The application of isotopic and biogeochemical markers to the study of the biochemistry of organic matter in a macrotidal estuary, the Loire, France

The biogeochemistry of organic matter in a macrotidal estuary, the Loire, France, has been studied for two years during different seasons. Both particulate matter and sediment have been sampled in the riverine zone, in the maximum turbidity zone and in the ocean near the river mouth. Two techniques have been used: carbon isotopic ratio determination and analysis of lipid-marker signatures in the n-alkane, n-alkene and fatty acid series. For the period corresponding to the output of the maximum turbidity zone in the ocean, the complete change of organic matter, continental in nature in the inner estuary, pure marine in the outer estuary is well illustrated by the decrease of δ¹³C values and of carbon preference index of n-alkanes. Input sources of organic matter by continental plants, plankton and micro-organisms are discussed from biogeochemical-marker analyses data along with the processes of accumulation of particles and their evolution with the season. Some criteria for evidencing the nature of various organic-matter pools are assessed and compared in different chemical-marker series as follows: high molecular weight n-alkanes and fatty acids, perylene for continental imprints, polyunsaturated 18-, 20- and 22-carbon fatty acids, n-C₁₇, n-alkenes and squalene for algae imprints, branched iso and anteiso fatty acids, Δ11-C_18:1 for microbial imprints.     

Diel fluctuations in dissolved free amino acids and monosaccharides in Chesapeake Bay dinoflagellate blooms

The accumulation of phytoplankton biomass in recurring summer dinoflagellate blooms of Chesapeake Bay is accompanied by large pools of dissolved organic matter (DOM). Two fractions of the DOM, free amino acids (DFAA) and monosaccharides (MONO), were measured at 3 h intervals in mixed species dinoflagellate blooms (Katodinium rotundatum, Gymnodinium spp.) and related to productivity, biomass and photoperiod. Peak chlorophyll levels for the three blooms were 28, 65 and 938 μg1⁻¹. In general, DFAA and MONO concentrations increased with increasing biomass of bloom-forming species, reaching 203 and 844 μg1⁻¹. MONO appeared to accumulate during the day while there was no consistent pattern for DFAA. The accumulations of DFAA and MONO in blooms indicate that bloom production might stimulate microheterotrophy, thereby enhancing carbon and nutrient cycling in bloom-impacted regions.     

Sugar and Lipid Components in Sea Foam near Kelp Beds

Abstract. A component analysis of the sugar and lipid fraction in foam layers around kelp beds on the South African west coast showed the following trends: In the residue of foam drainage of both 12 h and 120 h old foam the sugar fraction is represented by mannose (33–41 %), galactose (4–30%), fucose (3–29%) and glucose (19–26%). With the exception of fucose, the same components could be found in foam filtration. In the lipid fraction the main fatty acids are palmitic (23.3–27.3%), oleic (14.0–5.5%) and timnodonic acid (11.2–9.1%). Selacholeinic acid was only found in 12 h old foam while lignoceric acid could not be located in foam filtration. Against expectation mannitol was not identified in quantifiable amounts in foam samples although it is the dominant component of kelp mucilage, whose presence is of major importance for foam formation. Hypotheses explaining the lack of mannitol are forwarded. Component sugar and lipid content for 11 of foam was calculated and estimation of sugar and lipid content in an average foam patch (volume of 30001) is given. The importance of foam formation as a mechanism for binding and transfer of energy in the marine environment is emphasized.     

The impact of salt water inflows on the distribution of polycyclic aromatic hydrocarbons in the deep water of the Baltic Sea

Salt-water inflows into the Baltic Sea are important events for renewing the deep and bottom waters of the deep basins of the Baltic Sea. These events occur only at irregular intervals. The last strong event was in January 1993 followed by minor inflows in winter 1993/1994. As a result of these inflows, the deep water of the central Baltic basins was completely renewed.Based on extensive observations of polycyclic aromatic hydrocarbons (PAHs) in water, fluffy layer material and surface sediments between 1992 and 1998, the transformation of PAHs and the modification of their distribution in the Baltic deep water is discussed in connection with the spreading of the inflowing highly saline and oxygen-rich water along its pathway from the sills into the central basins. In the course of the inflows in 1993/1994, the PAH concentration in the deep water of the different basins increased significantly. The concentrations were elevated, at least by a factor of 2 and as much as seven to eight times (for the four-ring PAHs) compared to the previous and the following years. Two hypotheses for the causes were discussed: the inflowing salt water may have entrained more highly polluted surface water in the western Baltic Sea, or it may have entrained contaminated fluffy layer material or sediment particles along the route of transport.     

