Photochemical production of molecular hydrogen in lake water and coastal seawater   总被引：1，自引：0，他引：1  

Stephen Punshon  Robert M. Moore 《Marine Chemistry》2008,108(3-4):215-220

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

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

A.L. Hougham  S.B. Moran  J.P. Masterson  R.P. Kelly 《Marine Chemistry》2008,109(3-4):268

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

Seasonal and daily variation of mercury evasion at coastal and off shore sites from the Mediterranean Sea   总被引：3，自引：0，他引：3  

Maria E. Andersson  Katarina Grdfeldt  Ingvar Wngberg  Francesca Sprovieri  Nicola Pirrone  Oliver Lindqvist 《Marine Chemistry》2007,104(3-4):214-226

Dissolved gaseous mercury (DGM) was measured continuously using two newly developed techniques and a manual technique. The continuous techniques were based on the equilibrium between the aqueous and gaseous phase (DGM = Hg_extr / H', Hg_extr is the measured mercury concentration in the gas phase, H' is the Henry's Law coefficient at the desired temperature). In order to calculate the annual mercury evasion from the Mediterranean Sea, diurnal and seasonal measurements of DGM, total gaseous mercury in air (TGM), water temperature and wind speed were performed. During August 2003, March–April 2004 and October–November 2004 measurements of these parameters were conducted on board the RV Urania. The continuous measurements of DGM showed a diurnal variation in concentration, at both coastal and off shore sites, with higher concentrations during daytime than nighttime. The concentration difference could be as large as 130 fM between day and night. The degree of saturation was calculated directly from the measurements, S = Hg_extr / TGM and was found to vary between the different seasons. The highest average degree of saturation (850%) and the largest variation in saturation (600–1150%) was observed during the summer. The spring showed the lowest variation (260–360%) and the lowest average degree of saturation (320%). The autumn also showed a large variation in saturation (500–1070%) but a lower average (740%) compared to the summer cruise. This might be explained by the temperature difference between the different seasons, since that parameter varied the most. The flux from the sea surface was calculated using the gas exchange model developed by Nightingale et al. [Nightingale, P.D., Malin, G., Law, C.S., Watson, A.J., Liss, P.S., Liddicoat, M.I., Boutin, J., Upstill-Goddard, R. C., 2000. In situ evaluation of air–sea gas exchange parameterization using novel conservative and volatile tracers. Global Biogeochemical Cycles, 14(1):373–387]. The evasion varied between the different seasons with the highest evasion during the autumn, 24.6 pmol m^− 2 h^− 1. The summer value was estimated to 22.3 pmol m^− 2 h^− 1 and the spring to 7.6 pmol m^− 2 h^− 1. Using this data the yearly evasion from the Mediterranean Sea surface was estimated to 77 tons.  相似文献   

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

A.L. Hougham  S.B. Moran 《Marine Chemistry》2007,105(3-4):194-207

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).  相似文献   

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

F.J.G. Laurier  D. Cossa  C. Beucher  E. Brvire 《Marine Chemistry》2007,104(3-4):143-155

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.  相似文献   

The relationship between volatile halocarbons and phytoplankton pigments during a Trichodesmium bloom in the coastal eastern Arabian Sea     

Rajdeep Roy  Anil PratiharyGayatree Narvenkar  Sunita MochemadkarMangesh Gauns  S.W.A. Naqvi 《Estuarine, Coastal and Shelf Science》2011

