Trace metal distributions across the continental shelf near Otago Peninsula, New Zealand

The distributions of the trace metals iron (Fe), copper (Cu) and cadmium (Cd) along with hydrological parameters (salinity, temperature and reactive phosphate) across the New Zealand continental shelf near Otago Peninsula have been studied. This is a region in which the Subtropical Convergence (STC), a major oceanic front separating subtropical and subantarctic waters, is uniquely located close to land, permitting an examination of the influence of terrestrial sources of Fe and Cu on oceanic waters containing excess micronutrients. Acid-soluble (110 nmol kg⁻¹) and dissolved (6.3 nmol kg⁻¹) Fe concentrations were highest over the central shelf, and decreased rapidly across the mixing zone of the STC to about 5 nmol kg⁻¹ for both forms. The distribution of acid-soluble and dissolved Cu were similar to their counterparts for Fe. Depth-concentration profiles for acid-soluble Fe and Cu suggest resuspension of shelf sediments is the main source. The ratio of oxine-labile to acid-soluble Fe varied from 0.03 to 0.26, with the highest values found in the near surface waters. Oxine-labile Fe and Cu also decreased in concentration in a seawards direction, and with depth, indicating the influence of near surface processes on the reactivity of these elements. Cd concentrations across the continental shelf were very low (<200 pmol kg⁻¹) and exhibited no clear spatial trend and no correlation with phosphate. Comparison of the Cd/P ratio across the shelf indicated that the waters in this region were strongly depleted in Cd relative to P. Phosphate concentrations were lowest in neritic water and increased in the seawards direction because of mixing with nutrient-rich Subantarctic Surface Water.     

Cd, Pb, Cu, Ni and Co distribution in the German Bight

Cd, Pb and Cu concentrations, dissolved and total, have been determined in the German Bight. In 1975, 1977, 1978, 1980 and 1983 water samples were collected at 215 sampling stations. In the 1983 mission samples were also analysed for Ni and Co. The samples were filtered and acidified immediately after collection. Analysis was performed by voltammetry.The analytical data indicate that a net portion of the Cd, the Weser being a distinct source for it, will cross the estuarine zone. Open sea Cd levels in the German Bight are about a factor 10 higher than North Atlantic values. Pb, being transported mainly with the suspended particulate phase (up to 99.5%), is better eliminated by sedimentation in the estuaries. Ni and Cu occur mainly in the dissolved phase. Pollution by Co is distinct in the Elbe, but the output is rapidly diluted to background contents below 10 ng kg⁻¹. An interpretation of the results from the different years yields a rather steady state situation in the German Bight.     

Polycyclic Aromatic Hydrocarbons in the Arctic: Ob and Yenisei Estuaries and Kara Sea Shelf

Suspended matter (SM) and surface sediments were analysed for polycyclic aromatic hydrocarbons (PAH) throughout the Ob and Yenisei River estuaries and in the Kara Sea in order to evaluate the contamination of Arctic shelves by these two major Siberian rivers. PAH concentrations were extremely low, among the lowest measured up to now in the Arctic region. Particle-associated PAH were in many cases non-detectable. A total PAH maximum value of 3·2ngl ^{− 1}was found in surface waters. In surficial sediments, they spanned a range from 24 to 115ngg ^{− 2}in the Ob River, from 40 to 131ngg ^{− 2}in the Yenisei and from 16 to 94ngg ^{− 2}in the Kara Sea. Compositional features revealed a contribution of detrital material eroded from soils of the drainage basins and inputs from airborne pyrolytic PAH emitted at lower latitudes and from industrial complexes in Siberia. Particulate and sedimentary PAH distributions were highly variable both in type and concentration. The Ob and Yenisei estuaries are geographically large features where hydro-dynamical and sedimentary processes are complex. As a consequence, inhomogeneities—in the form of patch-structures—develop and make it difficult to resolve the fate of riverborne constituents based on ship measurements only. Remote sensing in conjunction with oceanographic observations may provide further guidance to study large river systems.     

