Some chemical characteristics of the brines in Bannock and Tyro Basins: salinity, sulphur compounds, Ca, F, pH, A_t, PO₄, SiO₂, NH₃     

Davide Bregant  Giulio Catalano  Giuseppe Civitarese  Anna Luchetta 《Marine Chemistry》1990,31(1-3)

Results of the chemical investigation on the Bannock and Tyro Basins are reported.Both basins were found to be hypersaline ( 10 times higher than salinity of normal seawater) and anoxic. In all investigated basins a region of transition, a few meters thick, was identified at depths > 3327 dbar. It is characterized by a sharp gradient of salinity, and all concentrations of analysed species increase strongly except for dissolved oxygen and nitrate, which immediately drop to zero. This region appears as a sharp boundary that prevents mixing. As a result, in the presence of organic matter, an anoxic condition developed with the complete depletion of dissolved oxygen. At the same time, hydrogen sulphide and ammonium accumulated within the brine. Between the Bannock and the Tyro brines differences occur in the measured concentrations of H₂S, SO²⁻₄, Ca²⁺ and NH₃. There are some differences also within the Bannock area sub-basins.The Libeccio sub-basin, in the Bannock area, contains a double-layered brine: the upper layer is 140 dbar thick and the lower layer is 300 dbar thick. A second interface between upper and lower brines develops at a depth of 3500 dbar. Nearly all of the measured concentrations vs. depth show the double layer, with the exception of ammonium, the concentration of which remains nearly constant throughout the anoxic column. Profiles of the other species analyzed show remarkable differences on passing from the upper to the lower brine. Hydrogen sulphide, sulphate and fluoride concentrations appear constant and then increase at the second interface. The calcium concentration is also constant in the upper brine, but decreases at the second interface. Total alkalinity and phosphate concentrations show a maximum peak just below the first interface. However, after passing through the second interface all the chemical parameters exhibit an almost constant behaviour down to the bottom.Hypersaline conditions are attributed to the dissolution of Messinian evaporite, and anoxia is suggested to originate from the oxidation of organic matter present in sediments and from the absence of bottom water circulation in such a deep and enclosed environment.The chemical conditions can be summarized as follows: in the Libeccio Basin the values for the species analysed have the ranges: 39–321 psu for ‘salinity’, 8.2−6.5 for pH, 2.7–4.0 mM for total alkalinity, 0.2-0 mM for dissolved oxygen, 0–1669 μM for hydrogen sulphide, 0–198 μM for thiol, 31–99 mM for sulphate, 11–21 mM for calcium, 7–100 μM for fluoride, 0.2–3080 μM for ammonium, 5.8-0 μM for nitrite, 0.2–12 μM for phosphate and 8–130 μM for silicate.  相似文献   

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

Urszula Nowostawska  Jonathan P. Kim  Keith A. Hunter   《Marine Chemistry》2008,110(3-4):205-210

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.  相似文献   

Indication of thiols in black sea deep water     

David Dyrssen  Conny Haraldsson  Stig Westerlund  Kerstin rn 《Marine Chemistry》1985,17(4):323-327

Potentiometric titrations of deep Black Sea water give reasonably precise values of sulphide in the concentration range 30–300 μmol l⁻¹ and a strong indication of thiols in the concentration range 10–30 μmol l⁻¹. Organic analysis of Black Sea water should therefore include the search for compounds containing SH groups. A simple stoichiometric model indicates that sulphur-containing proteins might be the main source of thiols after hydrolysis and deamination. The alkalinity and total sulphide are simply related by A_t = 3287 ± 30 + (3.84 ± 0.10) [H₂ S]_t μmol kg⁻¹. The slope of 3.84 instead of the stoichiometric slope of 2.31 indicates a lack of reduced sulphate in the form of hydrogen sulphide.  相似文献   

On the sulphur chemistry of a super-anoxic fjord, Framvaren, South Norway     

Leif G. Anderson  David Dyrssen  Per O.J. Hall 《Marine Chemistry》1988,23(3-4)

