Organic matter and surface properties of solid particles in the estuarine mixing zone

Two physicochemical parameters: specific surface area (SSA) and heat-of-wetting (Δ_wH) were measured in order to characterize the surface of sediments from river and marine environments. The data for the sediment samples of the Krka River Estuary were compared with polluted river and shelf marine sediment samples. It was found that organic free samples from the polluted river sediments show two to three times larger SSA compared to native samples. At the same time, Δ_wH was two to three times higher for native samples. The inverse of this trend was found for marine sediment samples. In the Krka River Estuary a narrow transition zone is evident, where such an inversion occurs. This inversion is attributed to significant compositional changes of organic matter within the estuary.     

Estuarine transformation of organic matter: single coalescence events of estuarine surface active particles

Individual surface-active particles (SAP) in aqueous environmental samples can be characterized through their coalescence at a model hydrophobic interface. Each coalescence event is recorded as an electrical signal. As the electrical signal is a current transient (time on a millisecond scale), the sequence of fast processes leading to the formation of a condensed film can be studied from the moment of first attachment at the interface.In the stratified Krka Estuary, SAP are present in maximum concentrations (10⁷−5 × 10⁸ particles l⁻¹ min the size range > 1 μm) at the halocline (freshwater-seawater interface). This highly surface-active fraction of particulate organic matter can be viewed as oily droplets. SAP are fluid, and are readily transformed at interfaces to films of molecular thickness (surface area per particle is in the range 10⁻⁵–10⁻² cm²).Comparison of response of individual SAP with model particles, and the frequency of their appearance in estuarine samples, shows that a majority of estuarine SAP has, in terms of viscosity and film permeability, the properties of oleic acid. A significant fraction of SAP have more rigid structures, comparable to moleic acid + cholesterol model particles. A small fraction ( > 1%) behaves as phytoplankton cells with fluid outer membranes.We have also presented evidence for a strong interaction between elemental mercury and SAP, which is not sensitive to the molecular structure of the organic phase. The puzzling accumulation of mercury at the halocline of the Krka Estuary may be regarded as the result of interaction of elemental mercury with SAP.     

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

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).     

Effects of wind on a stratified estuary

Before the onset of wind in the Krka Estuary, a sharp halocline extends from 2.5 to 4 m below the surface, separating the upper brackish water layer from the lower marine layer. Strong wind (20 m s⁻¹) induces a tilt of the halocline surface so that downwind (5-km wind fetch) the halocline is pushed to 4.6 m below the surface. Wind-driven surface currents induce a vertical gyre within the upper layer and a gyre in the opposite direction in the lower marine layer. As a consequence, the halocline close to the coast on the downwind side is not only deeper but is also steepened. The entrainment of marine water into the upper brackish water layer is intensified on the windward side. The possible role of wind in oxygenating the bottom layer is discussed.     

Nutrient enrichment and phytoplankton response in an Adriatic karstic estuary

Nutrients, chlorophyll a, primary production (¹⁴C), and standard oceanographic parameters were measured seasonally from 1983 to 1988 along the axis of a karstic estuary of the central Adriatic Sea (the Krka River estuary). Because of anthropogenic phosphorus discharges, the surface-layer orthophosphate concentrations (up to 1.7 mmol m⁻³), phytoplankton biomass (chlorophyll a up to 23 mg m⁻³) and primary production (up to 108 mg C m⁻³ h⁻¹) were significantly higher in ibenik Bay (lower estuary) than in the other estuarine subregions, and the coastal sea in particular. In contrast, nitrate and orthosilicate (up to 59 and 65 mmol m⁻³, respectively) distributions during autumn and winter were ascribed to dilution of Krka River nutrients along the estuary. As a consequence, the surface-layer inorganic N/P ratio was extremely high in the upper estuary (averages up to 180), but this ratio was reduced up to three times in ibenik Bay and the coastal sea. In spring and summer, nitrate and orthosilicate, but not orthophosphate, were almost exhausted from the water because of biological utilization. In the saline layer below the halocline (depth 2–5 m) oxygen saturation varied over a large range, particularly in the upper estuary (16–176%), and nutrient concentration ratios differed from those in the surface layer. A nutrient regeneration stoichiometric model was derived, based on a linear regression analysis: AOU:Si:N:P = 276:16:6:0.4. Anthropogenic nutrient inputs should be urgently reduced to re-establish a natural nutrient environment.     

