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1.
Measurements of sub-surface light attenuation (Kd), Secchi depth and suspended particulate material (SPM) were made at 382 locations in transitional, coastal and offshore waters around the United Kingdom (hereafter UK) between August 2004 and December 2005. Data were analysed statistically in relation to a marine water typology characterised by differences in tidal range, mixing and salinity. There was a strong statistically significant linear relationship between SPM and Kd for the full data set. We show that slightly better results are obtained by fitting separate models to data from transitional waters and coastal and offshore waters combined. These linear models were used to predict Kd from SPM. Using a statistic (D) to quantify the error of prediction of Kd from SPM, we found an overall prediction error rate of 23.1%. Statistically significant linear relationships were also evident between the log of Secchi depth and the log of Kd in waters around the UK. Again, statistically significant improvements were obtained by fitting separate models to estuarine and combined coastal/offshore data – however, the prediction error was improved only marginally, from 31.6% to 29.7%. Prediction was poor in transitional waters (D = 39.5%) but relatively good in coastal/offshore waters (D = 26.9%).SPM data were extracted from long term monitoring data sites held by the UK Environment Agency. The appropriate linear models (estuarine or combined coastal/offshore) were applied to the SPM data to obtain representative Kd values from estuarine, coastal and offshore sites. Estuarine waters typically had higher concentrations of SPM (8.2–73.8 mg l−1) compared to coastal waters (3.0–24.1 mg l−1) and offshore waters (9.3 mg l−1). The higher SPM values in estuarine waters corresponded to higher values of Kd (0.8–5.6 m−1). Water types that were identified by large tidal ranges and exposure typically had the highest Kd ranges in both estuarine and coastal waters. In terms of susceptibility to eutrophication, large macrotidal, well mixed estuarine waters, such as the Thames embayment and the Humber estuary were identified at least risk from eutrophic conditions due to light-limiting conditions of the water type.  相似文献   

2.
In April 2001, three instrumented surface drifters were deployed in the Mississippi River plume near the mouth of Southwest Pass. The plume was characterized by strong surface gradients of salinity, temperature, and chromophoric dissolved organic matter fluorescence (FCDOM). The drifters initially headed west and attained peak speeds of 1 m s−1 within 5 h after release. Thereafter, velocity decreased as the triad headed north in the Louisiana Bight. Linear relationships between FCDOM and salinity identified two subsurface sources of high salinity water (salinity >35) underlying the surface plume. The platforms stalled in a surface front about 40 h after deployment, and then slowly drifted south along the eastern perimeter of the plume. Shoreward of the plume front there were patches of low-salinity, high FCDOM ‘patches’ of surface waters that likely originated in the marshes, bayous, and other smaller distributaries of the delta.  相似文献   

3.
The variability and origin of the Coloured Dissolved Organic Matter (CDOM) were studied in the Belgian coastal and adjacent areas including offshore waters and the Scheldt estuary, through the parameters: absorption at 375 nm, aCDOM(375), and the slope of the absorption curve, S. aCDOM(375) varied between 0.20 and 1.31 m−1 and between 0.97 and 4.30 m−1 in the marine area and Scheldt estuary, respectively. S fluctuated between 0.0101 and 0.0203 nm−1 in the marine area and between 0.0167 and 0.0191 nm−1 in the Scheldt estuary. The comparative analysis of aCDOM(375) and S variations evidenced different origins of CDOM in the BCZ. The Scheldt estuarine waters showed decreasing aCDOM(375) values with increasing salinity but constant S value of ∼0.018 nm−1 suggesting a dominant terrestrial origin of CDOM. On the contrary, samples collected in the marine domain showed a narrow range of aCDOM(375) but highly variable S suggesting the additional presence of autochthonous sources of CDOM. This source was evidenced based on the sorting of the marine offshore data according to the stage of the phytoplankton bloom when they were collected. A clear distinction was made between CDOM released during the growth stage characterized by high S (∼0.017 nm−1) and low aCDOM(375) and the decay phase characterized by low S (∼0.013 nm−1) and high aCDOM(375). This observation was supported by CDOM measurements performed on pure phytoplankton cultures which showed increased CDOM release along the wax and wane of the bloom but decreasing S. We concluded that the high variability of the CDOM signature in offshore waters is explained by the local biological production and processing of CDOM.  相似文献   

