Uncoupled distributions of transparent exopolymer particles (TEP) and dissolved carbohydrates in the Southern Ocean

Transparent exopolymer particles (TEP) are formed by the assembly of dissolved precursors, mainly mono and polysaccharides (DMCHO and DPCHO) that are released by microorganisms. Although TEP formation plays a significant role in carbon export to deep waters and can affect gas exchange at the sea surface, simultaneous measurements of TEP and their precursors in natural waters have been scantly reported. In this study, we described the spatial (vertical and regional) distribution of TEP, DMCHO and DPCHO in a region located around the Antarctic Peninsula, assessed their contribution to the total organic carbon pool, and explored their relationships with phytoplankton (with chlorophyll a (chl a) as a proxy) and bacteria. TEP concentration ranged from undetectable values to 48.9 µg XG eq L^− 1 with a mean value of 15.4 µg XG eq L^− 1 (11.6 µg TEP-C L^− 1). DMCHO and DPCHO showed average values of 4.3 µmol C L^− 1 and 8.6 µmol C L^− 1, respectively. We did not find simple relationships between the concentrations of TEP and dissolved carbohydrates, but a negative correlation between DMCHO and DPCHO was observed. Chl a was the best regressor of TEP concentration in waters within the upper mixed layer, while bacterial production was the best regressor of TEP concentration below the mixed layer, underlining the direct link between these particles and bacterial activity in deep waters.     

Depth profiles of volatile iodine and bromine-containing halocarbons in coastal Antarctic waters

Measurements of bromoform (CHBr₃), diiodomethane (CH₂I₂), chloroiodomethane (CH₂ICl) and bromoiodomethane (CH₂IBr) were made in the water column (5–100 m depth) of the Southern Ocean within 0–40 km of the Antarctic sea ice during the ANTXX1/2 transect of the German R/V Polarstern, at five locations between 70–72°S and 9–11°W in the Antarctic spring/summer of 2003–2004. Some of the profiles exhibited a very pronounced layer of surface sea-ice meltwater, as evidenced by salinity minima and temperature maxima, along with surface maxima in concentrations of CHBr₃, CH₂I₂, CH₂ICl and CH₂IBr. These results are consistent with in situ surface halocarbon production by ice algae liberated from the sea ice, although production within the sea ice followed by transport cannot be entirely ruled out. Additional sub-surface maxima in halocarbons occurred between 20 and 80 m. At a station further from shore and not affected by surface sea-ice meltwater, surface concentrations of CH₂I₂ were decreased whereas CH₂ICl concentrations were increased compared to the stations influenced by meltwater, consistent with photochemical conversion of CH₂I₂ to CH₂ICl, perhaps during upward mixing from a layer at  70 m enhanced in iodocarbons. Mean surface (5–10 m) water concentrations of halocarbons in these coastal Antarctic waters were 57 pmol l^− 1 CHBr₃ (range 44–78 pmol l^− 1), 4.2 pmol l^− 1 CH₂I₂ (range 1.7–8.2 pmol l^− 1), 0.8 pmol l^− 1 CH₂IBr (range 0.2–1.4 pmol l^− 1), and 0.7 pmol l^− 1 CH₂ICl (range 0.2–2.4 pmol l^− 1). Concurrent measurements in air suggested a sea-air flux of bromoform near the Antarctic coast of between 1 and 100 (mean 32.3, median 10.4) nmol m^− 2 day^− 1 and saturation anomalies of 557–1082% (mean 783%, median 733%), similar in magnitude to global shelf values. In surface samples affected by meltwater, CH₂I₂ fluxes ranged from 0.02 to 6.1 nmol m^− 2 day^− 1, with mean and median values of 1.9 and 1.1 nmol m^− 2 day^− 1, respectively.     