Marine sampling by scuba diving. 3. Sampling procedures for measurement of mercury concentrations in estuarine waters and seawater

A method for sampling estuarine waters and seawater by scuba diving is described. Samples taken from the Krka River Estuary on the eastern Adriatic coast were analysed for mercury content using cold vapour atomic absorption spectrometry (CVAAS). Mercury levels as low as 1 ng dm⁻³ were determined and these are among the lowest values reported to date. A simple contamination free procedure for the preconditioning of sample containers in the sea was applied. Sampling of water by divers is particularly useful when the intermediate layer in an estuary has to be identified and sampled, as well as for obtaining detailed vertical concentration profiles for mercury and other trace elements.     

Distribution of algal chlorophyll and carotenoid pigments in a stratified estuary: the Krka River, Adriatic Sea

The detailed distribution of algal chlorophyll and carotenoid pigments was determined around the halocline (freshwater-seawater interface) in the Krka Estuary on the east coast of the Adriatic Sea; in May 1988. After collection of water along the estuary, particulate matter was extracted and analyzed for pigments by high-performance liquid chromatography coupled with absorbance and fluorescence detection. Bottom marine waters were characterized by lower chlorophyll a (chl a) concentrations than encountered in surface waters, decreasing downstream from 0.50 μg l⁻¹ to 0.16 μg l⁻¹ at the marine end-member. The highest concentrations of chl α (up to 26.34 μg l⁻¹) were found in the interfacial layer, an particularly at one station located off the city of ibenik, where high inputs of nutrients supported the accumulation of living algae at the halocline. Fucoxanthin was the most abundant carotenoid, which indicates a euryhaline dominance of diatoms in the estuary, whereas the dinoflagellate-derived carotenoid peridinin was confined to the interfacial and bottom saline waters of the inner estuary. High concentrations of alloxanthin and chl b were found in the interfacial layer, which also suggests an accumulation of Cryptophyceae and green algae in the inner estuary. Phaeophorbides showed higher concentrations in bottom waters than in surface waters, whereas the highest concentrations occurred in the interfacial layer. These high levels could reflect a density trapping of dead cells in an early degradation state, as suggested by the importance of allomerized chl a and chlorophyllide a vs. total chl a, or of faecal pellets originating from zooplankton grazing in the interfacial layer.     

The conservative and non-conservative behavior of chromophoric dissolved organic matter in Chinese estuarine waters

The spectral absorption properties of chromophoric dissolved organic matter (CDOM) and their distributions in two Chinese estuaries, the Yangtze River Estuary and the Jiulong River Estuary, were studied during August 2003 (wet season) and during different seasons between 2003−2005, respectively. The CDOM concentrations (a₃₅₅) of fresh end members in the Jiulong River Estuary varied seasonally, while its quality remained relatively stable. However, the a₃₅₅ of the marine end members exhibited less variability. Application of a conservative mixing model indicated that CDOM behaved conservatively in the Yangtze River Estuary. No photobleaching removal was observed at high salinity region of this estuary. Although CDOM showed conservative behavior for many cruises in the Jiulong River Estuary, there was evidence for removal in the low salinity regions during some cruises. Laboratory mixing experiments and a salt addition experiment suggested that particle sorption of CDOM maybe the possible reason for the removal. These results showed that absorption properties of CDOM can be used as a tool to observe the quantitative and qualitative dynamics of DOM during estuarine mixing.     

珠江口海域主导光学因子的遥感分类及其变化特征

基于2014年5月和8月珠江口海域的现场和实验测量数据,分析了光学因子和生态参数的动态变化特征,并找出该海域的主导光学因子;基于模拟的MODIS数据,构建了水体组分特征波长处吸收系数的遥感反演模型,并结合MODIS卫星遥感影像,依据IOCCG规则对主导光学因子进行遥感分类,揭示了珠江口海域2014年逐月水体主导光学因子的动态变化特征。结果表明,珠江口海域水体以a_d、a_g以及两种共同主导类型为主,并且a_g、a_d两种光学因子主导类型所占比例最大,其次是a_g主导类型,a_d主导类型所占比例最小。同时发现a_d（442）、a_dg（442）均与无机悬浮物浓度有较好的正相关关系,说明CDOM和悬浮泥沙具有相似的来源和动力变化过程。     