A comparative study of mercury contamination in the Tagus estuary (Portugal) and major French estuaries (Gironde,Loire, Rhône)

Concentrations of mercury were determined for the waters, suspended matter and sediments of the Tagus and of major French estuaries.The Tagus estuary is one of the most contaminated by mercury derived from the outfalls of a chloralkali plant and from other industrial sources. In deposited sediments the median level, 1·0 μg Hg g^?1, is twenty times higher than the natural background and Hg contents depend on the sediment grain-size, age and the distance from waste-outfalls. Suspended matter is more regularly and highly contaminated (median value: 4·5 μg Hg g^?1). In the French estuaries Hg levels in the suspended material decrease with salinity due to dilution and/or remobilization processes. In June 1982, in the Loire estuary, high values of Hg are observed in the middle estuary and attributed to urban and industrial sources.In the Tagus estuary, the general distribution of total dissolved Hg confirms the contamination: it increases seaward from 10 ng 1^?1 in the river to 80 ng 1^?1 in the estuary outlet. The dissolved Hg is almost totally organic in the river, inorganic in the middle estuary due to inorganic Hg effluents and again organic in the lower estuary. This variation is related to the dissolved organic carbon values. The dissolved Hg levels in the Loire Estuary (5–300 ng 1^?1) are much higher than in the Gironde estuary (3–6 ng 1^?1) and of the same order as those observed in the Tagus estuary.     

The barnacle Balanus amphitrite as a biomonitor for Cd: Radiolabelled experiments

Radiolabelled experiments were carried out to measure necessary parameters in the development of a biodynamic ecotoxicological simulation model of Cd accumulation in the barnacle biomonitor Balanus amphitrite. The Cd uptake rate constant from the dissolved phase, the Cd assimilation efficiency (AE) from suspended particulate matter (SPM) and the efflux rate constant were obtained using ¹⁰⁹Cd. A Cd uptake rate constant from the dissolved phase (k_u) of 0.0072 L g⁻¹ h⁻¹ was determined for the barnacle under environmentally realistic dissolved Cd concentrations (maximum of 400 ng L⁻¹). Cd AE from SPM was determined from the barnacle feeding on SPM with low and high chl a concentrations, resulting in AEs of 39.0% and 48.7%, respectively, and an efflux rate of 0.0072 d⁻¹. The difference between the AEs resulted from differences in chl a:SPM ratios suggesting a general tendency of higher AE when SPM is enriched with chl a. These results reinforce that the accuracy of ecotoxicological models for metal accumulation in organisms depends on how representative the selected food items are of the organism’s natural diet.     

Butyltins in marine waters of The Netherlands in 1988 and 1989; Concentrations and effects

Specific effects of tributyltin (TBT) on Crassostrea gigas—valve thickening, and Nucella lapillus—imposex, were measured on local populations, relatively clean unaffected species from England were transferred to the Netherlands and exposed during six weeks to ambient TBT concentrations. Near marinas 50% of the exposed species were sterile after six weeks. In general, no dissolved butyltins were detected in the Rhine and Scheldt estuaries. In 1988 TBT concentrations in marinas ranged from 120 to 4000 ng litre⁻¹. In sediments (fraction <60 μm) and suspended particulate matter TBT concentrations reached up to 1200 ng g⁻¹. TBT concentrations in mussel tissue ranged from <1 to 2300 ng g⁻¹ based on a dry weight. In 1989 concentrations of dissolved TBT ranged from <0·1 to 7200 ng litre⁻¹. In 1989 a seasonal study in the marina of Colijnsplaat showed that dissolved butyltins increased from April to the end of May due to the launching of freshly painted boats, and decreased afterwards.     

Ten-year observation of the Gironde tributary fluvial system: fluxes of suspended matter, particulate organic carbon and cadmium

A program of long-term observation of suspended solids (TSS), particulate organic carbon (POC) and cadmium transported into the Gironde estuary (France) by its major tributaries has been carried out between 1990 and 1999. This decade included contrasting hydrologic cycles and appears representative of a much longer period (1959–1999). The Garonne and the Dordogne river systems are the main tributaries of the Gironde estuary and derive their waters from drainage basins with different geological, industrial and agricultural features. To better understand their respective contributions, they have been observed separately and compared. Water and TSS fluxes of the Garonne River show greater temporal variations and discharge is more related to the hydrology of the drainage basin (e.g. wet/dry years, local flood events etc.). As POC and particulate Cd concentrations in suspended matter are much less variable than turbidity, their fluxes are mainly controlled by the TSS transport. A major part of annual fluxes of TSS and associated pollutants may occur within few flood days (depending on various parameters, e.g. intensity, duration, season, etc.), and also the succession of dry and wet years has an important influence on annual fluxes. The presented data allow calculating fluvial inputs into the Gironde as the sum of fluxes transported by its major tributaries, the Garonne and the Dordogne river systems. Mean annual fluxes into the Gironde observed in 1990–1999 are about 34×10⁹ m³ year⁻¹ for river water, 3.24×10⁶ t year⁻¹ for suspended solids (TSS) and 9.88×10⁹ mol year⁻¹ for particulate organic carbon (POC). Generally, these fluxes are dominated by the contributions of the Garonne River. However, in dry years, the mean contribution of the Dordogne river system (including Dronne and Isle rivers) to the POC input into the estuary exceeded that of the Garonne. This reflects significant differences in vegetation and soil due to natural properties and land management of the basins. Mean Cd fluxes into the estuary are about 110×10³ mol year⁻¹ of which 19.6×10³ mol year⁻¹ are transported in the dissolved and 90.8×10³ mol year⁻¹ in the particulate phases, respectively. In 1991 (dry year), the net (dissolved) Cd flux towards the ocean exceeded the gross fluvial input of total Cd, suggesting the release of Cd from an important stock in the maximum turbidity zone (MTZ) or the fluid mud of the Gironde estuary.     

