Occurrence and Distribution of Organic Contaminants in the Aquatic System in Berlin. Part III: Determination of Synthetic Musks in Berlin Surface Water Applying Solid-phase Microextraction (SPME) and Gas Chromatography-Mass Spectrometry (GC-MS)

Polycyclic musks and nitro musks were found as environmental pollutants in screening analyses of 30 representative surface water samples collected from rivers, lakes, and canals in Berlin. These synthetic musks, which are used as fragrances in cosmetics, detergents, and other products, are discharged by the municipal sewage treatment plants into Berlinπs surface waters. In particular, the polycyclic musks 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyrane (HHCB; Galaxolide®, Abbalide®) and 7-acetyl-1,1,3,4,4,6-hexamethyltetraline (AHTN; Tonalide®, Fixolide®) were found in the receiving surface waters at considerable concentrations up to the μg/L-level. In the Wuhle, a small brook almost totally consisting of sewage effluents, maximum concentrations were 12.5 μg/L for HHCB and 6.8 μg/L for AHTN. Additionally, the polycyclic musk 4-acetyl-1,1-dimethyl-6-tert-butylindane (ADBI; Celestolide®, Crysolide®) and 1-tert-butyl-3,5-dimethyl-2,6-dinitro-4-acetylbenzene (musk ketone) were detected at low concentrations in most of the samples. Two other nitro musks, namely 1,1,3,3,5-pentamethyl-4,6-dinitroindene (musk moskene) and 1-tert-butyl-3,5-dimethyl-2,4,6-trinitrobenzene (musk xylene), were only detected in a single surface water sample. Solid-phase microextraction (SPME) with detection by gas chromatography-mass spectrometry (GC-MS) has proven to be a rapid and reliable tool for the screening of synthetic musks in surface and sewage water samples. Internal calibration with a suitable internal standard enables reproducible quantitation of the analytes down to the low ng/L-level.     

钻井液侵入海洋含水合物地层的一维数值模拟研究

本文以墨西哥湾水合物区域为背景,利用数值模拟方法研究了过平衡钻井条件下,当钻井液温度高于地层中水合物稳定温度时,水基钻井液侵入海洋含水合物地层的动态过程及其一般性规律.与侵入常规油气地层相比,耦合水合物分解和再形成是钻井液侵入海洋含水合物地层的主要特征.模拟结果表明,钻井液密度、温度和盐度都对侵入过程有影响.在一定条件下,钻井液密度越大,温度和含盐量越高,则钻井液侵入程度越深,热量传递越远,水合物分解程度越大.分解的水气在合适条件下又会重新形成水合物,影响了钻井液进一步侵入.而重新形成的水合物的饱和度甚至可能高于原位水合物饱和度,在井周形成一个"高饱水合物"环带.这一现象归因于钻井液侵入的驱替推挤、水合物分解的吸热以及地层传热的滞后等因素共同作用.在地层物性一定的条件下,高饱水合物环带的出现与否主要受钻井液温度和盐度控制.水合物分解以及高饱水合物环带的出现对井壁稳定和电阻率测井解释有很大影响.因此,为维护井壁稳定、确保测井准确和减少水合物储层伤害,就必须对钻井液密度、温度和滤失量进行严格控制,防止地层中的水合物大量分解.最好采用控制压力钻井(MPD)和深侧向测井方式,同时尽量选用低矿化度的含水合物动力学抑制剂的钻井液体系,采取低温快速循环方式.     

Analytical laboratory comparison of major and minor constituents in an active crater lake

The crater lake water from Maly Semiachik volcano in Kamchatka was used for the international analytical laboratory comparison of major and minor elements, and hydrogen, sulfur, and oxygen isotope data. Eight institutions participated in this program, giving analytical results of 9 major and 20 minor elements mainly by using ICP-AES for cations and IC for anions. Among the major elements, Na, Mg and Si showed coefficients of variation (CV) of 10% or more, whereas B, Al, Fe, Mn had coefficients less than 7%. The CV% of the minor elements Co, Cu, P, Cr, Pb was much greater (>30%) while the V analyses agreed well (<10%). Ti, Sr, Zn, and F were intermediate (between 10 and 20 CV%). The errors observed for these constituents are inherent to the methods applied: large dilutions and spectrometric interferences. Even the major anions such as Cl (>2000 ppm) and SO₄ (>5000 ppm) gave considerable ranges (5.1 and 8.8 CV%, respectively) as did the obtained pH values (22 CV%). The measured δ¹⁸O of the water samples and δ³⁴S of sulfate are in excellent agreement but the δD values had CV% of 8. Technical recommendations are presented to improve the analytical results for these elements with significant deviations from the mean values.     

