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

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.     

Organic matter origin and distribution in suspended particulate materials and surficial sediments from the western Adriatic Sea (Italy)

In this study, organic carbon (OC), total nitrogen (TN), stable carbon isotopic (δ¹³C_OC) and CuO reaction product compositions were used to identify the sources of organic matter (OM) and to quantify the relative importance of allochthonous and autochthonous contributions to the western Adriatic Sea, Italy. Suspended particulate material (195 samples) and surficial sediments (0–1 cm, 70 samples) from shallow cross-shelf transects were collected in February and May 2003, respectively. Vertical water column profiles were acquired along the same transects. Data include depth, potential temperature, salinity, density and chlorophyll fluorimetry.Along the western Adriatic shelf in the near-shore region, the phytoplankton growth was influenced by dynamics of the buoyant plumes from the Po and Appennine rivers. A small amount of very fine terrigenous material remained suspended within the coastal current and was exported southward along the shelf to the slope. High variability in the bulk composition was detected in the Po prodelta surficial sediments, whereas the western Adriatic shelf, although a larger area, exhibited a narrower range of values.A significant decoupling was observed between suspended particles in the water column and surficial deposits. The organic material collected in the water column was compositionally heterogeneous, with contributions from marine phytoplankton, riverine–estuarine phytoplankton and soil-derived OM. Frequent physical reworking of surficial sediments likely leads to the efficient oxidation of marine OC, resulting in the observed accumulation and preservation of refractory soil-derived OC delivered by the Po and Appennine rivers.     

Carbon and nitrogen isotope composition of particulate organic matter in relation to mucilage formation in the northern Adriatic Sea

Carbon and nitrogen stable isotope ratios of particulate organic matter (POM) were studied approximately weekly during spring and summer 2003 and 2004 in the Gulf of Trieste (northern Adriatic Sea) in order to track the temporal variations and differences between two years. In parallel, particulate organic carbon (POC) and particulate nitrogen (PN), phytoplankton biomass (chlorophyll a), and N and P nutrients were monitored. All studied parameters, especially N and P nutrients and chlorophyll a, showed higher concentrations and larger variability in spring 2004. As a consequence the macroaggregates were produced in late spring 2004. The C and N isotope composition of POM was not directly linked to phytoplankton biomass dynamics. The δ¹³C_POC values covaried with temperature. In 2004, δ¹³C_POC variations followed the δ¹⁵N_PN values as well as the δ¹³C_DIC values which were probably more dependent on the photosynthetic use of ¹²C. Variations in δ¹⁵N_POM values were most probably the consequence of variations in N nutrient sources used in phytoplankton assimilation. The significant correlation between δ¹⁵N_PN values and nitrate concentrations in 2004 implies intense nitrate assimilation in the presence of higher nitrate concentration. This suggests nitrate as the key nutrient in the »new primary production«, later producing macroaggregates with a mean δ¹³C and δ¹⁵N values of − 19‰ and 5‰, respectively. A low fractionation factor ε, < 1‰, lower than that reported in other marine and lacustrine systems, was found probably to be a consequence of distinct phytoplankton species, i.e. several classes of autotrophic nanoflagellates, and specific growth conditions present in the Gulf of Trieste. The tentative use of C isotope composition of POM revealed a higher contribution of allochthonous organic matter in 2004 compared to 2003 due to higher riverine inflow.     

Influence of winds and oceanographic conditions on the mucilage aggregation in the Northern Adriatic Sea in 2003–2006