The behaviour of dissolved Cd, Co, Zn, and Pb in North Atlantic near-surface waters (30°N/60°W–60°N/2°W)

In September 1993 (M26) and June/July 1996 (M36), a total of 239 surface samples (7 m depth) were collected on two transects across the open Atlantic Ocean (224 samples) and northwest European shelf edge area. We present an overview of the horizontal variability of dissolved Cd, Co, Zn, and Pb in between the northwest and northeast Atlantic Ocean in relation to salinity and the nutrients. Our data show a preferential incorporation of Cd relative to P in the particulate material of the surface ocean when related to previously published parallel measurements on suspended particulate matter from the same cruise. There is a good agreement with results recently estimated from a model by Elderfield and Rickaby (Nature 405 (2000) 305), who predict for the North Atlantic Ocean a best fit for α_Cd/P=[Cd/P]_POM/[Cd/P]_SW of 2.5, whereas the approach of our transect shows a α_Cd/P value of 2.6. The Co concentrations of our transects varied from <5 to 131 pmol kg⁻¹, with the lowest values in the subtropical gyre. There were pronounced elevations in the low-salinity ranges of the northwest Atlantic and towards the European shelf. The Co data are decoupled from the Mn distribution and support the hypothesis of marginal inputs as the dominant source. Zinc varied from a minimum of <0.07 nmol kg⁻¹ to a maximum of 1.2 and 4.8 nmol kg⁻¹ in regions influenced by Labrador shelf or European coastal waters, respectively. In subtropical and northeast Atlantic waters, the average Zn concentration was 0.16 nmol kg⁻¹. Zinc concentrations at nearly three quarters of the stations between 40°N and 60°N were <0.1 nmol kg⁻¹. This suggests that biological factors control Zn concentrations in large areas of the North Atlantic surface waters. The Pb data indicated that significant differences in concentration between the northwest and northeast Atlantic surface waters presently (1996) do not exist for this metal. The transects in 1993 and 1996 exhibited Pb concentrations in the northeast Atlantic surface waters of 30 to 40 pmol kg⁻¹, about a fifth to a quarter of the concentrations observed in 1981. This decline is supported by our particle flux measurements in deep waters of the same region.     

The distribution and δC of dissolved organic carbon and its humic fraction in estuaries of southeastern USA

In this study, we examine the distribution and carbon stable isotope signature of dissolved organic carbon (DOC) and humic substances (HS) along a salinity gradient in the Altamaha and Satilla River estuaries. The maximum DOC concentrations in the Altamaha and Satilla were 10 and 29 mg C l⁻¹, respectively, though concentrations were similar at the mouth of both estuaries. There was a decrease in HS content of DOC from 50 to 80% at the head of the estuaries to 10% at salinities higher than 30‰. The δ¹³C DOC varied between −25.5 and −19‰ and between −27 and −21‰ in the Altamaha and Satilla estuaries, respectively. The tendency towards more depleted δ¹³C DOC in the Satilla, especially in the lower salinity portion of this estuary, suggests greater terrestrial inputs in the Satilla than in the Altamaha. Seasonal fluctuations were observed in the form of increased (two to three times) range in DOC concentration, heavier δ¹³C DOC and increased proportion of estuarine–marine-derived DOC (average enrichment of δ¹³C DOC from +1 to +2) during low river flow (July–October). The δ¹³C HS in both rivers showed a similar trend, but was consistently more depleted than DOC, with an average range from −28 to −24.5‰. This suggests that HS have larger proportions of terrestrial components (a maximum of >60% at the mouth of the estuary) than DOC. The less depleted δ¹³C values of DOC in comparison with HS indicate a different source for the non-humic (non-HS) component of DOC (range in δ¹³C non-HS, −22 to −16‰). That source could either be the decomposition of detrital material derived from saltmarsh environments or microalgal-derived DOC of estuarine or marine origins.     

