Dilution standard addition calibration: A practical calibration strategy for multiresidue organic compounds determination.

Among calibration approaches for organic compounds determination in complex matrices, external calibration, based in solutions of the analytes in solvent or in blank matrix extracts, is the most applied approach. Although matrix matched calibration (MMC) can compensates the matrix effects, it does not compensate low recovery results. In this way, standard addition (SA) and procedural standard calibration (PSC) are usual alternatives, despite they generate more sample and/or matrix blanks consumption need, extra sample preparations and higher time and costs. Thus, the goal of this work was to establish a fast and efficient calibration approach, the diluted standard addition calibration (DSAC), based on successive dilutions of a spiked blank sample. In order to evaluate the proposed approach, solvent calibration (SC), MMC, PSC and DSAC were applied to evaluate recovery results of grape blank samples spiked with 66 pesticides. Samples were extracted with the acetate QuEChERS method and the compounds determined by ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). Results indicated that low recovery results for some pesticides were compensated by both PSC and DSAC approaches. Considering recoveries from 70 to 120% with RSD <20% as adequate, DSAC presented 83%, 98% and 100% of compounds meeting this criteria for the spiking levels 10, 50 and 100µgkg(-1), respectively. PSC presented same results (83%, 98% and 100%), better than those obtained by MMC (79%, 95% and 97%) and by SC (62%, 70% and 79%). The DSAC strategy showed to be suitable for calibration of multiresidue determination methods, producing adequate results in terms of trueness and is easier and faster to perform than other approaches.

Different Analytical Procedures for the Study of Organic Residues in Archeological Ceramic Samples with the Use of Gas Chromatography-mass Spectrometry.

The analysis of the composition of organic residues present in pottery is an important source of information for historians and archeologists. Chemical characterization of the materials provides information on diets, habits, technologies, and original use of the vessels. This review presents the problem of analytical studies of archeological materials with a special emphasis on organic residues. Current methods used in the determination of different organic compounds in archeological ceramics are presented. Particular attention is paid to the procedures of analysis of archeological ceramic samples used before gas chromatography-mass spectrometry. Advantages and disadvantages of different extraction methods and application of proper quality assurance/quality control procedures are discussed.

Valoración económica en salud y medio ambiente del control de contaminantes orgánicos persistentes en Colombia / Economic assessment in health and environment from control of persistent organic pollutants in Colombia

Objetivo Estimar los beneficios económicos en salud y ambientales relacionados con la implementación del Convenio de Estocolmo para el control de Compuestos Orgánicos Persistentes (COP) en el país. Método La estimación se realizó teniendo en cuenta dos escenarios: cumplimiento del convenio y no cumplimiento del Convenio y el beneficio bruto se derivó de la diferencia en valor presente entre los costos en salud y ambientales que se asumen en cada escenario. Resultados Los beneficios brutos por la disminución de gastos en salud derivados de la implementación del Convenio se estiman entre USD $511 y USD $501 millones. Al introducir variables como los costos de gestión del convenio y los posibles beneficios por acceso a mercados internacionales, los beneficios para el país se estiman entre USD $1631 y USD $3118 millones. Discusión A pesar de los beneficios económicos generados por menores gastos en salud con la aplicación del Convenio, los costos asociados a la reducción de estos contaminantes, generan un balance negativo, que solo es compensado al cruzar estas cifras con la expectativa de mayores ingresos por acceso a mercados internacionales. Se considera que esta valoración económica como un primer ejercicio es un aporte importante, pero que debe ser actualizado a la luz de metodologías de valoración que involucren otras variables de rentabilidad social y diferentes escenarios por tecnologías emergentes, nuevo conocimiento sobre estos contaminantes, cambios en la legislación y/o cambios en las condiciones de tratados internacionales, entre otros.(AU)

Objective To estimate the economic benefits related to environment and health in the context of the implementation of the Stockholm Convention for the control of Persistent Organic Pollutants in the country. Method: The estimation was conducted based on two scenarios: non-compliance with the agreement and compliance with the Convention. Gross profit was derived from the difference in present value between the health and environmental costs that are assumed in each scenario. Results Gross profit by decreasing health costs arising from the implementation of the Convention was estimated at USD $ 511 and USD $ 501 million. By introducing variables such as management costs and agreement on potential benefits for access to international markets, the benefits to the country were estimated at between USD $1631 and USD $ 3118 million. Discussion Despite the economic benefits generated by lower expenditure on health for the Convention implementation, the costs associated with reducing pollutant emissions generated a negative balance, compensated only by the expectation of higher revenues for international market access. We consider this initial economic assessment an important contribution, but it should be reviewed to include valuation methodologies involving other social profitability variables and different scenarios for emerging technologies, new scientific knowledge about these pollutants, changes in legislation and / or changes in trade agreement conditions, among others.(AU)

High-throughput characterization of sediment organic matter by pyrolysis-gas chromatography/mass spectrometry and multivariate curve resolution: A promising analytical tool in (paleo)limnology.

