Microbial degradation of chloroethenes in groundwater systems

The chloroethenes, tetrachloroethene (PCE) and trichloroethene (TCE) are among the most common contaminants detected in groundwater systems. As recently as 1980, the consensus was that chloroethene compounds were not significantly biodegradable in groundwater. Consequently, efforts to remediate chloroethene-contaminated groundwater were limited to largely unsuccessful pump-and-treat attempts. Subsequent investigation revealed that under reducing conditions, aquifer microorganisms can reductively dechlorinate PCE and TCE to the less chlorinated daughter products dichloroethene (DCE) and vinyl chloride (VC). Although recent laboratory studies conducted with halorespiring microorganisms suggest that complete reduction to ethene is possible, in the majority of groundwater systems reductive dechlorination apparently stops at DCE or VC. However, recent investigations conducted with aquifer and stream-bed sediments have demonstrated that microbial oxidation of these reduced daughter products can be significant under anaerobic redox conditions. The combination of reductive dechlorination of PCE and TCE under anaerobic conditions followed by anaerobic microbial oxidation of DCE and VC provides a possible microbial pathway for complete degradation of chloroethene contaminants in groundwater systems. Résumé Les chloroéthanes, tétrachloroéthane (PCE) et trichloroéthane (TCE) sont parmi les polluants les plus communs trouvés dans les aquifères. Depuis les années 1980, on considère que les chloroéthanes ne sont pas significativement biodégradables dans les aquifères. Par conséquent, les efforts pour dépolluer les nappes contaminées par des chloroéthanes se sont limités à des tentatives de pompage-traitement globalement sans succès. Des travaux ultérieurs ont montré que dans des conditions réductrices, des micro-organismes présents dans les aquifères peuvent, par réduction, dégrader les PCE et TCE en composés moins chlorés, comme le dichloréthane (DCE) et le chlorure de vinyl (VC). Bien que des études de laboratoire réalisées avec des micro-organismes adaptés aux composés halogénés montrent que la réduction complète en éthane est possible, dans la plupart des nappes la réaction de déchloration par réduction s'arrête apparemment au DCE et au VC. Cependant, des recherches récentes menées sur des sédiments d'un aquifère et d'alluvions ont démontré que l'oxydation microbienne de ces descendants réduits peut se produire de manière significative dans des conditions de redox anérobies. La déchloration par réduction de PCE et de TCE dans des conditions anérobies suivie par une oxydation microbienne anérobie des DCE et VC fournit une piste microbienne possible pour obtenir une dégradation complète des chloroéthanes polluants dans les aquifères. Resumen Los cloroetanos (tetracloroetano PCE y tricloroetano TCE) son contaminantes muy habituales en los acuíferos. Hasta 1980 se consideraba que los cloroetanos no eran biodegradables y, por tanto, los métodos de rehabilitación en acuíferos contaminados con cloroetanos se limitaban al pump-and-treat, generalmente con poco éxito. Posteriormente se vio que, en condiciones reductoras, algunos microorganismos pueden reducir PCE y TCE a unos subproductos menos clorados, como el dicloroetano (DCE) y el cloruro de vinilo (VC). Aunque estudios de laboratorio recientes sugieren que la reducción completa a etano es posible, en la mayoría de los sistemas acuíferos la decloración suele detenerse en los DCE o VC. Sin embargo, investigaciones más recientes en acuíferos y sedimentos fluviales demuestran que la oxidación microbiana de estos subproductos puede ser importante bajo condiciones redox anaerobias. La combinación de la reducción de PCE y TCE en condiciones anaerobias seguida de la oxidación microbiana anaerobia de DCE y VC proporciona un método potencial para la degradación total de los cloroetanos en los sistemas acuíferos.     

天然石棉矿床地质学及其在公共卫生政策中的应用(英文)

