Characterization of dissolved organic matter across the Subtropical Convergence off the South Island,New Zealand

Dissolved organic matter (DOM) was investigated along a gradient across the Subtropical Convergence (STC) off the South Island, New Zealand. Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), excitation emission matrix fluorescence (EEM) spectroscopy, and molecular lignin analysis techniques were used to study this DOM. The analysis revealed a group of compounds found only in the coastal DOM samples, which were also characterized by an elevated terrestrial DOM fluorescence pattern and elevated lignin content if compared to the offshore samples. This group exhibited a high degree of carbon unsaturation, as evident from high double bond equivalence minus oxygen values (DBE-O > 9) and maximum fluorescence intensity. Sulfur-containing molecular formulae for summer DOM samples were much more abundant across the entire transect of the STC compared to winter and exhibited distinctly different hydrogen:carbon and oxygen:carbon elemental ratios, suggesting a possible correlation between biological activity and sulfur compounds. The molecular formulae common to all STC samples were compared with those calculated for DOM extracted from freshwater collected from a stream discharging into Doubtful Sound (West Coast, New Zealand). ESI-FT-ICR-MS measurements undertaken in negative electrospray ionization (ESI?) mode indicated that 30% of the molecular formulae were present in both types of DOM, while in positive ESI mode (ESI+) over 90% of the formulae were present in all samples. Hence, a significant portion of the molecular formulae assigned to the solid-phase extractable DOM pool (SPE-DOM) appear to be identical in oceanic and freshwater samples.     

Advanced characterization of marine dissolved organic matter by combining reversed-phase liquid chromatography and FT-ICR-MS

Marine dissolved organic matter (DOM) was separated by reversed-phase (RP) liquid chromatography method and analyzed with fluorescence/absorption detection and Fourier transform ion cyclotron mass spectrometry (FT-ICR-MS). The three key characteristics of the RP method are: (a) The C18-RP column chosen provides enhanced separation when the aqueous phase is 100% buffer-free water, and it does not degrade over time; (b) the water eluent adjusted to pH 7 significantly improves the resolution of water soluble compounds; (c) the initial flow maintained at low levels improves the separation of polar compounds. In samples, containing “fresh” DOM, specific peaks were detected, which were absent in “old” DOM samples. The combination with size exclusion chromatography (SEC) also demonstrated the relation between polarity and molecular size of DOM. FT-ICR-MS was applied to evaluate the quality of separation on a molecular scale demonstrating that physico-chemical characteristics of DOM can be related to molecular formulas. Sample extracts were separated into 4 preparative fractions, and a large suite of the identified molecular formulas only occurred in specific fractions. This is an important basis for the application of further analytical techniques in order to perform a more target-oriented analysis aiming at the determination of source and process biomarkers for DOM.     

pH对SPE-HPLC-ESI-Q-TOF-MS检测海水中小分子活性物质的影响研究

海水溶解有机物(dissolvedorganicmatter,DOM)中含有的生物活性物质在海洋生态系统中作用巨大,但因缺乏适合的分离提取方法而严重阻碍了对其不同组分在生态系统中作用的探索。固相萃取法对富集提取海水DOM十分有效,在用其提取海水DOM时,海水pH对活性物质提取效果的影响很大,但目前针对海水的这种影响尚存在很大争议。本文以天然近海海水作为基质,探究不同pH条件下用亲水-疏水平衡(hydrophilic-lipophilicbalanced,HLB)固相萃取小柱萃取海水中活性分子的提取效率,并使用高效液相色谱-四极杆飞行时间质谱(HPLC-Q-TOF-MS)在负离子(ESI-)模式下检测解析提取物的组成。研究结果表明,当海水样品pH为中性和强酸性时都能获得较好的提取效率,随着pH的降低,提取物质谱的整体响应值降低,但可识别的谱峰数目增加,提取出有机物的分子量和性质差异都更广泛。分析提取物分子在范克雷维伦(van Krevelen)图和质荷比-氢碳比(m/z-H/C)图上的分布发现,中性条件适合提取饱和度较高的小分子化合物,而具有生物活性的带有不饱和基团的化合物及蛋白质、糖类等生物大分子在强酸性提取条件时提取效果和分辨率更好。综合提取效率、有效峰数目和分子组成特征考虑,用HLB固相萃取小柱提取近海海水中的小分子活性物质时,将海水样品pH调节为2较为适宜。     

