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131.
Prohaska T Quétel CR Hennessy C Liesegang D Papadakis I Taylor PD Latkoczy C Hann S Stingeder G 《Journal of environmental monitoring : JEM》2000,2(6):613-620
Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2). 相似文献
132.
Improvement of the BCR three step sequential extraction procedure prior to the certification of new sediment and soil reference materials 总被引:47,自引:0,他引:47
Rauret G López-Sánchez JF Sahuquillo A Rubio R Davidson C Ure A Quevauviller P 《Journal of environmental monitoring : JEM》1999,1(1):57-61
The Standards, Measurements and Testing Programme (formerly BCR) of the European Commission proposed a three-step sequential extraction procedure for sediment analysis, following extensive expert consultations and two interlaboratory studies. This scheme was recently used to certify the extractable trace element contents of a sediment reference material (CRM 601). Although this procedure offers a means to ensure the comparability of data in this field, some difficulties concerning the interlaboratory reproducibility still remain, and a new project is currently being conducted to determine the causes of poor reproducibility in the extraction scheme. The final objective of the project is the certification of new sediment and soil reference materials for their extractable contents of Cd, Cr, Cu, Ni, Pb and Zn. This paper presents the results of a small-scale interlaboratory study, which aimed to test a revised version of the extraction schemes by comparing the original and the modified protocols using the CRM 601 sample. This work offers an improvement to the BCR sequential extraction procedure through intercomparison exercises. This improved procedure will allow the obtaining of CRMs to validate analytical data in the analysis of soils and sediments, and it will also facilitate comparability of data in the European Union. 相似文献
133.
Stin OC Carnahan A Singh R Powell J Furuno JP Dorsey A Silbergeld E Williams HN Morris JG 《Environmental monitoring and assessment》2003,81(1-3):327-336
Molecular methods, including DNA probes, were used to identify and enumerate pathogenic Vibrio species in the Chesapeake Bay; our data indicated that Vibrio vulnificus exhibits seasonal fluctuations in number. Our work included a characterization of total microbial communities from the Bay; development of microarrays that identify and quantify the diversity of those communities; and observation of temporal changes in those communities. To identify members of the microbial community, we amplified the 16S rDNA gene from community DNA isolated from a biofilm sample collected from the Chesapeake Bay in February, 2000. The resultant 75 sequences were 95% or more similar to 7 species including two recently described Shewanella species, baltica and frigidimarina, that have not been previously isolated from the Chesapeake. When the genera of bacteria from biofilm after culturing are compared to those detected by subcloning amplified 16S fragments from community DNA, the cultured sample exhibited a strong bias. In oysters collected in February, the most common bacteria were previously unknown. Based on our 16S findings, we are developing microarrays to detect these and other microbial species in these estuarine communities. The microarrays will detect each species using four distinct loci, with the multiple loci serving as an internal control. The accuracy of the microarray will be measured using sentinel species such as Aeromonas species, Escherichia coli, and Vibrio vulnificus. Using microarrays, it should be possible to determine the annual fluctuations of bacterial species (culturable and non-culturable, pathogenic and non-pathogenic). The data may be applied to understanding patterns of environmental change; assessing the health of the Bay; and evaluating the risk of human illness associated with exposure to and ingestion of water and shellfish. 相似文献
134.
The aim of this study was to evaluate the sediment quality in the mesotidal Douro River estuarine environment, in order to identify areas where sediment contamination could cause ecosystem degradation. Samples were obtained in five locations and sediment characterised for grain size, total organic matter, total-recoverable metals (Al, Fe, Cu, Pb, Cr, Ni, Cd, Zn and Mn), as well as acid volatile sulfide (AVS) and simultaneously extracted metals (SEM). In situ effects were evaluated by examining the macrobenthic community structure. An elutriate sediment toxicity test (ESTT) was used to estimate the amount of metals and nutrients that could be exchanged with the water column through resuspension, and its positive or negative effects on the growth of the micro-alga Emiliania huxleyi in a 10 day test. Anthropogenic metal contamination was identified at the north bank of the Douro estuary, with deleterious effects on the macrobenthic community, namely decrease in number of species and diversity. This contamination could possibly also be toxic for water column organisms, in case of resuspension, as shown by the ESTT. Sediments from the salt marsh at the south bank showed an impoverished macrobenthic community and elutriate toxicity, which appeared to be due to anaerobic conditions. This study clearly shows the usefulness of the ESST approach to assess the biological effect of resuspension of estuarine sediments. 相似文献
135.
