Filtern
Erscheinungsjahr
Dokumenttyp
Schlagworte
- PCB (5)
- Forest soil (3)
- Boden (2)
- Normung (2)
- O-horizon (2)
- OCP (2)
- Organic pollutants (2)
- PAHs (2)
- PAK (2)
- Soil (2)
- Soil organic matter (2)
- Soil standard (2)
- Standardization (2)
- Abfall (1)
- Analyseverfahren (1)
- Analysis (1)
- Analytical methods (1)
- Arrhenius model (1)
- Behandelter Bioabfall (1)
- Bodenluft (1)
- CEN/TC400 (1)
- Certified reference materials (1)
- Chrom(VI) (1)
- Comparison extraction methods (1)
- Content analysis (1)
- Cyanide (1)
- DDT (1)
- DDT breakdown (1)
- Dieldrin (1)
- Diffuse pollution (1)
- Dioxins (1)
- ERM (1)
- Emissions (1)
- Endosulfan (1)
- Enrichment factor (1)
- Evaluierung von Analyseverfahren (1)
- Extraction efficiency (1)
- Extraction methods (1)
- Furnaes (1)
- HCB (1)
- Humic layer (1)
- Humus (1)
- ICP-OES (1)
- Interlaboratory comparison (1)
- Klärschlamm (1)
- Long-range transport (1)
- Messunsicherheit (1)
- Method validation (1)
- Mineral soils (1)
- Multi-residue analysis (1)
- OCPs (1)
- Organic contaminants (1)
- Organic matter (1)
- Organic pollution (1)
- Organische Schadstoffe (1)
- Organochlorine Pesticides (OCP) (1)
- PAH (1)
- PCBs (1)
- PCDD/PCDF (1)
- PCP (1)
- POP (1)
- POPs (1)
- Pesticides (1)
- Polychlorinated Biphenyls (PCB) (1)
- Polycyclic aromatic hydrocarbon (PAH) (1)
- Pressurised liquid extraction (1)
- Referenzmaterialien (1)
- Ringversuche (1)
- Shelf life (1)
- Sludge (1)
- Soil monitoring (1)
- Solid-liquid-extraction (1)
- Spatial distribution (1)
- Stability (1)
- Standardisation (1)
- Stockholm-Convention (1)
- Säulenelution (1)
- TOC (1)
- Treted biowaste (1)
- Umweltrelevante Elemente (1)
- Validation ring tests (1)
- Validation trial (1)
- Validierung (1)
- Vor-Ort-Analytik (1)
- Waste (1)
- dl-PCB (1)
- pH (1)
Organisationseinheit der BAM
Eingeladener Vortrag
- nein (16)
Draft standards for the determination of organic pollutants in the solid matter of environmental matrices such as sludge, treated biowaste and soil have been basically developed in the framework of the European standardization project HORIZONTAL. A research project financed by the German Federal Environment Agency was initiated to finalize some of these CEN standard drafts, since fully validated standard procedures are crucial for the evaluation of their reliability in the context of implementation in legislation on environmental health.
Approach: Appropriate test materials (< 2mm particle size) were prepared and homogenized from contaminated soils, sludge and treated biowaste containing polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB), dioxins, furans and dioxin-like-PCB and served, along with reference solutions, as the basis for international interlaboratory comparisons. Performance data of three analytical standard procedures were obtained by the statistical evaluation of results received from 11 to 29 participants per test material.
Results: The overall variation coefficients of reproducibility (between-lab standard deviations) for the sum parameters were roughly between 10 and 35 %. The variation coefficients of repeatability (within-lab standard deviations) range between 3 % and 8 % and show no trend considering the substance groups or matrices.
The highest coefficients of reproducibility were found for the analysis of PAHs, which were between 26 and 35 %, depending on the matrix, whereas 7-17 % reproducibility was observed for toxicity equivalents (TEQ) comprising dioxins, furans and dl-PCB.
Conclusions: Overall, the results confirm that the procedures described in the Technical Specifications are fit for purpose for all three matrices and that the feasibility of the HORIZONTAL approach, to cover several matrices with one standard per analyte, was thereby proven.
Organochlorine pesticides (OCP) and polychlorinated biphenyls (PCB) are two classes of organic synthetic substances which are globally used. The vast majority of OCP have been released directly in the environment as agricultural insecticides but they have been also used as byproducts for different applications e.g. wood preserver. PCB have been widely used as additives in industrial applications where chemical stability has been required. OCP and PCB are persistent, bioaccumulating and prone to long-range atmosheric transport and deposition. They are ubiquitous in the environment (water, soil, sediment and waste) and their presence is regularly monitored and controlled.
At present determination of OCP and PCB is carried out in these matrices in most of the routine laboratories following the preceding steps for sampling, pre-treatment, extraction, clean-up by measurement of specific OCP and PCB by means of gas chromatography in combination with mass spectrometric detection (GC-MS) or gas chromatography with electron capture detector (GC-ECD).