Mechanisms of pore water organic matter adsorption to montmorillonite

The extent and mechanisms of adsorption of marine pore water organic matter to montmorillonite were studied in a series of batch and sequential adsorption experiments. Pore water natural organic matter (pNOM) and easily extracted natural organic matter (eNOM) were collected from Liberty Bay (Puget Sound, WA, USA) sediments. The pNOM and eNOM were each divided into two size fractions using a 1000 D ultrafilter. Batch adsorption isotherms were approximately linear, and the >1000 D fractions of both pNOM and eNOM had larger partition coefficients (K_d) than the <1000 D fractions. A two-component fit of the sequential adsorption data indicated that pNOM and eNOM contained a similar amount of NOM (30%) that was not surface reactive toward montmorillonite. After correcting the batch adsorption K_ds for the non-reactive components, the K_ds estimated by batch and sequential adsorption were identical (2.7 l/kg for >1000 D pNOM and eNOM, and 1.6 l/kg for <1000 D pNOM and eNOM). Mechanisms of adsorption were investigated by systematically changing conditions (pH, temperature and ionic composition) of >1000 D fractions during batch isotherm experiments. Adsorption of NOM was found to decrease with increased temperature, suggesting that hydrophobic effects were not the dominant adsorption mechanisms in this system. Ion exchange was also not an important adsorption mechanism because adsorption increased with ionic strength. The observed enhancement in adsorption with ionic strength indicated that van der Waals interactions were important in the adsorption of NOM. Ligand exchange was found to be a significant mechanism since the presence of SO₄²⁻ in solution reduced the amount of NOM adsorbed. Ca²⁺ enhanced adsorption slightly more than Na⁺, suggesting that cation bridging was involved. The relative contributions of van der Waals interactions, ligand exchange and cation bridging were estimated to be approximately 60%, 35% and 5%, respectively, for adsorption of NOM in a CaCl₂ solution.     

Tracing terrigenous dissolved organic matter and its photochemical decay in the ocean by using liquid chromatography/mass spectrometry

Reversed-phase liquid chromatography/mass spectrometry (LC/MS) is introduced as a new molecular fingerprinting technique for tracing terrigenous dissolved organic matter (DOM) and its photochemical decay in the ocean. DOM along a transect from the mangrove-fringed coast in Northern Brazil to the shelf edge was compared with mangrove-derived porewater DOM exposed to natural sunlight for 2–10 days in a photodegradation experiment. DOM was isolated from all samples via solid-phase extraction (C18) for LC/MS analysis. DOM in the estuary and ocean showed a bimodal mass distribution with two distinct maxima in the lower m/z range from 400 to 1000 Da (intensity-weighted average of 895 Da). Terrigenous porewater DOM from the mangroves was characterized by a broad molecular mass distribution over the detected range from 150 to 2000 Da (intensity-weighted average of 1130 Da). Polar compounds, i.e., those that eluted early in the reversed-phase chromatography, absorbed more UV light and had on average smaller molecular masses than the more apolar compounds.     

海洋球石藻(Emiliania huxleyi)活性物质分离鉴定及其抗菌抗氧化性能研究

以海洋球石藻Emiliania huxleyi为原料,提取分离生物活性物质,为该藻活性物质的研究与开发提供理论基础。通过对球石藻75%乙醇浸提物采用乙酸乙酯进行萃取,进一步利用薄层色谱、硅胶色谱、Sephadex LH-20凝胶色谱及高效液相色谱(HPLC)等方法,对化合物成分进行逐步分离纯化,获得纯度大于95%的单体化合物;通过~1HNMR、~(13)CNMR及HRMS等波谱分析技术鉴定化合物的结构,并对其抗菌、抗氧化性能进行初步分析。结果分离鉴定出3种单体化合物,分别为叶绿醇(C_(20)H_(40)O)、棕榈酸(C_(16)H_(32)O_2)和肉豆蔻酸(C_(14)H_(28)O_2),这些化合物均为首次从海洋球石藻中分离获得。其中叶绿醇具有较强的抗氧化能力,且对肝癌细胞Hep G2的增殖有较强的抑制作用,其他两种化合物对金黄色葡萄球菌、枯草芽孢杆菌及副溶血性弧菌均有不同程度的抗菌活性。另外,海洋球石藻中这些化合物除了具有一定的抗菌抗氧化性能外,可能在球石藻响应胁迫(如病毒感染)过程中也具有重要作用。     