The concentrations of total carbonate (C_t), sulphate, sulphide, thiols and oxygen, the ratio between the stable sulphur isotopes ³⁴S and ³²S in sulphate and sulphide, and the density (used to calculate salinity) were determined on samples from the water column of Framvaren, a superanoxic fjord in southern Norway. From a depth of 18m (the oxic-anoxic boundary) the initial sulphate concentration, ([SO₄]_init), as calculated from salinity, is significantly higher than the sum of the measured sulphur species. This is attributed to a loss of sulphur from the water column. The amount of total carbonate produced, corrected for the initial concentration (C_t - 2.4 Sal/35) is found to be proportional to the amount of sulphate consumed, ([SO₄]_init - [SO₄]), according to the following relation C_t- 2.4 Sal/35 = 1.84 ([SO₄]_init - [SO₄]). Isotopic fractionation caused by bacterial sulphate reduction in the anoxic part of the water column produces sulphide with a δ³⁴S 40‰ lower than the δ³⁴S for sulphate at corresponding depths. The isotopic fractionation also results in δ³⁴S value for the remaining sulphate at depths below 80 m being considerably higher than the mean value for ocean water, which is close to + 20‰. The δ³⁴S values for sulphate at depths between 10 and 50 m were lower than + 20‰ which indicates oxidation of sulphide, which follows upon diffusion of sulphide from deeper parts of the water column and inflow of oxygenated seawater over the sill into the anoxic water of the fjord. A conclusive scenario of the Framvaren sulphur chemistry is presented.  相似文献   

Retention of arsenic and phosphorus in iron-rich concretions of Tagus salt marshes   总被引：1，自引：0，他引：1  

Miguel Caetano  Carlos Vale 《Marine Chemistry》2002,79(3-4)

Iron-rich concretions are frequently found around plant roots in Tagus estuary (Portugal) where radial delivery of O₂ takes place. Salt marsh sediments exhibit cracks that are an additional feature to introduce O₂ and other solutes in the upper sediments. Metal concentrations in salt marsh sediments are clearly above the background levels reflecting the anthropogenic sources from a large city with 2.5 million inhabitants, and several industrial centres. In order to evaluate how both oxidised structures influences the redistribution of redox sensitive elements in salt marsh sediments, concretions were collected from roots of Halimione portucaloides below the oxygenated zone. These tubular cylindrical structures were analysed for Fe, Al, Mn, As, and P along 1-cm radial transect in a millimetre scale from the inner part to the adjacent anoxic sediment. In addition, oxidised cracks were analysed for the same spatial resolution, from the sediment–water interface to anoxic layers (2-cm transept). The parallelism between Fe, As, and P concentrations at this microscale is the most noticeable aspect. Iron and As presented very high concentrations in the 4-mm concretions (3.4 mmol g⁻¹ and 3.1 μmol g⁻¹, respectively) and decreased sharply to the host sediment. Oxygen released from roots oxidise the solid sulphides, and the reduced Fe and As are transported towards the root by both diffusion and pore water flow associated with the root water uptake. Subsequently, Fe(III) precipitates and As is retained by sorption and/or coprecipitation. These elements are also enriched in the first 2-mm of oxidised cracks, but in lower concentrations (50% and 30%, respectively). Manganese concentrations in concretions were low (11.8 μmol g⁻¹), indicating that Fe dominates the sediment chemistry. Phosphorus and iron concentrations in the ascorbate fraction were higher in the oxidising surfaces of concretions (10.7 μmol g⁻¹ and 1.6 mmol g⁻¹, respectively) and of cracks (5.1 μmol g⁻¹ and 0.47 mmol g⁻¹). The parallelism of Fe and As distributions includes not only their similar redox chemistries, but also that to phosphate, including control by coprecipitation of the host iron phases. The mechanisms involved in the mobilisation of As and P are however different, whereas As comes from the oxidation of iron sulphides; dissolved P derives from reduction of ferri-hydroxide phases.  相似文献   

Manganese and iron distributions off central California influenced by upwelling and shelf width   总被引：4，自引：1，他引：4  

Zanna Chase  Kenneth S. Johnson  Virginia A. Elrod  Joshua N. Plant  Steve E. Fitzwater  Lisa Pickell  Carol M. Sakamoto 《Marine Chemistry》2005,95(3-4):235-254

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.  相似文献   

Vertical profiles of nitrous oxide and dissolved oxygen in marine sediments     

Toshihiro Usui  Isao Koike  Norio Ogura   《Marine Chemistry》1998,59(3-4)