Meteorological and oceanographic conditions in the Northern Adriatic Sea in a year notable for massive mucilage formation (2004) were compared with those in years where this phenomenon did not occur (2003, 2005 and 2006) to suggest possible links. The months preceding the mucilage event in 2004 were considered the ‘incubation period’ and were characterized by a strong freshet in May which increased the water column stability. Winter cooling and scarcity of freshwater inputs from the Po River triggered the dense water formation and intrusion in the northern basin. Weak southeasterly winds and an increase in surface seawater temperatures contributed to maintain and reinforce the water column stability, and at the same time an intense diatom spring bloom created the conditions for accumulation of organic matter. The interplay of climatological forcings and biological processes caused temporal variations of dissolved organic carbon (DOC) and particulate organic carbon (POC) in the basin, with POC playing an important role in the aggregation process, as suggested by its increase relative to DOC before massive mucilage formation. We therefore suggest that high POC/total particulate nitrogen ratios in the suspended particulate organic fraction, a steep increase of POC/Chlorphyll a, and the decreased DOC/POC ratios represent ‘early warning’ signals of the main processes that lead to mucilage events in the Northern Adriatic Sea.     

由东海、黄海沉积物中有机碳含量及稳定同位素组成重建200a以来初级生产力历史记录

从20世纪80年代以来古生产力的重建研究一直是国内外海洋生态学研究的热点,但已有的大多数研究是在深海区;而陆架区的特点是来自陆源物质的影响往往比较明显,因此,研究难度远较深海区大。利用现代沉积物中的有机碳稳定同位素组成来估算海源碳的含量,在此基础上,结合调查区域表层沉积物中的几个初级生产力的代表性指标(浮游植物总量、叶绿素a浓度以及硅藻含量)的调查资料,寻求岩心中海源碳与古生产力指标的相关关系,再由南黄海冷涡沉积区3个典型柱状沉积物中海源碳重建了200a以来高分辨率的古生产力记录,这对陆架海生态环境演变规律的研究有重要意义。对重建所得到的南黄海近代初级生产演化因素的初步探讨表明,近200a来初级生产力波动升高与海水表层温度的升高趋势是一致的,但其最主要的控制因素还是营养盐的供应,其中陆源营养物质和污染物质的影响起到了重要的作用。     

High downward flux of mucilaginous aggregates in the Ligurian Sea during summer 2002: similarities with the mucilage phenomenon in the Adriatic Sea

The DYFAMED sediment trap station in the Ligurian Sea (NW Mediterranean) has been active since 1986 and today comprises the longest time‐series of downward particle flux in the Mediterranean Sea. As such, it provides valuable information on the interannual variability of the particle flux, and also documents possible recent changes in the NW Mediterranean pelagic ecosystems. We report an unprecedented episode of downward flux of mucilaginous material at the DYFAMED station during summer 2002 in association with singular hydrometeorological conditions. The rain of mucilaginous aggregates clogged a PPS5 sediment trap at 260 m depth and was also clearly detected at 1080 m depth. The possible factors governing the development and sinking of the mucilaginous material are discussed. A very sharp increase of sea surface temperature during June and the presence of freshened waters in the surface the following month resulted in a stronger than usual stratification of the upper water column throughout the summer season. We suggest that the steepness of the vertical density gradient was responsible for the unusual accumulation of mucous aggregates. Additionally, a diatom bloom took place during the nutrient‐depleted conditions typical of summer, a factor which may have contributed to feed the pycnocline with transparent exopolymer substances. A storm occurring in the beginning of August relaxed the stratification and promoted the deposition of the mucilaginous aggregates accumulated in the upper water column during the preceding months. Important similarities of ambient conditions preceding the apparition of mucilaginous material in our open‐sea site and those reported in the Adriatic Sea during major mucilage events, suggest that general climatic conditions, rather than local factors, drive the occurrence of major accumulations of mucilaginous material in the water column at both sub‐basins of the Mediterranean Sea. In this regard, the strength of the air temperature increase during the onset of the stratified season is proposed as a major controlling factor.     

