Plankton origin of particulate dimethylsulfoniopropionate in a Mediterranean oligotrophic coastal and shallow ecosystem

We report here dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) levels as a function of plankton communities and abiotic factors over a 12-month cycle in the Mediterranean oligotrophic coastal and shallow ecosystem of Niel Bay (N.W. Mediterranean Sea, France). Total particulate DMSP (DMSP_p) and DMS concentrations were highly seasonal, peaking during a spring (April) bloom at 8.9 nM and 73.9 nM, respectively. Significant positive correlations were found between total DMSP_p concentration and the abundance or biomass of the dinoflagellate Prorocentrum compressum (Spearman's rank correlation test: r = 0.704; p = 0.011). Similarly, DMS concentrations peaked during the development of blooms of P. compressum and Gymnodinium sp. There seemed to be a positive relationship between the chlorophyll a to pheopigment ratio and DMS concentrations, suggesting that DMS was released during phytoplankton growth. High DMS levels recorded in the shallow Niel Bay may also result from the activity of benthic macroalgae, and/or macrophytes such as Posidonia spp., or the resuspension of sulfur species accumulating in sediments. The fractionation of particulate DMSP into three size classes (>90 μm, 5–90 μm and 0.2–5 μm) revealed that 5–90 μm DMSP-containing particles made the greatest contribution to the total DMSP_p pool (annual mean contribution = 62%), with a maximal contribution in April (96%). This size class consisted mainly of dinoflagellates (annual mean contribution = 68%), with P. compressum and Gymnodinium sp. the predominant species, together accounting for up to 44% of the phytoplankton present. The positive correlation between DMSP concentration in the 5–90 μm size class and the abundance of P. compressum (Spearman's rank correlation test: r = 0.648; p = 0.023) suggests that this phytoplankton species would be the major DMSP producer in Niel Bay. The DMSP collected in the >90 μm fraction was principally associated with zooplankton organisms, dominated by copepods (nauplii and copepodites). DMSP_>90, not due to a specific zooplankton production, resulted from the phytoplankton cells ingested during grazing. The concomitant peaks of DMS concentration and zooplankton abundance suggest that zooplankton may play a role in releasing DMSP and/or DMS through sloppy feeding.     

Biogeochemistry of Dimethylsulfoniopropionate (DMSP) in the Surface Microlayer and Subsurface Seawater of Funka Bay,Japan

Twenty-eight sea surface microlayer samples, along with subsurface bulk water samples were collected in Funka Bay, Japan during October 2000–March 2001 and analyzed for dimethylsulfoniopropionate, dissolved (DMSP_d) and particulate (DMSP_p), and chlorophyll a. The aim of the study was to examine the extent of enrichment of DMSP in the microlayer and its relationship to chlorophyll a, as well as the production rate of dimethylsulfide (DMS) from DMSP and the factors that influence this. The enrichment factor (EF) of DMSP_d in the surface microlayer ranged from 0.81 to 4.6 with a mean of 1.85. In contrast, EF of DMSP_p in the microlayer varied widely from 0.85–10.5 with an average of 3.21. Chlorophyll a also appeared to be enriched in the microlayer relative to the subsurface water. This may be seen as an important cause of the observed enrichment of DMSP in the microlayer. The concentrations of DMSP_p in the surface microlayer showed a strong temporal variation, basically following the change in chlorophyll a levels. Moreover, the microlayer concentrations of DMSP_p were, on average, 3-fold higher than the microlayer concentrations of DMSP_d and there was a significant correlation between them. Additionally, there was a great variability in the ratios of DMSP_p to chlorophyll a over the study period, reflecting seasonal variation in the proportion of DMSP producers in the total phytoplankton assemblage. It is interesting that the production rate of DMS was enhanced in the microlayer and this rate was closely correlated with the microlayer DMSP_d concentration. Microlayer enrichment of chlorophyll a and higher DMS production rate in the microlayer provide favorable evidence supporting the view that the sea surface microlayer has a greater biological activity than the underlying water.     