Molecular characterization of dissolved organic matter (DOM) along a river to ocean transect of the lower Chesapeake Bay by ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

In this study, electrospray ionization coupled to Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) is utilized to molecularly characterize DOM as it is transported along a river to estuary to ocean transect of the lower Chesapeake Bay system. The ultrahigh resolving power (greater than 500,000) and mass accuracy of FTICR-MS allow for the resolution of the thousands of components in a single DOM sample, and can therefore elucidate the molecular-level changes that occur during DOM transformation from a terrestrial location to the marine environment. An important feature of FTICR-MS is that its sensitivity allows for direct analysis of low salinity samples without employing the traditional concentration approaches involving C₁₈ extraction or ultrafiltration. To evaluate the advantages of using direct analysis, a C₁₈ extract of riverine water is compared to its whole, unfractionated water, and it was determined that the C₁₈ extraction is selective in that it eliminates two major series of compounds. One group is aliphatic amines/amides that are not adsorbed to the C₁₈ disk because they exist as positive ions prior to extraction. The second group is tannin-like compounds with higher oxygen contents and a more polar quality that also allow them not to be adsorbed to the C₁₈ disk. This direct approach could not be used for brackish/saline waters, so the C₁₈ method is resorted to for those samples. Along the subject transect, a significant difference is observed in the molecular composition of DOM, as determined from assigned molecular formulas. The DOM tends to become more aliphatic and contain lower abundances of oxygen-rich molecules as one progresses from inshore to the offshore. A considerable amount of molecular formula overlap does exist between samples from sites along the transect. This can be explained as either the presence of refractory material that persists throughout the transect, due to its resistance to degradation, or that the assigned molecular formulas are the same but the chemical structures are different. ESI-FTICR-MS is a powerful technique for the investigation of DOM and has the ability to detect compositional variations along the river to ocean transect. Visualization tools such as two dimensional and three dimensional van Krevelen diagrams greatly assist in highlighting the shift from the more aromatic, terrestrial DOM to the more aliphatic, marine DOM.     

Hydrocarbons in the Bay of Bengal and Central Indian Basin bottom sediments: indicators of geochemical processes in the lithosphere

A study on the bulk distributions and molecular structures of n-alkanes and polycyclic aromatic hydrocarbons (PAH) in organic matter of the sediments from the Bay of Bengal and the Eastern and Central Indian Basins was undertaken. The former two regions represent areas characterised by “normal” sedimentation while the third one mainly represents a region of “active tectonism”. Content of the hydrocarbons in the sediments of “normal” sedimentation ranges between 4.6 and 10.5 μg/g and aromatic hydrocarbons ranges between 0 and 0.38 μg/g. n-Alkanes in the sediments of the northern deep part of the Bay of Bengal consist mostly of long-chain structures (total C₂₅–C₃₃ up to 70%) with a high carbon preference index (CPI=3.01–3.43), indicating a large contribution of organic matter from terrigenous sources. The sediments from the Eastern Indian Basin have n-alkane distributions in which the long-chain components did not exceed 52.5% and the CPI was 1.7–1.90, indicating that the hydrocarbons are mostly derived from marine sources. Sharp increases of hydrocarbons are found in the vicinity of the tectonically active region of the Central Indian Basin, particularly in the sediments collected from the fracture zone. The total concentration of hydrocarbons increase to 170 μg/g and the aromatic hydrocarbons fraction to 156.3 μg/g. The proportion of short-chain n-alkanes increases up to 70%, CPI decreases to 0.76–1.12, and high concentrations of n-C₁₆ (16–40%) occur, all of which are absent in the other samples. The molecular content of PAH includes the unsubstituted individual structures: biphenyl, fluorene, pyrene, perylene, benzo(ghi)perylene, and the groups of homologues of naphthalene, benzofluorene, phenanthrene and chrysene. The association of the PAH and composition of paraffin hydrocarbons in the surficial sediments of deformation zone indicate that these are the resultant products of hydrothermal processes. It is, therefore, suggested that the association and composition of the hydrocarbons in sediments can be utilised as a paleoceanographic parameter to decipher the history of tectonism of an area.     