Eukaryotic phytoplankton such as diatoms and prymnesiophytes produce biogenic halocarbons in the ocean that serve as important sources of chlorine and bromine to the atmosphere, but the role of cyanobacteria in halocarbon production is not well established. We studied distributions of chloroform (CHCl₃), carbon tetrachloride (CCl₄), methylene bromide (CH₂Br₂) and bromoform (CHBr₃) in relation to phytoplankton composition, determined from pigment analysis complemented by microscopic examination, for one month in coastal waters of the eastern Arabian that experienced a Trichodesmium bloom that typically occurs during the Spring Intermonsoon season. High concentrations of zeaxanthin (23 μg l⁻¹), alpha beta betacarotene (6 μg l⁻¹) and chlorophyll a (67 μg l⁻¹) were found within the bloom whereas the marker pigment concentrations were low outside the bloom. CHCl₃ and CCl₄ occurred in relatively high concentrations in surface waters whereas CH₂Br₂ and CHBr₃ were restricted to the subsurface layer. Chlorinated halocarbons were positively inter-correlated and with CHBr₃. The observed spatial and temporal trends in brominated compounds appear to be related to the abundance of Trichodesmium although correlations between concentrations of brominated compounds with various marker pigments were poor and statistically non-significant. The results support the existence of multiple sources and sinks of halogenated compounds, which might obscure the relationship between halocarbons and phytoplankton composition.  相似文献   

Rapid sediment accumulation and microbial mineralization in forests of the mangrove Kandelia candel in the Jiulongjiang Estuary, China   总被引：2，自引：0，他引：2  

D.M. Alongi  J. Pfitzner  L.A. Trott  F. Tirendi  P. Dixon  D.W. Klumpp 《Estuarine, Coastal and Shelf Science》2005,63(4):605-618

Rates of sediment accumulation and microbial mineralization were examined at three Kandelia candel forests spanning the intertidal zone along the south coastline of the heavily urbanized Jiulongljiang Estuary, Fujian Province, China. Mass sediment accumulation rates were rapid (range: 10–62 kg m⁻² y⁻¹) but decreased from the low- to the high-intertidal zone. High levels of radionuclides suggest that these sediments originate from erosion of agricultural soils within the catchment. Mineralization of sediment carbon and nitrogen was correspondingly rapid, with total rate of mineralization ranging from 135 to 191 mol C m⁻² y⁻¹ and 9 to 11 mol N m⁻² y⁻¹; rates were faster in summer than in autumn/winter. Rates of mineralization efficiency (70–93% for C; 69–92% for N) increased, as burial efficiency (7–30% for C; 8–31% for N) decreased, from the low-to the high-intertidal mangroves. Sulphate reduction was the dominant metabolic pathway to a depth of 1 m, with rates (19–281 mmol S m⁻² d⁻¹) exceeding those measured in other intertidal deposits. There is some evidence that Fe and Mn reduction-oxidation cycles are coupled to the activities of live roots within the 0–40 cm depth horizon. Oxic respiration accounted for 5–12% of total carbon mineralization. Methane flux was slow and highly variable when detectable (range: 5–66 μmol CH₄ m⁻² d⁻¹). Nitrous oxide flux was also highly variable, but within the range (1.6–106.5 μmol N₂O m⁻² d⁻¹) measured in other intertidal sediments. Rates of denitrification were rapid, ranging from 1106 to 3780 μmol N₂ m⁻² d⁻¹, and equating to 11–20% of total sediment nitrogen inputs. Denitrification was supported by rapid NH₄ release within surface deposits (range: 3.6–6.1 mmol m⁻² d⁻¹). Our results support the notion that mangrove forests are net accumulation sites for sediment and associated elements within estuaries, especially Kandelia candel forests receiving significant inputs as a direct result of intense human activity along the south China coast.  相似文献   

Copper complexing ligands and organic matter characterization in the northern Adriatic Sea     

Marta Plav&#x;i&#x;  Blaenka Ga&#x;parovi&#x;  Sla&#x;ana Strme ki  Vjero ka Vojvodi&#x;  Nata&#x;a Tepi&#x; 《Estuarine, Coastal and Shelf Science》2009,85(2):299-306

