Chesapeake Bay during 2000 and 2001. A multivariate analysis shows a strong positive correlation between U^K₃₇ (and U^K′₃₇) values and temperature, and a significant negative correlation between U^K₃₇ (and U^K′₃₇) values and nitrate concentrations. However, temperature and nitrate concentrations also co-vary significantly. The temperature vs. U^K₃₇ relationships (U^K₃₇=0.018 (T)−0.162, R²=0.84, U^K′₃₇=0.013 (T)−0.04, R²=0.80) have lower slopes than the open-ocean equations of Prahl et al. [1988. Further evaluation of long-chain alkenones as indicators of paleoceanographic conditions. Geochimica et Cosmochimica Acta 52, 2303–2310] and Müller et al. [1998. Calibration of the alkenone paleotemperature index U^K′₃₇ based on core-tops from the eastern South Atlantic and the global ocean (60°N–60°S). Geochimica et Cosmochimica Acta 62, 1757–1772], but are similar to the relationships found in controlled studies with elevated nutrient levels and higher nitrate:phosphate (N:P) ratios. This implies that high nutrient levels in Chesapeake Bay have either lowered the U^K₃₇ vs. temperature slope, or nutrient levels are the main controller of the U^K₃₇ index. In addition, particularly high abundances (>5% of total C₃₇ alkenones) of the tetra-unsaturated ketone, C_37:4, were found when water temperatures reached 25 °C or higher, thus posing further questions about the controls on alkenone production as well as the biochemical roles of alkenones.     

Glucuronidation in the polar bear (Ursus maritimus)

Polar bears bioaccumulate lipophilic pollutants, including polychlorinated biphenyls (PCBs), into their bodies from their exclusive diet of marine organisms. Hydroxylated PCB metabolites (OH-PCBs) have been found in plasma, presumably due to CYP-dependent biotransformation of PCBs in liver. Little is known about the phase 2 metabolism of hydroxylated xenobiotics in polar bears. The objective of this study was to examine UDP-glucuronosyltransferase (UGT) activity with OH-PCBs and a hydroxylated polycyclic aromatic hydrocarbon, 3-hydroxy-benzo(a)pyrene (3-OH-BaP), in polar bear liver. Samples of frozen polar bear liver were used to prepare microsomes. UGT activity with 3-OH-BaP in Brij-treated microsomes, measured by a fluorescence assay, was readily measurable with protein concentrations in assay tubes of up to 10 μg/ml, but dropped off very sharply at higher protein concentrations. The apparent K_m for 3-OH-BaP was 1.71 ± 0.04 μM, and V_max 1.26 ± 0.16 nmol/min/mg protein (mean ± SD, n=3). UGT activities with a model tetrachloro-OH-PCB (4^′-OH-CB72) and a model hexachloro-OH-PCB (4^′-OH-CB159) were assayed with [¹⁴-C]-UDPGA and separation of the [¹⁴-C]-glucuronide by ion-pair extraction and thin-layer chromatography. [¹⁴-C]-glucuronide conjugates were readily formed by polar bear liver microsomes in the absence of added substrate, apparently from contaminants present in liver. This phenomenon was not observed using hepatic microsomes from laboratory-held catfish. Glucuronidation efficiency was much higher with 4^′-OH-CB72 (K_m 7.3 μM; V_max 1.55 nmol/min/mg) than 4^′-OH-CB159 (K_m 16.1 μM; V_max 0.46 nmol/min/mg). The identities of the aglycones present in polar bear liver are not known, but could include OH-PCBs or hydroxylated metabolites of other persistent organic pollutants. This study demonstrates that UGT with high activity for 3-OH-BaP and other substrates is present in polar bear liver.