Natural organics as fluorescent tracers of river-sea mixing

The use of dissolved organic matter fluorescence as a tracer of river-sea mixing was examined in two South Carolina estuaries. Fluorescence declined linearly with seawater dilution in laboratory mixing studies, and also behaved conservatively in an estuary where a single river emptied into a bay. Fluorescence-salinity relationships were also studied in another estuary where a piedmont river (high suspended sediment, low fluorescence) and a coastal plains river (low sediment, high fluorescence) mixed with ocean water. The factor of 2 or greater difference in fluorescence between the two rivers allowed their relative contribution to the estuarine water mass to be distinguished. Petroleum hydrocarbons, measured in estuarine water at 0·7-1·8 μg l⁻¹ concentrations, contributed negligibly to water fluorescence.     

Trace metal fronts in Scottish coastal waters

Dissolved cadmium and copper concentrations have been determined in 76 surface water samples in coastal and ocean waters around Scotland by anodic stripping voltammetry (ASV). A trace metal/salinity ‘front’ is observed to the west, north and north-east of Scotland separating high salinity ocean water (>35 × 10⁻³) with low concentrations of dissolved Cd and Cu from lower salinity (<35 × 10⁻³) coastal water containing higher concentrations of Cd and Cu. Mean Cd concentrations in ocean and coastal waters are 7 ng dm⁻³ (0·06 n ) and 11 ng dm⁻³ (0·10 n ) respectively; for Cu the respective levels are 60 ng dm⁻³ (0·95 n ) and 170 ng dm⁻³ (2·68 n ). The observed distribution is attributed principally to freshwater runoff and the advection of contaminated Irish Sea water into the study area.     

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.     

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.     

Profiles of dissolved and acid-leachable selenium in a sediment core from the lower St. Lawrence estuary

Concentrations of Se in the pore-water and in the solid phase, and the concentrations of other diagenetic constituents (Fe, Mn, phosphate, ammonium and I) in pore-water, were determined in a sediment core from a 350-m deep station in the lower St. Lawrence Estuary. The concentration of dissolved Se in pore-water was 2.1 nmol kg⁻¹ at the surface of the core, increasing to a maximum of 7.6 nmol kg⁻¹ at a depth of 12 cm, and thereafter decreasing gradually with depth. This profile is similar to the profiles of Fe and phosphate, whose concentration maxima occur around 10 cm. The concentration of total sedimentary Se remained almost constant with depth (≈ 0.75 mg kg⁻¹); however, a significant enrichment of oxalate-leachable Se was observed in the top 2 cm. The sedimentary cycling of Se appears to be closely related to that of Fe: adsorption of Se onto Fe oxyhydroxide at or near the sediment-water interface, release of the adsorbed Se by the reduction of Fe oxyhydroxide, and removal by formation of ferroselite (FeSe₂) at depth. The pore-water flux of Se was estimated by two different methods, firstly from the pore-water gradient, and secondly by applying a box model to the oxalate-leachable solid-phase Se data. The methods agree well both giving values for the flux of 0.11 nmol cm⁻² year⁻¹. This agreement suggests that the loss of labile Se in the sediment is balanced by the upward flux of dissolved Se.     

Geochemical studies in the Godavari estuary, India

The dissolved O₂, Fe, dissolved organic carbon (DOC), particulate organic carbon (POC), silica and U isotope measurements in river-estuarine waters of the Godavari and the concentrations of 23 elements in the suspended matter of the waters are reported.The DOC and Fe concentrations are lower compared with those in other estuaries of the world and are below the average value reported for world rivers. Silicon behaves non-conservatively; its depletion which is most likely due to biological activity during the non-monsoon periods of sampling ranges from 25 to 37%. The U isotopes behave conservatively although there is some scatter in the low-chlorinity (≤ 2 gCl 1⁻¹) region. Based on the data collected during non-monsoon seasons, the annual U input from Godavari to the Bay of Bengal is estimated to be ≈ 52 tons, although this has to be considered an approximate value owing to the absence of data during the monsoon period.The suspended matter concentrations, ranging from 4.2 to 7.9 mg l⁻¹, are one to two orders of magnitude lower than those of the main rivers on the west coast of India. Of the elemental concentrations and metal/Su ratios reported, Ag, Ai, Ba, Br, Ca and Zn show a large degree of scatter which has yet to be explained. Others, notably, rare earth elements (REE) show a near-constancy to slightly decreasing trend with increasing chlorinity above the ≈ 2 gCll⁻¹ region.     

