Hypoxia in a pristine stratified estuary (Krka, Adriatic Sea)

The occurrence of hypoxia in October 1988 in the Krka estuary is described, with special reference to the Prokljan Lake. Hypoxia develops near the bottom in autumn in response to the temperature maximum that appears this time of the year. The decomposition rate of naturally present organic matter increases, creating higher biological oxygen demand. As the water column is stratified by salinity and temperature, mixing of seawater near the bottom with oxygen-supersaturated water which resides closer to the surface is very slow. When an extensive marine phytoplankton bloom appears below the halocline in the Prokljan Lake, then, because of the sinking and degradation of phytoplankton near the bottom, the dissolved oxygen concentration decreases further. The hypoxia becomes so severe that it causes massive mortality of benthic macrofauna. The decomposition of the macrofauna further decreases the dissolved oxygen concentration. The hypoxia may persist until an increase in the freshwater inflow occurs, which forces the arrival of colder marine water near the bottom via a compensating flow. In the absence of autumn rains, the hypoxia may be recorded throughout winter.     

Exchange of water in a stratified estuary with an application to Krka (Adriatic Sea)

A method of computing the exchange time of freshwater and marine water in a stratified estuary is presented. The method is based on the inflow of the river and its tributaries, the depth of the halocline and salinity in the upper brackish water layer. Exchange time of freshwater and seawater in the Krka Estuary is shorter during winter than during summer. During winter the exchange time of freshwater is between 6 and 20 days, whereas during summer it is up to 80 days. The exchange time of marine water during winter is from 50 to 100 days, whereas during summer it lengthens to 250 days. The renewal time of water in the Krka Estuary as a whole may be approximated by the exchange time.     

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).     

The role of suspended matter in the biogeochemical cycles in the Adige River estuary (Northern Adriatic Sea)

Suspended matter and sediments from the Adige River mouth were analysed in an attempt to elucidate the transfer of heavy metals from the river to the sea. The vertical profile of grain-size spectra of suspended matter in front of the river mouth has shown that the riverine particles are limited to the upper brackish layer.Particulate matter was found to have a large specific surface area, up to 20 m² g⁻¹ in the estuarine sample. High quantities of quartz and phyllosilicates (micas and clay minerals) were found in the riverine suspended matter. The quartz content of the suspended matter from the brackish layer was found to be diminishing and with the organic matter becoming the essential component (22%). Higher levels of trace metals were usually detected in suspended matter samples (40 ppm Ni, 200 ppm Cr, 60 ppm Pb, 100 ppm Cu, 320 ppm Zn, and 0·9 ppm Cd) than in sediments.The observed similarity of physico-chemical, mineralogical and geochemical characteristics of riverine suspended matter and recent marine sediments, indicates that most of the riverborne particulate matter is deposited in the proximity of the Adige River mouth.The peculiar characteristics of the chromium level (high bulk concentration and its abundance in the organic fraction of the particular matter) when compared to the other trace metals, indicates the anthropogenic influence on its biogeocycle.     

Plankton distribution and vertical flux of biogenic matter during high summer stratification in the Krka estuary (Eastern Adriatic)

The aim of this study was to investigate phytoplankton abundance, composition and vertical export in the highly stratified Krka estuary, Croatia. The estuary is stratified throughout the year, and an interface between fresh- and brackish water plays an important role in production and degradation of biogenic matter. Vertical export of particulate organic carbon (POC), phytoplankton carbon (PPC) and faecal pellet carbon (FPC) was studied by deploying sediment traps in the middle and lower reach of the estuary and in the adjacent coastal zone. Zooplankton faecal pellet (FP) production experiments were conducted to provide additional information on the potential contribution of FP to the total carbon flux. High suspended concentrations of POC, chlorophyll a and phytoplankton was found in the lower reaches of the Krka estuary, adjacent to a source of anthropogenic eutrophication. The fraction of organic detritus to the total POC flux was 61–69% inside the estuary but only 7% at the marine station. This indicates that the primary producers in the surface layer of the Krka estuary are decomposed in and below the interface and then settle as detritus to the bottom. Low sedimentation rates in the coastal zone outside the estuary revealed that the eutrophication does not spread out of the estuary. Mesozooplankton played a modest role in vertical flux regulation, due to their low abundance and dominance of smaller forms as well as low faecal pellet production rates. It is concluded that processes taking place at the freshwater-seawater interface are of major importance for the vertical carbon flux in the investigated area.     