The whole core squeezing method was used to simultaneously obtain profiles of nitrous oxide (N₂O), nitrogenous nutrients, and dissolved oxygen in sediments of Koaziro Bay, Japan (coastal water), the East China Sea (marginal sea), and the central Pacific Ocean (open ocean). In the spring of Koaziro Bay, subsurface peaks of interstitial N₂O (0.5–3.5 cm depth) were observed, at which concentrations were higher than in the overlying water. This was also true for nitrate (NO₃⁻) and nitrite (NO₂⁻) profiles, suggesting that the transport of oxic overlying water to the depth through faunal burrows induced in situ N₂O production depending on nitrification. In the summer of Koaziro Bay, sediment concentrations of N₂O, NO₃⁻ and NO₂⁻ were lower than in the overlying water. In most East China Sea sediments, both N₂O and NO₃⁻ decreased sharply in the top 0.5–2 cm oxic layer (oxygen: 15–130 μM), which may have indicated N₂O and NO₃⁻ consumption by denitrification at anoxic microsites. N₂O peaks at subsurface depth (0.5–6.5 cm) implied in situ production of N₂O and/or its supply from the overlying water through faunal burrows. However, the occurrence of the latter process was not confirmed by the profiles of other constituents. In the central Pacific Ocean, the accumulation of N₂O and NO₃⁻ in the sediments likely resulted from nitrification. Nitrous oxide fluxes from the sediments, calculated using its gradient at the sediment–water interface and the molecular diffusion coefficient, were −45 to 6.9 nmolN m⁻² h⁻¹ in Koaziro Bay in the spring, −29 to −21 nmolN m⁻² h⁻¹ in the summer, −46 to 37 nmolN m⁻² h⁻¹ in the East China Sea, 0.17 to 0.23 nmolN m⁻² h⁻¹ in the equatorial Pacific, and <±0.2 nmolN m⁻² h⁻¹ in the subtropical North Pacific, respectively.  相似文献   

Origin of iron and aluminium in large particles (> 53 µm) in the Crozet region, Southern Ocean     

Hlne Planquette  Gary R. Fones  Peter J. Statham  Paul J. Morris 《Marine Chemistry》2009,115(1-2):31-42

Natural iron fertilization processes are occurring around the Crozet Islands (46°26′S–52°18′E), thus relieving the water masses from the normally encountered High Nutrients Low Chlorophyll (HNLC) conditions of the Southern Ocean. During austral summers 2004/2005 and 2005/2006, iron and aluminium concentrations were investigated in large particles (> 53 µm) collected from just below the mixed layer at stations under the influence of island inputs, and also in adjacent HNLC waters. These large particles are anticipated to sink out of the mixed layer, and to reflect the net effects of input and cycling of these elements in the overlying mixed layer. Labile and refractory fractions were determined by a two-stage leaching technique. Data showed that water masses downstream of the islands were enriched in total iron and aluminium (0.25–2.68 nmol L^− 1 and 0.34–3.28 nmol L^− 1 respectively), relative to the southern HNLC control sites (0.15–0.29 nmol L^− 1 for Fe and 0.12–0.29 nmol L^− 1 for Al), with only a small fraction (typically < 1%) being acid leachable in both environments. Particulate iron predominantly derived from the island system represents a significant fraction of the total water column iron inventory and may complement dissolved Fe inputs that help support the high summer productivity around the Crozet islands.  相似文献   

Sulfur and iron speciation in surface sediments along the northwestern margin of the Black Sea   总被引：4，自引：0，他引：4  

Jeroen W. M. Wijsman  Jack J. Middelburg  Peter M. J. Herman  Michael E. Bttcher  Carlo H. R. Heip 《Marine Chemistry》2001,74(4)

