Trace element distributions in surficial sediments of the northern Tyrrhenian Sea: Contribution to heavy-metal pollution assessment

The trace element distributions in surficial sediment of Tyrrhenian Sea have been investigated as a part of a series of studies on the environmental quality of the area off the Tuscany coast (west-central Italy). This research has focused on the presence of possible contaminated zones; it also provides data for the identification and future monitoring and control of pollution sources. The study of numerous surface sediments and core samples has made it possible to distinguish between heavy-metal enrichments related to natural sources and other anomalies caused by anthropogenic contamination. Over much of the basin, the surface Pb, Cu, Zn, and As contents appear considerably enriched relative to those below 15 cm; among these metals, Pb shows the highest and most widespread enrichment. Only in the case of some coarse-grained sediments close to the mouth of Cecina River it is possible to relate anomalously high Zn contents to natural sources. In all other sampling stations, the enrichments of Pb, Cu, Zn, and As are ascribed to man's influence. The sediment distributions of Co, Cr, and Ni do not seem to be related to anthropogenic activities; rather they mirror influx of materials derived from sources of ophiolitic rock. The distribution of barium shows only two significant positive anomalies, and both are related to natural causes. Concentrations of vanadium are high in a zone close to an important smelting plant; these are thought to be of anthropogenic origin.     

Vitrinite reflectance distributions and thermal history of sediments: An end-member sensitivity analysis

An end-member analysis was performed using algorithms ofExtended cabfac qmodel on 21 sample distributions of vitrinite reflectance (VR) by depth from the Inigok well in the National Petroleum Reserve of Alaska (NPRA). Eight end members, which account for 99% of the variance, adequately recreate the VR distributions. These eight end members contain stratigraphic information based on systematically increasing or decreasing mixing proportions with depth. Paleoheat flux determined from end members, or from orthogonally filtered sets of end members, is not significantly different from paleoheat flux determined from arithmetic mean values of VR, indicating that the arithmetic mean provides an adequate representation of each VR distribution analyzed in this well. Additionally, use of filtering devices to assess the degree of trustworthiness of signal in VR distributions enables an assessment to be made of the degree of stability of paleoheat flux variation estimates.     

Diphytanyl glycerol ether distributions in sediments of the Orca Basin

Archaebacterially produced diphytanyl glycerol ether (DPGE) was examined in core sediments from the Orca Basin, an anoxic hypersaline basin in the northwestern Gulf of Mexico, to observe its spatial variability and potential origin. A differential extraction protocol was employed to quantify the isopranyl glycerol ethers associated with unbound, intermediate-bound, and kerogen-bound lipid fractions. Archaebacterial lipids were evident at all depths for the unbound and intermediate-bound fractions. Concentrations of DPGE ranged from 0.51 to 2.91 micrograms/g dry sediment at the surface and showed secondary maxima deeper in basin sediments. Intermediate-bound DPGE concentrations exhibited an inverse relationship to unbound DPGE concentrations. Kerogen-bound DPGE concentrations were normally below detection limits. Earlier studies describing the general homogeneity of lipid components within the overlying brine and at the brine/seawater interface suggest that the large-scale sedimentary DPGE variations observed in this study result from spatial and temporal variations in in situ production by methanogenic or extremely halophilic archaebacteria.     

Subboreal aridity and scytonemin in the Holocene Black Sea

Many species of cyanobacteria tolerate exposure to harmful levels of ultraviolet (UV) radiation by producing photoprotective pigments. Scytonemin, found in extracellular polysaccharide sheaths, is produced in abundance when terrestrial or benthic cyanobacteria are exposed to direct sunlight, such as in desert soil crusts and intertidal mats. It is exclusive to cyanobacteria and therefore can serve as a diagnostic biomarker, particularly for UV-exposure growth conditions. Here we report that it is preserved in abundance in mid-Holocene sedimentary intervals in the Black Sea, a novel deep sea occurrence that demonstrates that scytonemin is resistant to degradation during erosion and transport. C and N isotopic compositions support the interpretation that scytonemin was derived from cyanobacteria in cryptobiotic desert soil, suggestive of expanding aridity during the Subboreal Phase in the Black Sea region. Scytonemin has potential for preservation in black shales, where it may serve as an important biomarker for tracing the evolution and expansion of cyanobacterial populations, especially in association with elevated UV stress.     