A laboratory study on capillary sealing efficiency of Iranian shale and anhydrite caprocks

Caprock has the most important role in the long term safety of formation gas storage. The caprocks trap fluid accumulated beneath, contribute to lateral migration of this fluid and impede its upward migration. The rapid upward passage of invasive plumes due to buoyancy pressure is prevented by capillary pressure within these seal rocks. In the present study, two main seal rocks, from the Zagros basin in the southwest of Iran, a shale core sample of Asmari formation and an anhydrite core sample of Gachsaran formation, were provided. Absolute permeabilities of shale and anhydrite cores, considering the Klinkenberg effect, were measured as 6.09 × 10⁻¹⁸ and 0.89 × 10⁻¹⁸ m², respectively. Capillary sealing efficiency of the cores was investigated using gas breakthrough experiments. To do so, two distinct techniques including step by step and residual capillary pressure approaches were performed, using carbon dioxide, nitrogen and methane gases at temperatures of 70 and 90 °C, under confining pressures in the range 24.13–37.92 MPa. In the first technique, it was found that capillary breakthrough pressure of the cores varies in the range from 2.76 to 34.34 MPa. Moreover, the measurements indicated that after capillary breakthrough, gas effective permeabilities lie in range 1.85 × 10⁻²¹ – 1.66 × 10⁻¹⁹ m². In the second technique, the minimum capillary displacement pressure of shale varied from 0.66 to 1.45 MPa with the maximum effective permeability around 7.76 × 10⁻²¹ – 6.69 × 10⁻²⁰ m². The results indicate that anhydrite caprock of the Gachsaran formation provides proper capillary sealing efficacy, suitable for long term storage of the injected CO₂ plumes, due to its higher capillary breakthrough pressure and lower gas effective permeability.     

The effects of gas flaring on crops in the Niger Delta,Nigeria

Flaring of associated gas from oil exploitation has several consequences on the environment. This study explores the spatial variability effects of gas flaring on the growth and development of cassava (Manihot esculenta), waterleaf (Talinum triangulare), and pepper (Piper spp.) crops commonly cultivated in the Niger Delta, Nigeria. Data was collected on soil and atmospheric temperature and moisture at a 20-m interval, starting at 40 m from the flare point to a distance of 140 m. Lengths and widths of crop leaves, height of crop plants and cassava yields were measured at the specified distances. The amino acid, ascorbic acid, starch, and sugar constituents of the cassava yields were determined. The results suggest that a spatial gradient exists in the effects of gas flares on crop development. Retardation in crop development manifests in decreased dimensions of leaf lengths and widths of cassava and pepper crops closer to the gas flare point. Statistical analysis also confirms that cassava yields are higher at locations further away from the flare point. In addition, the amount of starch and ascorbic acid in cassava decreased when the plant is grown closer to the gas flare. High temperatures around the gas flare appear to be the most likely cause of this retardation. The waterleaf crop, on the other hand, appears to thrive better around the gas flare point.     

Seep mounds on the Southern Vøring Plateau (offshore Norway)

Multidisciplinary study of seep-related structures on Southern Vøring Plateau has been performed during several UNESCO/IOC TTR cruises on R/V Professor Logachev. High-resolution sidescan sonar and subbottom profiler data suggest that most of the studied fluid discharge structures have a positive relief at their central part surrounded by depression. Our data shows that the present day fluid activity is concentrated on the top of these “seep mounds”. Number of high hydrocarbon (HC) gas saturated sediment cores and 5 cores with gas hydrate presence have been recovered from these structures. δ¹³C of methane (between −68 and −94.6‰ VPDB) and dry composition of the gas points to its biogenic origin. The sulfate depletion generally occurs within the upper 30–200 cm bsf and usually coincides with an increase of methane concentration. Pore water δ¹⁸O ranges from 0.29 to 1.14‰ showing an overall gradual increase from bottom water values (δ¹⁸O ∼ 0.35‰). Although no obvious evidence of fluid seepage was observed during the TV surveys, coring data revealed a broad distribution of living Pogonophora and bacterial colonies on sea bottom inside seep structures. These evidences point to ongoing fluid activity (continuous seepage of methane) through these structures. From other side, considerable number and variety of chemosynthetic macro fauna with complete absence of living species suggest that present day level of fluid activity is significantly lower than it was in past. Dead and subfossil fauna recovered from various seep sites consist of solemyid (Acharax sp.), thyasirid and vesicomyid (cf. Calyptogena sp.) bivalves belonging to chemosymbiotic families. Significant variations in δ¹³C (−31.6‰ to −59.2‰) and δ¹⁸O (0.42‰ and 6.4‰) of methane-derived carbonates collected from these structures most probably related to changes in gas composition and bottom water temperature between periods of their precipitation. This led us to ideas that: (1) seep activity on the Southern Vøring Plateau was started with large input of the deep thermogenic gas and gradually decries in time with increasing of biogenic constituent; (2) authigenic carbonate precipitation started at the near normal deep sea environments with bottom water temperature around +5 °C and continues with gradual cooling up to negative temperatures recording at present time.     