Considered the different matrices and possible interfering compounds, this draft International Standard does not contain one single possible way of working. Several choices are possible, in particular relating to clean-up. Detection with both Mass Spectrometry and Electron Capture is possible. Three different extraction procedures and nine clean-up procedures are described. The use of internal and injection standards is described in order to have an internal check on choice of the extraction and clean-up procedure.
Polycyclic aromatic hydrocarbons (PAH) are ubiquitous because of the fact that they are released in appreciable quantities every year into the environment through the combustion of organic matters such as coal, fuel oils, petrol, wood, refuse and plant materials. Since some of these PAH compounds are carcinogenic or mutagenic, their presence in the environment (air, water, soil, sediment and waste) are regularly monitored and controlled. At present determination of PAH are carried out in these matrices in most of the routine laboratories following the preceding steps for sampling, pre-treatment, extraction, clean up by measurement of specific PAH by means of Gas chromatography in combination with mass spectrometric detection(GC-MS) or by HPLC in combination with UV-DAD- or Fluorescence-detection(HPLC-UV-DAD/FLD).
At present there two standards for the determination of PAH in soil, sludge and biowaste and in waste valid. The goal is the development of only one standard for solid materials.
Efficiency Evaluation of Extraction Methods for Analysis of OCPs and PCBs in Soils of Varying TOC
(2017)
Organochlorine pesticides and polychlorinated biphenyls are toxic, carcinogenic, and have a high potential for bioaccumulation. Due to their stability, they are still considered an environmental problem even though the use of most of them has been phased out several decades ago. Soil is a matrix which can retain these contaminants to a great extent. This ability is often associated with the total organic carbon content (TOC). In order to judge the pollution status of soil and to make monitoring data more easily comparable a simple, yet robust extraction method is needed. Agitation solid-liquid-extraction is well suited for this purpose. However, the influence of TOC on the analyte recovery has to be known. For the presented study, 12 organochlorine pesticides and 7 polychlorinated biphenyls were spiked into four model soils with organic carbon contents between 1.6% - 13.3%. The matrices were extracted using solid-liquid extraction between 45 minutes and 16 hours. For comparison, all soils were also extracted using pressurised liquid extraction and Soxhlet extraction. After clean-up the extracts were measured using a gas chromatography-mass spectrometry (GC-MS) system. Statistical analysis of the results implied that the TOC content of the soils did not have significant influence on the extraction efficiency. A longer solid-liquid extraction time did not necessarily increase analyte recovery: Extraction for one hour resulted in 88% recovery while 16 hour extraction led to 89%. Thus, the efficiency of all the methods was comparable for all model soils. Additional investigations regarding GC liner performance highlighted the need for isotopically labelled standards during the analysis of thermolabile pesticides.
The occurrence of persistent organic pollutants like polychlorinated biphenyls (PCB) and organochlorine pesticides (OCP) in the environment is still a matter of concern, even years after their use was abolished. Hence, threshold values are regulated by law which reference a number of national and international standards for determination of said contaminants. In this context, soil is an especially difficult matrix, because several defining parameters can vary in a wide range. Organic matter content in particular has a crucial influence on extractability of contaminants because it largely governs formation of non-extractable or bound residues.
For this study, four soils of different total organic carbon (TOC) content were generated from uncontaminated reference soil (RefeSol 01-A) and compost which were spiked to contaminant levels representative of the Bundes-Bodenschutz-Verordnung (BBodSchV). These test materials were extracted using accelerated solvent extraction (ASE), Soxhlet extraction, and liquid-liquid extraction. For the latter method, samples were initially extracted for 15 minutes employing acetone. The follow-up extraction step was carried out using cyclohexane and the extraction time varied between 15 minutes and 16 hours. After clean-up, extracts were analysed via gas chromatography-mass spectrometry (GC MS) and with a gas chromatograph equipped with an electron capture detector (GC ECD).
Statistical analysis of the experimental values showed that recovery was not dependent on matrix TOC content. Also, no clear preference for a single method could be detected. Concerning liquid-liquid-extraction, it is merely observed that prolonged extraction time results in slightly higher recoveries, while moderate extraction times appear to yield the most robust results. Although Soxhlet and ASE show high recoveries, they also lead to larger standard deviations and are not suitable for determination of thermolabile pesticides.
In addition to recovery by different extraction methods, the agreement of values obtained by ECD and MS was evaluated. For ECD, standard deviations are generally higher but overall the values obtained by MS and ECD are comparable.
The determination of organochlorine pesticides (OCP) and polychlorinated biphenyls is challenging because they are strongly physical and chemical bound to soil organic matter. There are various valid standards for the determination of these analytes in soil that differ especially in the extraction method and extraction time. In order to make profound assessments concerning the extraction efficiency seven extraction procedures namely pressurized liquid extraction (PLE), soxhlet and shaking with different extraction times 0.5 h, 1 h, 3 h, 6 h and 16 h were compared. For the study four soils of different total organic carbon (TOC) content were generated from uncontaminated reference soil and compost which were spiked to contaminant levels representative of the Bundes-Bodenschutz-Verordnung. Clean-up and measurement conditions using gas chromatography with mass spectrometry (GC-MS) were kept constant. Statistically analysis of the experimental values showed that recovery rates were not dependent on matrix TOC content. In consideration of measurement uncertainties of 10% - 20% for the determination of OCP and PCB in soil no differences in the efficiency between the tested extraction procedures could be observed.
