Sediments quality control

Complex environmental samples originate from diverse matrices (the predominant material of which the sample to be analyzed is composed). These matrices, usually either water or soil/sediment, can contain as many as 50 to 100 organic components at widely varying concentrations. The EPA approach to the analysis of these samples involves the analysis of specific (or target) compounds and the use of authentic standards for quality control. The current number of standards in the EPA repository is about 1500, and their analysis is covered by various approved methods. 

Chau ASY, Caeron J and Lee H-B (1979) Analytical reference materials. II. Preparation and sample integrity of homogeneous fortified wet sediment for polychlorinated hiphenyl quality control studies. J Assoc Off Anal Chem 62 1312-1314. 

The literature includes a number of mis-matches, the following standing as examples for the many The use of bovine liver and other animal tissues for QC in the analysis of hmnan body fluids should not be considered by analysts. The matrix and the levels of trace elements do not match the levels to be analyzed, which may lead to serious errors. An even more severe mis-use was recently reported by Schuhma-cher et al. (1996) for NIST SRM 1577a Bovine Liver, which was used for QC in the analysis of trace elements in plant materials and soil samples in the vicinity of a municipal waste incinerator. Also recently, Cheung and Wong (1997) described how the quality control for the analysis of trace elements in clams (shellfish) and sediments was performed with the same material NIST SRM 1646, Estuarine sediment. Whilst the selected SRM was appropriate for sediments, its usefulness as a QC tool for clams is difficult to prove see also Chapter 8. This inappropriate use is the more mystifying because a broad selection of suitable shellfish RMs from various producers is available. 

Quality Assurance/Quality Control. QA/QC measures included field blanks, solvent blanks, method blanks, matrix spikes, and surrogates. Percent recovery was determined using three surrogate compounds (nitrobenzene-d5, 2-fluorobiphenyl, d-terphenyl-diQ and matrix spikes (naphthalene, pyrene, benzo[ghi]perylene) the recoveries ranged from 80 to 102%. Separate calibration models were built for each of the 16 PAHs using internal standards (naphthalene-dg, phenanthrene-dio, perylene-di2). Validation was performed using a contaminated river sediment (SRM 1944) obtained from NIST (Gaithersburg, MD) accuracy was <20% for each of the 16 analytes. 

As part of this field study, relevant quality assurance/quality control (QA/QC) criteria and guidelines (SETAC, 1993 JAMP, 1998a,b) have to be set to insure the quality of data generated during the assessments. The development of QA/QC criteria for this study involved conducting a series of replicate bioassays with each of the methods. Samples tested included a control sediment, contaminated sediments and reference toxicants. Based on the results of the bioassay replicates, the variability associated with the tests was quantified and we were able to determine what we considered acceptable QA/QC criteria for these methods. 

Quevauviller, Ph., Astruc, M., Ebdon, L., Desauziers, V., Saraadin, P.M., Astruc, A., Kramer, G.N. and Griepink, B. (1994) Certified reference material (CRM 462) for the quality control of dibutyl- and tributyl-tin determinations in coastal sediment. Appl. Otganomet. Chem., 8, 629—637. 

An Improved disc centrifuge photosedimentometer (DCP) was developed for use in the determination of the particle size and size distribution of latices, pigments and other particulates. Separation is based on Stokes Law for the sedimentation of particles in a centrifugal force field and does not rely on the use of particle size calibrants or standards. The DCP Instrument provides accurate stable particle size analyses over a wide range of conditions while at the same time is rugged enough for heavy use in both a research and quality control environment. A stand-alone data collection, analysis and management system was developed both for routine quality control operation and for research use of the instrument. 