Seasonal dimethylsulfoniopropionate (DMSP) variability in Dona Paula bay

Data on temporal variations of total dimethylsulfoniopropionate (DMSP_t) and the environmental factors that influence DMSP_t concentrations are important in understanding the biogeochemical cycling of organic sulfur compounds. Annual and diurnal variations of DMSP_t were investigated in relation to environmental variables at a fixed station in Dona Paula bay (west coast of India). DMSP concentrations were high in the day and low at night and ranged from 3.69 to 84 nM with a maximum at 17.00 h. The high concentrations of DMSP_t during daytime closely followed that of Chl a concentrations. The DMSP utilizers averaged 0.8 ± 0.3 × 10³ cells l^?1 during night and 0.4 ± 0.1 × 10³ cells l^?1 during the day. The diel variation of DMSP_t was influenced more by biological variables than hydrographic parameters. In the year-round study, the concentrations ranged from 0.69 to 15.8 nM. It was fourfold higher during the southwest monsoon season (13.4 ± 2 nM) and threefold higher during the post-monsoon season (9.96 ± 5 nM) compared to the pre-monsoon season (3.1 ± 1 nM). DMSP_t concentrations showed temporal variability, both during diurnal and annual studies. Diatoms were identified as producers of DMSP in Dona Paula bay. Dinoflagellates also contributed during the non-monsoon seasons. Another factor involved in the variability of DMSP_t was DMSP utilizing bacteria, which ranged from 1 to 10% of the total heterotrophic count.     

Environmental controls on phytoplankton community composition in the Thames plume, U.K.

The aim of this study was to investigate controls on the phytoplankton community composition and biogeochemistry of the estuarine plume zone of the River Thames, U.K. using an instrumented moored buoy for in situ measurements and preserved sample collection, and laboratory-based measurements from samples collected at the same site. Instrumentation on the moored buoy enabled high frequency measurements of a suite of environmental variables including in situ chlorophyll, water-column integrated irradiance, macronutrients throughout an annual cycle for 2001 e.g. nitrate and silicate, and phytoplankton biomass and species composition. The Thames plume region acts as a conduit for fluvial nutrients into the wider southern North Sea with typical winter concentrations of 45 μM nitrate, 17 μM silicate and 2 μM phosphate measured. The spring bloom resulted from water-column integrated irradiance increasing above 60 W h m^− 2 d^− 1 and was initially dominated by a diatom bloom mainly composed of Nitzschia sp. and Odontella sinesis. The spring bloom then switched after  30 days to become dominated by the flagellate Phaeocystis reaching a maximum chlorophyll concentration of 37.8 μg L^− 1. During the spring bloom there were high numbers of the heterotrophic dinoflagellates Gyrodinium spirale and Katodinium glaucum that potentially grazed the phytoplankton bloom. This diatom–flagellate switch was predicted to be due to a combination of further increasing water-column integrated irradiance > 100 W h m^− 2 d^− 1 and/or silicate reaching potentially limiting concentrations (< 1 μM). Post spring bloom, diatom dominance of the lower continuous summer phytoplankton biomass occurred despite the low silicate concentrations (Av. 0.7 μM from June–August). Summer diatom dominance, generally due to Guinardia delicatula, was expected to be as a result of microzooplankton grazing, dominated by the heterotrophic dinoflagellate Noctiluca scintillans, controlling 0.7–5.0 μm ‘flagellate’ fraction of the phytoplankton community with grazing rates up to 178% of ‘flagellate’ growth rate. The Thames plume region was therefore shown to be an active region of nutrient and phytoplankton processing and transport to the southern North Sea. The use of a combination of moorings and ship-based sampling was essential in understanding the factors influencing nutrient transport, phytoplankton biomass and species composition in this shelf sea plume region.     

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.     

Seasonal methyltin and (3-dimethylsulphonio)propionate concentrations in leaf tissue of Spartina alterniflora of the Great Bay estuary (NH)

Concentrations of total recoverable inorganic tin (TRISn), monomethyltin (MeSn³⁺), dimethyltin (Me₂Sn²⁺), trimethyltin (Me₃Sn⁺) and (3-dimethylsulphonio)propionate (DMSP) were determined in leaves of Spartina alterniflora from three sites in the Great Bay estuary (NH) from 8 May to 15 September 1989. Total methyltin concentration increased from 8·9 ng g⁻¹ (fresh weight) on 8 May to 472 ng g⁻¹ on 23 May, decreased to 52 ng g⁻¹ on 7 June and 16ng g⁻¹ on 20 June, and remained low until the last sample on 18 September. Statistical calculations showed that methyltin concentrations varied significantly with sampling week, but not with site. DMSP concentrations showed very different behaviour. During the same sampling period DMSP concentrations varied only from 7·5 to 26 μmol g⁻¹ (fresh weight). DMSP concentrations varied significantly for site, but not sampling week.     