While organic pollutants have been extensively studied in urban and agricultural areas, data from forested regions are relatively rare.
Within the framework of a forest soil inventory in Germany polycyclic aromatic hydrocarbons (PAH), polychlorinated biphenyls (PCB) and organochlorine pesticides (OCP) were analyzed in 1500 soil samples taken from 3 soil horizons at 447 sites. An analytical protocol was developed and validated for the simultaneous extraction and measurement of all analytes in humic rich soil at trace level range. It included pressurized liquid extraction (PLE) and a two step cleanup procedure consisting of gel permeation chromatography (GPC) followed by solid phase extraction (SPE). Quantification was carried out using gas chromatography combined with mass spectrometry (GC-MS). In line with the monitoring campaign a comprehensive quality assurance concept was implemented to guarantee constant analytical measurement conditions for two years. The protocol is applicable for field laboratories with a high level of automation and for analyzing high sample amounts.
At most sampling sites pollutant concentrations gradually decrease with depth. Only few spots showed highest concentrations in the upper mineral soil. In the O-horizon the sum concentrations of 16 PAHs range from 104 to 14.000 µg/kg, of 6 PCBs from <1 to 106 µg/kg and the sum of DDT and metabolites range from <1 to ca. 4.000 µg/kg.
The observed concentration of PAH, PCB and OCP reflect an ubiquitous background contamination at most sites. Relatively high concentrations of PAH and PCB are related to industrial areas and peak concentrations only of PAH are associated with open cast mining of brown coal areas. The spatial distribution of the contents of DDT and metabolites in German forest soils can clearly be attributed to historic application. A contribution of ubiquitous background pollution derived from long-range atmospheric transport is likely for some compounds in the studied area, e.g., DDT in the western part of Germany. The results generally reflect the distribution of POPs in densely populated and industrialized countries located in temperate regions].
Samples of 474 forest stands in Germany were analysed for concentrations of polycyclic aromatic hydrocarbons (PAHs) in three sampling depths. Enhanced concentrations were mainly found at spots relatively close to densely industrialized and urbanized regions and at some topographically elevated areas. Average enrichment factors between mineral soil and humic layer depend on humus type i.e. decrease from mull via moder to mor. Based on their compound-patterns, the observed samples could be assigned to three main clusters. For some parts of our study area a uniform assignment of samples to clusters over larger regions could be identified. For instance, samples taken at vicinity to brown-coal strip-mining districts are characterized by high relative abundances of low-molecular-weight PAHs. These results suggest that PAHs are more likely originated from local and regional emitters rather than from long-range transport and that specific source-regions can be identified based on PAH fingerprints.
Die Normung von Analyseverfahren ermöglicht, dass Parameter unter standardisierten Bedingungen qualitätsgesichert ermittelt werden können. Insbesondere dann, wenn Verfahren in gesetzliche Regelwerke einfließen, ist es notwendig, dass die Ergebnisse sicher und vergleichbar sind und der Aufwand im Vollzug vertretbar ist. Derzeit werden viele Parameter in verschiedenen Verordnungen nach unterschiedlichen genormten Verfahren analysiert, was die Überwachungsarbeit erschwert und zudem unnötig teurer macht. Aus diesem Grund wir eine sogenannte horizontale Normung angestrebt, bei der geeignete Analyseverfahren auch Matrices-übergreifend genormt und anschließend EU-weit zitiert werden können. Grundvoraussetzung für die Verabschiedung als Norm ist die Validierung der Verfahren. Bereits vor einigen Jahren erteilte die EU ein Mandat an CEN (Europäisches Komitee zur Normung), um umweltrelevante Parameter Matrices-übergreifend zu validieren. Allerdings konnten nicht alle für diverse Verordnungsnovellen (z.B. Klärschlammverordnung) wichtigen Parameter im Rahmen dieses Projekts validiert werden. Aus diesem Grund wurde das aktuelle Vorhaben in den Umweltforschungsplan des BMUB aufgenommen und von der BAM durchgeführt. Im Forschungsvorhaben konnten im Bereich der anorganischen Parameter die CEN/TS 16170 (Elemente mit ICP-OES), CEN/TS 16171 (Elemente mit ICP-MS) und CEN/TS 16175-2 (Quecksilber mit CV-AFS) sowie im Bereich der organischen Parameter die CEN/TS 16181 (PAK mit HPLC und GC), die CEN/TS 16167 (PCB mit GC-MS und GC-ECD) und die CEN/TS 16190 (Dioxine, Furane und dl-PCB mit HR-GC-MS) für die Analyse von Klärschlamm, behandeltem Bioabfall und Boden erfolgreich validiert werden. Die validierten Verfahren stehen nun kurz vor der Verabschiedung als EN (Europäische Norm).