有机污染物稳定同位素在线测试技术研究

为了识别环境中有机污染物的来源和迁移转化,在线的单体稳定同位素分析(CSIA)是必不可少的关键技术,但是在实际应用中还存在问题.本文评价了目前已经开发的6种在线测定单体稳定同位素仪器的发展动态,包括气相色谱-同位素比值质谱计(GC-IRMS)、液相色谱-同位素比值质谱计(LC-IRMS)、直接引进-气相色谱-同位素比值质谱计(DI-GC-IRMS)、气相色谱-四极杆质谱计(GC-qMS)、气相色谱-多接收器电感耦合等离子体质谱计(GC-MC-ICPMS)、气相色谱-光强衰荡光谱仪(GC-CRDS).提出了在线测试中的5个值得注意的问题:①样品的预富集;②气相色谱(GC)和液相色谱(LC)分离;③多种仪器和多种方法选择使用;④有机化合物稳定同位素标准物质的开发;⑤安全保障.提出了三点建议:一是大力发展直接注入而不经过燃烧的有机污染物同位素测试技术,例如GC-qMS和GC-CRDS技术;二是继续开发研究GC-MC-ICPMS测定有机氯和有机溴同位素技术;三是快速研制有机化合物稳定同位素的国际标准物质.本文认为,在进行单体化合物同位素研究时应作多元素的同位素分析,而其最优的选择是采用直接样品注入而不经过燃烧的测试技术.     

The dynamics of sediment‐associated contaminants over a transition from drought to multiple flood events in a lowland UK catchment

Fine sediment in suspended form, recently deposited overbank and in temporary storage on or in channel beds, was collected in the Nene basin during a period of drought through to a period of four high flows. The sediment was analysed for arsenic, copper, lead, phosphorus and zinc concentrations with the aim of investigating their sources, movement, temporary storage and potential for environmental harm. Copper, lead and zinc probably originated from urban street dusts, phosphorus (originally in dissolved form) from sewage effluent and arsenic from natural soils developed over ironstone. There was little difference in the metal or arsenic concentrations in the sediment under different flow conditions; instead, proximity to pollutant sources appeared to control their concentrations. Phosphorus in tributary sub‐catchments probably adsorbed to sediment during periods of low flow but these sediments were flushed away during high flows and replaced by sediment with lower concentrations. However, concentrations of all pollutants in overbank sediments along the Nene's main channel were not reduced in successive flood events, suggesting no first flush effect. Only phosphorus accumulated on sediment at concentrations exceeding those of its catchment‐based sources (e.g. street dusts, channel banks and catchment soils). This scavenging of aqueous phosphate by sediment explained the difference in behaviour between phosphorus, arsenic and heavy metals. The surface area and organic matter content were shown to have a small effect on contaminant concentrations. Street dust contaminants only exceeded predicted effect levels in close proximity to urban areas, suggesting a small potential for harm to the aquatic environment. Arsenic concentrations exceeded predicted effect levels in most sediment samples. However, it has been shown to be largely non‐bioavailable in previously published research on the Nene, limiting its potential for significant environmental harm. Phosphorus concentrations in river sediments are high in comparison to the soils in the catchment and in comparison with sediment–P concentrations in other published lowland catchment studies, indicating a large potential for eutrophication should the Phosphorus be, or become, bioavailable. Copyright © 2015 John Wiley & Sons, Ltd.     

Geochemistry and Sr, Nd, Pb isotopic composition of the Central Atlantic Magmatic Province (CAMP) in Guyana and Guinea

The Central Atlantic Magmatic Province (CAMP) is one of the largest igneous provinces on Earth, extending more than 5000 km north to south, on both sides of the Atlantic Ocean. Its emplacement occurred about 200 Ma ago, at the Triassic–Jurassic boundary, and is linked to the initial breakup of Pangaea. Two areas of the province are studied here: French Guyana/Surinam (South America) and Guinea (West Africa), in order to document the petrogenesis and geodynamical significance of high-Ti and low-Ti basaltic magmas from the CAMP.