The speciation of sedimentary sulfur (pyrite, acid volatile sulfides (AVS), S⁰, H₂S, and sulfate) was analyzed in surface sediments recovered at different water depths from the northwestern margin of the Black Sea. Additionally, dissolved and dithionite-extractable iron were quantified, and the sulfur isotope ratios in pyrite were measured. Sulfur and iron cycling in surface sediments of the northwestern part of the Black Sea is largely influenced by (1) organic matter supply to the sediment, (2) availability of reactive iron compounds and (3) oxygen concentrations in the bottom waters. Biologically active, accumulating sediments just in front of the river deltas were characterized by high AVS contents and a fast depletion of sulfate concentration with depth, most likely due to high sulfate reduction rates (SRR). The δ³⁴S values of pyrite in these sediments were relatively heavy (−8‰ to −21‰ vs. V-CDT). On the central shelf, where benthic mineralization rates are lower, re-oxidation processes may become more important and result in pyrite extremely depleted in δ³⁴S (−39‰ to −46‰ vs. V-CDT). A high variability in δ³⁴S values of pyrite in sediments from the shelf-edge (−6‰ to −46‰ vs. V-CDT) reflects characteristic fluctuations in the oxygen concentrations of bottom waters or varying sediment accumulation rates. During periods of oxic conditions or low sediment accumulation rates, re-oxidation processes became important resulting in low AVS concentrations and light δ³⁴S values. Anoxic conditions in the bottom waters overlying shelf-edge sediments or periods of high accumulation rates are reflected in enhanced AVS contents and heavier sulfur isotope values. The sulfur and iron contents and the light and uniform pyrite isotopic composition (−37‰ to −39‰ vs. V-CDT) of sediments in the permanently anoxic deep sea (1494 m water depth) reflect the formation of pyrite in the upper part of the sulfidic water column and the anoxic surface sediment. The present study demonstrates that pyrite, which is extremely depleted in ³⁴S, can be found in the Black Sea surface sediments that are positioned both above and below the chemocline, despite differences in biogeochemical and microbial controlling factors.  相似文献   

Depth profiles of volatile iodine and bromine-containing halocarbons in coastal Antarctic waters   总被引：1，自引：0，他引：1  

L.J. Carpenter  D.J. Wevill  C.J. Palmer  J. Michels 《Marine Chemistry》2007,103(3-4):227-236

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.  相似文献   

Contents of strontinm-90 and ruthenium-106 in beach and shallow water deposits of noto peninsula     

Yoshikazu Yamamoto  Kikuo Takeda  Shunzo Ueda 《Journal of Oceanography》1976,32(2):83-88

⁹⁰Sr,¹⁰⁶Ru, natural strontium and major elements were studied in 12 samples of beach deposits from Togi, Fukuura and Shiga, and in 26 samples of shallow water sediments from sea off Fukuura, Noto Peninsula, Ishikawa Pref., Japan.The average contents of natural strontium and⁹⁰Sr in the beach deposits were 488 ppm ranging from 247 to 1,550 ppm and 45±9 pCi kg^–1-dry mud ranging from 18 to 72 pCi kg^–1-dry mud, respectively. While the average contents of natural strontium,⁹⁰Sr and¹⁰⁶Ru in the sediments were 234 ppm ranging from 136 to 415 ppm, 22±6 pCi kg^–1-dry sand ranging from 7 to 48 pCi kg^–1-dry sand and 0.6 ±0.2 nCi kg^–1-dry ranging from 0.3 to 1.2 nCi kg^–1-dry, respectively.The average contents of each natural strontium and⁹⁰Sr in the beach deposits were about two times higher than those in the shallow water sediments. But no obvious relation of natural strontium to⁹⁰Sr was found in all the samples. The enrichment of⁹⁰Sr and¹⁰⁸Ru in the beach deposits or tthe sediments were as high as 150320 and of 2,0003,000 compared with average contents of⁹⁰Sr and¹⁰⁶Ru in a liter of surface water from the Japan Sea. It is to be noticed that the average¹⁰⁶Ru to⁹⁰Sr ratio of 27 for the shallow water sediments is much higher than the average of 1.0 for surface sea water of the Japan Sea.As to major elements of the samples, the beach deposits are rich in silicon (Av. 70.89 ±0.92% SiO₂), but poor in iron (Av. 2.99±0.32% Fe₂O₃). Whereas the shallow water sediments are poor in silicon (Av. 52.96±10.33% SiO₂) and rich in iron (Av. 5.50±1.90% Fe₂O₃), calcium (Av. 9.64±9.22% CaO) and magnesium (Av. 2.83±1.58% MgO).  相似文献   

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     

A.C. Fischer  J.J. Kroon  T.G. Verburg  T. Teunissen  H.Th. Wolterbeek 《Marine Chemistry》2007,107(4):533-546

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.  相似文献   

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

Jennifer L. Mercer  Meixun Zhao  Steven M. Colman   《Estuarine, Coastal and Shelf Science》2005,63(4):675-682

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

The Significance of Diagenesis versus Riverine Input in Contributing to the Sediment Geochemical Matrix of Iron and Manganese in an Intertidal Region     