Molecular-level chemical information about organic matter (OM) in sediments helps to establish the sources of OM and the prevalent degradation/diagenetic processes, both essential for understanding the cycling of carbon (C) and of the elements associated with OM (toxic trace metals and nutrients) in lake ecosystems. Ideally, analytical methods for characterizing OM should allow high sample throughput, consume small amounts of sample and yield relevant chemical information, which are essential for multidisciplinary, high-temporal resolution and/or large spatial scale investigations. We have developed a high-throughput analytical method based on pyrolysis-gas chromatography/mass spectrometry and automated data processing to characterize sedimentary OM in sediments. Our method consumes 200 µg of freeze-dried and ground sediment sample. Pyrolysis was performed at 450°C, which was found to avoid degradation of specific biomarkers (e.g., lignin compounds, fresh carbohydrates/cellulose) compared to 650°C, which is in the range of temperatures commonly applied for environmental samples. The optimization was conducted using the top ten sediment samples of an annually resolved sediment record (containing 16-18% and 1.3-1.9% of total carbon and nitrogen, respectively). Several hundred pyrolytic compound peaks were detected of which over 200 were identified, which represent different classes of organic compounds (i.e., n-alkanes, n-alkenes, 2-ketones, carboxylic acids, carbohydrates, proteins, other N compounds, (methoxy)phenols, (poly)aromatics, chlorophyll and steroids/hopanoids). Technical reproducibility measured as relative standard deviation of the identified peaks in triplicate analyses was 5.5±4.3%, with 90% of the RSD values within 10% and 98% within 15%. Finally, a multivariate calibration model was calculated between the pyrolytic degradation compounds and the sediment depth (i.e., sediment age), which is a function of degradation processes and changes in OM source type. This allowed validation of the Py-GC/MS dataset against fundamental processes involved in OM cycling in aquatic ecosystems.

Method development in quantitative NMR towards metrologically traceable organic certified reference materials used as (31)P qNMR standards.

Quantitative nuclear magnetic resonance (qNMR) spectroscopy is employed by an increasing number of analytical and industrial laboratories for the assignment of content and quantitative determination of impurities. Within the last few years, it was demonstrated that (1)H qNMR can be performed with high accuracy leading to measurement uncertainties below 1 % relative. It was even demonstrated that the combination of (1)H qNMR with metrological weighing can lead to measurement uncertainties below 0.1 % when highly pure substances are used. Although qNMR reference standards are already available as certified reference materials (CRM) providing traceability on the basis of (1)H qNMR experiments, there is an increasing demand for purity assays on phosphorylated organic compounds and metabolites requiring CRM for quantification by (31)P qNMR. Unfortunately, the number of available primary phosphorus standards is limited to a few inorganic CRM which only can be used for the analysis of water-soluble analytes but fail when organic solvents must be employed. This paper presents the concept of value assignment by (31)P qNMR measurements for the development of CRM and describes different approaches to establish traceability to primary Standard Reference Material from the National Institute of Standards and Technology (NIST SRM). Phosphonoacetic acid is analyzed as a water-soluble CRM candidate, whereas triphenyl phosphate is a good candidate for the use as qNMR reference material in organic solvents. These substances contain both nuclei, (1)H and (31)P, and the concept is to show that it is possible to indirectly quantify a potential phosphorus standard via its protons using (1)H qNMR. The same standard with its assigned purity can then be used for the quantification of an analyte via its phosphorus using (31)P qNMR. For the validation of the concept, triphenyl phosphate and phosphonoacetic acid have been used as (31)P qNMR standards to determine the purity of the analyte tris(2-chloroethyl) phosphate, and the resulting purity values perfectly overlap within their expanded measurement uncertainties.

