超临界二氧化碳萃取－GC／MS测定土壤中的多环芳烃

本文开发了一种采用超临界二氧化碳萃取土壤中多环芳烃、不须经过纯化步骤，直接可用于ＧＣ／ＭＳ分析的简便、高效的方法。本实验中超临界革取的流体是二氧化碳，改善剂是５％的二氯甲烷／甲醇，萃取温度为１２０℃、压力为３４ＭＰａ。ＧＣ／ＭＳ分析时除了采用外标外，还加入了６种同位素ＰＡＨｓ内标以校正各段ＰＡＨｓ的响应因子。采用本方法成功地测定了我国未开垦森林土壤中的ＰＡＨｓ。     

Laboratory-polluted soils: a methodological approach to establish equilibrium conditions for different metal chemical forms in soils

An approach based on the number of extractions performed over time was applied to study the time necessary to attain equilibrium conditions between the different chemical forms present in two natural soils laboratory-loaded with heavy metals (Cu(II), Pb(II), Zn(II)). The influence of some soil parameters, such as pH value, cation exchange capacity and organic matter content, on the equilibrium time was evidenced both by the different nature of the soils and by the treatment of soils with paper mill sludge. Equilibrium conditions were determined by studying the metal partitioning in the soil on a case by case basis. The behaviour of the three metals was not the same, and the conditions of equilibrium among the different chemical forms were the result of the amount of heavy metals added as well as of the nature of the soil.     

Microbiological characteristics in a zero-valent iron reactive barrier

Zero-valent iron (Fe⁰)-based permeable reactive barriertreatment has been generating great interest for passivegroundwater remediation, yet few studies have paid particularattention to the microbial activity and characteristics withinand in the vicinity of the Fe⁰-barrier matrix. The presentstudy was undertaken to evaluate the microbial population andcommunity composition in the reducing zone of influence byFe⁰ corrosion in the barrier at the Oak Ridge Y-12 Plantsite. Both phospholipid fatty acids and DNA analyses were usedto determine the total microbial population and microbialfunctional groups, including sulfate-reducing bacteria,denitrifying bacteria, and methanogens, in groundwater andsoil/iron core samples. A diverse microbial community wasidentified in the strongly reducing Fe⁰ environment despitea relatively high pH condition within the Fe⁰ barrier (up topH 10). In comparison with those found in the backgroundsoil/groundwater samples, the enhanced microbial populationranged from 1 to 3 orders of magnitude and appeared to increase from upgradient of the barrier to downgradient soil. Inaddition, microbial community composition appeared to change overtime, and the bacterial types of microorganismsincreased consistently as the barrier aged. DNA analysisindicated the presence of sulfate-reducing and denitrifyingbacteria in the barrier and its surrounding soil. However, theactivity of methanogens was found to be relatively low,presumably as a result of the competition by sulfate/metal-reducing bacteria and denitrifying bacteria because of the unlimited availability of sulfate and nitrate in the site groundwater. Results of this study provide evidenceof a diverse microbial population within and in the vicinity ofthe iron barrier, although the important roles of microbial activity, either beneficially or detrimentally, on the longevityand enduring efficiency of the Fe⁰ barriers are yet to be evaluated.     

A national framework for monitoring and reporting on environmental sustainability in Canada

In 1991, a collaborative project to revise the terrestrial component of a national ecological framework was undertaken with a wide range of stakeholders. This spatial framework consists of multiple, nested levels of ecological generalization with linkages to existing federal and provincial scientific databases. The broadest level of generalization is the ecozone. Macroclimate, major vegetation types and subcontinental scale physiographic formations constitute the definitive components of these major ecosystems. Ecozones are subdivided into approximately 200 ecoregions which are based on properties like regional physiography, surficial geology, climate, vegetation, soil, water and fauna. The ecozone and ecoregion levels of the framework have been depicted on a national map coverage at 1:7 500 000 scale. Ecoregions have been subdivided into ecodistricts based primarily on landform, parent material, topography, soils, waterbodies and vegetation at a scale (1:2 000 000) useful for environmental resource management, monitoring and modelling activities. Nested within the ecodistricts are the polygons that make up the Soil Landscapes of Canada series of 1:1 000 000 scale soil maps. The framework is supported by an ARC-INFO GIS at Agriculture Canada. The data model allows linkage to associated databases on climate, land use and socio-economic attributes.     

Development of Ecological Land Classification and mapping in support of forest management in northern Newfoundland,Canada

For the sustainable development of forest land, as recently prescribed by the Canadian Forest Strategy, a land classification project in northern Newfoundland was initiated to support the local forest management activities. The method adopted here is a modification of the Canadian Committee for Ecological Land Classification's (CCELC) system, and it applies various levels of mapping to uniform areas based on geomorphology, soils, vegetation, climate, water, and fauna.In this study, all CCELC levels were mapped; resulting maps were digitized and imported into a Geographic Informations System (GIS). The GIS data base contained the following maps: 1) digital terrain model, 2) bedrock geology, 3) surficial geology, 4) forest inventory, and 5) various levels of the ecological land classification, including Vegetation Types at the lowest level. In addition to the mapping, mensurational data were analyzed to provide stand and stock tables for each of the forest types, including growth curves that could be entered into specific forest growth modelling systems to predict wood supply scenarios based upon different management interventions.     