20世纪,越来越多的证据使人们意识到,吸入含石棉的灰尘会使从事与石棉有关的几种职业(如石棉采矿、造船和石棉产品组装)的工人患上几种严重的呼吸道疾病(石棉沉着病,肺癌和mesotheliuma)。为此已经制定了若干规定,以控制工人们在特殊的制造、采矿和其他工作地点与石棉尘埃的接触。比较间接的是控制和管理"天然产生的石棉"(NOA),这一问题近年来也引起了管理机构、健康机构和居民团体的注意。NOA包括在自然状态下原地找到的被描述为石棉的矿物,例如在基岩或土壤中的这种矿物。NOA之所以引起关注,是因为如果含石棉的岩石受到自然侵蚀或人类活动(例如修路、城市开挖、农业、采矿、压碎和碾磨)的影响,就有可能暴露并变成空中尘埃的微小纤维。天然石棉矿床的规模差异很大,从薄的四散的细脉一直到大的矿体。它们的地理分布与地质条件直接有关。石棉产出的地质背景是含镁丰富的主岩,这些岩石受到低压低温的变质作用蚀变而成。已知的容矿主岩包括变质的和已被交代的超基性岩(尤其是蛇纹岩)、一些基性火成岩、变质白云岩和变质的铁建造。石棉形状的角闪石在几种热液蚀变型的碱性火成侵入体中也能作为副矿物存在。石棉形成于可预见和可鉴别的地质环境。这种认识是一种信息,而这种信息使公众健康机构可以执行有情报根据的屏蔽和管理规划。第一步是在区域的或国家规模的尺度上确定和描述已知的(报道过的)石棉矿床。第二步是对容纳已知石棉矿的单位进行填图,以划定可能的其他石棉矿化的范围。这种地质研究使有关机构对遇到石棉的可能性做出规划,而尽量节省在不太可能遇到石棉矿的地区的管理费用。对石棉地质条件的认识可以事先应用于岩石和土壤的挖掘项目,而不管挖掘的规模有多大。这种对石棉管理的科学探索能有助于缓解对挖掘所发现的自然石棉矿床的连续不断地做出反应。因此,通过对很可能含有石棉矿床的地区做填图,规划者可开发出一些控制尘埃的程序,这些程序适用于工人和附近居民最容易暴露于空气携带的石棉的地区。     

Assessment of natural attenuation of aromatic hydrocarbons in groundwater near a former manufactured-gas plant, South Carolina, USA

 Shallow, anaerobic groundwater near a former manufactured-gas plant (MGP) in Charleston, South Carolina, USA, contains mono- and polycyclic aromatic hydrocarbons (MAHs and PAHs, respectively). Between 1994 and 1997, a combination of field, laboratory, and numerical-flow and transport-model investigations were made to assess natural attenuation processes affecting MAH and PAH distributions. This assessment included determination of adsorption coefficients (K _ad ) and first-order biodegradation rate constants (K _bio ) using aquifer material from the MGP site and adjacent properties. Naphthalene adsorption (K _ad =1.35×10^–7 m³/mg) to aquifer sediments was higher than toluene adsorption (K _ad =9.34×10^–10 m³/mg), suggesting preferential toluene transport relative to naphthalene. However, toluene and benzene distributions measured in January 1994 were smaller than the naphthalene distribution. This scenario can be explained, in part, by the differences between biodegradation rates of the compounds. Aerobic first-order rate constants of ¹⁴C-toluene, ¹⁴C-benzene, and ¹⁴C-naphthalene degradation were similar (–0.84, –0.03, and 0.88 day^–1, respectively), but anaerobic rate constants were higher for toluene and benzene (–0.002 and –0.00014 day^–1, respectively) than for naphthalene (–0.000046 day^–1). Both areal and cross-sectional numerical simulations were used to test the hypothesis suggested by these rate differences that MAH compounds will be contained relative to PAHs. Predictive simulations indicated that the distributions of toluene and benzene reach steady-state conditions before groundwater flow lines discharge to an adjacent surface-water body, but do discharge low concentrations of naphthalene. Numerical predictions were "audited" by measuring concentrations of naphthalene, toluene, and benzene at the site in early 1997. Measured naphthalene and toluene concentrations were substantially reduced and the areal extent of contamination smaller than was both observed in January 1994 and predicted for 1997. Measured 1997 benzene concentrations and distribution were shown to be relatively unchanged from those measured in 1994, and similar to predictions for 1997. Received: 26 June 1997 · Accepted: 25 August 1997     

Isotopic anomalies in organic nanoglobules from Comet 81P/Wild 2: Comparison to Murchison nanoglobules and isotopic anomalies induced in terrestrial organics by electron irradiation

