Stable Sulfur Isotope Effects Related to Local Intense Sulfate Reduction in a Tidal Sandflat (Southern North Sea): Results from Loading Experiments

Abstract

Anoxic sediment surfaces coloured black by iron monosulfides (“black spots”) evolve in tidal sandflats of the Wadden Sea (southern North Sea) as a result of the degradation of buried organic matter. To follow the short- and long-term effects of organic matter burial on pore water and sediment isotopic biogeochemistry, formation of artificial black spots was initiated on the Groninger Plate (site RP63) in the backbarrier tidal flats of Spiekeroog island. Changes in concentrations (DOC, TA, TOC, sulfate, sulfide, TRS, Fe) and isotopic compositions (sulfate, sulfide, TRS, pyrite, TOC) were followed for up to 12 months and compared to reference areas. 13°C ratios of TOC clearly mirror the early diagenetic degradation of organic matter. At least temporarily closed system sulfate reduction is inferred for the artificial black spot from the variation of sulfate concentrations and stable sulfur isotope partitioning, In the interstitial waters of the black spot, 34S/32S values of coexisting dissolved sulfate and sulfide yield fractionation degrees between ?5 and ?25%. On the reference area, 34S/32S are fractionated by ?32 to ?42% as calculated from the isotope composition of solid phase reduced sulfur and pore water sulfate. Sulfur isotope fractionation seems to increase with decreasing sulfate reduction rate. Limiting factor seems to be the availability of DOC. Between the pyrite pool and the dissolved sulfide in the black spot, no significant isotope exchange is observed within 12 months.     

P-T stability conditions of methane hydrate in sediment from South China Sea

For reasonable assessment and safe exploitation of marine gas hydrate resource, it is important to determine the stability conditions of gas hydrates in marine sediment. In this paper, the seafloor water sample and sediment sample (saturated with pore water) from Shenhu Area of South China Sea were used to synthesize methane hydrates, and the stability conditions of methane hydrates were investigated by multi-step heating dissociation method. Preliminary experimental results show that the dissociation temperature of methane hydrate both in seafloor water and marine sediment, under any given pressure, is depressed by approximately -1.4 K relative to the pure water system. This phenomenon indicates that hydrate stability in marine sediment is mainly affected by pore water ions.     

缺氧沉积物中重金属形态连续萃取方法的稳定性研究

考察了海水养殖区域缺氧沉积物中重金属形态连续萃取法萃取过程中溶液pH值、温度变化和胶体形成对形态分离结果的影响。结果表明,连续萃取法Step1萃取酸溶态时,萃取液pH值的轻微升高使Pb和Zn的萃取结果明显降低;Step2萃取还原态时,萃取液pH值明显升高对重金属的萃取结果影响很小;Step3萃取有机质结合态时,萃取液pH值的降低对重金属萃取结果影响较小(除Pb外)。由于连续萃取法中各步萃取反应的热力学过程不同,Step1和Step2萃取后溶液温度轻微升高而在Step3中溶液温度稍微降低,溶液温度变化(<2.5℃)对重金属形态的影响很小。在Step1、Step2和Step4萃取过程中胶体的形成和存在,对萃取液Cd、Zn和Cu有明显的吸附影响;而在Step3萃取中萃取剂的分散作用有效控制了溶液中胶体的形成。因此采用连续萃取方法评价沉积物中的重金属形态时,控制萃取液pH值和胶体形成有利于提高萃取结果的稳定性和准确性。     

河流沉积物中重金属来源分析方法研究进展

河流沉积物中重金属来源分析方法主要有元素形态分析法、剖面分析法、空间分布法、Pb同位素示踪法、多元统计分析法等.对各种方法的优缺点、适用条件和适用范围进行了对比.介绍了重金属来源分析方法的研究进展.     

Flow Injection On-Line Two-Stage Solvent Extraction Preconcentration Coupled with Et-Aas for Determination of Bismuth in Biological and Environmental Samples

ABSTRACT

A robust flow injection/sequential injection(FIA/SIA) on-line two-stage solvent extraction separation/preconcentration procedure coupled to electrothermal atomic absorption spectrometry (ETAAS) is described and demonstrated for the determination of trace-levels of bismuth. In 1-4% (v/v) nitric acid medium, diethyldithiophosphate (DDPA) chelates bismuth and the chelating complex formed is extracted into isobutyl methyl ketone (IBMK), which is separated from the aqueous phase by means of cavity gravitational phase separation. Both single and two-stage separations are used. In each case, 40 μl of the concentrate is entrapped and metered in a loop, and subsequently delivered via air-segmentation into a pyrolytically coated graphite tube. The ETAAS determination is performed in parallel with the preconcentration process of the ensuing sample. Enrichment factors of 17.8 and 31.5, detection limits of 12 ng 1^?1 and 10.5 ng 1^?1 for single and two-stage extractions, respectively, along with a sampling frequency of 13 h^?1 were obtained with 100 s of sample loading time at a sample flow rate of 5.4 ml min^?1. The relative standard deviations were 2.8% and 1.9% for single and two-stage extractions, respectively. The procedure was validated by determining the bismuth content in a certified reference material and i8543220 human urine samples.     