In Guyana, doleritic and gabbroic dykes are located on the edge of the Guiana Shield, and represent limited volumes of magma. They display low SiO₂ (47–50%), high TiO₂ (2.5–3.5%) and high FeO tholeiitic trends and show variably enriched trace element patterns ((La/Yb)_n=1.5–5.1). Their isotopic signature and ratios of very incompatible elements (εNd_i=+5.8 to +4.2, (⁸⁷Sr/⁸⁶Sr)_i=0.703–0.705, (²⁰⁷Pb/²⁰⁴Pb)_i=15.46–15.64) match a depleted PREMA (prevalent mantle)-like source. Their genesis can be modeled by ca. 15% partial melting of a lherzolite source, and a subsequent limited fractional crystallization (5–10%) or a slight upper crustal assimilation–fractional crystallization (AFC, r=0.1, Proterozoic contaminant). In Guinea, in contrast, huge volumes of CAMP magmas were intruded along the Rockelides suture and the West African craton, forming the Fouta Djalon sills and the Kakoulima laccolith. The laccolith is more than 1000 m thick. These features consist of gabbros, dolerites, diorites and mafic (gabbro) and ultramafic (dunite, wherlite) cumulates. Guinean tholeiites show high SiO₂ (51–58%), low TiO₂ (0.7–1.2%) and FeO trends, with high LILE/HFSE ratios and slight negative Nb–Ta anomalies. Isotopic signatures (εNd_i=+0.4 to −5.3, (⁸⁷Sr/⁸⁶Sr)_i=0.705–0.710, (²⁰⁷Pb/²⁰⁴Pb)_i=15.57–15.66) indicate a more enriched source than for Guyana as well as a higher rate of magma–upper crust interaction through an AFC process (r=0.3, Birimian crust contaminant) and, probably, an additional upper crustal contamination for the most differentiated sample.

This geochemical study supports the prevalence in Guinea, as for other low-Ti CAMP tholeiites, of a lithospheric mantle source, previously enriched during ancient subduction events, and preferentially reactivated in late Triassic times by edge-driven convection between cratonic and mobile belt domains. A larger contribution from a depleted asthenospheric source is required to generate high-Ti tholeiites in Guyana, which may reflect the development of CAMP rifting towards the initiation of the Central Atlantic oceanic crust.     

Uptake and depuration of PAHs and chlorinated pesticides by semi-permeable membrane devices (SPMDs) and green-lipped mussels (Perna viridis)

Semi-batch seawater experiments were conducted to follow the uptake and release of selected PAHs (anthracene, fluorathene, pyrene and B[a]P) and organochlorine pesticides (-HCH, aldrin, dieldrin, p,p′-DDT) in semi-permeable membrane devices (SPMDs) and green-lipped mussels (Perna viridis). Mathematical models were applied to describe the uptake and elimination curves of the contaminants for SPMDs, and kinetic parameters, such as uptake rate constants, and equilibrium triolein/water partitioning coefficients were calculated. SPMD data showed a good fit to estimate rate constant and partition coefficient equations, but only those contaminants which partitioned mainly in the dissolved phase (-HCH and dieldrin) were well explained for mussels. Poor conformity of the other contaminants indicated mussels uptake by routes other than diffusion, such as ingestion of algae. An apparent equilibrium state was only noted for -HCH in mussels. Aldrin was not detected in mussels in the first few days of exposure, indicating potential metabolism of this compound. B[a]P was not detected in the triolein of SPMDs, which suggests that the membrane may act as a reservoir. Loss of spiked B[a]P from the triolein was evident in a depuration experiment, which may indicate transfer to the membrane. Rate constants for mussels were higher than those for SPMDs, but the reverse was true for partition coefficients. Overall, mussels and SPMDs had similar uptake rates for all compounds in this study, excluding p,p′-DDT and dieldrin. Contaminant elimination took place more rapidly in mussels, implying that SPMDs are better candidates for detecting episodic discharge of organic contaminants.     