长江口上升流海区的生态环境特征

根据 1 985年 8月的调查资料 ,讨论了长江口上升流海区的生态环境特征。研究表明 ,在长江口外 ,大约在 1 2 2°2 0′— 1 2 3°1 0′E、31°0 0′— 32°0 0′N海区存在着明显的下层高盐冷水的抬升现象 ;伴随这种上升运动 ,于 5— 1 0m层 ,在上述高盐冷水区明显地存在一个低溶解氧、高营养盐区。资料表明 ,该低氧、高营养盐海水不是直接来自表层的长江冲淡水 ,而是来自深底层的变性后的台湾暖流水。分析表明 ,长江口外的浮游植物高值区的分布位置与上升流区基本一致 ,两者比较浮游植物高值区略向东南方向偏移约 1 5— 2 0km。作者认为形成这种偏离现象的原因可能与上升流中心区水温偏低有关     

秋、夏季珠江口、南海北部陆坡溶解态铝的分布及其影响因素

于2014年10月和2015年6月对珠江口、南海北部陆坡区域溶解态铝的分布进行观测,探讨影响其分布及季节差异的主要因素,并以其作为示踪因子探讨潜在的陆源物质跨陆架输送途径。研究结果显示,夏、秋季珠江口盐度为0时溶解态铝的浓度分别为690.0 nmol/L和360.0 nmol/L,在淡咸水混合初期溶解态铝迅速自水体清除,夏季的清除率(55.8%)大于秋季(29.7%)。在南海北部陆坡区域,夏季表层溶解态铝浓度表现为沿纬线方向西高东低的分布特点,秋季则相反;夏、秋季底层溶解态铝浓度均呈现出随着离岸距离增加逐渐降低的分布趋势。秋季溶解态铝浓度的分布与盐度呈现显著的负相关关系,表明其行为近乎保守,陆架混合水及黑潮次表层水等水团混合是影响南海北部陆坡区域溶解态铝分布的主要因素。并且以溶解态铝作为示踪因子发现,在21.6～22.2 kg/m³密度面区间存在自陆架向陆坡方向的跨陆架输送。而夏季陆坡中部受到珠江冲淡水的影响出现低盐水舌,但溶解态铝的浓度相对较低,表现出明显的不保守行为。浮游植物的清除作用是导致夏季陆坡区域溶解态铝分布异常的重要因素。     

Behaviour of proteinaceous substances in the estuary of the Tama River

Behaviour of dissolved and particulate proteinaceous substances in the estuary of the Tama River was investigated through field observations and laboratory experiments. Concentrations of dissolved proteinaceous substances in estuarine water were determined at eight stations between the mouth of the Tama River (TA-15) and a point 16km upstream (TA-8), using the colorimetric method of Lowryet al. (1951) that employs Folin phenol reagent. The results were expressed in terms of Folin phenol active substances (FPAS). It was found that FPAS decreased with increasing salinity and that the proportion of high molecular weight FPAS (molecular weight greater than 100,000) decreased rapidly in the estuary.The shapes, sizes and numbers of amorphous particulate substances stained by Amido Black 10B, called Amido Black active substances (ABAS), were determined under a microscope. The numbers of ABAS retained on Millipore HA filters (mean diameter: 10–80µm) amounted to 450ml^–1 in the estuarine water about 6km from the mouth of the estuary (Station TA-12M). Some of these aggregates are considered to be producedin situ by flocculation of high molecular weight FPAS during estuarine mixing. ABAS were also produced in experiments by mixing filtered river water with sea water.     

The partial pressure of carbon dioxide and air-sea fluxes in the Changjiang River Estuary and adjacent Hangzhou Bay

The distributions of partial pressure of carbon dioxide (p CO2 ) in the surface waters of the Changjiang River Estuary and adjacent Hangzhou Bay were examined in the summer of 2010. Surface water p CO2 ranged from 751-2 095 μatm (1 atm=101 325 Pa) in the inner estuary, 177-1 036 μatm in the outer estuary, and 498-1 166 μatm in Hangzhou Bay. Overall, surface p CO2 behaved conservatively during the estuary mixing. In the inner estuary, surface p CO2 was relatively high due to urbanized pollution and a high respiration rate. The lowest p CO2 was observed in the outer estuary, which was apparently induced by a phytoplankton bloom because the dissolved oxygen and chlorophyll a were very high. The Changjiang River Estuary was a significant source of atmospheric CO2 and the degassing fluxes were estimated as 0-230 mmol/(m2 d) [61 mmol/(m2 d) on average] in the inner estuary. In contrast, the outer estuary acted as a CO2 sink.     