Time- and method-dependent size distributions of fine-grained sediments

ABSTRACT With increased interest in fine-grained sediments it is imperative that a firm basis exist for comparative studies of these cohesive sediments. In this study the size distributions of continental slope and rise muds are shown to be dependent on both method and duration of sample pretreatment. Statistical analysis of 171 size distributions indicates that of the four most frequently used sample preparation methods (soak, stir, shake and ultrasonify) the time required to reach a 'terminal' distribution beyond which no 'fine-shift' was detected varied from 15 minutes to > 90 hours for a given sample solely as a function of preparation method. Data from this study also indicate that sample preparation by simple soaking alone will probably yield fine-grained sediments which, when analysed by pipette or microsedimentation accumulation balance, undergo a continuous change in size distribution during analysis and may never reach a 'terminal' distribution during the analysis time. On the other hand stirring and ultrasonification were shown to be the most rapid and consistent methods for obtaining a sample's'terminal'distribution.     

Two-dimensional pH distributions and dynamics in bioturbated marine sediments

The seafloor is the site of intense biogeochemical and mineral dissolution-precipitation reactions which generate strong gradients in pH near the sediment-overlying water interface. These gradients are usually measured in one-dimension vertically with depth. Two-dimensional pH distributions in marine sediments were examined at high resolution (65 × 65 μm pixel) and analytical precision over areas of ∼150 to 225 cm² using a newly developed pH planar fluorosensor. Dramatic three-dimensional gradients, complex heterogeneity, and dynamic changes of pH occur in the surficial zone of deposits inhabited by macrofauna. pH can vary by ±2 units horizontally as well as vertically over millimeter scales. pH minima zones often form in association with redoxclines within a few millimeters of inner burrow walls, and become more pronounced with time if burrows remain stable and irrigated for extended periods. Microenvironmental pH minima also form locally around decaying biomass and relict burrow tracks, and dissipate with time (∼5 d). H⁺ concentrations and fluxes in sandy mud show complex acid-base reaction distributions with net H⁺ fluxes around burrows up to ∼12 nmol cm⁻² d⁻¹ and maximum net reaction rates varying between −90 (consumption) to 120 (production) μM d⁻¹ (∼90 nmol cm⁻¹ d⁻¹ burrow length). Acid producing zones that surround irrigated burrows are largely balanced by acid titration zones along inner burrow walls and outer radial boundaries. The geometry and scaling of pH microenvironments are functions of diagenetic reaction rates and three-dimensional transport patterns determined by sediment properties, such as diffusive tortuosity, and by benthic community characteristics such as the abundance, mobility, and size of infauna. Previously, undocumented biogeochemical phenomena such as low pH regions associated with in-filled relict biogenic structures and burrowing tracks are readily demonstrated by two-dimensional and time-dependent images of pH and sedimentary structure.     

Algal pigments in sediments as a measure of eutrophication in the Baltic environment

A method of quantitative comparison of eutrophication of an area is proposed for the Baltic Sea, based on pigment content in sediments. The pigments concerned were chlorins a (i.e. chlorophylls a, b and selected chlorophyll a derivatives) and chlorophylls c. The analyses were performed on 300 samples from different layers of recent (0–10 cm) sediments, collected from about 50 stations, at different sites of the southern Baltic, including the estuaries of the two largest Polish rivers, in different seasons between 1992 and 2001, before and after the great flood of July 1997. The results are related to sampling site, sediment layer and hydrological conditions and also to organic carbon and E_h in sediments, oxygen and salinity in near-bottom waters. Depending on different chlorin a content in 0–1 and 0–10 cm layers, the sampling sites are classified into one of three groups: 1. Szczecin Lagoon and the Deep of Gda sk stations (permanently eutrophic, chl a in 0–1 cm >40 nmol/g, Σchlns a in 0–1 in 0–10 cm layer, Σchlns a_A in Σchlns a=55–65%), 2. Open sea stations (mesotrophic/oligotrophic, chl a in 0–1 cm <10 nmol/g, Σchlns a in 0–1 in 0–10 cm layer, Σchlns a_A in Σchlns a 50%; and 3. Coastal stations (periodically eutrophic, chl a in 0–1 cm 10–40 nmol/g, Σchlns a_A in Σchlns a 40%). The correlation coefficient between chlorophyll a and chlorophylls b and c indicates the classes of algae, which could be the main source of organic matter in the sediments. A high correlation with chlorophylls c is a marker of diatoms; a high correlation with chlorophyll b is a marker of green algae; and low correlation both with chlorophylls b and c—indicates a high blue–green algae input.     