The carbohydrates in relation to mineralogic and granulometric composition of surface sediments in the karst estuary (River Krka estuary,Yugoslavia)

The investigation of mineral, granulometric and chemical composition of sediments of the River Krka estuary (Yugoslavia) were performed in order to elucidate the origin of the sediments and the pattern of sedimentation. Estuarine surface sediments were found to be fine-grained with a bimodal distribution. Environmental conditions in estuarine sediments favour conservation of the organic matter (anoxic conditions). The carbohydrates in the sediments were investigated to determine whether they are of terrigenous or authigenous origin. Glucose, galactose, mannose, xylose, rhamnose, glucosamine and glucuronic acid were detected in the sediments. Their mutual relationship indicates a preferentially terrigenous source of sedimented organic material in estuarine sediments.     

Distribution of surface-active substances in the northern Adriatic Sea

Spatial distribution and seasonal variability of surfactant activity (SA) of seawater were studied in the northern Adriatic Sea and compared to the temperature and salinity patterns in the 2-year period from February 1998 to January 2000, based on monthly surveys. Surface-active substances (SAS) were determined with alternating current voltammetry (in-phase mode) using o-nitrophenol as an electrochemical probe. A general characteristic of the SA seasonal variability for the northern Adriatic is the sinusoidal change of SA within the period of 1 year; similar behaviour was observed for the seasonal variations of temperature. Maximum SA values appeared during the summer period, while minimum SA values were measured in winter, during the period of well-mixed water layers and lower phytoplankton production. In May and October, the highest SA values were obtained in the upper seawater layer, which was ascribed to the influence of high inflow of nutrient-rich Po River freshwater. Riverine inputs indirectly favour autochthonous production processes, which result in increased concentration of organic matter (OM), particularly surface-active substances.     

Chemical and biological characterization of particles by flow cytometry in the Krka estuary, Croatia

Flow cytometry was used to characterize suspended particles in the Krka estuary (Croatia). This technique allows a rapid characterization and quantification of individual particles; it is based on the simultaneous measurement of the light scatter and natural or induced fluorescence. The relative size of the particles was determined by light scatter signals and by a calibration with fluorescent beads.The determination of organic particles was carried out by staining with fluorescein isothiocyanate (FITC). The autofluorescence of photosynthetic pigments (chlorophyll and phycoerythrin) present in the phytoplankton population was measured. The carbohydrates (galactose and glucose-mannose) were stained by lectins conjugated to FITC. The abundance of organic coatings or mineral particles and detritus was obtained from the difference between the total number of particles stained by specific carbohydrate fluorochromes and living cells.Results show that the Krka estuary is characterized by the occurrence of very small particles. About 80% of suspended particles are organic, most of these particles being living cells. The only exception is the Guduca River, a small tributary.     

Distribution of trace metals in anchialine caves of Adriatic Sea,Croatia

This study presents results of the first comprehensive research on ecotoxic trace metals (Cd, Pb, Cu and Zn) in aquatic anchialine ecosystems. Data show the influence of hydrological and geological characteristics on trace metals in highly stratified anchialine water columns.     