4.
Chromophoric dissolved organic matter (CDOM) is the major light absorber in the Baltic Sea. In this study, excitation emission matrix (EEM) fluorescence spectra and UV–visible absorption spectra of CDOM are reported as a function of salinity. Samples from different locations and over different seasons were collected during four cruises in 2002 and 2003 in the Baltic Sea in both Pomeranian Bay and the Gulf of Gdansk. Absorption by CDOM decreased with increased distance from the riverine source and reached a relatively stable absorption background in the open sea. Regression analysis showed that fluorescence intensity was linearly related to absorption by CDOM at 375 nm and aCDOM(375) absorption coefficients were inversely related to salinity. Analysis of CDOM-EEM spectra indicated that a change in composition of CDOM occurred along the salinity gradient in the Baltic Sea. Analysis of percent contribution of respective fluorophore groups to the total intensity of EEM spectra indicated that the fluorescence peaks associated with terrestrial humic components of the CDOM and total integrated fluorescence decreased with decreasing CDOM absorption. In contrast, the protein-like fraction of CDOM decreased to a lesser degree than the others. Analysis of the percent contribution of fluorescence peak intensities to the total fluorescence along the salinity gradient showed that the contribution of protein-like fluorophores increased from 2.6% to 5.1% in the high-salinity region of the transect. Fluorescence and absorption changes observed in the Baltic Sea were similar to those observed in similar transects that have been sampled elsewhere, e.g. in European estuaries, Gulf of Mexico, Mid-Atlantic Bight and the Cape Fear River plume in the South Atlantic Bight, although the changes in the Baltic Sea occurred over a much smaller salinity gradient.  相似文献   

5.
We report a study of the attenuation of submarine Photosynthetically Active Radiation (PAR) in relation to the concentrations of Optically Active Constituents (OACs) in a range of water types around the United Kingdom. 408 locations were visited between August 2004 and December 2005. The diffuse attenuation coefficient (Kd) was estimated from profiles of downwelling PAR. Concentrations of Suspended Particulate Matter (SPM) were measured gravimetrically and concentrations of phytoplankton chlorophyll (chl) were measured by fluorometrically. Chromophoric Dissolved Organic Matter (CDOM) was measured either by fluorescence or as its proxy, salinity.  相似文献   

6.
In this study, the CDOM absorption coefficient at 350 nm [aCDOM(350)] and CDOM excitation emission matrix (EEM) fluorescence were used to estimate annual fluxes of dissolved organic carbon (DOC) from the Cape Fear River to Long Bay in the South Atlantic Bight. Water samples were collected during a 3.5 year period, from October 2001 through March 2005, in the vicinity of the Cape Fear River (CFR) outlet and adjacent Onslow Bay (OB). Parallel factor analysis (PARAFAC) of CDOM EEM spectra identified six components: three terrestrial humic-like, one marine humic-like and two protein-like. Empirical relationships were derived from the PARAFAC model between DOC concentration and aCDOM(350), total fluorescence intensity and the intensities of respective EEM components. DOC concentration and CDOM optical parameters were very well correlated and R2 values ranged from 0.77 to 0.90. Regression analyses revealed that the non-absorbing DOC fraction, in DOC concentration estimated from CDOM optical parameters, varied with the qualitative composition of the CDOM. DOC concentration and intensity of the humic-like CDOM components characterized by excitation maxima at longer wavelengths have significantly higher estimated non-absorbing DOC compared to the analogous relationships between DOC and intensity of the humic-like CDOM components characterized by excitation maxima at shorter wavelengths. The relationships between DOC concentration and intensity of one of the protein-like components resulted in significantly reduced non-absorbing DOC fraction in DOC concentration estimation. Results of regression analyses between fluorescence intensities of specific EEM components and CDOM-specific absorption coefficients suggest that the relative proportion of humic-like CDOM components (characterized by excitation maximum at longer wavelengths) and the main protein-like component have the most impact on the values of a?CDOM(350). Based on the relationships between aCDOM(350), Cape Fear River flow, and DOC concentrations, DOC fluxes were estimated for 2002, 2003 and 2004. DOC fluxes varied from 1.5 to 6.2 × 1010 g C yr? 1, depending on river flow.  相似文献   