九龙江口潮滩表层沉积物有机质的分布、来源及沉积环境指示意义

本研究旨在揭示九龙江口潮滩有机质含量及其来源的时空分异规律,寻找有效识别潮滩沉积环境的有机碳指标,以便更好地将有机碳应用于河口沉积微相识别和古环境研究。在九龙江口潮滩不同地貌单元,于夏季和冬季采集41个表层沉积物,进行粒度、总有机碳（TOC）、总氮（TN）和稳定碳同位素（δ¹³C）测试。结果显示：从高潮滩至低潮滩,沉积物粒度逐渐变粗,TOC、TN和C/N变小,δ¹³C值偏正。高潮滩有机质来源以陆源和红树林贡献为主,中潮滩以海源和互花米草贡献为主,低潮滩以海源贡献为主。九龙江口潮滩有机质的分布和来源受控于河口陆海相互作用的季节变化、潮滩沉积动力分异和潮滩植被分布。高潮滩与中–低潮滩之间,TOC存在显著性差异,TN、δ¹³C存在极显著性差异,因此参数组合TOC、TN和δ¹³C可作为高潮滩与中–低潮滩的有效判别指标。     

Characterizing the depositional settings for sedimentary organic matter distributions in the Lower Yangtze River-East China Sea Shelf System

Grain-size distributions, total organic carbon (TOC) and total nitrogen (TN) concentrations, and TOC/TN ratios (C/N) were analysed for surface sediments from the Lower Yangtze River-East China Sea (ECS) shelf system. Hierarchical cluster analysis of grain-size parameters (mode, mean, sorting, skewness and kurtosis) has been employed to characterize grain-size compositions. The results suggest there are five grain-size compositional types (type-I–V) that fingerprint distinct depositional conditions. In areas with high sedimentation rates, hydrological sorting preferentially enriches the fraction coarser than 6.4ø (12 μm) in shallow seafloor sediments (water depth<30 m) by transporting the finer fraction to the deeper seafloor (water depth>30 m), and thus forms grain-size compositional type-I (shallow) and type-II (deep). In the open shelf, where modern sediment supply is very limited, grain-size types-III–V are identified according to different winnowing intensity. Overall TOC contents significantly correlate with mud proportions, suggesting muddy sediments are the primary control on OM accumulation. However, de-association of terrestrial OM from fine sediments in the Estuary and the occurrence of presumably relict OM in the open shelf exert additional controls on OM dispersal and carbon cycling in the ECS. By considering geography, oceanography, sediment source, and the relation between sedimentation conditions and sedimentary OM distributions, we define six depositional settings: the lower river, the estuary, the coast, the offshore upwelling area, the erosional area, and the open shelf. These settings describe the sediment dispersal and associated organic matter cycling in the Lower Yangtze River-ECS shelf system.     

Dissolved organic carbon variability in a shallow coastal marine system (Gulf of Trieste,northern Adriatic Sea)

The variability of dissolved organic carbon (DOC) over days to a multi-year time span has been investigated in the Gulf of Trieste (northern Adriatic Sea) over a period of 5 years (January 1999 to December 2003). Samples were collected in a grid of 9 to 12 stations on monthly frequency and in one station on weekly (2003) and daily (1-month) frequency. DOC samples were analyzed by the HTCO method. DOC concentration varied over the five years in the range of 50 to 194 μM with annual median values ranging from 88 to 98 μM. Over the years 1999–2002, DOC showed a clear annual periodicity with winter minima and late summer maxima, higher in 1999 and 2000. During 2003 no seasonality was detected. The absence of DOC seasonality and the lower DOC concentrations during 2003 are most likely related to the drought that characterized the whole year. Accumulation was calculated as the difference between averaged winter minima (59 ± 7 μM) and the monthly averaged integrated value. DOC that had accumulated from spring to summer totally disappeared from the water column in winter when DOC concentrations reached the background value. The Gulf of Trieste, as with the rest of the Northern Adriatic each year, seems to be able to bring back DOC concentrations at low levels despite the significant external (mainly Isonzo River inputs) and internal organic matter loads. DOC concentration exhibited quite wide fluctuations weekly and daily, suggesting there might be DOC of different turnover time through production, consumption, migration and accumulation.     