Distribution of chlorophyll a and diatom in the sea ice of the Weddell Sea, Antarctica

Diatoms are major primary producers of microbial biomass in the Antarctica. They are found in the water and sea ice. The distribution, abundance of the ice diatoms and their relation to the environmental factors inside and outside the ice have been studied for its special role in the Antarctic Ocean ecology. In this paper we describe the abundance, distribution and composition of diatom assemblages in     

Freshwater Phytoplankton Bloom in Visovac Lake - A Possible Cause of Benthic Mortality in Krka Estuary (Adriatic Sea, Croatia)

Abstract. In late summer and early autumn of 1989 benthic mortality in the upper part of Krka estuary extended from the Skradinski buk waterfalls to approximately 5 km downstream. Dead benthic organisms were found on the bottom at depths of up to 4.5 m. During August, a freshwater phytoplankton bloom was recorded in Visovac lake (which supplies the Skradinski buk waterfalls). The green tide in the lake was composed of up to 11.9 million cells. 1^--¹, predominantly of Synedra acus and Dinobtyon sertularia . At that time the maximal total inflow of phytoplankton cells through the waterfalls was approx. 0.41 S^-I (38000 1. d^-1). Cells of these two species died after reaching the salt wedge and the cummulative effect of their decomposition apparently caused an oxygen demand sufficient enough to trigger the benthic mortality. Due to the water mass dynamics, the spreading of mortality downstream was slow (from August to October, approx. 5 km). Certain benthic fishes (like Gobius sp.) were observed on the bottom of the affected area in mid-October 1989.     

Adsorption of lead and cadmium ions on calcite in the Krka estuary

The adsorption of Pb²⁺ and of Cd²⁺ ions from calcareous Krka river water of various salinities (3, 14, 20 and 38 psu) on calcite (CaCO₃, Merck p.a.) was investigated. Simultaneous adsorption of Pb²⁺ and Cd²⁺ ions was studied as well. The results suggest that the two ions are adsorbed at different calcite surface sites; Pb²⁺ remained firmly bound to calcite at all salinities, whereas Cd²⁺ was firmly bound at low salinities and released at high salinities. Dissolved natural organic ligands at the freshwater-seawater interface (FSI; at 14 psu) promoted and below the FSI (at 20 psu) decreased the adsorption of Cd²⁺. The experiments were performed at metal concentrations of 8 × 10⁻⁸ mol l⁻¹ and at natural pH values around pH 8. Adsorbed amounts of trace metal ions were determined in filtered samples by differential pulse anodic stripping voltammetry (DPASV) with a three-electrode system, after 24 h of equilibration with calcite. Several adsorption models were tested, such as Freundlich's, Langmuir's and Schindler-Stumm's surface coordination model. Adsorption isotherms belong to S-1 class of empirical adsorption isotherms. None gave reasonable values of adsorption constants. The fractional partitioning of adsorbent to the solid phase when normalized to the quantity of adsorbent present (K_d) declined as solid concentration increased. It was found that the surface charge is not responsible for the observed effect. Instead, aggregate size increased, which effected a loss in surface area. This is a reasonable explanation for the observed S-shaped adsorption isotherms curves.     

茅尾海钦江河口光滩时空变化过程研究

河口潮滩一般由生长于中高潮滩的植被和植被前缘光滩（裸滩）构成,光滩的时空变化直接关联潮滩冲淤及植被演替状态。本文基于Landsat 5 TM及Sentinel-2 MSI等多期遥感影像,利用随机森林分类算法与数字岸线分析系统探讨茅尾海钦江河口光滩在1986—2021年期间的变化过程。结果表明：①近40年钦江河口光滩面积总体呈现明显损失的状态,可分为1986—2002年冲淤平衡、2002—2007年快速淤积、2007—2014年急剧降低和2014—2021年缓慢淤涨4个阶段;②光滩淤积的区域主要分布于钦江沙井河口口门及内侧河槽与潮汐通道边缘,侵蚀出现在钦江沙井河口及钦江沙冲河口航道及潮沟区域;③茅尾海清淤工程是引起钦江河口光滩自2008年到2014年面积减少的直接因素,潮间带植被扩张和2015年之后大范围生蚝养殖引起的水动力减弱导致光滩向海淤涨。当前海平面上升未对光滩造成明显影响,但入海泥沙的变化一定程度上影响光滩冲淤演变。本研究可为区域河口潮滩资源的可持续高效利用提供部分理论与技术支撑。     