Reduction of SO2 emissions by ammonia gas during unstaged combustion

The reduction of SO₂ by the addition of ammonia gas has been studied in a 2 m high fluidized bed combustor having a 30 cm static bed height and a freeboard height of 170 cm. Ammonia gas was injected at 52 cm above the distributor where the temperature is ca. 700° C by an uncooled stainless steel tube injector. Experiments were carried out to investigate the effects of amminia gas injection on sulphur dioxide emissions at unstaged conditions of: (i) excess air level, (ii) NH₃:SO₂ molar ratio, (iii) fluidizing velocity and (iv) bed height.A maximum reduction of 75% in SO₂ emissions was found at 40% excess air, at an NH₃:SO₂ molar ratio of 5.4. The onset of SO₂ reduction occurred at an NH₃:SO₂ ratio of 1.5 However, the most effective ratio was found to be between 3 and 5. Fluidizing velocity and bed height were also found to have significant influence on SO₂ reduction.It is difficult to determine how the SO₂ reduction varied with operating conditions. When ammonia is added in the main combustor zone, the temperature is much higher than that required for the occurrence of sulphur dioxide-ammonia and sulphur trioxide-ammonia reactions. However, this paper points out the significance of ammonia addition in the reduction of sulphur dioxide.     

A simple,cost-effective multispecies toxicity test using organisms with a cosmopolitan distribution

Difficulties in making accurate, ecosystem-level predictions of environmental effects of chemicals, mixtures, and effluents based solely on the results of tests on single species have necessitated the development of more environmentally realistic, predictive testing methods. This paper describes a multispecies, community-level toxicity test based on the colonization of artificial substrates by microbial species. Tests examined the colonization of initially barren polyurethane foam artificial substrates by Protozoa from a species source colonized in a natural system. Differences in colonization were examined in microecosystems amended with low levels of cadmium, a very toxic heavy metal, and TFM, an organic biocide used against larval sea lamprey. Tests examined differences in colonization over 28 days. For cadmium, effect levels were estimated to be near 1 g 1^–1, in the low range of effect levels determined from chronic single species tests. For TFM, effect levels were estimated to be between 1 and 10 ppm, overlapping the concentrations used in environmental applications. The colonization response, which depends on naked microbial cells reproducing and migrating through toxicant amended water to new substrates, is very sensitive. Tests based on colonization can be adapted to use species from a target receiving system or can use species from a designated natural source. Field validation of these tests can employ nearly identical methods to those used in laboratory studies to assess the accuracy of predictions based on test system data.     

A study on the behaviour of pesticides and their transformation products in the Scheldt estuary using liquid chromatography-electrospray tandem mass spectrometry

Off-line solid-phase extraction (SPE) combined with liquid chromatography-electrospray tandem mass spectrometry (LC-ESI-MS-MS) was used to study the estuarine behaviour of the polar pesticides, atrazine, chloridazon, diuron and metolachlor, and their transformation products (TPs), hydroxyatrazine (HA), desisopropylatrazine (DIA), desethylatrazine (DEA), 3,4-dichlorophenylmethylurea (DPMU) and monuron. The compounds were identified by comparing their LC retention times and product-ion spectra with those of standard solutions. In all but one case the detection limits of the method were sufficient to determine the compounds of interest over the entire salinity range in the estuary. The concentrations of the dissolved pesticides ranged from 70 ng l-1 for chloridazon to 1350 ng l-1 for diuron. The levels of TPs were 3-8% of the levels of their parent pesticide. The mixing plots of polar pesticides and their TPs indicated that TPs, which are present in fresh river water, are conservatively transported to the sea and that no additional amounts of TPs are formed during their transport through the estuary. The one exception was HA, of which approximately 10% of the amount transported to the North Sea is formed in the lower part of the estuary by photochemical oxidation of atrazine. The latter was concluded from the ratios of each analyte over the sum total of the parent pesticide and all TPs along the salinity gradient, which proved to be a useful tool for identifying such estuarine transformations.     

Quantification of protein adducts of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride in human plasma

Hexahydrophthalic anhydride (HHPA) and methylhexahydrophthalic anhydride (MHHPA) are two highly allergenic compounds used in the chemical industry. A method was developed for quantification of protein adducts of HHPA and MHHPA in human plasma. The plasma was dialysed and the anhydrides were hydrolysed from the proteins at mild acidic conditions. The released hexahydrophthalic acid (HHP acid) and methylhexahydrophthalic acid (MHHP acid) were purified by reversed solid phase extraction followed by derivatisation with pentafluorobenzyl bromide. The derivatives were analysed using GC-MS in negative ion chemical ionisation mode with ammonia as moderating gas. As internal standards, deuterium labelled HHP and MHHP acids were used. The detection limits were 0.06 pmol mL(-1) plasma for HHP acid and 0.03 pmol mL(-1) plasma for MHHP acid. The between-day precisions for HHP acid were 18% at 0.3 pmol mL(-1) and 8% at 4 pmol mL(-1). For MHHP acid, the precisions were 13% at 0.3 pmol mL(-1) and 9% at 4 pmol mL(-1). There were strong correlations (r=0.94 for HHPA and 0.99 for MHHPA) between total plasma protein adduct concentrations and serum albumin adduct levels. Workers exposed to time-weighted average air levels of HHPA between < 1 and 340 microg m(-3) and between 2 and 160 microg m(-3) for MHHPA had plasma adduct levels between the detection limits of the methods and 8.40 and 19.0 pmol mL(-1), respectively.