末次盛冰期以来南海北部神狐海域沉积有机质的组成特征及其古气候/环境意义

通过对两根沉积柱GHE27L和GHE24L的总有机碳（TOC）、总氮（TN）、C/N比值及稳定碳同位素（δ13C_org）的分析,本文探讨了21.1 ka BP以来南海北部陆坡神狐海域沉积有机质的组成特征及可能的古气候/环境信息。沉积柱GHE27L的TOC含量、TN含量、C/N比值及δ13C_org值分别为0.53%~1.81%,0.07%~0.18%,8.2~16.0和-23.6‰~-20.3‰。沉积柱GHE24L各参数则分布为0.45%~1.65%,0.09%~0.24%,5.3~12.2和-22.6‰~-20.4‰。沉积柱总体有机质的剖面变化显示,末次盛冰期以来南海北部沉积有机质具有海洋和陆地混合来源,但以海洋有机质来源为主。冰期陆源有机质对总有机质的相对贡献比全新世高。末次盛冰期南海北部气候相对干旱,C₄植被发育。全新世夏季风增强、降雨增多。自2.0 ka BP以来,人类活动对南海北部海洋初级生产力产生一定的影响。     

黄、渤海沉积物中陆源脂类有机质的组成分布与转化特征

本文对黄、渤海表层沉积物中脂类化合物的组成进行了分析研究。结果表明,黄、渤海表层沉积物有机碳的含量为0.03%~1.02%,以黄河口含量最低,黄河口外和双台子河口外,以及北黄海和南黄海中部含量较高。有机质碳稳定同位素δ13C的分布为-21.55‰~-24.28‰,表征其陆海双重来源特征,并且海源特征由河口向海、由近岸向离岸逐渐增强。陆源脂类化合物以河口处略高,河道处略低,由河口向渤海中部和靠近渤海海峡方向迅速降低,表现出显著的河流输入特征;其形态组成由河道的游离态接近100%的绝对优势,迅速转变为渤海中部的以皂化结合态为主（大于50%）,仅在渤海中部和渤海海峡附近存在小于5%的矿物结合态,转化程度较低。北黄海中部和南黄海中部泥质区的有机碳和陆源脂类化合物显著富集,但其对总有机碳的相对贡献较小;其中皂化结合态超过50%,矿物结合态小于10%,说明其具有中等偏高的转化程度。     

Chemical parameters characterizing the sedimentary environment in a NW Adriatic coastal area (Italy)

Organic matter constituents (C, N, P) have been measured in surficial sediment samples from a coastal area often subjected to eutrophication phenomena. Chemical and physico-chemical parameters are substantially homogeneous throughout the area investigated, indicating a mainly autochthonous origin of the sedimented organic matter and allowing some considerations on the diagenetic processes possibly occurring at the sediment-water interface in relation to nutrient release.     

Relationship between the optical properties of chromophoric dissolved organic matter and total concentration of dissolved organic carbon in the southern Baltic Sea region

Absorption and fluorescence of chromophoric dissolved organic matter (CDOM) and dissolved organic carbon (DOC) measurements were performed during three oceanographic surveys in 1994 in the southern Baltic Sea (Polish area of the Baltic Proper). DOC was measured both by high-temperature catalytic oxidation (HTCO) and low-temperature oxidation (LTO) conventional persulphate methods. CDOM fluorescence was shown to be highly correlated with absorption, with the same regression parameters, despite the seasonal change in different hydrographic conditions and the fluorescence quantum yield variations (1.23 ± 0.07 in April and 0.97 ± 0.12 in September). The results show a good correlation between the optical parameters and DOC although ˜ 70% of the DOC does not display significant absorption in the UV-visible range (350–750 nm). The non-absorbing DOC measured with HTCO method appears unaffected by seasonal changes. Consequently, total DOC can be predicted by optical methods using remote sensing techniques. The non-absorbing DOC measured by LTO method varies from 62% (April) to 76% (September), which implies that there is requirement for estimates on a seasonal basis.     