7.
Light attenuation (Kd) of photosynthetically active radiation (PAR) by chromophoric dissolved organic matter (CDOM), total suspended solids (TSS) and chlorophyll a (Chl a) were measured at nine stations along an estuarine gradient in the Swan River, Western Australia, over 15 months. There were strong spatial gradients associated with the marine-freshwater transition along the 32 km of estuary sampled, as well as seasonal gradients mainly associated with rainfall, 80% of which occurs between May and September. CDOM absorbances at 440 nm reached a maximum of 10.9 m−1 with the freshwater inflow but concentrations of suspended matter remained low throughout the sampling period (1.0–21.0 mg l−1) under the diurnal tides of the estuary. CDOM was the dominant constituent of Kd and a stepwise multiple regression showed that 66% (p < 0.0001) of the variation in Kd can be explained by CDOM and an additional 8% (p < 0.0001) by TSS. As a consequence of this result, analysis into the influence of river discharge rates on CDOM absorbance levels was examined for 2002 using data collected during this study, and for 2000 and 2001 using historical dissolved organic carbon (DOC) and river discharge data. The outcome of this analysis infers that greater river discharge rates result in increased CDOM absorbances in the Swan River estuary.  相似文献   

8.
The direct photooxidation of coloured dissolved organic matter (CDOM) to dissolved inorganic carbon (DIC) may provide a significant sink for organic carbon in the ocean. To calculate the rate of this reaction on a global scale, it is essential to know its quantum yield, or photochemical efficiency. We have determined quantum yield spectra, φ(λ), (moles DIC/mole photons absorbed) for 14 samples of seawater from environments ranging from a turbid, eutrophic bay to the Gulf Stream. The spectra vary among locations, but can be represented quite well by three pooled spectra for zones defined by location and salinity: inshore φ(λ)=e−(6.66+0.0285(λ−290)); coastal φ(λ)=e−(6.36+0.0140(λ−290)); and open ocean φ(λ)=e−(5.53+0.00914(λ−290)). Production efficiency increases offshore, which suggests that the most highly absorbing and quickly faded terrestrial chromophores are not those directly responsible for DIC photoproduction.  相似文献   

9.
Apparent oxygen utilization (AOU), dissolved organic carbon (DOC), coloured dissolved organic matter (CDOM) absorption spectra, and CDOM fluorescence characteristic of aromatic amino acids (excitation/emission 280 nm/320 nm; F(280/320)) and marine-humic like substances (320 nm/410 nm; F(320/410)) were measured in full depth during a cruise in the temperate Eastern North Atlantic (ENA). An optimum multi-parameter (OMP) inverse method was run to calculate water mass proportion-weighted average (archetypal) concentrations of these chemical parameters for all water masses and samples. Archetypal concentrations retain the variability due to water mass mixing and basin scale mineralization from the water mass formation sites to the study area. Conversely, the difference between measured and archetypal concentrations, retain the variability due to dissimilarities in mineralization processes within the study area. Our analysis indicates that DOC supported 26±3% of the AOU in the dark temperate ENA and that basin scale processes occurring at and from the formation area of the water masses explained 63% of the total DOC variability. Our data also suggests that DOC remineralized at the basin scale was of lower molecular weight, and with a lower proportion of fluorescent aromatic amino acids than found within the study area. The relationship between the absorption coefficient at 254 nm (aCDOM(254)) and AOU indicates that aCDOM(254) was consumed during organic matter remineralization in the dark ocean, with 55% of the variability being explained by basin scale processes. The relationships of F(320/410) with AOU and DOC confirmed that marine humic-like substances are produced by microbial degradation processes, at a rate of 6.1±0.9×10−3 mg equivalents of QS mol AOU−1. Our results also indicate that basin-scale remineralization processes account for 85% of the total variability of F(320/410), emphasizing that large scale processes control the formation of humic-like substance in the dark ENA.  相似文献   