东海海域海水中颗粒氨基酸(PAA)的组成与含量的分布调查研究

海水中的有机物的含量微少，约为0.5~2.0 C mg/L，但其种类复杂。其中以溶解有机物(DOM)为主，而颗粒有机物(POM)所占比例则更少。大洋海水中的POM主要来源于浮游生物等的死骸及其分解碎屑；另外还有海水中受风浪影响所进行的DOM-POM的动力平衡产物。近岸海水还受河流和大气带入的陆源尘影响。POM主要由颗粒氨基酸(PAA)组成。即由Asp、Glu、Thr、Ser、Ala、Gly、Leu、Ile、Val、Met、Cys、Tyr、Lys、His、Arg、Phe、Pro等17种氨基酸组成。它们是食碎动物的主要食物，构成海洋食物链的一环，与该水域生产力有直接联系。纪明侯等(1992)于1983年和1984年首次对青岛胶州湾海水中的颗粒氨基酸的组成和含量的变化及其季节变化进行了调查研究。并且在1982年和1984年前后对渤海湾、黄河口和长江口附近水域同样调查研究了表层海水中PAA的组成与含量分布。他们还于1981年7、8月和1982年7、8月乘“科学一号”考察船进一步研究了长江口外东中国海，包括福建省外海、济州岛附近海域和黑潮流域26°00′-33°00′N、123°00′-129°00′E范围内海域的20余个站位的表层海水和部分站位上不同水深中的PAA的组成和含量。兹将调查研究结果报道如下。     

Study of Adsorption Isotherm Curves of Amino Acids on the Kaolinite

This paper studies the adsorption isotherm curves of four amino acids (glyucine,aspartic acid,glutamic acid and lysine)and the effects of existences of different concentrations of Cu(Ⅱ) on them.Both the adsorption isotherm of the amino acids on the kaolinite and that when the copper ion Cu(Ⅱ） exists belong to the Langmuir type.The slopes of these adsorption isotherm increase with the increasing concentrations of Cu(Ⅱ） added.It can be explained in terms of formation of the type(Ⅰ） ternary surface complexes in these systems.The regular pattern of the effects of copper ion Cu(Ⅱ) on the adsorption isotherm of amino acids on the kaolinite is identical with that of its effects on the exchange and adsorption percentage E(%)-pH on the kaolinite in the same system.     

Variation in microbial biomass and community structure in sediments of peter the great bay (sea of japan/east sea), as estimated from fatty acid biomarkers

Variation in the microbial biomass and community structure found in sediment of heavily polluted bays and the adjacent unpolluted areas were examined using phospholipid fatty acid analysis. Total microbial biomass and microbial community structure were responding to environmental determinants, sediment grain size, depth of sediment, and pollution due to petroleum hydrocarbons. The marker fatty acids of microeukaryotes and prokaryotes - aerobic, anaerobic, and sulfate-reducing bacteria -were detected in sediments of the areas studied. Analysis of the fatty acid profiles revealed wide variations in the community structure in sediments, depending on the extent of pollution, sediment depth, and sediment grain size. The abundance of specific bacterial fatty acids points to the dominance of prokaryotic organisms, whose composition differed among the stations. Fatty acid distributions in sediments suggest the high contribution of aerobic bacteria. Sediments of polluted sites were significantly enriched with anaerobic bacteria in comparison with clean areas. The contribution of this bacterial group increased with the depth of sediments. Anaerobic bacteria were predominantly present in muddy sediments, as evidenced from the fatty acid profiles. Relatively high concentrations of marker fatty acids of sulfate-reducing bacteria were associated with organic pollution in this site. Specific fatty acids of microeukaryotes were more abundant in surface sediments than in deeper sediment layers. Among the microeukaryotes, diatoms were an important component. Significant amounts of bacterial biomass, the predominance of bacterial biomarker fatty acids with abundance of anaerobic and sulfate-reducing bacteria are indicative of a prokaryotic consortium responsive to organic pollution.     