Copper in the resurrection fjord, Alaska

Copper concentrations have been measured in more than 200 samples collected from an Alaskan fjord and continental shelf and slope regions in the northwestern Gulf of Alaska. Concentrations were lowest (2·1 nmol kg⁻¹) at depths of 400–1000 m in the continental slope waters of the Gulf of Alaska. Copper increased systematically with decreasing salinities shoreward to concentrations >30 nmol kg⁻¹ in fjord surface waters during summer months of high freshwater runoff. Copper concentrations increased with depth at an inner fjord station where deep basin waters have restricted circulation, and these data together with surface (<5 cm) pore water copper concentrations (mean=122 nmol kg⁻¹) about an order of magnitude higher than bottom water copper concentrations are indicative of a flux of copper across the sediment-seawater interface. This latter was estimated at 32±12 nmol cm⁻² annually, and represented less than 20% of the annual input to fjord surface water (228–411 nmol cm⁻²) added during summer months. Mass balances in bottom waters indicate a vigorous recycling of copper with a residence time estimated at 21±11 days. Most copper that is remobilized in surface sediments is returned to bottom waters and little (3%) is removed by subsequent diagenetic reaction in the buried sediments. However, an estimate of copper accumulating in anoxic fjord sediments was comparable with copper added to fjord surface waters suggesting that input-removal reactions rather than internal cycling controls copper geochemistry in this estuary.     

Silver in Tokyo Bay estuarine waters and Japanese rivers

Dissolved and particulate concentrations of silver in Tokyo Bay estuarine waters and Japanese rivers were determined in this study. The dissolved silver concentrations in the surface water of Tokyo Bay range from 5.9 to 15.1 pmol kg⁻¹, which is comparable to those in the surface water of the Japan Sea, but two or three times higher than those in the surface water of the open ocean. However, elevated concentrations of dissolved silver are not found in Tokyo Bay compared with those in other highly urbanized estuaries, such as San Francisco Bay (20∼243 pmol kg⁻¹). In the Tokyo Bay estuary, silver typically exhibits non-conservative mixing behavior, which is a common feature in the other estuaries reported previously. Dissolved silver concentrations decrease with salinity from the rivers to the mouth of Tokyo Bay. Silver is efficiently scavenged by suspended particulates, as evidenced by the high conditional distribution coefficients for silver throughout the estuary (log K_d > 5.0 ± 0.6). The silver fluxes into Tokyo Bay via inflowing rivers and atmospheric deposition were estimated as 83 kg y⁻¹ and 15 kg y⁻¹, respectively. A simple budget calculation shows that the silver supplied from rivers and atmosphere must be rapidly scavenged within the Tokyo Bay estuary.     

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.     

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

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

Seasonal variations in river discharge and nutrient export to a Northeastern Pacific estuary

Seasonal variations in dissolved nitrogen and silica loadings were related to seasonal variability in river discharge. Dissolved nutrient concentrations measured weekly at three stations in the Yaquina River, Oregon from 1999 through 2001, and then monthly in 2002 were used as the basis for developing a nutrient loading regression as part of a larger agency program for evaluating nutrient processes. Because realistic models of nutrient transport require dense data sets to capture both long and short term fluctuations in nutrient concentrations, data at one freshwater station also were collected hourly for the same years using an in-stream monitor.The effects of storm events on dissolved nutrient transport were examined during three storms, including one in a high rainfall-discharge year, and two in average years, one of which followed a drought year. During the drought year (WY2001), total dissolved nitrate input was considerably less than in wetter years. Dissolved nitrate concentrations, however, were unusually high in the first winter storm runoff after the drought. The freshwater dissolved nitrate nitrogen loads varied from 40,380 kg day⁻¹ during a high-flow storm event to 0.11 kg day⁻¹ during late summer, low flow conditions. Dissolved silica dynamics differed from those of nitrate because during storm events, silica concentrations in the Yaquina River decreased to near zero at the storm height, probably due to dilution by near surface or overland flow, and later recovered.During the time interval studied, over 94% of the dissolved nitrate and silica were transported from the watershed during the winter months of greater rainfall, indicating that seasonality and river flow are primary factors when considering nutrient loadings from this watershed system.