C. A. Thomas  L. I. Bendell-Young 《Estuarine, Coastal and Shelf Science》1999,48(6):635

Summer porewater and spring and summer surficial sediment samples were collected from 26 locations in the intertidal region of the Fraser River estuary. Porewaters were analysed for dissolved iron and manganese (as defined by species <0·2μm in diameter) to assess the contribution of diagenesis to concentrations of iron and manganese oxides at the sediment–water interface. Surficial sediment samples were geochemically characterized as: % organic matter (% LOI); reducible iron (RED Fe, iron oxides) and easily reducible manganese (ER Mn, manganese oxides). Grain size at each site was also determined. The sediment geochemical matrix, as defined by the above four parameters, was highly heterogeneous throughout the intertidal region (three-way ANOVA;P<0·0001). For RED Fe and ER Mn, this heterogeneity could be explained by either diagenetic processes (RED Fe) or by a combination of the proximity of the sample sites to the mouth of the Fraser River estuary plus diagenetic processes (ER Mn). Correlation (Spearman Rank Correlation Test (r_s), of dissolved iron within the subsurface sediments with amounts of RED Fe recovered from the associated surface sediments was highly significant (r_s=0·80, P<0·0001); high concentrations of RED Fe at the sediment–water interface co-occurred with high concentrations of dissolved iron, regardless of the proximity of the sample locations to riverine input. Compared with iron, the relationship between dissolved manganese and ER Mn from surface sediments was lower (r_s=0·58;P<0·0008). Locations most strongly influenced by the Fraser River contained greater concentrations of ER Mn at the sediment–water interface than that which would be expected based on the contribution from diagenesis alone. Sediment grain size and organic matter were also influenced by the proximity to riverine input. Surficial sediment of sites close to the river mouth were comprised primarily of percent silt (2·0μm–50μm) whereas sites not influenced by riverine input were primarily percent sand (grain size >50μm). Concentrations of organic matter declined from the mouth to the foreslope of the estuary. With the exception of RED Fe, temporal variation (May vs July) was insignificant (P>0·05, three-way ANOVA). Concentrations of RED Fe recovered from the surficial sediments were in general greater in the summer vs spring months, although spring and summer values were highly correlated (Pearson Product Moment Correlation Coefficient; PPCC; R=0·89;P<0·0001). As the bioavailability of metals is dependent on sediment geochemistry, availability throughout the intertidal region will also be spatially dependent. This heterogeneity needs to be taken into account in studies addressing the impact of metals on estuarine systems.  相似文献   

Measurement of the redox speciation of iron in seawater by catalytic cathodic stripping voltammetry     

Martha Gledhill  Constant M. G. van den Berg 《Marine Chemistry》1995,50(1-4)

Catalytic cathodic stripping voltammetry (CSV) preceded by adsorptive collection of complexes of 1-nitroso-2-napthol (NN) can be used to determine iron in seawater. It is shown here that iron(II) is effectively masked in the presence of 2,2-dipyridyl (Dp) so that iron(III) is measured selectively. The concentration of iron(II) is then calculated as the difference between the concentrations of reactive iron (Fe_R) in the absence and presence of 2 μM Dp, Fe_R being defined as that which was complexed by 20 μM NN at pH 6.9 in the presence of 1.8 mM H₂O₂ and 5 ppm sodium dodecyl sulphate. A 30 min reaction time was allowed for Dp to react with iron(II) in seawater prior to the determination of reactive iron(III) using the same conditions as used for Fe_R. Detection limits of 0.08 nM, 0.077 nM and 0.12 nM were obtained for Fe_R, iron(III) and iron(II), respectively, using a 60 s deposition time.The method was utilised to determine the redox speciation of iron in the northern North Sea. Concentrations of Fe_R ranged between 0.8 and 3.5 nM with nutrient-like depth profiles. Iron(II) was found to be present at concentrations up to 1.2 nM, the highest concentrations occurring in the upper 20 m of the water column.  相似文献   

Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia)     

Yoann Louis  Cdric Garnier  Vronique Lenoble  Stphane Mounier  Neven Cukrov  Dario Omanovi&#x;  Ivanka Pieta 《Marine Chemistry》2009,114(3-4):110-119

An interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (K_i^equ), total ligands concentration (L_iT) and association/dissociation rate constants (k_i¹,k_i^- 1).A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater–seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K₁^equ: 11.2–13.0, log K₂^equ:8.8–10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter.Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by at-equilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k₁¹:6.1–20 × 10³ (M s)^− 1, k₂¹: 1.3–6.3 × 10³ (M s)^− 1) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h.It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µM_C, i.e. 1 mg_CL^− 1) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM).  相似文献   