A critical assessment of methods of correcting for drift from the yield surface in elasto-plastic finite element analysis

The analysis of elasto-plastic boundary value problems using the finite element method involves many discretizations. These lead to the problem of yield surface drift in which the stress state predicted at the end of an elasto-plastic increment of loading does not lie on the current yield surface. As such discrepancies are comulative it is important to ensure that the stresses are corrected back to the yield surface during each increment of loading. In this paper five methods of accounting for this drift are examined. These involve correcting the stresses by projecting back along the plastic flow, the total strain increment and the accumulated effective stress direction. In addition a ‘correct’, method which accounts for the changes in elastic strains which accompany any stress correction is considered. This method is theoretically more sound than the other approximate approaches. All five methods have been used in finite element analyses of the stress changes that occur adjacent to a single pile installed in a uniform deposit of soil on pile loading. The soil was assumed to be normally consolidated and was modelled using a form of modified Cam Clay. Comparison of these results with an analysis, in which yield surface drift was negligible indicated that only the ‘correct’ method and the method involving projecting back along the plastic flow direction give accurate predictions. Substantiai errors occur if the other methods of correcting for yield surface drift are employed. It is recommended that the ‘correct’ method be adopted for finite element calculations.     

柳江流域沉积物重金属生态风险评价及来源分析

以柳江中下游流域沉积物为研究对象,采集91件水系沉积物样品,计算并分析As、Cd、Cr、Cu、Hg、Ni、Pb、Zn等元素地球化学参数特征,对当前污染现状及潜在风险进行预测评价,并解析重金属元素来源。结果显示:柳江流域重金属元素含量分布表现出较强的地域特征;柳江流域污染等级以轻度及偏中度为主,潜在生态风险等级为中低等级,主要影响因子为Cd;As、Cr、Cu、Hg、Ni来源以自然源为主,Cd、Pb以人为源为主,其中Cd自然源贡献率高值区主要分布于龙江流域,工矿业源贡献率高值区主要分布于金城江周边以及柳江柳州市区段。     

Palygorskite in sediments: Detrital,diagenetic or neoformed — A critical review

The origin of palygorskite in sediments is critically reviewed. In sediments, palygorskite may be detrital, diagenetic (formed by the transformation of a precursor mineral) or neoformed (formed by precipitation from solution).The most reliable information on palygorskite has been obtained from hydrothermal alteration products of igneous rocks, where palygorskite forms pseudomorphically, and from soils and paleosols, where palygorskite precipitates from solution. Palygorskite formation is also described from alkaline paleolake sediments. From these occurrences requirements for palygorskite formation could be specified: Alkaline pH, high Si and Mg and low Al activities.A detrital origin for palygorskite in marine sediments is proposed when it is associated with other clay minerals of accepted detrital origin, when a direct relation to continental deposits of the mineral exists and when conditions for its detrital accumulation appear favourable. In the Mediterranean, East Atlantic, North-Western Indian Ocean and Gulf of Aden large palygorskite occurrences are detrital. The formation of palygorskite in marine sediments occurred whenever the geochemical requirements were met, in following situations: (a) — near sites of hydrothermal activity; (b) — in peri-marine, shallow water environments, adjacent to landmasses undergoing intensive desilication by weathering: (c) — in response to fluctuations in ocean water temperature that affected solubility levels of limiting chemicals, such as Si. Various considerations of published field and laboratory data appear to favour a formation of palygorskite by neoformation rather than by diagenesis.