Seasonal changes in submarine groundwater discharge to coastal salt ponds estimated using Ra and Ra as tracers

Submarine groundwater discharge (SGD) to coastal southern Rhode Island was estimated from measurements of the naturally-occurring radioisotopes ²²⁶Ra (t_1/2 = 1600 y) and ²²⁸Ra (t_1/2 = 5.75 y). Surface water and porewater samples were collected quarterly in Winnapaug, Quonochontaug, Ninigret, Green Hill, and Pt. Judith–Potter Ponds, as well as nearly monthly in the surface water of Rhode Island Sound, from January 2002 to August 2003; additional porewater samples were collected in August 2005. Surface water activities ranged from 12–83 dpm 100 L^− 1 (60 dpm = 1 Bq) and 21–256 dpm 100 L^− 1 for ²²⁶Ra and ²²⁸Ra, respectively. Porewater ²²⁶Ra activities ranged from 16–736 dpm 100 L^− 1 (2002–2003) and 95–815 dpm 100 L^− 1 (2005), while porewater ²²⁸Ra activities ranged from 23–1265 dpm 100 L^− 1. Combining these data with a simple box model provided average ²²⁶Ra-based submarine groundwater fluxes ranging from 11–159 L m^− 2 d^− 1 and average ²²⁸Ra-derived fluxes of 15–259 L m^− 2 d^− 1. Seasonal changes in Ra-derived SGD were apparent in all ponds as well as between ponds, with SGD values of 30–472 L m^− 2 d^− 1 (Winnapaug Pond), 6–20 L m^− 2 d^− 1 (Quonochontaug Pond), 36–273 L m^− 2 d^− 1 (Ninigret Pond), 29–76 L m^− 2 d^− 1 (Green Hill Pond), and 19–83 L m^− 2 d^− 1 (Pt. Judith–Potter Pond). These Ra-derived fluxes are up to two orders of magnitude higher than results predicted by a numerical model of groundwater flow, estimates of aquifer recharge for the study period, and values published in previous Ra-based SGD studies in Rhode Island. This disparity may result from differences in the type of flow (recirculated seawater versus fresh groundwater) determined using each technique, as well as variability in porewater Ra activity.     

Water masses and currents of deep circulation southwest of the Shatsky Rise in the western North Pacific

We conducted full-depth hydrographic observations in the southwestern region of the Northwest Pacific Basin in September 2004 and November 2005. Deep-circulation currents crossed the observation line between the East Mariana Ridge and the Shatsky Rise, carrying Lower Circumpolar Deep Water westward in the lower deep layer (θ<1.2 °C) and Upper Circumpolar Deep Water (UCDW) and North Pacific Deep Water (NPDW) eastward in the upper deep layer (1.3–2.2 °C). In the lower deep layer at depths greater than approximately 3500 m, the eastern branch current of the deep circulation was located south of the Shatsky Rise at 30°24′–30°59′N with volume transport of 3.9 Sv (1 Sv=10⁶ m³ s⁻¹) in 2004 and at 30°06′–31°15′N with 1.6 Sv in 2005. The western branch current of the deep circulation was located north of the Ogasawara Plateau at 26°27′–27°03′N with almost 2.1 Sv in 2004 and at 26°27′–26°45′N with 2.7 Sv in 2005. Integrating past and present results, volume transport southwest of the Shatsky Rise is concluded to be a little less than 4 Sv for the eastern branch current and a little more than 2 Sv for the western branch current. In the upper deep layer at depths of approximately 2000–3500 m, UCDW and NPDW, characterized by high and low dissolved oxygen, respectively, were carried eastward at the observation line by the return flow of the deep circulation composing meridional overturning circulation. UCDW was confined between the East Mariana Ridge and the Ogasawara Plateau (22°03′–25°33′N) in 2004, whereas it extended to 26°45′N north of the Ogasawara Plateau in 2005. NPDW existed over the foot and slope of the Shatsky Rise from 29°48′N in 2004 and 30°06′N in 2005 to at least 32°30′N at the top of the Shatsky Rise. Volume transport of UCDW was estimated to be 4.6 Sv in 2004, whereas that of NPDW was 1.4 Sv in 2004 and 2.6 Sv in 2005, although the values for NPDW may be slightly underestimated, because they do not include the component north of the top of the Shatsky Rise. Volume transport of UCDW and NPDW southwest of the Shatsky Rise is concluded to be approximately 5 and 3 Sv, respectively. The pathways of UCDW and NPDW are new findings and suggest a correction for the past view of the deep circulation in the Pacific Ocean.     