Land disturbance and exposure of buried geologic strata to the open environment leads to sulfide oxidation (if present) and, as a consequence, water-quality degradation of runoff. For water-quality-control purposes, sedimentation ponds required by law are used as water treatment basins. Often, the pH of such basin waters is below 6, and the concentration of heavy metals is above acceptable levels. Water treatments include neutralization and removal of heavy metals as precipitates. Similar water-quality problems arise from other industrial sources, including heavy steel industries, electronics, food processing, mineral processing, and waste-disposal leachates. This portion of the chapter deals with some of the chemical agents used for neutralization purposes and some of their limitations. 

During subcellular fractionation, various markers can be used as a quality control measure, giving an assessment of the quality of separation of individual fractions for example, DNA can be used as a marker for the step sedimenting nuclei, while the enzyme succinate dehydrogenase can be used as a marker for the step sedimenting mitochondria. Of course, to obtain a pure organelle fraction from differential centrifugation is virtually impossible. 

CRM for road dust (BCR-723) containing 81.3 2.5 Jg/kg Pt, 6.1 1.9 ig/ kg Pd, and 12.8 1.3 Jg/kg Rh, was introduced [49, 228]. It is widely used for quality control of results obtained in the analysis of environmental materials (e.g., airborne particulate matters, dusts, soils, and sediments). Comparison of results obtained using different analytical procedures and interlaboratory studies are recommended when there is a lack of suitable CRM (e.g., in examination of clinical samples). The use of standards based on real matrices (e.g., saliva, plasma, ultrafiltrates, and lung fluids) instead of synthetic solutions is recommended in such analyses. Difficulties with the identification and quantification of different metal species in examined samples make the reliability of results of great importance. The use of various instrumental techniques for examination of particular samples can be helpful. The application of chromatography, mass spectrometry, and electrochemistry [199] HPLC ICP MS and HPLC MS/MS [156] ESI MS and MALDI [162] micellar electrokinetic chromatography, NMR, and MS [167] AAS, ESI MS, and CD spectroscopy [179] SEC IC ICP MS and EC ESI MS [180] and NMR and HPLC [229] are examples of such approaches. 

During each analysis, replicates of samples collected in the Genesee River were analyzed as quality-control check samples. The coefficients of variation for total phosphorus analysis of three sediments used as quality-control check samples were 0.12 (n =... 

In the case of rocks, soils, and sediments, sufficient material to be representative of the medium to be analyzed should be collected. Soil and sediment samples should be dried at temperatures <35 °C to avoid volatilization losses of arsenic or selenium (Rowell, 1994) and ideally freeze-dried (BGS, 1979-2002). Sampling, analysis, and quality control should be carried out with recognized procedures wherever possible (Darnley et al., 1995 Salminen and Gregorauskiene, 2000). 

In this section a concise overview of the most widely used analytical procedures for the determination of PCBs in environmental matrices (namely, air, sea water, snow/firn/ice, sediment/soil and biota) is given. Regardless of the nature of the sample, the following steps are generally included in an analytical procedure i) sample collection and storage ii) sample preparation (extraction of the analytes and cleanup of the extract) iii) instrumental analysis iv) data evaluation, including analytical quality control. 

The role and use of reference materials are in principle well known, in particular for Certified Reference Materials (CRMs) used as calibration materials or matrix materials representing - as far as possible - real matrices used for the verification of the measurement process, or (not certified) laboratory reference materials (LRMs also known as quality control (QC) materials) used, for example, in interlaboratory studies or in the maintenance of internal quality control (control charts). Examples of reference materials relevant to WFD monitoring (water, sediment and biota) are described in the literature (Quevauviller, 1994 Quevauviller and Maier, 1999). 

Standard quality control procedures were followed. These Included a) careful washing of all glassware In strong oxidizing solutions and with Type I water b) frequent analyses of glassware and reagent blanks c) analyses of procedural blanks with each batch of samples and d) calibration of Instruments before each set of analyses by analyzing standard solutions. Analytical proficiency In the analysis of biota and sediment samples have been demonstrated by participation In round-robin type Interlaboratory calibration exercises (2 ). 

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