Alkaline phosphatase in a littoral Mediterranean marine ecosystem: role of the main plankton size classes

This work investigates the alkaline phosphatase activity in a littoral marine ecosystem (Toulon Bay and Le Niel Bay, France) in order to study its biochemical characteristics with respect to pH, sea water composition and phosphate sensitivity. We also characterise the active forms in sea water and determine the extent to which zooplankton generate phosphatase activity with respect to other plankton classes. In Toulon Bay, phosphatase was produced mostly by the microplankton fraction (>90 μm), accounting for more than 90% of total activity. In contrast, most of the phosphatase activity in Le Niel Bay was generated by the nanoplankton fraction (5–90 μm) and the picoplankton fraction (0.25–5 μm). The microplankton enzymes had non Michaelis-Menten kinetics suggesting the involvement of multiple enzyme processes with distinct kinetic constants. This activity is in major part secreted into the sea water and is stimulated by the ionic strength and the pH of the sea water. Cypris larvae of the genus Balanus played a special role in this release. For the nanoplankton and picoplankton, part of this activity was due to non-secreted enzymes, probably bound to membranes or occurring intracellularly. Moreover, nano and picoplankton phosphatase required higher pH than microplankton enzyme. For all plankton size classes, there was no activity at low pH, suggesting that acid phosphatases were not involved in reactions with substrates dissolved in water.     

Iron-induced alterations of bacterial DMSP metabolism in the western subarctic Pacific during SEEDS-II

The effect of added iron on bacterial cycling of the climate-active gas dimethylsulfide (DMS) and its precursor dimethylsulfoniopropionate (DMSP) was tested during the second Subarctic Pacific Iron Experiment for Ecosystem Dynamics Study (SEEDS II) from 19 July to 21 August 2004 aboard the R/V Hakuho-Maru. The study area in the northwest Pacific Ocean (48°N 165°E) was enriched with Fe and the conservative tracer, SF₆, allowing the fertilized patch to be tracked. Microbial DMSP cycling rates were determined in the surface mixed layer (5 m) during incubations using the ³⁵S-DMSP technique. The addition of iron resulted in a 4-fold increase in concentrations of chlorophyll a (chl a) within the surface mixed layer (5 m depth), and the length of the sampling period allowed the observation of both bloom and post-bloom conditions. Inside the fertilized patch, the alleviation of resource limitation gave rise to the concurrent increase in bacterial abundance and production. Changes in the phytoplankton community within the Fe-enriched patch translated into a sustained decrease in chl a-normalized particulate DMSP (DMSP_p) concentrations, suggesting a preferential stimulation of the growth of DMSP_p-poor phytoplankton species. Despite short-lived peaks of DMSP_p within the Fe-enriched area, concentrations of DMSP_p generally remained stable during the entire sampling period inside and outside the fertilized patch. During the Fe-induced bloom, microbial DMSP-sulfur (DMSP-S) assimilation efficiency increased 2.6-fold inside the Fe-enriched area, which indicated that as bacterial production increased, a greater proportion of DMSP-S was assimilated and possibly diverted away from the bacterial cleavage pathway (i.e. production of DMS). Our results suggest that iron-induced stimulation of weak DMSP_p-producers and DMSP-assimilating bacteria may diminish the potential production of DMS and thus limit its flux towards the atmosphere over the subarctic Pacific Ocean.     

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.     