Transformation dynamics and reactivity of dissolved and colloidal iron in coastal waters

We have investigated the chemical forms, reactivities and transformation kinetics of Fe(III) species present in coastal water with ion exchange and filtration methods. To simulate coastal water system, a mixture of ferric iron and fulvic acid was added to filtered seawater and incubated for a minute to a week. At each incubation time, the seawater sample was acidified with hydrochloric acid and then applied to anion exchange resin (AER) to separate negatively charged species (such as fulvic acid, its complexes with iron and iron oxyhydroxide coated with fulvic acid) from positively charged inorganic ferric iron (Fe(III)′). By monitoring the acid-induced Fe(III)′ over an hour, it was found that iron complexed by fulvic acid dissociated rapidly to a large extent (86–92% at pH 2), whereas amorphous ferric oxyhydroxide particles associated with fulvic acid (AFO-L) dissociated very slowly with the first-order dissociation rate constants ranging from 6.1 × 10^− 5 for pH 3 to 2.7 × 10^− 4 s^− 1 for pH 2. Therefore, a brief acidification followed by the AER treatment (acidification/AER method) was likely to be able to determine fulvic acid complexes and thus differentiate the complexes from the AFO-L particles (the dissolution of AFO-L was insignificant during the brief acidification). The acidification/AER method coupled with a simple filtration technique suggested that the iron–fulvic acid complexes exist in both the < 0.02 μm and 0.02–0.45 μm size fractions in our coastal water system. The truly dissolved iron (< 0.02 μm) was relatively long-lived with a life-time of 14 days, probably due to the complexation by strong ligands. Such an acid-labile iron may be an important source of bioavailable iron in coastal environments, as a significant relationship between the chemical lability and bioavailability of iron has been well recognised.     

Water mass ages of coastal ponds estimated using Ra and Ra as tracers

Measurements of the naturally occurring radioisotopes ²²³Ra (t_1/2 = 11.4 days) and ²²⁴Ra (t_1/2 = 3.66 days) in southern Rhode Island salt ponds were combined with a simple model to obtain independent estimates of the age of these coastal waters. Surface water and porewater samples were collected quarterly in Winnapaug, Quonochontaug, Ninigret, Green Hill, and Pt. Judith-Potter Ponds, as well as nearly monthly in the surface water of Rhode Island Sound, beginning January 2002 through August 2003. Surface water activities ranged from 1–78 dpm 100 L^− 1 and 5–885 dpm 100 L^− 1 for ²²³Ra and ²²⁴Ra, respectively. Porewater radium activities ranged from 3 to 715 dpm 100 L^− 1 for ²²³Ra, and 57–4926 dpm 100 L^− 1 for ²²⁴Ra. Results indicate seasonally varying water mass ages for Ninigret (5–12 days), Winnapaug (2–6 days) and Pt. Judith-Potter Ponds (1–9 days) and, in contrast, relatively constant ages for Green Hill (5–7 days) and Quonochontaug Ponds (3–6 days).     

Winkler's method overestimates dissolved oxygen in seawater: Iodate interference and its oceanographic implications

Dissolved oxygen in seawater has been determined by using the Winkler's reaction scheme for decades. An interference in this reaction scheme that has been heretofore overlooked is the presence of naturally occurring iodate in seawater. Each mole of iodate can result in an apparent presence of 1.5 mol of dissolved oxygen. At the concentrations of iodate in the surface and deep open ocean, it can lead to an overestimation of 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 of oxygen in these waters respectively. In coastal and inshore waters, the effect is less predictable as the concentration of iodate is more variable. The solubility of oxygen in seawater was likely overestimated in data sources that were based on the Winkler's reaction scheme for the determination of oxygen. The solubility equation of García and Gordon [Garcia H.E., Gordon, L.I., 1992. Oxygen solubility in seawater: Better fitting equations. Limnol. Oceanogr. 37, 1307–1312] derived from the results of Benson and Krause [Benson, F.B., Krause, D. Jr., 1984. The concentration and isotopic fractionation of oxygen dissolved in freshwater and seawater in equilibrium with the atmosphere. Limnol. Oceanogr. 29, 620–632] is free from this source of error and is recommended for general use. By neglecting the presence of iodate, the average global super-saturation of oxygen in the surface oceans and the corresponding efflux of oxygen to the atmosphere both have been overestimated by about 8%. Regionally, in areas where the degree of super-saturation or under-saturation of oxygen in the surface water is small, such as in the tropical oceans, the net air–sea exchange flux can be grossly under- or overestimated. Even the estimated direction of the exchange can be reversed. Furthermore, the presence of iodate can lead to an overestimation of the saturation anomaly of oxygen in the upper ocean attributed to biological production by 0.23 ± 0.07%. AOU may have been underestimated by 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 in the surface mixed layer and deep water, while preformed phosphate and preformed nitrate may have been overestimated by 0.004 ± 0.001 and 0.06 ± 0.02 μmol kg^− 1 in the surface mixed layer, and 0.005 ± 0.0004 and 0.073 ± 0.006 μmol kg^− 1 in the deep water. These are small but not negligible corrections, especially in areas where the values of these parameters are small. At the increasing level of sophistication in the interpretation of oxygen data, this source of error should now be taken into account. Nevertheless, in order to avoid confusion, an internationally accepted standard needs to be adopted before these corrections can be applied.     