The study on dissolved organic ligands capable to complex copper ions (L_T), surface-active substances (SAS) and dissolved organic carbon (DOC) in the Northern Adriatic Sea station (ST 101) under the influence of Po River was conducted in period from 2006–2008. The acidity of surface-active organic material (Ac_r) was followed as well. The results are compared to temperature and salinity distributions. On that way, the contribution of the different pools of ligands capable to complex Cu ions could be determined as well as the influence of aging and transformation of the organic matter. The L_T values in the investigated period were in the range of 40–300 nmol l⁻¹. The range of DOC values for surface and bottom samples were 0.84–1.87 mg l⁻¹ and 0.80–1.30 mg l⁻¹, respectively. Total SAS concentrations in the bottom layer were 0.045–0.098 mg l⁻¹ in equiv. of Triton-X-100 while those in the surface layer were 0.050–0.143 mg l⁻¹ in equiv. of Triton-X-100. The majority of organic ligands responsible for Cu binding in surface water originate from new phytoplankton production promoted by river borne nutrients. Older, transformed organic matter, possessing higher relative acidity, is the main contributor to the pool of organic ligands that bind copper in the bottom samples. It was estimated that 9% of DOC in surface samples and 12% of DOC in the bottom samples are present as ligands capable to complex copper ions.  相似文献   

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

Abdirahman M. Omar  Truls Johannessen  Are Olsen  Staffan Kaltin  Francisco Rey 《Marine Chemistry》2007,104(3-4):203-213

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

Carbon disulfide in the estuarine, coastal, and oceanic environments     

Ki-Hyun Kim  M. O. Andreae 《Marine Chemistry》1992,40(3-4)

The concentration of carbon disulfide (CS₂) in surface water and relevant hydrographic parameters were determined in coastal waters of the eastern USA (Delaware Bay and Chesapeake Bay, including the Potomac River; 7–11 September 1986). The CS₂ concentration varied extensively along the cruise track, from 4 to 510 pmol S(CS₂) l⁻¹ (n = 103). The average values in estuarine, shelf, and oceanic waters were found to be 118 ± 100 pmol S(CS₂) l⁻¹ (n = 54), 51 ± 34 pmol S(CS₂) l⁻¹ (n = 14), and 28 ± 12 pmol S(CS₂) l⁻¹ (n = 35), respectively. To help interpret the geochemical behavior of CS₂, we analyzed the depth distribution of CS₂ in the North Atlantic Ocean during an earlier cruise (23 April–2 May 1986). In most cases, these depth profiles show a near-surface maximum at about 10–20 m depth and a relatively steep gradient below this maximum. Based on the distribution pattern in the water column and evidence provided by earlier workers, we propose that diffusion of CS₂ from bottom sediments may contribute to CS₂ levels in surface seawater. The atmospheric concentration of CS₂ was also investigated at some locations during the September cruise. Except during periods when there was a significant anthropogenic input, the concentration of CS₂ in air was generally in the range of 4–15 pptv (parts per trillion by volume) with a mean of 10.4 ± 4.0 pptv (n = 10). The calculated sea-to-air emission rates of CS₂ at each of our sampling stations show a decreasing trend across estuarine, shelf, and oceanic areas, in agreement with the trend in surface water concentrations.  相似文献   

Biogeochemical transport in the Loxahatchee River estuary, Florida: The role of submarine groundwater discharge   总被引：3，自引：1，他引：2  

Peter W. Swarzenski  William H. Orem  Benjamin F. McPherson  Mark Baskaran  Yongshan Wan 《Marine Chemistry》2006,101(3-4):248-265

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

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

Y.W. Watanabe  H. Yoshinari  A. Sakamoto  Y. Nakano  N. Kasamatsu  T. Midorikawa  T. Ono 《Marine Chemistry》2007,103(3-4):347-358

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.  相似文献   

Submarine groundwater discharge and nutrient addition to the coastal zone and coral reefs of leeward Hawai'i     

Joseph H. Street  Karen L. Knee  Eric E. Grossman  Adina Paytan 《Marine Chemistry》2008,109(3-4):355