Effects of salinity downshock on dimethylsulfide production

During time-series observations in Sagami Bay, Japan, the concentration of dissolved dimethylsulfoniopropionate (DMSP_d), a precursor of dimethylsulfide (DMS), was negatively correlated with salinity. In the laboratory, low-salinity shock reduced DMS production rates of the natural bacterial community and induced rapid DMSP release from a dinophyte, Heterocapsa triquetra, suggesting that low-salinity shock reduced DMSP_d consumption but enhanced DMSP_d production, which agrees with the negative correlation between DMSP_d and salinity observed in Sagami bay. In addition, low-salinity shock did not affect DMSP lyase activity of H. triquetra. Low-salinity shock would increase the contribution from algae in DMS production, leading to an increase in potential DMS productivity in the environment.     

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

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

A high accuracy method for determining nitrogen, argon and oxygen in seawater

An improved gas chromatographic system was constructed to analyze oceanic dissolved N₂, Ar and O₂ with a higher accuracy and shorter analytical time. To obtain a higher accuracy of N₂, Ar and O₂ measurements, the following was added to the system: (I) an air trapping system; (II) a N₂–CO₂ trapping system after the operation of the air trapping system; (III) an active carbon column system for separating N₂ and CO₂ completely and (IV) the introduction of automatic valves controlling most of the system. Compared to previous studies, the precision of the measurements of N₂, Ar and O₂ concentrations was higher at 0.04%, 0.05% and 0.02%, respectively, and our analytical time was shorter at 600 s. Using the improved analytical technique, concentrations of N₂ (C_N2, 561.69–611.81 μmol/kg) and Ar (C_Ar, 15.126–16.238 μmol/kg), saturation states of N₂ (ΔN₂, − 5.1–0.9%) and Ar (ΔAr, − 7.0 to − 1.1%) from 0 m to 3000 m depth in the western North Pacific were observed during March 2005. Based on these data, we propose a new concept for estimating the amount of bubble injection (B). The total error in calculating B was estimated to be about 20%. We estimated B from 12 to 43 μmol/kg in this region using the observational values of N₂ and Ar. As each water mass had a significantly different value of B even with an error of 20%, it is possible to use it as an index of sea surface state for when each water mass is produced in the sea surface mixed layer. Moreover, based on our values of B, we estimated preformed dissolved oxygen (DO) (C_preDO, 309–332 μmol/kg) and the saturation state of C_preDO (ΔpreDO, − 7.0 to − 1.2%) in this region. Thus, the difference between C_preDO and DO content in the ocean interior may be a more useful index for biogenic organic decomposition in the ocean field compared to Apparent Oxygen Utilization (AOU). Until now, the estimation of oceanic uptake of anthropogenic CO₂ has used AOU as a major parameter. Therefore, it may be necessary to re-evaluate the oceanic uptake of anthropogenic CO₂ based on our new concept of B.     

Time-series of surface water CO2 and oxygen measurements on a platform in the central Arkona Sea (Baltic Sea): Seasonality of uptake and release

High resolution measurements of carbon dioxide and oxygen were made in surface waters of the central Arkona Sea (Baltic Sea) from May 2003 to September 2004. Sensors for CO₂ partial pressure (pCO₂^w) and oxygen (O₂) concentration were mounted in 7 m depth on a moored platform which is used for hydrographic and meteorological monitoring. The pCO₂^w data were obtained in half hour intervals and O₂ was measured each hour as an average of a 10 min measurement. To check the performance of the sensors, pCO₂^w and O₂ were determined by shipboard measurements on a research vessel which visited the site in 1–2 month intervals. In addition, pCO₂^w was measured on a “volunteer observing ship” (VOS) passing the platform each second day at a distance of about 25 km. Minima of 220 to 250 μatm of pCO₂^w were observed at the time of the spring bloom and a cyanobacteria bloom in mid-summer. During winter the pCO₂^w was mostly close to equilibrium with the atmosphere but maxima of 430 to 530 μatm were also observed. The seasonality of oxygen and pCO₂^w showed an opposing pattern. From a multiple regression analysis, we concluded that two processes primarily controlled pCO₂^w during our study: biological turnover and mixing. A parameterization, based on apparent oxygen utilisation (AOU) and salinity (S) only (pCO₂^w = 1.23 AOU + 43 S), reproduced the seasonality of pCO₂^w in surface water reasonably well. Based on our pCO₂, salinity, and temperature data set, we attempted to separate processes changing total inorganic carbon concentrations (C_T) by using an alkalinity–salinity relation for the area. The contribution of CO₂ gas exchange and mixing were calculated and from this the biological turnover was deduced to reveal the calculated C_T changes.The net annual uptake of CO₂ in the central Arkona Sea was estimated to be about 1.5 Tg (1.5·10¹² g) which was approximately balanced by a net oxygen release considering the uncertainties of the flux calculations. Near-coast CO₂ emission due to episodic upwelling partly compensated the uptake of the central part of the Arkona Sea reducing the overall magnitude of the CO₂ uptake.     