Reconstruction of sea surface dimethylsulfide in the North Pacific during 1970s to 2000s

We proposed an empirical equation of sea surface dimethylsulfide (DMS, nM) using sea surface temperature (SST, K), sea surface nitrate (SSN, μM) and latitude (L, °N) to reconstruct the sea surface flux of DMS over the North Pacific between 25°N and 55°N: ln DMS = 0.06346 · SST − 0.1210 · SSN − 14.11 · cos(L) − 6.278 (R² = 0.63, p < 0.0001). Applying our algorithm to climatological hydrographic data in the North Pacific, we reconstructed the climatological distributions of DMS and its flux between 25 °N and 55 °N. DMS generally increased eastward and northward, and DMS in the northeastern region became to 2–5 times as large as that in the southwestern region. DMS in the later half of the year was 2–4 times as large as that in the first half of the year. Moreover, applying our algorithm to hydrographic time series datasets in the western North Pacific from 1971 to 2000, we found that DMS in the last three decades has shown linear increasing trends of 0.03 ± 0.01 nM year^− 1 in the subpolar region, and 0.01 ± 0.001 nM year^− 1 in the subtropical region, indicating that the annual flux of DMS from sea to air has increased by 1.9–4.8 μmol m^− 2 year^− 1. The linear increase was consistent with the annual rate of increase of 1% of the climatological averaged flux in the western North Pacific in the last three decades.     

On the relevance of iron adsorption to container materials in small-volume experiments on iron marine chemistry: Fe-aided assessment of capacity, affinity and kinetics

Iron chemistry in seawater has been extensively studied in the laboratory, mostly in small-volume sample bottles. However, little has been reported about iron wall sorption in these bottles. In this paper, radio-iron ⁵⁵Fe was used to assess iron wall adsorption, both in terms of capacity, affinity and kinetics. Various bottle materials were tested. Iron sorption increased from polyethylene/polycarbonate to polymethylmetacrylate (PMMA)/high-density polyethylene/polytetrafluoroethylene to glass/quartz, reaching equilibrium in a 25–70 h period. PMMA was studied in more detail: ferric iron (Fe(III)) adsorbed on the walls of the bottles, whereas ferrous iron (Fe(II)) did not. Considering that in seawater the inorganic iron pool mostly consists of ferric iron, the wall will be a factor that needs to be considered in bottle experiments.The present data indicate that for PMMA with specific surface (S)-to-volume (V) ratio S/V, both iron capacity (42 ± 16 × 10^− 9 mol/m² or 1.7 × 10^− 9 mol/L recalculated for the S/V-specific PMMA bottles used) and affinity (log K_Fe'W = 11.0 ± 0.3 m²/mol or 12.4 ± 0.3 L/mol, recalculated for the S/V-specific PMMA bottles used) are of similar magnitude as the iron capacity and -affinity of the natural ligands in the presently used seawater and thus cannot be ignored.Calculation of rate constants for association and dissociation of both Fe'L (iron bound to natural occurring organic ligands) and Fe'W (iron adsorbed on the wall of vessels) suggests that the two iron complexes are also of rather similar kinetics, with rate constants for dissociation in the order of 10 ⁻⁴–10^− 5 L/s and rate constants for association in the order of 10⁸ L/(mol s). This makes that iron wall sorption should be seriously considered in small-volume experiments, both in assessments of shorter-term dynamics and in end-point observations in equilibrium conditions. Therefore, the present data strongly advocate making use of iron mass balances throughout in experiments in smaller volume set-ups on marine iron (bio) chemistry.     