10.
The photochemical oxidation of colored, dissolved organic matter (CDOM) is important for carbon cycling in the ocean. This oxidation process produces a number of products, including carbon monoxide (CO). While the photochemical production efficiency of CO (apparent quantum yield, AQY, defined in terms of CDOM absorbance) has been reported to be similar for many water types, a full evaluation of the observed natural variability in CO AQY requires additional study. Here we use a polychromatic irradiation system to determine twenty AQY spectra at sea on fresh samples ranging from the near coastal waters of the Gulf of Maine to the offshore waters of the Northwest Atlantic. Despite the geographic variability of these marine samples the AQY of CO production in the Gulf of Maine and Northwest Atlantic exhibited only a small degree of variability, none of which was not correlated with measured environmental parameters. Consequently, a single aggregate AQY spectrum λ = e(−(9.134+0.0425(λ−290)))+e(−(11.316+0.0142(λ−290))) was found to adequately represent the entire data set. Significantly, the accuracy of an AQY spectrum determined using this multispectral/statistical technique was confirmed with data obtained from a monochromatic irradiation technique on a single open ocean sample. Taken together, the AQY spectra determined in this study were similar in magnitude and shape to those previously published for marine samples and, overall, were somewhat lower than those previously reported for freshwater studies.  相似文献   

11.
河口有色溶解有机物（colored dissolved organic matter,CDOM）的分布是各种物理-生物地球化学过程共同作用的结果。为实现河口高动态变化CDOM的监测，遥感是一种重要的手段。由珠江口四个不同季节的航次获得的实测数据，本文构建了一个遥感算法以反演CDOM在400 nm的吸收系数（aCDOM （400））。该算法使用以波段反射率比值Rrs （667）/Rrs （443）和Rrs （748）/Rrs （412）为自变量。将构建的算法应用于2002-2014年的MODIS/Aqua数据，本文计算了珠江口不同季节的aCDOM （400）气候态分布。CDOM的分布主要受珠江径流量和区域水下地形特征的影响。沿着垂直于水深梯度的断面，气候态aCDOM （400）呈指数减少（y=aebx,b<0），但不同季节差异很大。珠江口CDOM主要是河流淡水输运而来。其中，富里酸比例随盐度的增加而降低。基于构建的算法、CDOM保守混合方程和径流量，本文由MODIS/Aqua数据进一步估算了2002-2014年夏季和冬季珠江DOC的有效入海浓度和有效入海通量。珠江的有效入海浓度和有效入海通量都与流量存在正相关关系，且在夏季的相关性更明显，R2分别为0.698和0.9657。  相似文献   

12.
Dissolved Al carried in river water apparently undergoes a fractional removal at the early stages of mixing in the Conway estuary. On the other hand, dissolved Al behaves almost conservatively in high salinity (>13) estuarine waters. In order to understand the geochemistry of Al in these estuarine waters, simple empirical sorption models have been used. Partitioning of Al occurs between solid and solution phases with a distribution coefficient, Kd, which varies from 0.67 × 105 to 3.38 × 106 ml g−1 for suspended particle concentrations of 2–64 mg l−1. The Kd values in general decrease with increasing suspended particulate matter and this tendency termed the “particle concentration effect” is quite pronounced in these waters. The sorption model derived by previous workers for predicting concentrations of dissolved Al with changing suspended sediment loads has been applied to these data. Reasonable fits are obtained for Kd values of 105, 106 and 107 ml g−1 with various values of α. Further, a sorption model is proposed for particulate Al concentrations in these waters that fits the data extremely well defined by a zone with Kd value 107 ml g−1 and C0 values 16 × 10−6 mg ml−1 and 92 × 10−6 mg ml−1. These observations provide strong evidence of sorption processes as key mechanisms influencing the distribution of dissolved and particulate Al in the Conway estuary and present new insight into Al geochemistry in estuaries.  相似文献   

13.
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 (ku) 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.  相似文献   