Seasonal Changes in Nitrogen, Free Amino Acids, and C/N Ratio in Mediterranean Seagrasses

Abstract. Seasonal changes in nitrogen, free amino acids, and carbon were investigated in the three Mediterranean seagrasses Posidonia oceanica, Cymodocea nodosa , and Zostera noltii. Leaves, rhizomes, roots, as well as dead plant material were analysed separately. Highest N-concentrations were obtained in the winter months, regardless of species or plant part. In contrast to the other two species, the N-content in Posidonia was higher in the rhizomes than in the leaves.
In the investigated species, marked differences in the free amino acid (FAA) composition were detected between species: Proline, lacking in Posidonia , was the main component in Cymodocea. In Posidonia , FAA decreased from 320umol g^-1 (dry wt) in leaf sheaths to 1.5 umol g^-1 (dry wt) in the leaf tips. The function of proline as a possible storage and/or stress metabolite is discussed.
High C/N values in dead P. oceanica and C. nodosa rhizomes as well as in P. oceanica wrack seem to be related to considerable resistance to decomposition. Low C/N ratios did not increase in detached C. nodosa and Z. noltii leaves, which began to decompose shortly after detachment from the plants.     

Probing molecular-level transformations of dissolved organic matter: insights on photochemical degradation and protozoan modification of DOM from electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Molecular-level characterization of natural organic matter (NOM) has been elusive due to the inherent complexity of natural organic mixtures and to the fact that individual components are often polar and macromolecular. Electrospray ionization (ESI) is a “soft” ionization technique that ionizes polar compounds from aqueous solution prior to injection into a mass spectrometer. The highest resolution and mass accuracy of compounds within NOM have been achieved when ESI is combined with an ultrahigh-resolution mass spectrometer such as the Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). With this technique, individual molecules within a variety of natural organic mixtures can be detected and their elemental composition can be determined. At low mass-to-charge (m/z) ratio, the resolution is high enough to assign exact molecular formulas allowing specific components of these mixtures to be identified. In addition to molecular identification, we can now use ESI FT-ICR MS to examine molecular-level changes in different organic mixtures as a function of relevant geo-processes, such as microbial alterations and photochemistry. Here we present the results from the application of ESI FT-ICR MS to two geochemical questions: (1) the effect of photoirradiation on the molecular composition of fulvic acids and (2) the role of protozoan grazers in the modification of DOM in aquatic systems.     

Particulate and dissolved amino acids in the lower Mississippi and Pearl Rivers (USA)

In this study, we present seasonal changes (monthly samples from September 2001 to August 2003) in the abundance and composition of dissolved and particulate amino acids, at one station in the lower Mississippi and Pearl Rivers (LA, MS: USA). Spatial changes over a 4-day transmit from river km 390 to river mouth (Head of Passes, LA) in the Mississippi River, and a two-day downstream sampling from Jackson (MS) to Stennis Space Center (MS) were also determined. Temporal data in the lower Mississippi River showed significantly lower concentrations of dissolved combined amino acids (DCAA, 0.8 to 2.2 μM) and dissolved amino acids in high molecular weight fraction (HMW DAA, 0.2–0.4 μM) than in the Pearl River (DCAA, 1.4–4.3 μM; HMW DAA, 0.4–1.4 μM). Dissolved free amino acids (DFAA) were significantly lower than DCAA in both rivers, and displayed minimal seasonal variability. DCAA, HMW DAA, and particulate amino acids (PAA) were generally higher during high-flow periods, which may have suggested dominance in terrestrial sources. Carbon-normalized yield of PAA (%C-PAA) was generally higher during low-flow conditions and positively correlated with chlorophyll-a (chl-a), reflective of in situ sources. Downstream variability in the lower Mississippi River showed stable DCAA concentrations, a decline in PAA (from 1.06 to 0.43 μM), and a gradual increase in mole percent of non-protein amino acids (%NPAA). This likely reflected bacterial degradation of phytoplankton biomass during falling discharge. Nitrogen-normalized yield of PAA (%N-PAA) was inversely correlated with PAA (R = − 0.7, n = 48), indicative of short-term sedimentation and resuspension events. Conversely, downstream decreases in DCAA and middle-reach peaks of PAA and %N-PAA in the Pearl River, likely resulted from photochemical degradation of DOM as well as algal production during base-flow conditions. The comparisons in abundance and composition of DAA and PAA in these different river systems provides important information on in situ nitrogen and carbon cycling as related to riverine inputs of organic matter to coastal ocean.