Fluid sources for the La Guitarra epithermal deposit (Temascaltepec district, Mexico): Volatile and helium isotope analyses in fluid inclusions

The La Guitarra deposit (Temascaltepec district, South-Central Mexico), belongs to the low/intermediate sulfidation epithermal type, has a polymetallic character although it is currently being mined for Ag and Au. The mineralization shows a polyphasic character and formed through several stages and sub-stages (named I, IIA, IIB, IIC, IID, and III). The previous structural, mineralogical, fluid inclusion and stable isotope studies were used to constrain the selection of samples for volatile and helium isotope analyses portrayed in this study. The N₂/Ar overall range obtained from analytical runs on fluid inclusion volatiles, by means of Quadrupole Mass Spectrometry (QMS), is 0 to 2526, and it ranges 0 to 2526 for stage I, 0 to 1264 for stage IIA, 0 to 1369 for stage IIB, 11 to 2401 for stage IIC, 19 to 324 for stage IID, and 0 to 2526 for stage III. These values, combined with the CO₂/CH₄ ratios, and N₂-He-Ar and N₂-CH₄-Ar relationships, suggest the occurrence of fluids from magmatic, crustal, and shallow meteoric sources in the forming epithermal vein deposit. The helium isotope analyses, obtained by means of Noble Gas Mass Spectrometry, display R/Ra average values between 0.5 and 2, pointing to the occurrence of mantle-derived helium that was relatively diluted or “contaminated” by crustal helium. These volatile analyses, when correlated with the stable isotope data from previous works and He isotope data, show the same distribution of data concerning sources for mineralizing fluids, especially those corresponding to magmatic and crustal sources. Thus, the overall geochemical data from mineralizing fluids are revealed as intrinsically consistent when compared to each other.The three main sources for mineralizing fluids (magmatic, and both deep and shallow meteoric fluids) are accountable at any scale, from stages of mineralization down to specific mineral associations. The volatile and helium isotope data obtained in this paper suggest that the precious metal-bearing mineral associations formed after hydrothermal pulses of predominantly oxidized magmatic fluids, and thus it is likely that precious metals were carried by fluids with such origin. Minerals from base-metal sulfide associations record both crustal and magmatic sources for mineralizing fluids, thus suggesting that base metals could be derived from deep leaching of crustal rocks. At the La Guitarra epithermal deposit there is no evidence for an evolution of mineralizing fluids towards any dominant source. Rather than that, volatile analyses in fluid inclusions suggest that this deposit formed as a pulsing hydrothermal system where each pulse or set of pulses accounts for different compositions of mineralizing fluids.The positive correlation between the relative content of magmatic fluids (high N₂/Ar ratios) and H₂S suggests that the necessary sulfur to carry mostly gold as bisulfide complexes came essentially from magmatic sources. Chlorine necessary to carry silver and base metals was found to be abundant in inclusion fluids and although there is no evidence about its source, it is plausible that it may come from magmatic sources as well.     

Carbons at the heart of questions on energy and environment: A nanostructural approach

The organization of disordered carbons at the nanometer scale, or nanostructure, reveals very precisely their formation conditions, either in Nature or in the laboratory or in industry. Its study allows a better understanding of the properties of such solids. Only High-Resolution Transmission Electron Microscopy (HRTEM) allows a direct imaging of the nanostructure, whereas Raman microspectrometry provides quantitative but averaged structural data. Applications of the original coupling of Raman with HRTEM, especially in the fields of Energy and Environment, are numerous and promising. Two examples are given concerning the decontamination of irradiated nuclear graphite waste and detection of hydrocarbons trapped in oil and gas shales. Moreover, the study of wood carbonization led our team to propose a novel Raman-based paleothermometer. This approach finds an unexpected application in archeology (e.g., the study of fire marks in prehistoric caves).     

Geochemistry of pore waters from the Xisha Trough, northern South China Sea and their implications for gas hydrates

This paper reports all available geochemical data on sediments and pore waters from the Xisha Trough on the northern continental margin of the South China Sea. The methane concentrations in marine sediments display a downhole increasing trend and their carbon isotopic compositions (δ ¹³C = −25 to −51‰) indicate a thermogenic origin. Pore water Cl⁻ concentrations show a range from 537 to 730 mM, and the high Cl⁻ samples also have higher concentrations of Br⁻, Na⁺, K⁺, and Mg²⁺, implying mixing between normal seawater and brine in the basin. The SO₄ ²⁻ concentrations of pore waters vary from 19.9 to 36.8 mM, and show a downhole decreasing trend. Calculated SMI (sulfate-methane interfaces) depths and sulfate gradients are between 21 and 47 mbsf, and between −0.7 and −1.7 mM/m, respectively, which are similar to values in gas hydrate locations worldwide and suggest a high methane flux in the basin. Overall, the geochemical data, together with geological and geophysical evidence, such as the high sedimentation rates, high organic carbon contents, thick sediment piles, salt and mud diapirs, active faulting, abundant thermogenic gases, and occurrence of huge bottom simulating reflector (BSR), are suggestive of a favorable condition for occurrence of gas hydrates in this region.