14.
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   

15.
This paper assesses the feasibility of applying remote sensing algorithms based on blue/green reflectance ratios to Case 2 waters. Two algorithms from the SeaDAS (NASA) image processing package, OC4v4 for surface chlorophyll concentration, Chl, and K(490) for the attenuation coefficient for downward irradiance at 490 nm, Kd(490), were investigated using an extensive set of observations from the Irish and Celtic Seas. In situ data from a profiling radiometer were used as inputs for the algorithms to avoid uncertainties in atmospheric correction procedures, and direct measurements of Chl and Kd490 and were used for validation purposes. The standard versions of the algorithms performed poorly: OC4v4 generally overestimated Chl (with a very low coefficient of determination), and K(490) progressively underestimated Kd490 for values greater than 0.3 m−1. A two-step procedure for level 2 product generation was therefore devised in which the numerical coefficients of OC4v4 and K(490) were tuned for the two optical water types known to occur most frequently in this region (McKee, D., Cunningham, A., 2006. Identification and characterisation of two optical water types in the Irish Sea from in situ inherent optical properties and seawater constituents. Estuarine, Coastal and Shelf Science 68, 305–316) by statistical regression on a data set of 102 stations from the Irish and Celtic Seas. The water types were distinguished by the magnitude of their normalised water leaving radiance signals at 665 nm, nLw(665), and appropriate versions of the tuned algorithms applied to each water type. When this procedure was tested on an independent data set of 19 stations from the Bristol Channel, Chl values were recovered with an RMS error of 0.36 mg m−3 and Kd(490) values with an RMS error of 0.095 m−1. The identification of water types from water-leaving radiance signals, and the application of band-ratio algorithms tuned for specific water types, may therefore provide a simple means of improving the quality of remote sensing products in optically complex shelf seas.  相似文献   

16.
The chemical speciation of Cu and Zn was investigated by voltammetric titration methods in the surface waters (10 m) of the western Black Sea during an Istanbul–Sevastopol cruise conducted in November 1998. Supporting parameters (temperature (T), salinity (S), pH, alkalinity (Alk), suspended particulate matter (SPM) and dissolved and particulate 234Th) were obtained in order to distinguish hydrographic features against involvement of the metals in biogeochemical processes. In the Turkish continental slope region, the cruise track intersected a narrow vein of colder water originating on the western shelf. The core of this cold water vein was characterised by a relatively low salinity, higher specific alkalinity and higher metal (especially Cu) and metal-binding ligand concentrations.A very large portion of Cu (93–99.8%) and Zn (82–97%) was organically complexed. The degree of complexation was highest in shelf waters and lowest in the central gyre. Titration data for Cu were modelled by two classes of organic binding ligands characterised by (CL1=3–12 nM, log K1′=13.1–13.9) and (CL2=20–70 nM, log K2′=9.4–11.2). These ligands occurred mainly in the ‘dissolved’ phase, as defined by 0.4-μm filtration. The stronger Cu-binding ligand seemed to be produced in situ in response to Cu concentration, whereas the weaker Cu-binding ligand appeared to be derived from terrestrial sources and/or reducing shelf sediments. Titration results for Zn were generally represented by one class of ligands (CL1=8–23 nM, log K1′=9.4–10.2), which were almost uniformly distributed between the ‘dissolved’ (78±8%) and the particulate phase (22±8%). The concentration of these strong Zn-binding ligands showed a very good correlation with SPM (r2=0.64), which improved when the dissolved ligands alone were considered (r2=0.78). It is hypothesised that these ligands were produced in situ by the bacterial breakdown of particulate organic matter.  相似文献   