Population structure, size at maturity and condition of sardine, Sardina pilchardus (Walb., 1792), in the nursery ground of the eastern Adriatic Sea (Krka River Estuary, Croatia)

A total of 1125 specimens of sardine, Sardina pilchardus, ranging in total length from 4.9 to 12.5 cm (mean 8.31 ± 1.41 cm) and in weights between 1.02 g and 11.18 g (mean 4.40 ± 1.87 g) were randomly sampled using a beach seine from the Krka River estuary. Samples were collected monthly according to their occurrence in this area from October to February during 2002/03, 2003/04 and 2004/05, which is during the spawning period of this species. Monthly fluctuations in the length frequency distributions of sardine were observed during that time. The length–weight relationship of all sardine specimens was described by the equation: W=0.007L^2.9587(r² = 0.9626); and the isometric nature of relative growth was established (t = −5.1495; p < 0.05). According to the allometric condition factor K_a, sardine specimens were in better somatic condition at the beginning of their appearance (spawning period) in the Krka River estuary. The length at which 50% of sardines were mature (L₅₀) was calculated to be 7.9 cm.     

Dissolved iron(III) speciation in the high latitude North Atlantic Ocean

On voyages in the Iceland Basin in 2007 and 2009, we observed low (ca. 0.1 nM) total dissolved iron concentrations [dFe] in surface waters (<150 m), which increased with depth to ca. 0.2–0.9 nM. The surface water [dFe] was low due to low atmospheric Fe inputs combined with biological uptake, with Fe regeneration from microbial degradation of settling biogenic particles supplying dFe at depth. The organic ligand concentrations [L_T] in the surface waters ranged between 0.4 and 0.5 nM, with conditional stability constants (log K′_FeL) between 22.6 and 22.7. Furthermore, [L_T] was in excess of [dFe] throughout the water column, and dFe was therefore largely complexed by organic ligands (>99%). The ratio of [L_T]/[dFe] was used to analyse trends in Fe speciation. Enhanced and variable [L_T]/[dFe] ratios ranging between 1.6 and 5.8 were observed in surface waters; the ratio decreased with depth to a more constant [L_T]/[dFe] ratio in deep waters. In the Iceland Basin and Rockall Trough, enhanced [L_T]/[dFe] ratios in surface waters resulted from decreases in [dFe], likely reflecting the conditions of Fe limitation of the phytoplankton community in the surface waters of the Iceland Basin and the high productivity in the Rockall Trough.Below the surface mixed layer, the observed increase in [dFe] resulted in a decrease of the [L_T]/[dFe] ratios (1.2–2.6) with depth. This indicated that the Fe binding ligand sites became occupied and even almost saturated at enhanced [dFe] in the deeper waters. Furthermore, our results showed a quasi-steady state in deep waters between dissolved organic Fe ligands and dFe, reflecting a balance between Fe removal by scavenging and Fe supply by remineralisation of biogenic particles with stabilisation through ligands.     

东海中北部海域秋季表层海水中无机碳与海气界面碳的迁移

基于2010 年11 月对长江口外东海中北部海域的综合调查, 系统研究了该海域的无机碳体系参数的分布特征、海?气界面二氧化碳通量及其影响因素。研究结果表明, 该海域秋季溶解无机碳(DIC)高值区主要出现在调查海域东北部及长江口附近海域, 而调查海域南部DIC 含量较少且变化平缓, 其主要是受台湾东部流向东北方向的黑潮支流及长江冲淡水的影响; 表层海水CO₂分压(pCO₂)值变化范围为40.8～63.5 Pa, 呈现沿黑潮支流流入方向由东南向西北逐渐增高的趋势。秋季表层海水pCO₂与温度(T)、盐度(S)有较好的负相关性, 说明海水温度升高和盐度增加, pCO₂降低, 反之亦然。另外, 通过估算得出, 秋季CO₂海-气交换通量为2.69～33.66 mmol/(m²·d), 平均值为(14.35 ± 7.06 )mmol/(m²·d),其在长江口邻近海域相对较大, 而在调查海域南部相对较小; 2010 年秋季水体向大气释放CO₂的量(以碳计)为(2.35 ± 1.16)×104 t/d, 是大气CO₂较强的源, 说明东海中北部海域秋季总体上是CO₂的源。     

Contrasting chemical and isotopic compositions of organic matter in Changjiang (Yangtze River) estuarine and East China Sea shelf sediments