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Zusammenfassung Palygorskit kann in Sedimenten detritisch, diagenetisch (aus der Umwandlung vorhandener Minerale) oder neoform (aus Lösung gefällt) vorliegen.Die wichtigsten Informationen über Palygorskit stammen aus hydrothermalen Umwandlungsprodukten magmatischer Gesteine, wo Palygorskit Pseudomorphosen bildet. In Böden und Paläoböden wird Palygorskit direkt aus Lösungen gefällt. Er wird auch aus alkalischen See-Sedimenten beschrieben. Hier kann man folgende Bildungsbedingungen bestimmen: alkalisches Milieu, hohe Si und Mg und niedrige Al Aktivitäten.Der detritische Ursprung in marinen Sedimenten liegt nahe, wenn Palygorskit mit anderen detritischen Tonmineralen vergesellschaftet ist, und eine Beziehung zu terrestrischen Ablagerungen besteht sowie die marinen Sedimentationsbedingungen günstig sind. Im Mittelmeer, im Ost-Atlantik, im nordwestlichen Indischen Ozean und Golf von Aden treten große Palygorskite-Vorkommen detritisch auf.Palygorskit kommt in marinen Sedimenten unter bestimmten geochemischen Bedingungen vor: nahe von Hydrothermen; in Landnähe unter Flachwasser, wobei im Hinterland kräftige sialitische Verwitterung vorherrschen muß; als Folge schwankender Temperaturen des Meereswassers, die den Chemismus bestimmter Elemente wie den des Si beeinflussen. Aus allen bisher bekannten Daten läßt sich ableiten, daß die neomorphe Bildung von Palgorskit am häufigsten zu beobachten ist. Diagenetisch gebildete Palygorskite sind dagegen seltener.

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Résumé L'origine de la palygorskite dans les sédiments fait l'objet d'une revue critique. Dans les sédiments, la palygorskite peut Être détritique, diagénétique (formée par la transformation d'un minéral précurseur) ou de néoformation (formée par précipitation à partir d'une solution).L'information la plus crédible sur la palygorskite est fournieo par les produits d'altération hydothermale des roches ignées, où la palygorskite se forme par pseudomorphose, et par les sols et paléosols, où la palygorskite est précipitée à partir de solutions. La formation de la palygorskite est également décrite à partir de sédiments alcalins paléolacustres. Sur la base de ces occurrences, les conditions pour la formation de la palygorskite peuvent Être définies: pH alcalin, activité forte en Si et Mg, et basse en Al.Une origine détritique pour la palygorskite dans les sédiments marins peut Être proposée lorsqu' elle est associée avec d'autres minéraux argileux dont l'origine détritique est acceptée, quand une relation directe existe avec des dépÔts continentaux renfermant ce minéral, et quand des conditions pour son accumulation détritique apparaissent favorables. Dans la Méditerranée, dans l'Atlantique oriental, dans le nord-ouest de l'Océan Indien et dans le Golfe d'Aden, les grandes occurrences de palygorskite sont détritiques. La formation de palygorskite dans les sédiments marins se présente chaque fois que les conditions géochimiques sont rencontrées, dans les cadres suivants: a) sites proches d'une activité hydrothermale; b) dans des milieux d'eau peu profonde péri-marins, attenant à des masses continentales subissant une désilicatation intense par voie d'altération athmosphérique; c) en réponse à des fluctuations dans la température de l'eau océanique, affectant les niveaux de solubilité de certains éléments chimiques, comme le Si. Des considérations diverses concernant les données de terrain et de laboratoire semblent favoriser pour la palygorskite une formation par néoformation plutÔt que par diagénèse.

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Stabilization procedures in coupled poromechanics problems: A critical assessment

Numerical solutions for problems in coupled poromechanics suffer from spurious pressure oscillations when small time increments are used. This has prompted many researchers to develop methods to overcome these oscillations. In this paper, we present an overview of the methods that in our view are most promising. In particular we investigate several stabilized procedures, namely the fluid pressure Laplacian stabilization (FPL), a stabilization that uses bubble functions to resolve the fine‐scale solution within elements, and a method derived by using finite increment calculus (FIC). On a simple one‐dimensional test problem, we investigate stability of the three methods and show that the approach using bubble functions does not remove oscillations for all time step sizes. On the other hand, the analysis reveals that FIC stabilizes the pressure for all time step sizes, and it leads to a definition of the stabilization parameter in the case of the FPL‐stabilization. Numerical tests in one and two dimensions on 4‐noded bilinear and linear triangular elements confirm the effectiveness of both the FPL‐ and the FIC‐stabilizations schemes for linear and nonlinear problems. Copyright © 2010 John Wiley & Sons, Ltd.     