硫酸皮肤素寡糖的分离与制备

利用软骨素酶 ABC (Chondroitinase ABC,EC4 .2 .2 .4 )对硫酸皮肤素 (Dermatan Sul-fate,DS)进行控制降解。对得到的混合寡糖首先采用低压凝胶渗透色谱 (L PGPC)进行分级 ,然后对每一组分再利用强阴离子交换高压液相色谱 (SAX- HPL C)进行分离 ,最终制备出聚合度为 2 ,4 ,6 ,8,10 ,12的寡糖纯品。寡糖纯度采用 SAX- HPL C,毛细管电泳 (CE)以及聚丙烯酰胺凝胶电泳(PAGE)进行检验 ,结构采用电喷雾离子化质谱 (ESI- MS)以及核磁共振波谱 (NMR)技术确定     

海洋有机质的光谱分析方法评述

海洋有机质的光谱分析已成为海洋碳循环的研究热点之一。本文从天然有机质吸收光谱和荧光光谱分析的基本原理入手,系统梳理了有机质光谱分析中容易被忽视的基本概念,讨论了过滤与保存方式、p H值、荧光内滤效应等对有机质光谱分析的影响。结合色氨酸、酪氨酸、腐殖酸及大量现场样品的实验结果,对吸收光谱和三维荧光光谱的不同解析方法进行了系统的分析与对比。基于在南海、西菲律宾海获取的现场调查数据,对于文献中常用的荧光指数(FI)、腐殖化指数(HIX)、自生源指数(BIX)等光谱参数的内在含义及其在海洋环境中的适用性进行了评述。此外,还归纳和总结了胶体有机质和颗粒有机质荧光分析的最新进展,并对今后在光谱分析与观测领域有待完善和突破的一些关键领域进行了展望。     

TSR-altered oil with high-abundance thiaadamantanes of a deep-buried Cambrian gas condensate reservoir in Tarim Basin

The first exploratory well, the ZS1C well, with 158,545 m³ daily gas production was discovered in 6861–6944 m deep strata of the Cambrian gypsolyte layer of the Tarim Basin, China in 2014. The discovery opens a new target for the Cambrian-reservoired oil and gas exploration, and directly leads to large-scale oil and gas exploration of the deep-reservoired Cambrian oil and gas fields in the Basin. Comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry and a comprehensive two-dimensional gas chromatography–flame ionization detector revealed the presence of abundant adamantane compounds, 2-thiaadamantanes and 2-thiadiamantanes, and a large amount of sulfur-containing compounds in the condensate oil. The formation of organic sulfur-containing compounds, such as 2-thiaadamantanes, is an indication of sulfur incorporation from the gypsum in the stratum into oil and gas in the course of TSR. This reservoir has apparently suffered severe TSR alteration because (1) High content of H₂S, (2) H₂S sulfur isotopes, (3) CO₂ carbon isotopes, and others abundant data to support this findings. Similar sulfur isotopic composition of H₂S, oil condensate and the gypsum in the Cambrian strata indicate that the produced condensate is experienced TSR alteration. Therefore, the deep-accumulated Cambrian oil reservoir has experienced severe TSR alteration, and accumulated natural gas and condensate contains high sulfur content.     

