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101.
It is generally assumed that estuarine mixing is continuous for metals from terrestrial sources, gradually decreasing towards the open ocean endmember. Here we show that, chemical reactivity, determined by ion exchange method, and molecular weight distributions, obtained using cross-flow ultrafiltration, of dissolved Cd, Cu, and Ni in the surface waters of the Gulf of Mexico varied systematically across the estuarine mixing zone of the Mississippi River. Most size or chemical affinity fractions of dissolved metals (<0.4 μm) were linearly related to salinity (10.8–36.6), suggesting that the distribution of these elements was mainly controlled by continuous mixing processes. Dissolved concentrations across the salinity gradient ranged for Cd: 87–187 pM; Cu: 1.4–18.3 nM; and Ni: 2.6–18.8 nM, with highest values near the Mississippi river mouth, and lowest concentrations in a warm core ring in the Gulf of Mexico. Dissolved Cd was mostly present as a truly dissolved (<10 kDa, 97 ± 1%) and cationic fraction (Chelex-100 extractable, 94 ± 4%). A novel observation across the estuarine mixing zone was that colloidal metal concentrations were identical to either inert (for Cu, Ni) or AMPG-labile anionic (Cu, Cd) fractions. The difference in behavior between Cu and the other two metals might indicate differences in the biopolymeric nature of the metal–organic chelates. In particular, the anionic-organic Cd fractions accounted for just 3 ± 1%, on average. However, for Cu, it was 24 ± 4%, and for Ni, it was 9 ± 6%. The fractions of the total dissolved metal fractions that were “inert” averaged 31 ± 10% for Cu and 29 ± 12% for Ni. Small but noticeable amounts (6 ± 3%) of dissolved inert Cd fractions were also present. Apparent non-local transport processes, likely associated with cross-shelf sediment resuspension processes, could have been responsible for the relatively high concentrations of ‘inert’ and ‘anionic’ metal fractions in high salinity coastal waters, and accounting for the persistence of metals bound to humic substances in the Gulf of Mexico.  相似文献   
102.
The concentrations of Cu, Zn, Cr, Ni, Pb, As, Mn and Co were determined by Inductively Coupled Plasma–Mass Spectrometry both in recent sediments from different locations of the Huelva littoral (SW Iberian Peninsula) and in their humic acid (HA) fractions in order to evaluate distribution and binding capacity of those trace elements to HAs. In addition, elemental composition (C, N, S) and δ13C values were determined to appraise the sources of organic matter in the area. This study involved the comparison of selected samples taken from different environments including the estuary of the Guadiana River, the main fluvial system of the region, the Tinto and Odiel estuary system and the proximal shelf. Significant positive correlations were found among Cu, Zn, As and Pb in bulk sediments, suggesting a common origin of all of those elements: the mining activities and pyrite deposits located hinterland. On the other hand, results for Cr, Co and Ni pointed to the basic rocks from the low basin of the Guadiana River as their main source. Elemental (C, N) and isotopic (δ13C) composition of sediments indicated a significant contribution of autochthonous plankton in coastal shelf sediments, whereas estuarine and riverine sediments showed a major contribution of terrestrial biomass. Geochemical values for their corresponding HAs suggested a greater terrestrial contribution in the sedimentary OM of the coastal shelf sediments than in bulk sediments, which evidenced the influence of coastal currents and sediment fluxes. Humic acids sequester considerable amounts of Cu and Zn contributing to reduce the bioavailability of these contaminants.  相似文献   
103.
黑海参(Holothuria atra)体壁经Folch法提取总脂,用HCl-甲醇进行甲酯化处理,以气相色谱/质谱法分析总脂中的脂肪酸组成。从黑海参中共分析出28种化合物,包括25种脂肪酸甲酯和3种脂肪醛二甲基缩醛。黑海参体壁中的饱和脂肪酸含量为22.93%,以C16:0(5.49%)和C18:0(4.38%)为主;不...  相似文献   
104.
基于动物油脂的脂肪酸单体碳同位素模型开展古代样品的脂肪酸单体碳同位素分析可细化脂肪来源,有助于探究动物资源的加工利用、相关载体的使用功能及先民饮食策略,从而为古代人类的生活方式和古代社会的经济形态提供重要信息.目前该模型已得到国外诸多地区现代动物样品的验证,但其在中国的适用性尚不明晰.文章对陕北地区石峁遗址和高家洼遗址...  相似文献   
105.
In the present study,humic acid was used as an adsorbent for the investigation of the adsorption kinetics,isotherms,and thermo-dynamic parameters of hexavalent chromium from aqueous solution at varying pH,temperatures,and concentrations.Adsorption isotherms and equilibrium adsorption capacities were determined by the fittings of the experimental data to three well-known iso-therm models:Langmuir,Freundlich,and Redlich-Peterson.The results showed that the Langmuir and Redlich-Peterson models appear to fit the adsorption better than did the Freundlich adsorption model for the adsorption of chromium onto humic acid.The equilibrium constants were used to calculate thermodynamic parameters such as the change of free energy,enthalpy,and entropy.The derived adsorption constants (logaL) and their temperature dependencies from Langmuir isotherm have been used to calculate the corresponding thermodynamic quantities such as the free energy of adsorption,heat,and entropy of adsorption.The thermo-dynamic data indicate that Cr (VI) adsorption onto humic acid is entropically driven and characterized by physical adsorption.  相似文献   
106.