Nanoglobules are a form of organic matter found in interplanetary dust particles and primitive meteorites and are commonly associated with ¹⁵N and D isotopic anomalies that are suggestive of interstellar processes. We report the discovery of two isotopically-anomalous organic globules from the Stardust collection of particles from Comet 81P/Wild 2 and compare them with nanoglobules from the Murchison CM2 meteorite. One globule from Stardust Cometary Track 80 contains highly aromatic organic matter and a large ¹⁵N anomaly (δ¹⁵N = 1120‰). Associated, non-globular, organic matter from this track is less enriched in ¹⁵N and contains a mixture of aromatic and oxidized carbon similar to bulk insoluble organic material (IOM) from primitive meteorites. The second globule, from Cometary Track 2, contains non-aromatic organic matter with abundant nitrile (CN) and carboxyl (COOH) functional groups. It is significantly enriched in D (δD = 1000‰) but has a terrestrial ¹⁵N/¹⁴N ratio. Experiments indicate that similar D enrichments, unaccompanied by ¹⁵N fractionation, can be reproduced in the laboratory by electron irradiation of epoxy or cyanoacrylate. Thus, a terrestrial origin for this globule cannot be ruled out, and, conversely, exposure to high-energy electron irradiation in space may be an important factor in producing D anomalies in organic materials. For comparison, we report two Murchison globules: one with a large ¹⁵N enrichment and highly aromatic chemistry analogous to the Track 80 globule and the other only moderately enriched in ¹⁵N with IOM-like chemistry. The observation of organic globules in Comet 81P/Wild 2 indicates that comets likely sampled the same reservoirs of organic matter as did the chondrite parent bodies. The observed isotopic anomalies in the globules are most likely preserved signatures of low temperature (<10 K) chemistry in the interstellar medium or perhaps the outer regions of the solar nebula. In other extraterrestrial samples, D isotopic anomalies, but not those of ¹⁵N, may be explained in part by exposure to ionizing electron radiation.     

Chemical Separation of Tungsten and Other Trace Elements for TIMS Isotope Ratio Measurements Using Organic Acids

One requirement for isotope ratio measurement results with small measurement uncertainties is that the element of interest is effectively separated from the sample matrix. Efficient chemical separation of W from matrix components, especially Ti, can be challenging, particularly for large test portion masses (> 1 g). We present a new W separation procedure that takes advantage of the distinct complexation behaviour of Ti and W with citrate ligand in a moderately low pH, oxidising solution. This preparation procedure can reduce the Ti/W ratio of large (4–10 g) basaltic (i.e., high‐matrix) test portions by a factor of 10⁵, relative to their original compositions, in a two‐step separation procedure. The procedure additionally provides a separate, well‐purified Mo fraction. We show that optimal separation requires precise selection of reagent concentrations and sample load. The procedure was employed to determine the μ¹⁸²W composition of BHVO‐2 as ?6.7 ± 4.2 (2 standard deviation, 2s). The principles derived from this method may prove useful for chemical separation of other elements used for geochemical and cosmochemical applications given an appropriate selection of organic acid. Future successful applications of this method may reveal that the use of organic acids as procedural reagents is a currently under‐utilised tool for efficient chemical separation protocols.     

Secondary flows in the lee of porous shelterbelts

The results of wind-tunnel experiments indicate that the flow close to the surface behind shelterbelts is quite sensitive to the orientation of the barrier to the mean flow direction, and that orientation is more important for short than long windbreaks. The implications of these findings are discussed in the context of field experiments to validate mathematical models of shelter effects.     

Highly N-enriched chondritic clasts in the CB/CH-like meteorite Isheyevo

The metal-rich carbonaceous chondrites (CB and CH) have the highest whole-rock ¹⁵N-enrichments (δ¹⁵N up to 1500‰) among planetary materials. They are also characterized by the absence of interchondrule fine-grained matrix. The only fine-grained material is present as lithic clasts, which experienced extensive aqueous alteration in contrast to the surrounding high-temperature components (chondrules, refractory inclusions, metal grains). Hence, the clasts are foreign objects that were incorporated at a late stage into the final parent body of Isheyevo. Their origin is poorly constrained. Based on mineralogy, petrography, and thermal processing of the aromatic carbonaceous component, different types of clasts have been previously identified in the CB/CH-like chondrite Isheyevo. Here, we focus on the rare lithic clasts characterized by the presence of anhydrous silicates (chondrules, chondrule fragments, and CAIs). Their mineralogy and oxygen isotopic compositions reveal them to be micro-chondrules, fragments of chondrules, and refractory inclusions related to those in the Isheyevo host, suggesting accretion in the same region. In contrast to previously studied IDPs or primitive chondritic matrices, the fine-grained material in the clasts we studied is highly and rather uniformly enriched in heavy nitrogen, with bulk δ¹⁵N values ranging between 1000‰ and 1300‰. It is also characterized by the presence of numerous ¹⁵N hotspots (δ¹⁵N ranging from 1400‰ to 4000‰). No bulk (δD <-240‰) or localized deuterium enrichments were observed. These clasts have the highest bulk enrichment in heavy nitrogen measured to date in a fine-grained material. They represent a unique material, of asteroidal or cometary origin, in our collection of cosmomaterials. We show that they were ¹⁵N-enriched before their incorporation in the final parent body of Isheyevo. They experienced an extensive aqueous alteration that most likely played a role in redistributing ¹⁵N over the whole fine-grained material and may have significantly modified its initial hydrogen isotopic composition. Based on a review of isotopic fractionation models, we conclude that the nitrogen isotopic fractionation process, its timing, and its location are still poorly constrained. The ¹⁵N-rich clasts may represent the surviving original carrier of the ¹⁵N anomaly in Isheyevo whole-rock.     