Sánchez López FJ Gil García MD Martínez Vidal JL Aguilera PA Garrido Frenich A 《Environmental monitoring and assessment》2004,93(1-3):17-29
Water quality assessment in the Aznalcollar area was attempted using multivariate methods based on heavy metal concentrations in red swamp crayfish (Procamburus clarkii). Trace levels of four heavy metals, copper (Cu), zinc (Zn), cadmium (Cd) and lead (Pb), were detected in crayfish from eleven different stations. Principal component analysis (PCA) highlighted a gradient of contamination between the sampling stations. Cluster analysis (CA) distinguished three groups of stations. Discriminant analysis also differentiated three groups. The group centroids of the first discriminant function were used to devise an index that varies according to the source of the crayfish. These standardized values are proposed for use as a water quality index. The ability of this index to successfully predict environmental quality was proved with random samples. 相似文献
136.
Virendra Misra Farhat N. Jaffery P. N. Viswanathan 《Environmental monitoring and assessment》1994,29(1):29-40
The sources of toxic xenobiotics and different factors such as ecological diversity, differences in comparative anatomy, physiology and biochemistry, food chain variation, interrelationship within species and life span, etc., are considered during risk assessment of pollutants, and their impact on aquatic ecotoxicology is identified. A fugacity and multimedia compartment model is suggested, based on toxicodynamic (toxicity of the chemical) and toxicokinetic (metabolism of the chemical) considerations to predict and screen the behaviour of pollutants quantitatively in the aquatic environment. The significance of the risk analysis approach in anticipatory actions and regulation of pollution levels is discussed. 相似文献
137.
J. P. Kimmins 《Environmental monitoring and assessment》1990,15(3):231-240
The Canadian forest environment is characterized by high spatial and temporal variability, especially in the west. Our forests vary according to climate, landform, and surficial geology, and according to the type, intensity, extent of, and the time since the last disturbance. Most Canadian forests have had a history of repeated acute, episodic disturbance from fire, insects, wind, diseases and/or logging, with a frequency of disturbance varying from a few decades to many centuries. These sources of variability have resulted in a complex and continually changing mosaic of forest conditions and stages of successional development.Monitoring the quality of this dynamic forested landscape mosaic is extremely difficult, and in most cases the concept of a relatively simple index of forest ecosystem quality or condition (i.e. an ecological indicator) is probably inappropriate. Such ecological indicators are better suited for monitoring chronic anthropogenically induced disturbances that are continuous in their effect (e.g. acid rain, heavy metal pollution, air pollution, and the greenhouse effect) in ecosystems that, in the absence of such chronic disturbance, exhibit very slow directional change (e.g. lakes, higher order streams and rivers). Monitoring the effects of a chronic anthropogenic disturbance to forest ecosystems to determine if it is resulting in a sustained, directional alteration of environmental quality will require a definition of the expected pattern of episodic disturbance and recovery therefrom (i.e. patterns of secondary succession in the absence of the chronic disturbance). Only when we have such a temporal fingerprint of forest ecosystem condition for normal patterns of disturbance and recovery can we determine if the ecosystem condition is being degraded by chronic human-induced alteration of the environment. Thus, degradation is assessed in terms of deviations from the expected temporal pattern of conditions rather than in terms of an instantaneous assessment of any particular condition. The concept of ecological rotation (the time for a given ecosystem to recover from a given disturbance back to some defined successional condition) is useful in the definition of these temporal fingerprints. This requires information on the intensity of disturbance, the frequency of disturbance, and the rate of successional recovery. Only when all three of these are known or estimated can statements be made as to whether the ecosystem is in a longterm sustainable condition or not.The somewhat overwhelming complexity of this task has led forest ecologists to use ecosystem-level computer simulation models. Appropriately structured and calibrated models of this type can provide predictions of the overall temporal patterns of ecosystem structure and functions that can be expected to accompany a given frequency and character of episodic disturbance. Such models can also be used to examine the long-term consequences of chronic disturbances such as acid rain and climatic change. Predictive ecosystem-level models should be used in conjunction with some method of stratifying the inherent spatial biophysical variability of the forest environment, such as the biogeoclimatic classification system of British Columbia. 相似文献
138.