最新国际天然气水合物研究现状与资源潜力评估(上)

地层骨架孔隙中水合物的高质量形成是开展水合物实验研究的前提和物质基础,可为我国深水油气及水合物资源开发提供理论指导。依据南海GMGS2-07井水合物层地质条件,利用TOUGH+HYDRATE数值模拟软件和自主研制的水合物反应生成装置开展数值模拟和实验研究,在验证数值模拟方法准确性和可靠性的基础上,通过控制变量法分别开展不同地层导热系数和含水饱和度条件下水合物生成质量的影响研究。结果表明：(1) 数值模拟与室内实验过程中,水合物形成时温度、压力与三相物质变化趋势一致且特征值十分接近,验证了数值模拟方法的准确性和可靠性。(2) 导热系数越大,水合物生成越快,最终形成的水合物饱和度越大,分布也更加均匀。但导热系数与最终形成水合物的饱和度的正负相关性,存在临界边界。本次所选用的反应釜尺寸,临界边界距上、右边界距离为1.8 cm,临界边界内导热系数与水合物饱和度呈正相关性,临界边界外呈负相关性。临界边界随着反应釜尺寸的增大而增大,但临界边界位置不受地层渗透率的影响。(3) 随地层含水饱和度增加,最终形成的水合物饱和度先增大后减小,峰值处含水饱和度小于初始压力条件下的理论气水比。当初始压力为7.8 MPa,含水饱和度约22.23%时,所形成的水合物饱和度最大且分布最不均匀。由此可知,选用高导热系数材料制备地层骨架、使初始含水饱和度低于气水理论比以及调整初始温压条件使之偏向相平衡曲线左方有利于形成分布均匀的高饱和水合物。研究认为深水油气含水合物固井和水合物资源钻采提供依据,为水合物商业化开采提供技术储备。

     

Steroid and triterpenoid distributions in bransfield strait sediments: Hydrothermally-enhanced diagenetic transformations

Recent sediments from Bransfield Strait, Antarctica have been analyzed for triterpenoid and steroid hydrocarbons, sterols and steroid ketones to consider the effects of hydrothermal fluids on the sedimentary organic matter. The steroid distributions in unaltered and altered sediments are controlled more by inputs from source organisms than by the effects of hydrothermal activity, which is suggested to be limited to low temperature alteration. Nevertheless, chemical reactions occurred in altered sediments and include dehydration of sterols to sterenes, isomerization of triterpenes and sterenes, rearrangement of sterenes to diasterenes and reductive processes leading to generation of phytane from phytol via phytenes.     

Long-chain alkenone distributions and temperature dependence in lacustrine surface sediments from China

Long-chain alkenones (LCK) of lacustrine surface sediments were analyzed in 37 lakes from China. The results obtained were complemented by published data from 13 other Chinese lakes. These lakes are located across large temperature and precipitation gradients, therefore allowing for an assessment of the distribution pattern of LCK and their temperature dependency. Different distribution patterns of LCK (C₃₇ predominant pattern and C₃₈ predominant pattern) were detected in the surface sediment samples. The ratio of C_37:4 methyl ketone to the sum of C₃₇ alkenones observed in the different lakes is highly variable (5%-96%, with mean value of 55%), and more than that seen in marine systems. The finding that some of the ocean LCK precursor algae (Gephyrocapsa oceanica, Coccolithus pelagicus) were also present in the limnic systems suggested that both systems might have similar biosynthetic sources. Empirical relationships between the alkenone unsaturation index U₃₇^k′ and different temperature sets (mean annual air temperature, mean annual air temperature in different seasons, and lake surface water temperature of July) were tested. The best correlation between U₃₇^k′ and temperature was obtained using mean annual air temperature. A general linear regression of U₃₇^k′ and MAAT can be expressed as U₃₇^k′ = 0.0328 × T + 0.126 (n = 38, r² = 0.83). Although questions such as species-uncertainty and other unknown factors for U₃₇^k′ temperature dependence still remain, the equation might be representative of the average contribution of LCK to sediments for these data over a wide range of surface temperatures, water chemistry and different alkenones-producer algal populations. The general relationship of U₃₇^k′ and mean annual air temperature is consistent with that in marine systems. It supports the suggestion that the biosynthetic pathway of alkenones and the mechanism of their temperature signal may be similar in both marine and limnic systems. LCK might be used as an important paleotemperature proxy in limnic environment.     