Dimethylsulfide production in Sargasso Sea eddies

Lagrangian time series of dimethylsulfide (DMS) concentrations from a cyclonic and an anticyclonic eddy in the Sargasso Sea were used in conjunction with measured DMS loss rates and a model of vertical mixing to estimate gross DMS production in the upper 60 m during summer 2004. Loss terms included biological consumption, photolysis, and ventilation to the atmosphere. The time- and depth (0–60 m)-averaged gross DMS production was estimated to be 0.73±0.09 nM d⁻¹ in the cyclonic eddy and 0.90±0.15 nM d⁻¹ in the anticyclonic eddy, with respective DMS replacement times of 5±1 and 6±1 d. The higher estimated rate of gross production and lower measured loss rate constants in the anticyclonic eddy were equally responsible for this eddy's 50% higher DMS inventory (0–60 m). When normalized to chlorophyll and total dimethylsulfoniopropionate (DMSP), estimated gross production in the anticyclonic eddy was about twice that in the cyclonic eddy, consistent with the greater fraction of phytoplankton that were DMSP producers in the anticyclonic eddy. Higher rates of gross production were estimated below the mixed layer, contributing to the subsurface DMS maximum found in both eddies. In both eddies, gas exchange, microbial consumption, and photolysis were roughly equal DMS loss terms in the surface mixed layer (0.2–0.4 nM d⁻¹). Vertical mixing was a substantial source of DMS to the surface mixed layer in both eddies (0.2–0.3 nM d⁻¹) owing to the relatively high DMS concentrations below the mixed layer. Estimated net biological DMS production rates (gross production minus microbial consumption) in the mixed layer were substantially lower (by almost a factor of 3) than those estimated in a previous study of the Sargasso Sea, which may explain the relatively low mixed-layer DMS concentrations found here during July 2004 (3 nM) compared to previous summers (4–6 nM).     

The impact of groundwater discharges on mercury partitioning, speciation and bioavailability to mussels in a coastal zone

The Mussel Watch program conducted along the French coasts for the last 20 years indicates that the highest mercury concentrations in the soft tissue of the blue mussel (Mytilus edulis) occur in animals from the eastern part of Seine Bay on the south coast of the English Channel, the “Pays de Caux”. This region is characterized by the presence of intertidal and submarine groundwater discharges, and no particular mercury effluent has been reported in its vicinity. Two groundwater emergence systems in the karstic coastal zone of the Pays de Caux (Etretat and Yport with slow and fast water percolation pathways respectively) were seasonally sampled to study mercury distribution, partitioning and speciation in water. Samples were also collected in the freshwater–seawater mixing zones in order to compare mercury concentrations and speciation between these “subterranean” or “groundwater” estuaries and the adjacent macrotidal Seine estuary, characterized by a high turbidity zone (HTZ). The mercury concentrations in the soft tissue of mussels from the same areas were monitored at the same time.The means of the “dissolved” (< 0.45 μm) mercury concentrations (HgT_D) in the groundwater springs were 0.99 ± 0.15 ng l^− 1 (n = 18) and 0.44 ± 0.17 ng l^− 1 (n = 17) at Etretat and Yport respectively. High HgT_D concentrations were associated with strong runoff over short water pathways during storm periods, while low concentrations were associated with long groundwater pathways. Mean particulate mercury concentrations were 0.22 ± 0.05 ng mg^− 1 (n = 16) and 0.16 ± 0.10 ng mg^− 1 (n = 17) at Etretat and Yport respectively, and decreased with increasing particle concentration probably as a result of dilution by particles from soil erosion. Groundwater mercury speciation was characterized by high reactive-to-total mercury ratios in the dissolved phase (HgR_D/HgT_D: 44–95%), and very low total monomethylmercury concentrations (MMHg < 8 pg l^− 1). The HgT_D distributions in the Yport and Etretat mixing zones were similar (overall mean concentration of 0.73 ± 0.21 ng l^− 1, n = 43), but higher than those measured in the adjacent industrialized Seine estuary (mean: 0.31 ± 0.11 ng l^− 1, n = 67). In the coastal waters along the Pays de Caux dissolved monomethylmercury (MMHg_D) concentrations varied from 9.5 to 13.5 pg l^− 1 (2 to 8% of the HgT_D). Comparable levels were measured in the Seine estuary (range: 12.2– 21.1 pg l⁻¹; 6–12% of the HgT_D). These groundwater karstic estuaries seem to be mostly characterized by the higher HgT_D and HgR_D concentrations than in the adjacent HTZ Seine estuary. While the HTZ of the Seine estuary acts as a dissolved mercury removal system, the low turbid mixing zone of the Pays de Caux receives the dissolved mercury inputs from the groundwater seepage with an apparent Hg transfer from the particulate phase to the “dissolved” phase (< 0.45 μm). In parallel, the soft tissue of mussels collected near the groundwater discharges, at Etretat and Yport, exhibited significantly higher values than those found in the mussel from the mouth of the Seine estuary. We observe that this difference mimics the differences found in the mercury distribution in the water, and argue that the dissolved phase of the groundwater estuaries and coastal particles are significant sources of bioavailable mercury for mussels.     