Robert G. Lewis Andrew E. Bond Donald E. Johnson J. P. Hsu 《Environmental monitoring and assessment》1988,10(1):59-73
Air concentrations of 28 of the most commonly used household pesticides were measured inside nine homes in Jacksonville, Florida, and compared with corresponding outdoor levels. The households selected were sorted into three categories according to the degree of pesticide indoor usage. Personal air monitoring was also performed on one resident of each household by means of a portable sampler, which was kept with the person at all times. Five of the pesticides were found in the air inside of the majority of the homes at concentrations as high as 15 gm–3 (average concentrations, 12 ngm–3 to 2.4 gm–3). Indoor levels were generally one to two ordrrs of magnitude higher than surrounding outdoor air levels and personal air measurements were within ± 50% of corresponding indoor values. All samples were collected over 24-hr periods on polyurethane foam and analyzed by capillary colum gas chromatography with mass spectrometric and/or electron capture detection. 相似文献
139.
This paper compares the efficiencies of two sampling techniques for estimating a population mean and variance. One procedure, called grab sampling, consists of collecting and analyzing one sample per period. The second procedure, called composite sampling, collectsn samples per period which are then pooled and analyzed as a single sample. We review the well known fact that composite sampling provides a superior estimate of the mean. However, it is somewhat surprising that composite sampling does not always generate a more efficient estimate of the variance. For populations with platykurtic distributions, grab sampling gives a more efficient estimate of the variance, whereas composite sampling is better for leptokurtic distributions. These conditions on kurtosis can be related to peakedness and skewness. For example, a necessary condition for composite sampling to provide a more efficient estimate of the variance is that the population density function evaluated at the mean (i.e.f()) be greater than
. If
, then a grab sample is more efficient. In spite of this result, however, composite sampling does provide a smaller estimate of standard error than does grab sampling in the context of estimating population means. 相似文献
140.
P. M. Lutz Selena Bauer N. L. Gale J. Hewett P. E. Phillips F. M. Looney H. Bengsch 《Environmental geochemistry and health》1994,16(3-4):179-189
Lead has been found to depress the immune system in animal studies at levels far below those responsible for overt toxicity. Literature studies in animal systems most clearly showed an effect of lead on response to a specific immunogenic stimulus. Data are sparse concerning the effects of lead on the immune system in the human population at greatest risk for exposure-children up to six years of age. This portion of the Phase I study reports concentrations of IgG, IgM, IgA, and IgE, as well as antibody titers to the specific antigenic stimuli provided by the vaccines against diphtheria, tetanus, and Rubella. The study population consisted of a group of 193 children, ages 9 months to 6 years, who participate in the WIC (Women, Infants and Children) and Lead Poisoning Prevention Programs in the urban area of Springfield-Greene County Missouri. Blood lead levels ranged from 1 to 50 g dL–1. Total Ig levels were determined and the data were analysed. No consistent significant differences were observed among the risk categories in the five age groups examined. A single Ig class in each of three age groups showed apparent significant differences among the various risk categories, but these differences were not correlated with blood lead. An analysis of specific antibody titers to diphtheria, tetanus, and Rubella was performed. Regression analyses of current data in Phase I of this study suggest a detrimental effect of lead on the antibody titres to diphtheria and Rubella. 相似文献