Polyfluorinated compounds (PFCs) were investigated in waste water treatment plant (WWTP) effluents and surface waters of the River Elbe from samples collected in 2007. Concentrations of various PFCs, including C4–C8 perfluorinated sulfonates (PFSAs), C6 and C8 perfluorinated sulfinates, 6:2 fluorotelomer sulfonate, C5–C13 perfluorinated carboxylic acids (PFCAs), C4 and C8 perfluoroalkyl sulfonamides and 6:2, 8:2 and 10:2 unsaturated fluorotelomercarboxylic acids were quantified. ∑PFC concentrations of the river water ranged from 7.6 to 26.4 ng L−1, whereas ∑PFC concentrations of WWTP effluents were approximately 5–10 times higher (30.5–266.3 ng L−1), indicating that WWTPs are potential sources of PFCs in the marine environment. PFC patterns of different WWTP effluents varied depending on the origin of the waste water, whereas the profile of PFC composition in the river water was relatively constant. In both kinds of water samples, perfluorooctanoic acid (PFOA) was the major PFC, whereas perfluorobutane sulfonate (PFBS) was the predominant PFSA.  相似文献   
107.
The incorporation of fullerenes and carbon nanotubes into electronic, optical and consumer products will inevitably lead to the presence of these anthropogenic compounds in the environment. To date, there have been few studies isolating these materials from environmental matrices. Here we report a method commonly used to quantify black carbon (BC) in soils, the benzene polycarboxylic acid (BPCA) method, for measurement of two types of single walled carbon nanotubes (SWCNTs), two types of fullerenes and two forms of soot. The distribution of BC products (BPCAs) from the high pressure and high temperature oxidation illustrates the condensed nature of these compounds because they form predominantly fully substituted mellitic acid (B6CA). The conversion of carbon nanoparticles to BPCAs was highest for fullerenes (average of 23.2 ± 4.0% C recovered for both C60 and C70) and lowest for non-functionalized SWCNTs (0.5 ± 0.1% C). The recovery of SWCNTs was 10 times higher when processed through a cation-exchange column, indicating the presence of metals in SWCNTs compromises the oxidation chemistry. While mixtures of SWCNTs, soot and sediment revealed small losses of black carbon during sample processing, the method is suitable for quantifying total BC. The BPCA distribution of mixtures did not agree with theoretical mixtures using model polyaromatic hydrocarbons, suggesting the presence of a matrix effect. Future work is required to quantify different types of black carbon within the same sample.  相似文献   
108.
The contribution of terrigenous organic matter (TOM) to high molecular weight dissolved and particulate organic matter (POM) was examined along the salinity gradient of the Delaware Estuary. Dissolved organic matter (DOM) was fractionated by ultrafiltration into 1–30 kDa (HDOM) and 30 kDa–0.2 μm (VHDOM) nominal molecular weight fractions. Thermochemolysis with tetramethylammonium hydroxide (TMAH) was used to release and quantify lipids and lignin phenols. Stable carbon isotopes, fatty acids and lignin content indicated shifts in sources with terrigenous material in the river and turbid region and a predominantly algal/planktonic signal in the lower estuary and coastal ocean. Thermochemolysis with TMAH released significant amounts of short chain fatty acids (C9–C13), not seen by traditional alkaline hydrolysis, which appear to be associated with the macromolecular matrix. Lignin phenol distributions in HDOM, VHDOM and particles followed predicted sources with higher concentrations in the river and turbid region of the estuary and lower concentrations in the coastal ocean. TOM comprised 12% of HDOM within the coastal ocean and up to 73% of HDOM within the turbid region of the estuary. In the coastal ocean, TOM from high molecular weight DOM comprised 4% of total DOC. The annual flux of TOM from the Delaware Estuary to the coastal ocean was estimated at 2.0×1010 g OC year−1 and suggests that temperate estuaries such as Delaware Bay can be significant sources of TOM on a regional scale.  相似文献   
109.
A new method for analysis of acidic polar compounds, is described and discussed. It allows the simultaneous quantification of carboxylic acids, phenols and carbazoles and combines accuracy with a short turnaround time, a requirement strictly necessary for industrial applications. Routinely use of this methodology (more than 50 applications in many different sedimentary basins) has supplied many important pieces of information about oil origin, maturity, biodegradation and, in particular, has allowed to define a molecular migration index (MMI), based on relative abundance of phenol and alkyl phenols. The combination of well-established geochemical tools focused on saturated and aromatic fractions (such as biomarkers, compound specific isotope ratio analysis, and GC fingerprinting) with this methodology results in the definition of an integrated interpretative sequence. This last enhances the quality of interpretations through cross-checks and permits a better exploitation of oil samples by using also their less explored fraction, i.e. the polar compounds. Application results of this methodology are only shortly mentioned in this paper, which is mainly focused on analytical aspects. The results will be more extensively discussed in a future publication.  相似文献   
110.
盆地流体中有机组分的成矿效应   总被引:12,自引:0,他引:12  
盆地流体含有丰富的有机组分。有机质-金属耦合作用是盆地流体金属成矿机制的关键,具有极其重要的意义。有机质的成矿作用主要表现为:1)沉积有机质对盆地流体物理化学特征的制约;2)有机组分对金,属成矿元素在盆地流体中的迁移能力、迁移形式以及沉淀就位机制的制约;3)富有机质的地层作为地球化学还原障和H2S障对于流体中金属沉淀就位的制约;4)沉积有机质的演化对于盆地流体运移的制约(通过油气的阵发性析出和二次孔隙的产生)。  相似文献   
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