Multiple tracers of groundwater input (salinity, Si, ²²³Ra, ²²⁴Ra, and ²²⁶Ra) were used together to determine the magnitude, character (meteoric versus seawater), and nutrient contribution associated with submarine groundwater discharge across the leeward shores of the Hawai'ian Islands Maui, Moloka'i, and Hawai'i. Tracer abundances were elevated in the unconfined coastal aquifer and the nearshore zone, decreasing to low levels offshore, indicative of groundwater discharge (near-fresh, brackish, or saline) at all locations. At several sites, we detected evidence of fresh and saline SGD occurring simultaneously. Conservative estimates of SGD fluxes ranged widely, from 0.02–0.65 m³ m^− 2 d^− 1at the various sites. Groundwater nutrient fluxes of 0.04–40 mmol N m^− 2 d^− 1 and 0.01–1.6 mmol P m^− 2 d^− 1 represent a major source of new nutrients to coastal ecosystems along these coasts. Nutrient additions were typically greatest at locations with a substantial meteoric component in groundwater, but the recirculation of seawater through the aquifer may provide a means of transferring terrestrially-derived nutrients to the coastal zone at several sites.  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   

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   

Improving estuarine net flux estimates for dissolved cadmium export at the annual timescale: Application to the Gironde Estuary     

Aymeric Dabrin  Jrg Schfer  Grard Blanc  Emilie Strady  Matthieu Masson  Ccile Bossy  Sabine Castelle  Naïg Girardot  Alexandra Coynel 《Estuarine, Coastal and Shelf Science》2009,84(4):429-439

Dissolved Cd (Cd_D) concentrations along the salinity gradient were measured in surface water of the Gironde Estuary during 15 cruises (2001–2007), covering a wide range of contrasting situations in terms of hydrology, turbidity and season. During all situations dissolved Cd concentrations displayed maximum values in the mid-salinity range, reflecting Cd addition by chloride-induced desorption and complexation. The daily net Cd_D fluxes from the Gironde Estuary to the coastal ocean were estimated using Boyle's method. Extrapolating Cd_D concentrations in the high salinity range to the freshwater end member using a theoretical dilution line produced 15 theoretical Cd concentrations (Cd_D⁰), each representative of one distinct situation. The obtained Cd_D⁰ concentrations were relatively similar (201 ± 28 ng L⁻¹) when freshwater discharge Q was >500 m³ s⁻¹ (508 ≤ Q ≤ 2600 m³ s⁻¹), but were highly variable (340 ± 80 ng L⁻¹; 247–490 ng L⁻¹) for low discharge situations (169 ≤ Q ≤ 368 m³ s⁻¹). The respective daily Cd_D net fluxes were 5–39 kg day⁻¹, mainly depending on freshwater discharge. As this observation invalidates the existing method of estimating annual Cd_D net fluxes, we proposed an empirical model, using representative Cd_D⁰ values and daily freshwater discharges for the 2001–2007 period. Subsequent integration produced reliable Cd_D net flux estimates for the Gironde Estuary at the annual timescale that ranged between 3.8–5.0 t a⁻¹ in 2005 and 6.0–7.2 t a⁻¹ in 2004, depending on freshwater discharge. Comparing Cd_D net fluxes with the incoming Cd_D fluxes suggested that the annual net Cd_D addition in the Gironde Estuary ranged from 3.5 to 6.7 t a⁻¹, without any clear temporal trend during the past seven years. The annual Cd_D net fluxes did not show a clearly decreasing trend in spite of an overall decrease by a factor 6 in Cd gross fluxes during the past decade. Furthermore, in six years out of seven (except 2003), the annual Cd_D net fluxes even exceeded river borne total (dissolved + particulate) gross Cd fluxes into the estuary. These observations were attributed to progressive Cd desorption from both suspended particles and bottom sediment during various sedimentation–resuspension cycles induced by tidal currents and/or continuous dredging (navigation channel) and diverse intra-estuarine sources (wet deposition, urban sources, and agriculture). Provided that gross fluxes remain stable over time, dissolved Cd exportation from the Gironde Estuary to the coastal ocean may remain at the present level for the coming decade and the estuarine sedimentary Cd stock is forecast to decrease slowly.  相似文献   

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

E. Ortega-Retuerta  I. Reche  E. Pulido-Villena  S. Agustí  C.M. Duarte   《Marine Chemistry》2009,115(1-2):59-65

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

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

Nicholas R. Bates  Andrew J. Peters   《Marine Chemistry》2007,107(4):547-558

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.  相似文献   

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

C. Guguen  P.D. Tortell 《Marine Chemistry》2008,108(3-4):184-194

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