An experimental method for determining the frequency-dependent added mass and added mass moment of inertia for a floating body in heave and pitch motions

Most of the existing relevant materials have been obtained from experiments, in which evaluating the added mass at the resonant frequency corresponding to the peak of a frequency-response curve obtained from the “forced” vibration analysis is the most popular technique. In this paper, a simple experimental method was presented where the “free” vibration responses instead of the “forced” ones were used to determine the values of m_ah and I_ap. The main part of the experimental system is composed of a floating body (model) and a spring–shaft shaker. The “free” vibration of this main part was induced by imposing on it an initial displacement (and/or an initial velocity), and from the time histories of displacements information such as the “damped” natural frequencies, damping ratios, sectional added mass coefficients (C_V and C_P) were obtained. Since the displacements of the spring–shaft shaker are “translational” and those of the floating body due to pitch motions are “angular”, a technique for the transformation between the associated parameters of the two components of the main part was presented.     

Correlation of the absorption coefficient with a reduction in mean mass for dissolved organic matter in southwest Florida river plumes

Results are presented from an investigation of the relationship between molecular mass distribution and optical properties for colored dissolved organic matter (CDOM); a complex assembly of organic macromolecules of marine and freshwater origin found throughout the surface ocean. Unique data are derived from the application of a new technique, a combination of a hydrophilic–lipophilic copolymer-based solid phase extraction (SPE) with electrospray ionization (ESI) continuous flowing ion trap mass spectrometry (cf-MS), for the direct determination of CDOM mass distribution. An evaluation of this copolymer-based extraction technique for the analysis of Suwannee River Natural Organic Matter (SRNOM) reference material revealed that the current method compares favorably with C₁₈ modified silica or XAD resin-based extraction methods reported in the literature when considering extraction efficiency or low extraction bias for CDOM. The mass distribution of CDOM in several freshwater to marine transition zones along coastal southwestern Florida has been determined with this technique. All rivers in the study region had a bimodal distribution of masses. A case study of the Caloosahatchee River outflow CDOM mass distribution data are presented as an example of the modification in mass distributions. The lower mass mode of the bimodal distribution was observed to have a relatively stable mean throughout the study region at 406±9 Da, while decreasing in concentration in a non-conservative manner with salinity. In contrast, the upper mass mode of the bimodal distribution was observed to have a variable mean, reaching 1408 Da in the least saline waters and decreasing by 174 Da through the transect toward higher salinity coastal waters. Coinciding with this reduction in mean mass for the upper distribution is a non-conservative reduction in concentration when compared with salinity. We define apparent organic carbon (AOC) as a function of the cf-MS determined total integrated area and use this value to determine concentration of the total extracted CDOM. Unique correlations between the CDOM fluorescence (350-nm excitation/450-nm emission) and the AOC for these coastal samples have been observed for each of three rivers in the study region. The steepest slope and highest correlation between optical and mass spectral properties are observed in rivers with strongly absorbing waters originating in the Florida Everglades and lowest in rivers draining clearer waters from widely variable and anthropogenic influenced regions. The trends in molecular mass distribution and corresponding optical properties support the theory that CDOM in coastal zones is environmentally processed material from terrestrial sources. Probable cause of the reduction in mean mass and suggestions for further investigation of sources and transformations of CDOM are discussed.     

Chemical and GC-MS characterization of marine particulate lipids

The lipid fraction of particulate organic matter in seawater was analyzed by gravimetry, liquid chromatography, gas chromatography (GS), and gas chromatography—mass spectrometry (GS—MS). Gravimetric concentrations in the Gulf of Mexico were in the range of 12–70 μg 1^?1 for near-surface samples and 9–52 μg 1^?1 for near-bottom samples. The lipids accounted for ～20% of the particulate organic carbon. Particulate lipids were found to be a much more complex mixture of organic compounds than the dissolved lipids and their composition was much more variable. The majority of the extracted weight was recovered in the polar liquid chromatography fraction (49–85%). The major components of the analyzable particulate lipids were similar to those of the dissolved lipids, namely, n-alkanes, pristane, phytane, and methyl, ethyl and propyl fatty acid esters. Often olefins, alkylated benzenes, quinones, and the unresolved GC area contribute a substantial part to the total particulate lipids. Minor components included ketones, phenols, indanes, acids, benzoates, aromatics and possibly derivatives of inositol, dioxane, and pyran. The low concentrations observed confirm that the area is relatively pristine though some evidence for chronic low-level oil pollution was present. Seasonal, diurnal, vertical and areal variations were observed in the particulate lipids. Lipid concentrations not only decreased with depth but they were also a decreased percentage of the organic carbon present. This may indicate the loss of labile carbon with depth due to reworking in the euphotic zone. Anoxic conditions appeared to promote the preservation of lipid materials in the particulate phase, n-Alkanes and fatty acid esters were common to both the particulate and dissolved phases and had similar distributions.     