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.     

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.     

Growth and reproduction of the bivalve Spisula subtruncata (da Costa) in Dutch coastal waters

The bivalve Spisula subtruncata is usually abundant in shallow coastal waters along the Dutch coast. However, its biomass has been decreasing since 1995. In order to assess whether reproductive failure may be the cause of the observed decline over the last decades, the energy investment in reproduction of a population of S. subtruncata from central Dutch coastal waters was studied. The population studied consisted of individuals of up to four years old. Shell length reached maximum values of around 32 mm and individual total body, somatic and gonadal ash-free dry mass reached maximum values of about 278 mg AFDM, 252 mg AFDM and 76 mg AFDM, respectively. A clear seasonal cycle in somatic and gonadal mass was observed. Somatic and gonadal mass indices increased in early spring and reached maximum values during summer, followed by a decrease to minimum values at the beginning of the following year. Spawning was in June–July and settlement of spat seems to have occurred in July–August. Mean oocyte diameter was 57.43 ± 0.03 μm, corresponding to a volume of 98972 μm³. These results suggested that reproductive failure was not the cause of the current population decline. Most likely, unsuccessful settlement of spat and/or severe predation during the first months of life were responsible for the observed patterns.     

Seasonal survey of copper-complexing ligands and thiol compounds in a heavily utilized, urban estuary: Elizabeth River, Virginia

Concentrations of thiol compounds, copper-complexing ligands, and total dissolved copper were followed over the course of 1 year (October 2002 until September 2003) in the Elizabeth River, Virginia to evaluate seasonality. Copper-complexing ligand concentrations were determined by competitive ligand equilibration-adsorptive cathodic stripping voltammetry (CLE/ACSV). Thiol detection was carried out by high performance liquid chromatography (HPLC) and calibration using a suite of nine thiol compounds (cysteine, glutathione, mercaptoacetic acid, 2-mercaptoethanesulfonic acid, 2-mercaptoethanol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, and monothioglycerol). Total dissolved copper concentrations reached a January low of 13.1 nM to a June high of 24.7 nM and were found to vary seasonally with higher concentrations occurring from June to September. With a low of 26 nM during April to a high of 56 nM in October, copper-complexing ligand (average log K′_CuL of 12.0 ± 0.2) concentrations displayed a similar seasonal pattern to that of total dissolved copper. Free cupric ion concentrations remained below 1.5 pM for a majority of the year except during March, April, and December when values reached pM levels greater than 1.5. Six of the nine thiol compounds surveyed were detected in the Elizabeth River samples and ranged in concentration from below detectable concentrations (< 5 nM) to individual highs ranging from 25.3 to168.5 nM. The thiol compound concentrations displayed a clear seasonality fluctuating at below detection limits during November to February then increasing with increasing surface water temperatures from March to July. CLE/ACSV was used to assess whether or not the suite of thiol compounds detected by HPLC could contribute to the copper-complexing ligand pool. Conditional stability constants for each one of six thiol standards (average log K′_CuL  12.1 ± 0.5) were found to be statistically equivalent to the naturally occurring copper-complexing ligands (average log K′_CuL  12.0 ± 0.2). This suggests that these thiol compounds could act as copper-complexing ligands in natural samples and could contribute to the copper-complexing ligand pool detected by CLE/ACSV. This study involving seasonality of copper-complexing ligands and thiols in an industrialized, urban estuary underscored several points that have to be substantiated in future research efforts including copper-complexing ligands sources and the role that thiol compounds as well as other unidentified organic compounds play in the copper-complexing ligand pool.     

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

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

The 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.     

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).