Manganese and iron distributions off central California influenced by upwelling and shelf width

In July 2002, a combination of underway mapping and discrete profiles revealed significant along-shore variability in the concentrations of manganese and iron in the vicinity of Monterey Bay, California. Both metals had lower concentrations in surface waters south of Monterey Bay, where the shelf is about 2.5 km wide, than north of Monterey Bay, where the shelf is about 10 km wide. During non-upwelling conditions over the northern broad shelf, dissolvable iron concentrations measured underway in surface waters reached 3.5 nmol L⁻¹ and dissolved manganese reached 25 nmol L⁻¹. In contrast, during non-upwelling conditions over the southern narrow shelf, dissolvable iron concentrations in surface waters were less than 1 nmol L⁻¹ and dissolved manganese concentrations were less than 5 nmol L⁻¹. A pair of vertical profiles at 1000 m water depth collected during an upwelling event showed dissolved manganese concentrations of 10 decreasing to 2 nmol L⁻¹, and dissolvable iron concentrations of 12–20 nmol L⁻¹ in the upper 100 m in the north, compared to 3.5–2 nmol L⁻¹ Mn and 0.6 nmol L⁻¹ Fe in the upper 100 m in the south, suggesting the effect of shelf width influences the chemistry of waters beyond the shelf.These observations are consistent with current understanding of the mechanism of iron supply to coastal upwelling systems: Iron from shelf sediments, predominantly associated with particles greater than 20 μm, is brought to the surface during upwelling conditions. We hypothesize that manganese oxides are brought to the surface with upwelling and are then reduced to dissolved manganese, perhaps by photoreduction, following a lag after upwelling.Greater phytoplankton biomass, primary productivity, and nutrient drawdown were observed over the broad shelf, consistent with the greater supply of iron. Incubation experiments conducted 20 km offshore in both regions, during a period of wind relaxation, confirm the potential of these sites to become limited by iron. There was no additional growth response when copper, manganese or cobalt was added in addition to iron. The growth response of surface water incubated with bottom sediment (4 nmol L⁻¹ dissolvable Fe) was slightly greater than in control incubations, but less than in the presence of 4 nmol L⁻¹ dissolved iron. This may indicate that dissolvable iron is not as bioavailable as dissolved iron, although the influence of additional inhibitory elements in the sediment cannot be ruled out.     

Uptake and metabolism of arsenate by anexic cultures of the microalgae Dunaliella tertiolecta and Phaeodactylum tricornutum

Axenic cultures of the microalgae species, Dunaliella tertiolecta and Phaeodactylum tricornutum were grown at arsenic (As) concentrations typically found in uncontaminated marine environments ( 2 µg L^− 1) under different phosphorus concentrations. D. tertiolecta accumulated higher arsenic concentrations (mean: 13.7 ± 0.7 µg g^− 1 dry mass) than P. tricornutum (mean: 1.9 ± 0.2 µg g−1 dry mass). Media phosphorus concentrations (0.6–3 mg/L) had little influence on microalgae growth rates or arsenic accumulation. Arsenic was present as lipid bound (29–38%; 4.2–9.5%), water-soluble (20–29%; 26–34%) and residue bound (41–45%; 57–69%) arsenic species in D. tertiolecta and P. tricornutum respectively. Hydrolysed lipids contained mostly glycerol arsenoribose (OH- ribose), dimethylarsinate (DMA) and inorganic arsenic (As(V)) moieties. Water-soluble species of microalgae were very different. D. tertiolecta contained inorganic arsenic (54–86%) with variable amounts of DMA (7.4–20%), arsenoriboses (5–25%) and traces of methylarsonate (MA) ( 1%). P. tricornutum contained mostly DMA (32–56%) and phosphate arsenoribose (PO₄-ribose, 23–49%) and small amounts of OH-ribose (3.8–6.5%) and As(V) (9–16%). Both microalgae contained an unknown cationic arsenic species. The residue fractions of both microalgae contained predominately inorganic arsenic (99–100%). These results show that at natural seawater arsenic concentrations, both algae take up substantial amounts of inorganic arsenic that is complexed with structural elements or sequestered in vacuoles as stable complexes. A significant portion is also incorporated into lipids. Arsenic is metabolised to simple methylated species and arsenoriboses.     