A study of natural and artificially generated light hydrocarbons (C4–C13) in source rocks and petroleum fluids from offshore Mid-Norway and the southernmost Norwegian and Danish sectors

The “free” or “natural” light hydrocarbon composition obtained by thermal extraction-GC of source rock samples is compared with the light fraction generated by pyrolysis products of the kerogens. Even though there are large differences between the composition of the “free” C₄–C₁₃ hydrocarbon fraction and the same fraction generated by pyrolysis, some characteristics have been detected which can be used interchangeably for both data types. Visual inspection of gas chromatograms from thermal extracts and pyrolysates indicates that in particular the relative content of m+p xylene corresponds well between these two analytical methods. The source rock samples used are Upper Jurassic marine shales and Middle and Lower Jurassic coals and coaly shales from offshore Mid-Norway and Denmark. More detailed analysis of the data shows that the most effective parameter which can distinguish between different source rock types in both thermal extracts and pyrolysates is the m+p xylene/nC₈ ratio. This parameter has been used to derive classification diagrams for interpreting the source of light hydrocarbons of both natural petroleum fluids analysed by gas chromatography and the same fraction generated by pyrolysis of asphaltenes from the fluids.The model was first tested on 17 natural petroleum fluids from Mid-Norway since a comprehensive study of light hydrocarbon distributions already has been published. Further, the parameter was applied to correlate with asphaltene pyrolysates of the fluids from Mid-Norway and a total of 22 natural oils and condensates from the southernmost Norwegian and Danish sectors.     

Modelling of natural and synthetic polyelectrolyte interactions in natural waters by using SIT, Pitzer and Ion Pairing approaches

In this paper SIT and Pitzer models are used for the first time to describe the interactions of natural and synthetic polyelectrolytes in natural waters. Measurements were made potentiometrically at 25 °C in single electrolyte media, such as Et₄NI and NaCl (for fulvic acid 0.1 < I /mol L^− 1 < 0.75), and in a multi-component medium simulating the composition of natural waters at a wide range of salinities (for fulvic and alginic acids: 5 < S < 45) with particular reference to sea water [Synthetic Sea Water for Equilibrium studies, SSWE]. In order to simplify calculations, SSWE was considered to be a “single salt” BA, with cation B and anion A representing all the major cations (Na⁺, K⁺, Mg²⁺, Ca²⁺) and anions (Cl⁻, SO₄²⁻) in natural sea water, respectively. The ion pair formation model was also applied to fulvate and alginate in artificial sea water by examining the interaction of polyanions with the single sea water cation. Results were compared with those obtained from previous speciation studies of synthetic polyelectrolytes (polyacrylic and polymethacrylic acids of different molecular weights). Results indicate that the SIT, Pitzer and Ion Pairing formation models used in studies of low molecular weight electrolytes may also be applied to polyelctrolytes with a few simple adjustments.     

The chemical changes of DOM from black waters to coastal marine waters by HPLC combined with ultrahigh resolution mass spectrometry