Organic geochemistry of sediments from chemosynthetic communities,Gulf of Mexico slope   总被引：5，自引：2，他引：5  

R. Sassen  I. R. MacDonald  A. G. Requejo  N. L. Guinasso Jr.  M. C. Kennicutt II  S. T. Sweet  J. M. Brooks 《Geo-Marine Letters》1994,14(2-3):110-119

We used a research submersible to obtain 33 sediment samples from chemosynthetic communities at 541–650 m water depths in the Green Canyon (GC) area of the Gulf of Mexico slope. Sediment samples from beneath an isolated mat of H₂S-oxidizing bacteria at GC 234 contain oil (mean = 5650 ppm) and C₁–C₅ hydrocarbons (mean = 12,979 ppm) that are altered by bacterial oxidation. Control cores away from the mat contain lower concentrations of oil (mean = 2966 ppm) and C₁–C₅ hydrocarbons (mean = 83.6 ppm). Bacterial oxidation of hydrocarbons depletes O₂ in sediments and triggers bacterial sulfate reduction to produce the H₂S required by the mats. Sediment samples from GC 185 (Bush Hill) contain high concentrations of oil (mean = 24,775 ppm) and C₁–C₅ hydrocarbons (mean = 11,037 ppm) that are altered by bacterial oxidation. Tube worm communities requiring H₂S occur at GC 185 where the sea floor has been greatly modified since the Pleistocene by accumulation of oil, thermogenic gas hydrates, and authigenic carbonate rock. Venting to the water column is suppressed by this sea-floor modification, enhancing bacterial activity in sediments. Sediments from an area with vesicomyid clams (GC 272) contain lower concentrations of oil altered by bacterial oxidation (mean = 1716 ppm) but C₁–C₅ concentrations are high (mean = 28,766 ppm). In contrast to other sampling areas, a sediment associated with the methanotrophic Seep Mytilid I (GC 233) is characterized by low concentration of oil (82 ppm) but biogenic methane (C₁) is present (8829 ppm).  相似文献   

Thermodynamic characterization of the partitioning of iron between soluble and colloidal species in the Atlantic Ocean   总被引：2，自引：1，他引：2  

Jay T. Cullen  Bridget A. Bergquist  James W. Moffett 《Marine Chemistry》2006,98(2-4):295-303

Recent electrochemical measurements have shown that iron (Fe) speciation in seawater is dominated by complexation with strong organic ligands throughout the water column and have provided important thermodynamic information about these compounds. Independent work has shown that iron exists in both soluble and colloidal fractions in the Atlantic Ocean. Here we have combined these approaches in samples collected from a variety of regimes within the Atlantic Ocean. We measured the partitioning of Fe between soluble (< 0.02 μm) and colloidal (0.02 to 0.4 μm) size classes and characterized the concentrations and conditional stability constants of Fe ligands within these size classes. Results suggest that equilibrium partitioning of Fe between soluble and colloidal ligands is partially responsible for the distribution of Fe between soluble and colloidal size classes. However, a significant fraction of the colloidal Fe was inert to ligand exchange as soluble Fe concentrations were generally lower than values predicted by a simple equilibrium partitioning model.In surface waters, strong ligands with conditional stability constants of 10¹³ relative to total inorganic Fe appeared to dominate speciation in both the soluble and colloidal fractions. In deep waters these ligands were absent, and instead we found ligands with stability constants 12–15 fold smaller that were predominantly in the soluble pool. Nevertheless, significant levels of colloidal Fe were found in these samples, which we inferred must be inert to coordination exchange.  相似文献   

Potential source and diagenetic signatures of oceanic dissolved and particulate organic matter as distinguished by lipid biomarker distributions   总被引：1，自引：0，他引：1  

Ai Ning Loh  Elizabeth A. Canuel  James E. Bauer   《Marine Chemistry》2008,112(3-4):189-202