On the velocity covariance for steady flows in heterogeneous porous formations and its application to contaminants transport

We consider groundwater steady flow in a heterogeneous porous formation of random and stationary log-conductivity Y = ln K, characterized by the mean 〈Y〉, and the two point correlation function C _Y which in turn has finite, and different horizontal and vertical integral scales I and I _v , respectively. The fluid velocity V, driven by a given head drop applied at the boundary, has constant mean value U ≡ (U, 0, 0). Approximate explicit analytical expressions for transverse velocity covariances are derived. The adopted methodology follows the approach developed by Dagan and Cvetkovic (Spatial moments of kinetically sorbing plume in a heterogeneous aquifers, Water Resour. Res. 29 (1993) 4053) to obtain a similar result for the longitudinal velocity covariance. Indeed, the approximate covariances of transverse velocities are determined by requiring that they have the exact first order variances as well as zero integral scale (G. Dagan, Flow and Transport in Porous Formations (Springer, 1989)) , and provide the exact asymptotic limits of the displacement covariance of the fluid particles obtained by Russo (On the velocity covariance and transport modeling in heterogeneous anisotropic porous formations 1. Saturated flow, Water Resour. Res., 31 (1995) 129). Comparisons with numerical results show that the proposed expressions compare quite well in the early time regime, and for Ut/I >100. Since most of the applications, like assessing the effective mobility of contaminants or quantifying the potential hazards of nuclear repositories, require predictions over higher times the proposed approximate expressions provide acceptable results. The main advantage related to such expressions is that they allow obtaining closed analytical forms of spatial moments pertaining to kinetically sorbing contaminant plumes avoiding the very heavy computational effort which is generally demanded. For illustration purposes, we consider the movement of one contaminant species, and show how our approximate spatial moments compare with the numerical simulations.     

富含Na+ 、Ca2+、Al3+、Cr3+蒙脱石对垃圾渗滤液中有机物的吸附

由于层间含有高价态金属阳离子的蒙脱石对特定有机物的吸附能力可大大增强,故分别用层间含有Na+、Ca2+、Al3+和Cr3+的蒙脱石对垃圾渗滤液中的有机物进行吸附实验,研究它们吸附苯酚、二甲苯和COD的能力及离子形态对吸附效果的影响.结果表明,含高价金属阳离子的蒙脱石对苯酚和COD的吸附能力较高,吸附能力由小到大的顺序为Na+<Ca2+<Al3+<Cr3+蒙脱石;各种类型蒙脱石对二甲苯的吸附能力相对较低,并且没有一定的规律可循.并对氢键吸附机制进行了探讨.     

Evaluation of shredded tyre chips as sorption media for passive treatment walls

The potential of shredded tyre chips, either on their own or mixed with gravel, to act as a permeable reactive barrier has been examined by carrying out tests for assessing sorption characteristics and establishing their mechanical properties. Sorption–desorption tests have been carried out using free product petrol and paraffin and aqueous phase phenol and cresols.

Compaction and compressibility tests have been carried out to establish optimum tyre–chip mixes in order to optimise the mix in terms of compressibility behaviour. The results demonstrate that tyre chips show significant promise for incorporation in a permeable reactive barrier. The evidence indicates that they would be particularly effective for the retardation of aqueous phase hydrophobic organic contaminants and residual free product. Optimum mixes of 2–6 mm tyre chips and 20 mm gravel, in terms of mechanical stability, will contain just under 10% of tyre chips.     

LINKING SEDIMENT EXPOSURE WITH EFFECTS: MODELING TECHNIQUES, ORGANIC AVAILABILITY AND UPTAKE

1 INTRODUCTION Sediments are the ultimate sink for many hydrophobic contaminants and represent biologically important environmental habitats. Exposure of the sediment-associated contaminants is not only influenced by the fate and transport of sediment but also is influenced by a variety of physical, chemical, and biological processes that involve no net movement of sediments. These processes include pore water transport processes such as advection and diffusion, and sediment mixing process…     

地表稠油污染物地球化学研究现状

关于石油轻组分对环境的污染问题相对研究较多，而针对稠油污染物的研究则较薄弱。本文着重介绍了目前地表稠油污染物的研究进展，涉及稠油污染的潜在严重性和危害性，其赋存形态、迁移方式和演化机制，以及目前常用的修复方法。进一步开展稠油污染物在地表土壤以及水体中的地球化学特征及演化机制方面的研究工作，将有助于为稠油开采和炼制地区的环境保护和修复治理提供更多的科学依据。