To examine the source and preservation of organic matter in the shelf sediments of the East China Sea (ECS), we measured bulk C/N and isotopes, organic biomarkers (n-alkanes and fatty acids) and compound-specific (fatty acids) stable carbon isotope ratios in three sediment cores collected from two sites near the Changjiang Estuary and one in the ECS shelf. Contrasting chemical and isotopic compositions of organic matter were observed between the estuarine and shelf sediments. The concentrations of total n-alkanes and fatty acids in the shelf surface sediments (0–2 cm) were 5–10 times higher than those in estuarine surface sediments but they all decreased rapidly to comparable levels below the surface layer. The compositions of n-alkanes in the estuarine sediments were dominated by C₂₆-C₃₃ long-chain n-alkanes with a strong odd-to-even carbon number predominance. In contrast, the composition of n-alkanes in the shelf sediment was dominated by nC₁₅ to nC₂₂ compounds. Long-chain (>C₂₀) fatty acids (terrestrial biomarkers) accounted for a significantly higher fraction in the estuarine sediments compared to that in the shelf sediment, while short-chain (<C₂₀) saturated and unsaturated fatty acids were more abundant in the shelf surface sediments than in the estuarine sediments. Stable carbon isotopic ratios of individual fatty acids showed a general positive shift from estuarine to shelf sediments, consistent with the variations in bulk δ ¹³C_TOCTOC. These contrasts between the estuarine and shelf sediments indicate that terrestrial organic matter was mainly deposited within the Changjiang Estuary and inner shelf of ECS. Post-depositional diagenetic processes in the surface sediments rapidly altered the chemical compositions and control the preservation of organic matter in the region.     

Mixed layer depth front and subduction of low potential vorticity water in an idealized ocean GCM

It is known that there is a front-like structure at the mixed layer depth (MLD) distribution in the subtropical gyre, which is called the MLD front, and is associated with the formation region of mode water. In the present article, the generation mechanism of the MLD front is studied using an idealized ocean general circulation model with no seasonal forcing. First, it is shown that the MLD front occurs along a curve where u _g ·∇T _s = 0 is satisfied (u _g is the upper ocean geostrophic velocity vector, T _s is the sea surface temperature and ∇ is the horizontal gradient operator). In other words, the front is the boundary between the subduction region (u _g ·∇T _s > 0) and the region where subduction does not occur (u _g ·∇T _s < 0). Second, we have investigated subduction of low potential vorticity water at the MLD front, which has been pointed out by past studies. Since u _g ·∇T _s = 0 at the MLD front, the water particles do not cross the outcrop at the MLD front. The water that is subducted at the MLD front has come from the deep mixed layer region where the sea surface temperature is higher than that at the MLD front. The temperature of the water in the deep mixed layer region decreases as it is advected eastward, attains its minimum at the MLD front where u _g ·∇T _s = 0, and then subducts under the warmer surface layer. Since the deep mixed layer water subducts beneath a thin stratified surface layer, maintaining its thickness, the mixed layer depth changes abruptly at the subduction location.     

长江口及邻近海域沉积物中四醚脂类的来源及其对底层溶解氧指示作用探究

甘油二烷基甘油四醚(glycerol dialkyl glycerol tetraethers,GDGTs)作为一种重要的膜脂化合物,广泛存在于海洋水体和沉积物中。基于GDGTs对温度的敏感性, TEX₈₆(Tetra Etherinde Xoftetraethers consisting of 86 carbons)指标被广泛用于海洋古温度重建。然而,研究表明GDGTs母源生物古菌也会受到环境中溶解氧(DO)变化的影响,进而影响其膜脂组成,但边缘海DO对GDGTs组成的影响仍不清楚。本文研究了夏季长江口及其邻近海域颗粒物与表层沉积物中GDGTs的含量与组成,探讨了表层沉积物中GDGTs的来源及其组成对底层DO的响应。结果表明,长江口及其邻近海域颗粒物GDGTs的含量随水深的增加而增加,同时表层沉积物中的GDGT-2/GDGT-3和GDGT-0/Cren比值均与底层颗粒物相近,表明沉积物中GDGTs主要来源于底层颗粒物的沉降输入。进一步对受陆源有机质输入影响较小的站位研究发现有机质来源BIT(Branched and Isoprenoid Tetractter)指...     

黄河口区及其附近海域溶解氧的分布变化

本文讨论了1984年5月、8月、11月调查的黄河口区溶解氧的分布。黄河口区溶解氧的分布主要受水温的影响,在春季还受硅藻的影响,而夏季受微型浮游植物的影响。 夏季,黄河口门底层水的表观耗氧量高达2.04ml╱L。反映了黄河悬浮物所携带的有机物氧化的结果。