夏季黄海不同水团溶解有机物分布特征

依据2017年8—9月对黄海海域溶解有机物(DOM)的调查,探讨了夏季黄海海水中溶解有机碳(DOC)和有色溶解有机物(CDOM)的空间分布特征。在表层海水中,受陆源影响较大的近岸海域CDOM含量相对较高,北黄海冷水团区域由于水产养殖的饵料引起DOC浓度升高,且该部分DOC以无色为主。DOC浓度随深度逐渐降低,而CDOM逐渐升高,该特征在冷水团区域更为显著,因此DOC和CDOM在冷水团区域的表底差异远大于浅水区的非冷水团区域。陆源输入和初级生产是引起表层DOC升高的主要原因,而光漂白则引起CDOM降低,同时光漂白还导致表层水体中CDOM分子量和芳香性低于底层。底层溶解氧饱和度在冷水团为80%～93%,均表现为弱不饱和状态。层化不仅阻碍了O₂向底层水体输送,还抑制了DOC和CDOM的垂向混合,这是引起冷水团区域表底层DOC和CDOM差异较大的主要原因。     

Spatial and temporal prokaryotic variability in the northern Adriatic Sea

The prokaryotic community, both in terms of abundance and activity (exoenzymatic hydrolysis of proteins, polysaccharides and phosphorylated molecules and leucine uptake), was investigated seasonally for a 3‐year period (2004–2006) in the Gulf of Venice (northern Adriatic Sea). By focusing on spatial and temporal variability, the prokaryote dynamics showed significant variations on a horizontal and seasonal scale, but no substantial differences were observed among years. The basin‐scale variability was mainly influenced by allochthonous inputs from the Po river and the Venice Lagoon, which were the main source of nutrients, acting as a ‘bottom up’ control on prokaryotes. On a seasonal scale, all the microbial parameters (except the polysaccharide degradation) showed significant variations following the temperature fluctuations. The annual rate of change was very low for all the chemical, physical and biological parameters and only the abundance and phosphatase activity of the prokaryotes differed significantly among years.     

Coralligenous habitat in the northern Adriatic Sea: an overview

The rocky outcrops irregularly scattered in the sandy‐muddy sea bed of the Northern Adriatic, formed by a base rock and a superimposed concretion of vegetal and animal organisms, are considered an infralittoral coralligenous habitat, according to the most recent definition. In the last four decades, research has mainly concentrated on their geology because of the question of the origin of the base rock – very similar to beachrock – which has only recently been attributed to sedimentary cementation induced by methane seeps. Studies on their macrobenthic assemblages have also been published recently, but true comparisons among them are difficult because they mostly refer only to a few selected phyla or to short‐term observations. Very few papers deal with the whole of the animal and plant communities, including all taxonomic groups and the most important environmental variables. On the basis of the literature data concerning several outcrops in the Gulf of Venice, we suggest that the Adriatic reefs differ slightly from the classic deeper coralligenous assemblages around the Mediterranean coast because they have smaller concretions of algae builders. We also suggest that the Northern Adriatic coralligenous reefs are younger than the other reefs occurring in the Mediterranean Sea.     

The Influence of Mucous Aggregates on the Microphytobenthic Community in the Northern Adriatic Sea