珠江口水体叶绿素荧光特性研究

利用2003年1月和2004年1月珠江口实测的遥感反射率和叶绿素浓度,建立了基于实测1nm带宽及其模拟MERIS遥感反射率数据的叶绿素荧光特征与叶绿素浓度之间的拟合关系。基于实测1nm带宽遥感反射率光谱,叶绿素荧光峰的位置和高度分别与叶绿素浓度之间存在良好的线性关系和指数关系;基于模拟MERIS遥感反射率数据,叶绿素荧光峰的高度与叶绿素浓度之间存在良好的线性关系,叶绿素荧光峰位置与叶绿素浓度之间不存在明显的相关关系,但可作为叶绿素浓度数量级的有效探针。利用2006年5月和8月的珠江口实测遥感反射率和叶绿素浓度对拟合结果进行了检验,结果表明其精度较高,说明叶绿素荧光特征在探测叶绿素浓度时效果良好且MERIS数据在近岸二类水体叶绿素浓度反演、水质监测等方面有着良好的应用前景。     

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.     

Reproductive cycle and minimal length at sexual maturity of Engraulis encrasicolus (L.) in the Zrmanja River estuary (Adriatic Sea, Croatia)

The reproductive cycle of anchovy, Engraulis encrasicolus (L.), was studied from monthly random samples of purse seine catches. A total of 1477 anchovy specimens were collected from January to December 2003 in the Zrmanja River estuary (Novigrad Sea). The analysis was based on the temporal evolution of gonadosomatic index, mass and stage of gonads. The total length of anchovy ranged from 4.5 to 14.5 cm and mass from 0.56 to 19.80 g. Sex ratio was slightly different from 1:1; the females were insignificantly predominated (♂/♀ = 0.99). The period of reproductive activity was from April to September coinciding with the most developed stages of gonads as well as with the highest gonad weights, and gonadosomatic indices. To estimate the length at maturity, a sub sample of 454 anchovy was taken from May to July (peak of anchovy spawning period). The length at which 50% of anchovy were mature (L₅₀) was calculated to be 8.2 cm. The length–weight relationship of anchovy was described by the expression: W = 3.51 × 10⁻³ L_T^3.211 (r² = 0.998). The relationships between total length–standard length and total length–fork length are L_T = 1.1405L_S + 0.2420 and L_T = 1.0425 L_F + 0.3944, respectively.     

Sea ice,hydrological, and biological processes in the Churchill River estuary region,Hudson Bay

A conceptual scheme for the transition from winter to spring is developed for a small Arctic estuary (Churchill River, Hudson Bay) using hydrological, meteorological and oceanographic data together with models of the landfast ice. Observations within the Churchill River estuary and away from the direct influence of the river plume (Button Bay), between March and May 2005, show that both sea ice (production and melt) and river water influence the region's freshwater budget. In Button Bay, ice production in the flaw lead or polynya of NW Hudson Bay result in salinization through winter until the end of March, followed by a gradual freshening of the water column through April–May. In the Churchill Estuary, conditions varied abruptly throughout winter–spring depending on the physical interaction among river discharge, the seasonal landfast ice, and the rubble zone along the seaward margin of the landfast ice. Until late May, the rubble zone partially impounded river discharge, influencing the surface salinity, stratification, flushing time, and distribution and abundance of nutrients in the estuary. The river discharge, in turn, advanced and enhanced sea ice ablation in the estuary by delivering sensible heat. Weak stratification, the supply of riverine nitrogen and silicate, and a relatively long flushing time (∼ 6 days) in the period preceding melt may have briefly favoured phytoplankton production in the estuary when conditions were still poor in the surrounding coastal environment. However, in late May, the peak flow and breakdown of the ice-rubble zone around the estuary brought abrupt changes, including increased stratification and turbidity, reduced marine and freshwater nutrient supply, a shorter flushing time, and the release of the freshwater pool into the interior ocean. These conditions suppressed phytoplankton productivity while enhancing the inventory of particulate organic matter delivered by the river. The physical and biological changes observed in this study highlight the variability and instability of small frozen estuaries during winter–spring transition, which implies sensitivity to climate change.