17.
To characterize the current status and historical trends in organochlorine pesticides (OCPs) contamination in Deep Bay, an important water body between Hong Kong and mainland China with a Ramsar mangrove wetland (Maipo), samples from seawater, suspended particulate matter (SPM), surface sediment, sediment core and fish were collected to determine the OCPs concentrations. Sediment core dating was accomplished using the 210Pb method. The average concentrations of DDTs, HCHs and chlordanes in water were 1.96, 0.71, 0.81 ng l−1, while in SPM were 36.5, 2.5, 35.7 ng g−1 dry weight, in surface sediment were 20.2, 0.50, 2.4 ng g−1 dry weight, and in fish were 125.4, 0.43, 13.1 ng g−1 wet weight, respectively. DDTs concentrations in various matrices of Deep Bay were intermediate compared with those in other areas. Temporal trends of the targeted OCPs levels in sediment core generally increased from 1948 to 2004, with the highest levels in top or sub-surface sediment. Both DDT composition and historical trends indicated an ongoing fresh DDT input. A positive relationship between the bioconcentration factor (BCF) of target chemicals and the corresponding octanol–water partition coefficient (Kow), and between the biota-sediment accumulation factors (BSAF) and the Kow were observed in the Bay. The risk assessment indicated that there were potential ecological and human health risks for the target OCPs in Deep Bay.  相似文献   

18.
The release of ammonium from the photochemical degradation of dissolved organic matter (DOM) has been proposed by earlier studies as a potentially important remineralisation pathway for refractory organic nitrogen. In this study the photochemical production of ammonium from Baltic Sea DOM was assessed in the laboratory. Filtered samples from the Bothnian Bay, the Gulf of Finland and the Arkona Sea were exposed to UVA light at environmentally relevant levels, and the developments in ammonium concentrations, light absorption, fluorescence and molecular size distribution were followed. The exposures resulted in a decrease in DOM absorption and loss of the larger sized fraction of DOM. Analysis of the fluorescence properties of DOM using parallel factor analysis (PARAFAC) identified 6 independent components. Five components decreased in intensity as a result of the UVA exposures. One component was produced as a result of the exposures and represents labile photoproducts derived from terrestrial DOM. The characteristics of DOM in samples from the Bothnian Bay and Gulf of Finland were similar and dominated by terrestrially derived material. The DOM from the Arkona Sea was more autochthonous in character. Photoammonification differed depending on the composition of DOM. Calculated photoammonification rates in surface waters varied between 121 and 382 μmol NH4+ L− 1 d− 1. Estimated areal daily production rates ranged between 37 and 237 μmol NH4+ m− 2 d− 1, which are comparable to atmospheric deposition rates and suggest that photochemical remineralisation of organic nitrogen may be a significant source of bioavailable nitrogen to surface waters during summer months with high irradiance and low inorganic nitrogen concentrations.  相似文献   

19.
The Wadden Sea, a shallow coastal area bordering the North Sea, is optically a complex area due to its shallowness, high turbidity and fast changes in concentrations of optically active substances. This study gathers information from the area on concentrations of suspended particulate matter (SPM), Chlorophyll-a (Chl-a), and Coloured Dissolved Organic Matter (CDOM), on total absorption and beam attenuation, and on reflectances from the whole area. It examines the processes responsible for variations in these. Sampling took place at 156 stations in 2006 and 2007. At 37 locations also the specific inherent optical properties (SIOPs) were determined. Results showed large concentration ranges of 2–450 (g m-3) for SPM, 2–67 (mg m-3) for Chl-a, and 0–2.5 m−1 for CDOM(440) absorption. Tides had a large influence on the SPM concentration, while Chl-a had a mainly seasonal pattern. Resuspension lead to a correlation between SPM and Chl-a. The absorption of CDOM had a spatial variability with extremely high values in the Dollard, although the slope of CDOM absorption spectra was comparable with that of the North Sea. The Chl-a specific pigment absorption proved to be influenced by phytoplankton species and specific absorption of non-algal particles at 440 nm was correlated with the mud content of the soil at the sample locations. SPM specific absorption was not found to correlate with any measured factor. As the concentrations of optically active substances changed, we also found spatial and temporal variability in the absorption, beam attenuation and reflectances. Reflectance spectra categorized in groups with decreasing station water depths and with extreme CDOM and SPM concentrations showed distinguishable shapes.  相似文献   

20.
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 (Kiequ), total ligands concentration (LiT) and association/dissociation rate constants (ki1,ki- 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 K1equ: 11.2–13.0, log K2equ: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 µMC, i.e. 1 mgCL− 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   

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