How dissolved organic matter (DOM) undergoes chemical changes during its transit from river to ocean remains a challenge due to its complex structure. In this study, DOM along a river transect from black waters to marine waters is characterized using an offline combination of reversed-phase high performance liquid chromatography (RP-HPLC) coupled to electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS), as well as tandem ESI-FTICR-MS. In addition, a water extract from degraded wood that mainly consists of lignins is used for comparison to the DOM from this transect. The HPLC chromatograms of all DOM samples and the wood extract show two major well-separated components; one is hydrophilic and the other is hydrophobic, based on their elution order from the C₁₈ column. From the FTICR-MS analysis of the HPLC fractions, the hydrophilic components mainly contain low molecular weight compounds (less than 400 Da), while the hydrophobic fractions contain the vast majority of compounds of the bulk C₁₈ extracted DOM. The wood extract and the DOM samples from the transect of black waters to coastal marine waters show strikingly similar HPLC chromatograms, and the FTICR-MS analysis further indicates that a large fraction of molecular formulas from these samples are the same, existing as lignin-like compounds. Tandem mass spectrometry experiments show that several representative molecules from the lignin-like compounds have similar functional group losses and fragmentation patterns, consistent with modified lignin structural entities in the wood extract and these DOM samples. Taken together, these data suggest that lignin-derived compounds may survive the transit from the river to the coastal ocean and can accumulate there because of their refractory nature.     

The PAH composition of surface sediments from Stagnone coastal lagoon, Marsala (Italy)

This paper examines the presence, distribution, nature and sources of 22 Aromatic Hydrocarbons (PAHs), which are important environmentally and toxicologically, in sediments from the Stagnone coastal lagoon at Marsala (Italy). Analysis was performed by gas chromatography/mass spectrometry (GC/MS) with selected ion monitoring (SIM). The total concentration of polycyclic aromatic hydrocarbons ranged from 72 to 18381 μg/kg of dry matrix. The relative standard deviation (RSD) of the replicates on the concentrations of individual compounds ranged from 5% to 20%. The accuracy of method was estimated by analyzing “blank” samples added of known quantities of analytes and the recover percentage was 88 ± 9%. The detection limit (LOD) of analytical procedure was less than 0.2 μg/kg d.w. for all analytes. The quantification limit (LOQ) of analytical procedure was less than 0.7 μg/kg d.w.The resulting distributions and weight ratios of specific compounds are discussed in terms of sampling location and origin of organic matter. A comparison with other studies of total PAHs suggests that the levels are within the concentration ranges already reported by other authors. From an eco-toxicological point of view, total PAH concentrations at seven out of the eight sites studied represent a relatively clean environment when compared to other sites.Organic matter content and PAH concentrations were found to be correlated and the compounds present in Stagnone sediments were shown to be mainly of pyrolitic origin, while a negligible quantity of PAHs may derive from biogenic sources since all the sediments contain perylene traces. There is no evidence of coal-tar contamination.Cluster analysis was carried out in order to discriminate between different PAH origins.     

Seasonal variations in dissolved organic carbon concentrations and characteristics in a shallow coastal bay

Dissolved organic matter (DOM) composition and dynamics in temperate shallow coastal bays are not well described although these bays may be important as local sources of organic carbon to ocean waters and are often sites of economically-important fisheries and aquaculture. In this study surface water samples were collected on a monthly to bi-monthly basis over two years from a mid-Atlantic coastal bay (Chincoteague Bay, Virginia and Maryland, USA). Dissolved organic carbon (DOC) concentrations and light absorbance characteristics were measured on sterile-filtered water, and high-molecular weight (> 1 kDa) dissolved OM (DOM) was isolated to determine stable isotope composition and molecular-level characteristics. Our time series encompassed both a drought year (2002) and a year of above-average rainfall (2003). During the dry year, one of our sites developed a very intense bloom of the brown tide organism Aureococcus anophagefferens while during the wet year there were brown tide bloom events at both of our sampling sites. During early spring of the wet year, there were higher concentrations of > 1 kDa DOC; this fraction represented a larger proportion of overall DOC and appeared considerably more allochthonous. Based upon colored dissolved organic matter (CDOM) and high-molecular weight DOM analyses, the development of extensive phytoplankton blooms during our sampling period significantly altered the quality of the DOM. Throughout both years Chincoteague Bay had high DOC concentrations relative to values reported for the coastal ocean. This observation, in conjunction with the observed effects of phytoplankton blooms on DOM composition, indicates that Chincoteague Bay may be a significant local source of “recently-fixed” organic carbon to shelf waters. Estimating inputs of DOC from Chincoteague Bay to the Mid-Atlantic Bight suggests that shallow productive bays should be considered in studies of organic carbon on continental shelves.