National Inventories of Terrestrial Carbon Sources and Sinks: The U.K. Experience

The U.K. has extensive databases on soils, land cover and historic land use change which have made it possible to construct a comprehensive inventory of the principal terrestrial sources and sinks of carbon for approximately the year 1990, using methods that are consistent with, and at least as accurate as, the revised 1996 guidelines recommended by IPCC where available – and including categories which are not currently considered under the UN Framework Convention on Climate Change. This country inventory highlights issues concerning methodology, uncertainty, double counting, the importance of soils and the relative magnitude of sources and sinks which are reported to the UNFCCC relative to other sources and sinks. The carbon sinks (negative values in MtC a^-1) for categories reported to the UNFCCC, based on the IPCC categories, were estimated to be: forest trees and litter (–2.1), U.K. forest products (–0.5, ignoring imports and exports), non-forest biomass (–0.3), forest soils (–0.1) and soils on set-aside land (–0.4). The carbon sources (positive values) reported under the UNFCCC were estimated to be: losses of soil organic carbon resulting from cultivation of semi-natural land (6.2) and from urbanization (1.6), drainage of peatlands (0.3) and fenlands (0.5), and peat extraction (0.2). A range of other sources and sinks not covered by the IPCC guidelines were also quantified, namely, the accumulation of carbon in undrained peatlands (–0.7, ignoring methane emission), sediment accretion in coastal marshes (–0.1), the possible U.K. share of the CO₂ and N fertilization carbon sink (–2.0) and riverine organic and particulate carbon export to the sea (1.4, which may be assumed to be a source if most of this carbon is released as CO₂ in the sea). All sinks totalled –6.2 and sources 10.2, giving a net flux to the atmosphere in 1990 of 4.0 MtC a^-1. Uncertainties associated with categories, mostly based on best guesses, ranged from ±15% for forest biomass and litter to ±60% for CO₂ and N fertilization.     

Introducing the Volcanic Unrest Index (VUI): a tool to quantify and communicate the intensity of volcanic unrest

Accurately observing and interpreting volcanic unrest phenomena contributes towards better forecasting of volcanic eruptions, thus potentially saving lives. Volcanic unrest is recorded by volcano observatories and may include seismic, geodetic, degassing and/or geothermal phenomena. The multivariate datasets are often complex and can contain a large amount of data in a variety of formats. Low levels of unrest are frequently recorded, causing the distinction between background activity and unrest to be blurred, despite the widespread usage of these terms in unrest literature (including probabilistic eruption-forecasting models) and in Volcanic Alert Level (VAL) systems. Frequencies and intensities of unrest episodes are not easily comparable over time or between volcanoes. Complex unrest information is difficult to communicate simply to civil defence personnel and other non-scientists. The Volcanic Unrest Index (VUI) is presented here to address these issues. The purpose of the VUI is to provide a semi-quantitative rating of unrest intensity relative to each volcano’s past level of unrest and to that of analogous volcanoes. The VUI is calculated using a worksheet of observed phenomena. Ranges for each phenomenon within the worksheet can be customised for individual volcanoes, as demonstrated in the companion paper for Taupo Volcanic Centre, New Zealand (Potter et al. 2015). The VUI can be determined retrospectively for historical episodes of unrest based on qualitative observations, as well as for recent episodes with state-of-the-art monitoring. This enables a long time series of unrest occurrence and intensity to be constructed and easily communicated to end users. The VUI can also assist with VAL decision-making. We present and discuss two approaches to the concept of unrest.