Potential biogenic sources of ultrafiltered dissolved and suspended particulate organic matter (UDOM and POM, respectively) from the Sargasso Sea (SS) and North Central Pacific (NCP) Ocean were investigated using lipid biomarker compounds. Organic carbon (OC) concentrations were ~ 20–40 times greater in UDOM than POM and decreased with depth. However, total OC-normalized lipid concentrations were 2–3 orders of magnitude higher in POM than in UDOM. Particulate total lipids decreased 3–10-fold with depth, compared to 10–20% for dissolved total lipids. Total fatty acids (FA), the most abundant lipids, showed similar patterns as total lipids, comprising ~ 62–88% of the total lipids analyzed in UDOM and ~ 57–84% in POM.FA were dominated by straight-chain saturated compounds followed by monounsaturated, polyunsaturated, and branched FA. Polyunsaturated FA were enriched in POM vs. UDOM and in surface vs. deep waters for both UDOM and POM, likely reflecting the algal origins and greater reactivity of surface-derived materials. In both UDOM and POM, sterols of planktonic origin dominated, including cholest-5-en-3β-ol (C₂₇Δ⁵), 24-methylcholesta-5,24(28)E-dien-3β-ol (C₂₈Δ^5,24(28)) and 24-ethylcholest-5-3β-ol (C₂₉Δ⁵), with varying contributions from cholesta-5,22E-3β-ol (C₂₇Δ^5,22), 24-methylcholesta-5,22E-3β-ol (C₂₈Δ^5,22) and 24-ethylcholesta-5,22E-3β-ol (C₂₉Δ^5,22).Factor analysis of lipid biomarkers showed major differences between the UDOM and POM pools and for each pool as a function of depth, but not between the SS and NCP. While UDOM and POM biomarkers were both dominated by autochthonous sources, differences between the two pools suggest potential effects from some combination of source and diagenetic factors. The lipid biomarker data are further evaluated relative to previous studies of radiocarbon (¹⁴C) and elemental (C:N:P) characteristics of UDOM and POM in the SS and NCP.  相似文献   

Comparison of β-dimethylsulfoniopropionate (DMSP) levels in two mediterranean ecosystems with different trophic levels     

Natacha Jean  Grard Boge  Jean-Louis Jamet  Dominique Jamet 《Marine Chemistry》2006,101(3-4):190-202

β-dimethylsulfoniopropionate (DMSP) and dimethylsulfide (DMS) concentrations were recorded from September 1999 to September 2000 in two geographically close ecosystems, differently affected by eutrophication: the Little Bay of Toulon and the Niel Bay (N.W. Mediterranean Sea, France). Little Bay had higher nutrient levels ([NO₃⁻]_max. = 30.3 μM; [PO₄³⁻]_max. = 0.46 μM) and higher chlorophyll a concentrations ([chl a]_mean = 2.4 μg/L) compared to Niel Bay ([NO₃⁻]_max. = 19.7 μM; [PO₄³⁻]_max. = 0.17 μM; [chl a]_mean = 0.4 μg/L). In the two sites, we measured dissolved (DMSP_d < 0.2 μm) and particulate DMSP (DMSP_p > 0.2 μm) concentrations. The DMSP_p was particularly analysed in the 0.2–5, 5–90 and > 90 μm fractions. In the eutrophicated Little Bay, DMSP_d concentrations showed a clear seasonality with high values from January to March (124–148 nM). The temporal profile of the DMSP_p concentrations was similar, peaking in February–March (38–59 nM). In the less eutrophic Niel Bay, DMSP_p concentrations were much lower (6–9 nM in March–April), whereas DMSP_d concentrations were relatively high (110–92 nM in February–March). DMS concentrations were elevated from the end of the winter to the spring in Little Bay, ranging from 3 nM in October to 134 nM in March. In the less eutrophic Niel Bay, lower DMS levels were observed, generally not exceeding 20 nM. Each particulate fraction (0.2–5; 5–90; > 90 μm) contained less DMSP in Niel Bay than in Little Bay. At both sites, the 5–90 μm fraction made up most of the DMSP_p. This 5–90 μm fraction consisted of microphytoplankton, principally Dinophyceae and Bacillariophyceae. The 5–90 μm biomass calculated from cell biovolumes, was more abundant in Little Bay where the bloom at the end of the winter (165 μg/L in March) occurred at the same time as the DMSP peaks. The estimated DMSP_p to biomass ratio for the 5–90 μm fraction was always higher in Little Bay than in Niel Bay. This suggests that the high DMSP levels recorded in Little Bay were not only due to a large Dinophyceae presence in this ecosystem. Indeed, the peak of DMSP_p to biomass ratio obtained from cell biovolumes (0.23 nmol/μg in March) was consistent with the proliferation of Alexandrium minutum. This Dinophyceae species may account for between 50% (2894 cells/L) and 63% (4914 cells/L) of the total phytoplankton abundance in the Little Bay of Toulon.  相似文献