Methylbiphenyl,ethylbiphenyl and dimethylbiphenyl isomer distributions in some sediments and crude oils

Petroleum samples and organic extracts from two sedimentary sequences have been analysed using capillary gas chromatography and GC-MS techniques for isomeric methylbiphenyls, ethylbiphenyls and dimethylbiphenyls. The relative abundances of isomers with substituents in the ortho positions decrease with increasing depth (maturity) in both sedimentary sequences. Accordingly, these compounds appear to offer potential as indicators of thermal maturity of sediments.     

Preliminary assessment of trace metals and polycyclic aromatic hydrocarbons in the sediments

Total concentrations of Cd, Cr, Co, Fe, Pb, Ni, Mn and Zn were determined by atomic absorption spectrophotometry in the surface sediments of Taylor Creek, Southern Nigeria. The most concentrated trace metals, ranging from 113.2 to 5160.7 mg/g-dry weights were Fe, Pb, Mn, Ni and Zn. There was no significant variation in sediment-associated metal levels (P>0.05). The metal pollution index was highest at Agbia/Nedugo and is attributed to local contamination of the Creek. The concentrations of low molecular weight polycyclic aromatic hydrocarbons (PAHs) were also detected and quantified in the sediments by capillary gas chromatography equipped with a flame ionization detector. The concentration levels of 178.1-1266.3 mg/g-wet weights were high for the PAHs. The results indicate that the pollutants, which are bio-accumulatable, could contribute to inferior biodiversity, and shifts in community composition from sensitive to tolerant taxa.     

长江口吴淞-浏河滨岸带沉积物AVS和SEM含量的空间分布特征

对长江口吴淞-浏河滨岸带37个站位沉积物中酸可挥发性硫化物（AVS）和同时可提取态重金属（SEM）含量及其空间分布特征进行了研究。结果表明,SEM在37个站位沉积物中浓度范围为0．20～1．37μmol／g,平均值为0．74μmol／g;AVS的浓度范围为0．20—0．80μmol／g,平均值为0．23μmol／g;沉积物中AVS含量与总有机碳（TOC）和含水率呈显著正相关关系,而SEM分别与TOC和含水率呈显著正相关关系,与沉积物中值粒径呈显著负相关关系。依据SEM／AVS比值评价方法以及美国EPA（SEM—AVS）差值评价方法对沉积物中重金属的生物有效性的判断表明,除了B2站点无显著生物毒性外,吴淞-浏河滨岸带沉积物中重金属对水生生物均处于中等毒性水平。     

Heavy metal and arsenic distributions in sediments of the Elba-Argentario basin, southern Tuscany, Italy

 Arsenic, chromium, cobalt, copper, lead, nickel, vanadium and zinc distributions in surficial and core sediments of the Elba-Argentario marine basin (southern Tuscany, central-western Italy) are reported. Analysis of such distributions compared with grain size and mineralogical data allowed the identification of areas showing trace element enrichments with respect to natural background. These enrichments are moderate and essentially restricted to Pb and Zn; only As shows a widespread, though not high, positive anomaly. This general pattern is in good agreement with the minor industrialization affecting the basin's watershed. An unexpected anomaly, concerning Co, Pb, and As, as well as Fe and Ti, has been pointed out close to Montecristo Island. This has been ascribed to illegal local dumping of chemical waste. Received: 12 January 1996 / Accepted: 9 September 1996     

A critical analysis of some variational methods in slope stability analysis

During the last ten years the Calculus of variations technique has been applied to solve the problem of stability of slopes. All published methods are essentially based on the attainment of a functional and the search for its absolute minimum or maximum by vanishing its first variation. Obviously this statement of the problem is valid only if such a minimum or maximum exists and can be obtained by making the first variation of the functional equal to zero. So, these implicit hypotheses must be checked. This work analyses from this point of view the validity of the methods proposed by ‘Baker and Garber’, ‘Chen’ and ‘Castillo and Revilla’, and demonstrates that the first two methods are incorrectly stated while the third one is correct at least in the case of a frictionless soil.