Photochemical production of molecular hydrogen in lake water and coastal seawater

Samples of lake water and coastal seawater from Nova Scotia, Canada, were irradiated with natural or artificial sunlight to investigate the potential for photochemical hydrogen production. Hydrogen photo-production was observed in all natural water samples. Rates of hydrogen formation were highest in coloured lake water (range: 98–163 pmol L^− 1h^− 1) and lower in seawater (range: 19–45 pmol L^− 1 h ^− 1). Dilutions of the most highly coloured lake sample (Kejimkujik Lake) showed a positive linear relationship between H₂ production rates and CDOM concentration. Photo-production rates normalised to UV absorption coefficients at 350 nm indicated that the photochemical efficiency of hydrogen formation varied between samples, perhaps due to differences in the CDOM composition. Photochemical hydrogen formation was also seen in solutions of syringic acid and acetaldehyde: two low-molecular-weight carbonyl compounds found in natural waters. Photochemistry may therefore offer least a partial explanation for the persistently high levels of hydrogen observed in the low-latitude surface ocean.     

The carbon dioxide system and net community production within a cyclonic eddy in the lee of Hawaii

The dynamics of dissolved inorganic carbon (DIC) and processes controlling net community production (NCP) were investigated within a mature cyclonic eddy, Cyclone Opal, which formed in the lee of the main Hawaiian Islands in the subtropical North Pacific Gyre. Within the eddy core, physical and biogeochemical properties suggested that nutrient- and DIC-rich deep waters were uplifted by 80 m relative to surrounding waters, enhancing biological production. A salt budget indicates that the eddy core was a mixture of deep water (68%) and surface water (32%). NCP was estimated from mass balances of DIC, nitrate+nitrite, total organic carbon, and dissolved organic nitrogen, making rational inferences about the unobserved initial conditions at the time of eddy formation. Results consistently suggest that NCP in the center of the eddy was substantially enhanced relative to the surrounding waters, ranging from 14.1±10.6 (0–110 m: within the euphotic zone) to 14.2±9.2 (0–50 m: within the mixed layer) to 18.5±10.7 (0–75 m: within the deep chlorophyll-maximum layer) mmol C m⁻² d⁻¹ depending on the depth of integration. NCP in the ambient waters outside the eddy averaged about 2.37±4.24 mmol C m⁻² d⁻¹ in the mixed layer (0–95 m). Most of the enhanced NCP inside the eddy appears to have accumulated as dissolved organic carbon (DOC) rather than exported as particulate organic carbon (POC) to the mesopelagic. Our results also suggest that the upper euphotic zone (0–75 m) above the deep chlorophyll maximum is characterized by positive NCP, while NCP in the lower layer (>75 m) is close to zero or negative.     

Temporal variability of dimethylsulfide and dimethylsulfoniopropionate in the Sargasso Sea

Vertical profiles of dimethylsulfide (DMS) and β-dimethylsulfoniopropionate, particulate (pDMSP) and dissolved (dDMSP), were measured biweekly in the upper 140 m of the Sargasso Sea (32°10′N, 64°30′W) during 1992 and 1993. DMS and pDMSP showed strong, but different, seasonal patterns; no distinct intra-annual pattern was observed for dDMSP. During winter, concentrations of DMS were generally less than 1 nmol l⁻¹ at all depths, dDMSP was less than 3 nmol l⁻¹ and pDMSP was less than 8 nmol l⁻¹. In spring, concentrations of both dDMSP and pDMSP rose, on a few occasions up to 20 nmol l⁻¹ in the dissolved pool and up to 27 nmol l⁻¹ in the particulate pool. These increases, due to blooms of DMSP-containing phytoplankton, resulted in only minor increases in DMS concentrations (up to 4 nmol l⁻¹). Throughout the summer, the concentrations of DMS continued to increase, reaching a maximum in August of 12 nmol l⁻¹ (at 30 m depth). There was no concomitant summer increase in dDMSP or pDMSP. The differences among the seasonal patterns of DMS, dDMSP, and pDMSP suggest that the physical and biological processes involved in the cycling of DMS change with the seasons. There is a correlation between the concentration of DMS and temperature in this data set, as required by some of the climate feedback models that have been suggested for DMS. A full understanding of the underlying processes controlling DMS is required to determine if the temperature-DMS pattern is of significance in the context of global climate change.     