Limitations of the Quantification of Organic Carbon in Sediment from C–H Stretching Vibrations in DRIFT Spectra

Abstract

The limitations of quantifying organic carbon (OC) or various organic substances in sediment from the integration of infrared C–H stretching bands using diffuse reflectance infrared Fourier transform (DRIFT) spectra are pointed out, both from theoretical arguments and by presenting experimental data. Such determinations are inaccurate and imprecise because (i) the band at 2930 cm^?1 is not exclusively due to CH₂ groups; (ii) there is a spectral interference from CO₃ ^2? absorption; and (iii) the proportion of CH₂ groups in organic matter varies for different sediments. The measurement of aliphatic C–H stretching band areas only provides an approximate measurement of aliphatic carbon bonded to hydrogen, which turns out to be a factor of about 3 to 3.5 times smaller than the OC content for Hong Kong marine sediments, depending on their nature and origin.     

Ultrasonic Extraction–Ozonation Sequential Sample Treatment for the Determination of Arsenic in Environmental Certified Reference Materials by Hydride Generation–Atomic Fluorescence Spectrometry

Abstract

A sample pretreatment method based on ultrasound‐assisted extraction followed by ozonation is developed for sensitive determination of total As in biological and environmental certified reference materials and an unknown plant sample (Acacia dealbata) by flow injection and continuous‐flow hydride generation–atomic fluorescence spectrometry. The method is meant to minimize the use of corrosive and oxidizing acids for sample decomposition and common errors in trace analysis. Problems derived from introduction of sonicated extracts in continuous flow and flow injection manifolds in combination with an atomic fluorescence detector, such as excessive foaming and flame instability, are addressed. The following certified reference materials (CRMs) were employed for method assessment: BCR CRM 482 lichen; BCR CRM 60 and 61 aquatic plants; BCR CRM 279 sea lettuce; NIST 1633b fly ash; BCR 320 river sediment; RTC CRM 024‐050 soil. Effect of variables such as extraction time, ultrasound amplitude, concentration of extractant acid, sample mass, drying mode, and particle size was investigated. Leaves of Acacia dealbata were also employed for method development. Limits of detection ranged from 0.03 to 0.15 µg/g As depending on the sample. Between‐batch precision values ranged from 2% to 11%. Sample throughput was 40 hr^?1 with flow injection.     

Speciation Analysis of Mercury in Aquatic Environment

Abstract

This review considers methods for mercury speciation with low limits of detection that can be applied to real aquatic environmental samples (waters, sediments, biological tissues). Special attention is given to the necessity of clean sampling procedures and the proper storage of the samples. In this review, different extraction techniques for sediments and biological tissues are considered. The performance of different separation techniques, like liquid chromatography and off‐line and on‐line gas chromatography, are compared for their environmental applications.     

太湖地区全沉积物毒性识别评估研究

本研究用淡水单孔蚓（Monopylephorus limosus）和铜锈环棱螺（Bellamya aeruginosa）作为受试生物,对太湖沉积物的毒性进行筛查,采用全沉积物毒性识别评估（TIE）技术描述和鉴定太湖沉积物的主要毒性来源（重金属、氨氮或非极性有机物）．通过初始毒性实验筛选出4个对铜锈环棱螺具有毒性和1个对淡水单孔蚓具有毒性的沉积物样点．通过TIE,对于铜锈环棱螺,高风险点T6的毒性来源是非极性有机物和重金属;对于淡水单孔蚓,高风险点T12的毒性来源是非极性有机物、氨氮、重金属．T6和T12中4种多环芳烃（苯并[b＋k]荧葸、苊、二氢苊、茚并[1,2,3．cd]芘）是非极性有机物中产生生物毒性的来源之一,而Pb是T6和T12中产生毒性的主要重金属．     

A flux-limiter method for dam-break flows over erodible sediment beds

Finite volume methods for dam-break flows over erodible sediment beds require a monotone numerical flux. In the present study we present a new flux-limiter scheme based on the Lax–Wendroff method coupled with a non-homogeneous Riemann solver and a flux limiter function. The non-homogeneous Riemann solver consists of a predictor stage for the discretization of gradient terms and a corrector stage for the treatment of source terms. The proposed method satisfy the conservation property such that the discretization of the flux gradients and the source terms are well-balanced in the numerical solution of suspended sediment models. The flux-limiter method provides accurate results avoiding numerical oscillations and numerical dissipation in the approximated solutions. Several standard test examples are considered to verify the performance and the accuracy of the proposed method.