Abstract. An extended reappearance of mumus aggregates in the Northern Adriatic Sea in 1991 gave rise to the hypothesis of a possible influence of the mucus, settled on the bottom, on benthic flora and fauna.
This work investigates the variations in the microphytobenthic community in three stations of the Gulf of Trieste (AA1, AA2, AA3) during 1991, when mucous aggregates were present, and during the two following years, when no such aggregates were observed.
Water samples were collected by N iskin bottle in the bottom layer for nutrient analysis, and sediment samples were collected by divers. The diatom species and cell densities were determined under an inverted microscope. All the data were processed with the aim to evaluate community composition and possible relations with the presence of mucous aggregates in 1991.
The results showed a general decrease of benthic diatoms from 1991 to 1993, both in quality and quantity, for all the investigated sites. Statistical analyses on microphytobenthos, hydrological parameters, and nutrient concentrations indicated differences among the considered years. The microphytobenthic community in summer 1991 appeared to be quite different from those of the other years. The density of benthic diatoms was apparently not correlated with nutrient availability in the bottom layer, but was rather influenced by changes in temperature.
The presence of a dense microphytobenthic community in 1991 might be explained by a combination of adequate conditions related to the presence of mucous aggregates, including a more undisturbed substratum caused by the interruption of dredging, decreased grazing pressure due to a declined filtering capacity of epifauna, and nutrient-rich sediment for extra nutrient disposal remineralized at the mucus-sediment interface. The mucilage aggregates therefore apparently stimulated the microphytobenthic community, in contrast to the effects on the benthic macrofauna, which were perturbed by the mucus.     

Isotopic signatures of organic matter in sediments of the continental shelf facing the Orinoco Delta: Possible contribution of organic carbon from savannas

The ⁸⁷Sr, ¹³C, and ¹⁵N isotopic signatures of organic matter in sediments from the continental shelf facing the Orinoco Delta were measured to determine the contribution of sediments transported from the Amazon River by the coastal Guayana current and the sediments transported by the Orinoco River. Box core samples between 60 and 300 m water depth collected along 4 transects located eastwards to the Orinoco Delta were analyzed. Carbon and nitrogen concentrations decreased with depth under water on the shelf, and were strongly correlated indicating homogeneity of organic matter composition. Phosphorus content was also associated to organic matter in most samples, but some of them revealed deposition of P-enriched sediments. The ⁸⁷Sr/⁸⁶Sr ratios showed a strong continental signature averaging 0.7117, therefore, limiting the possible carbon and nitrogen sources associated with these sediments to C3 trees, C4 grasses, or freshwater phytoplankton. The δ¹³C values were relatively high averaging −21‰, above values reported for sediments on the Amapá shelf and the Amazon River in Brazil. Average δ¹³C values did not differ significantly among transects. High δ¹³C values point to the influence of organic matter transported from the C4-plants dominated savannas in the northern fringe of the Orinoco River. δ¹⁵N values were positive and averaged 5‰, being within the range of values measured in the Marajo island (Amazon River) and the estuary of the Pará River. The δ¹⁵N values differed significantly among transects (4.9–5.2‰), lowest values corresponding to the northernmost transect near the coast of Trinidad, and the highest values corresponding to the transect located at the southernmost position.     

Genesis of the Northern Adriatic Sea (Northern Italy) since early Pliocene

The Northern Adriatic Sea is a shallow and very flat shelf area located between the northern Apennines, the southern Alps and the Dinarides; its present day physiography is the result of the filling of a relatively deep Quaternary foredeep basin, developed due to the northeastward migration of the Apennine chain. Multichannel seismic profiles and well data have allowed documenting the stratigraphic architecture, the depositional systems and the physiographic evolution of the Northern Adriatic sea since early Pliocene time. In particular, three main depositional sequences bounded by regional unconformities were recognized. The Zanclean Sequence 1 documents first the drowning of late Messinian incised valleys and then the southward progradation of a shelf-slope system, which is inferred to be related to a tectonic phase of the Apenninic front. The Piacenzian-Gelasian Sequence 2 records a relatively rapid transgressive episode followed by minor southward progradation; the top of the sequence is associated with a major late Gelasian drowning event, linked to the NE-ward migration of the Apennine foredeep. The Calabrian to upper Pleistocene Sequence 3 testifies the infilling of accommodation previously created by the late Gelasian drowning event, and it initially accumulated in deep-water settings and then in shallow-water to continental settings. The upper part of Sequence 3, consisting of the paleo-Po deltaic system, is composed of seven high-frequency sequences inferred to record late Quaternary glacio-eustatic changes. These high-frequency sequences document the stepwise filling of the remaining accommodation, resulting in the development of the modern shelf.