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.     

Aggregation of riverine colloidal iron in estuaries: A new kinetic study using stopped-flow mixing

The kinetics of aggregation of riverine colloidal iron have been examined using a stopped-flow technique which probes the first few seconds of mixing between river and sea water end members. A significant fraction, up to 80%, of the colloidal iron is aggregated during the first 1–2 s of mixing, indicating that the aggregation process is much faster than previously thought. Most of the aggregation induced by seawater results from the divalent cations Mg²⁺ and Ca²⁺, with the overall ionic strength having little influence. At equal concentrations of 27 mM, the rate of aggregation by alkaline earth cations increased with ionic size Mg²⁺ < Ca²⁺ < Sr²⁺ < Ba²⁺. The aggregation rates were indifferent to the anion (Cl⁻ or SO₄²⁻) present. Very high aggregation rates were also induced by the common water treatment coagulant Al₂(SO₄)₃ at concentrations in the range 20–30 µM Al(III), several orders of magnitude lower that those used for the seawater cations. Our results support the view that specific chemical interactions between the cations and the colloid particle surface, rather than simple electrical effects, control the colloid stability.     

Biogeochemical transport in the Loxahatchee River estuary, Florida: The role of submarine groundwater discharge

The distributions of dissolved organic carbon (DOC), Ba, U, and a suite of naturally occurring radionuclides in the U/Th decay series (²²²Rn, ^{223,224,226,228}Ra) were studied during high- and low-discharge conditions in the Loxahatchee River estuary, Florida to examine the role of submarine groundwater discharge in estuarine transport. The fresh water endmember of this still relatively pristine estuary may reflect not only river-borne constituents, but also those advected during active groundwater/surface water (hyporheic) exchange. During both discharge conditions, Ba concentrations indicated slight non-conservative mixing. Such Ba excesses could be attributed either to submarine groundwater discharge or particle desorption processes. Estuarine dissolved organic carbon concentrations were highest at salinities closest to zero. Uranium distributions were lowest in the fresh water sites and mixed mostly conservatively with an increase in salinity. Suspended particulate matter (SPM) concentrations were generally lowest (< 5 mg L^− 1) close to zero salinity and increased several-fold ( 18 mg L^− 1; low discharge) toward the seaward endmember, which may be attributed to dynamic resuspension of bottom sediments within Jupiter Inlet.Surface water-column ²²²Rn activities were most elevated (> 28 dpm L^− 1) at the freshwater endmember of the estuary and appear to identify regions of the river most influenced by the discharge of fresh groundwater. Activities of four naturally occurring isotopes of Ra (^{223,224,226,228}Ra) in this estuary and select adjacent shallow groundwater wells yield mean estuarine water-mass transit times of less than 1 day; these values are in close agreement to those calculated by tidal prism and tidal frequency. Submarine groundwater discharge rates to the Loxahatchee River estuary were calculated using a tidal prism approach, an excess ²²⁶Ra mass balance, and an electromagnetic seepage meter. Average SGD rates ranged from 1.0 to 3.8 × 10⁵ m³ d^− 1 (20–74 L m^− 2 d^− 1), depending on river-discharge stage. Such calculated SGD estimates, which must include both a recirculated as well as fresh water component, are in close agreement with results obtained from a first-order watershed mass balance. Average submarine groundwater discharge rates yield NH₄⁺ and PO₄^− 3 flux estimates to the Loxahatchee River estuary that range from 62.7 to 1063.1 and 69.2 to 378.5 μmol m^− 2 d^− 1, respectively, depending on river stage. SGD-derived nutrient flux rates are compared to yearly computed riverine total N and total P load estimates.     

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.