A multicenter nationwide reference intervals study for common biochemical analytes in Turkey using Abbott analyzers.

BACKGROUND: A nationwide multicenter study was organized to establish reference intervals (RIs) in the Turkish population for 25 commonly tested biochemical analytes and to explore sources of variation in reference values, including regionality. METHODS: Blood samples were collected nationwide in 28 laboratories from the seven regions (≥400 samples/region, 3066 in all). The sera were collectively analyzed in Uludag University in Bursa using Abbott reagents and analyzer. Reference materials were used for standardization of test results. After secondary exclusion using the latent abnormal values exclusion method, RIs were derived by a parametric method employing the modified Box-Cox formula and compared with the RIs by the non-parametric method. Three-level nested ANOVA was used to evaluate variations among sexes, ages and regions. Associations between test results and age, body mass index (BMI) and region were determined by multiple regression analysis (MRA). RESULTS: By ANOVA, differences of reference values among seven regions were significant in none of the 25 analytes. Significant sex-related and age-related differences were observed for 10 and seven analytes, respectively. MRA revealed BMI-related changes in results for uric acid, glucose, triglycerides, high-density lipoprotein (HDL)-cholesterol, alanine aminotransferase, and γ-glutamyltransferase. Their RIs were thus derived by applying stricter criteria excluding individuals with BMI >28 kg/m2. Ranges of RIs by non-parametric method were wider than those by parametric method especially for those analytes affected by BMI. CONCLUSIONS: With the lack of regional differences and the well-standardized status of test results, the RIs derived from this nationwide study can be used for the entire Turkish population.

Soil quality in the Lomellina area using in vitro models and ecotoxicological assays.

Soil quality is traditionally evaluated by chemical characterization to determine levels of pollutants. Biological tools are now employed for soil monitoring since they can take account of the global biological effects induced by all xenobiotics. A combined monitoring of soils based on chemical analyses, human-related in vitro models and ecotoxicological assay was applied in the Lomellina, a semirural area of northern Italy. Chemical characterization indicated overall good quality of the soils, with low levels of toxic and carcinogenic pollutants such as heavy metals, PAHs, PCDD/Fs and PCBs. HepG2 cells were used as a model for the human liver and BALB/c 3T3 cells to evaluate carcinogenic potential. Cells were treated with soil extractable organic matter (EOM) and the MTS assay, DNA release and morphological transformation were selected as endpoints for toxicity and carcinogenicity. Soil EOMs induced dose-dependent inhibition of cell growth at low doses and cytotoxicity only at doses of 500 and 1000 mg soil equivalents/ml. Potential issues for human health can be hypothesized after ingestion of soil samples from some sites. No statistically significant inductions of foci were recorded after exposure to EOMs, indicating that the levels of the soil-extracted organic pollutants were too low to induce carcinogenesis in our experimental conditions. An acute phytotoxicity test and studies on Caenorhabditis elegans were used as ecotoxicological assays for plants and small invertebrates. No significant alerts for ecotoxicity were found. In this proposed case study, HepG2 cells detected differences in the toxicity of soil EOMs, indicating that this cell line could be appropriate to assess the potential harm caused by the ingestion of contaminated soil. Additional information on the carcinogenic potential of mixtures was provided by the cell transformation assay, strengthening the combined approach.

Using high-performance ¹H NMR (HP-qNMR®) for the certification of organic reference materials under accreditation guidelines--describing the overall process with focus on homogeneity and stability assessment.

Quantitative NMR spectroscopy (qNMR) is gaining interest across both analytical and industrial research applications and has become an essential tool for the content assignment and quantitative determination of impurities. The key benefits of using qNMR as measurement method for the purity determination of organic molecules are discussed, with emphasis on the ability to establish traceability to "The International System of Units" (SI). The work describes a routine certification procedure from the point of view of a commercial producer of certified reference materials (CRM) under ISO/IEC 17025 and ISO Guide 34 accreditation, that resulted in a set of essential references for (1)H qNMR measurements, and the relevant application data for these substances are given. The overall process includes specific selection criteria, pre-tests, experimental conditions, homogeneity and stability studies. The advantages of an accelerated stability study over the classical stability-test design are shown with respect to shelf-life determination and shipping conditions.

Body burden of metals and persistent organic pollutants among Inuit in the Canadian Arctic.

Inuit living in the Arctic are exposed to elevated levels of environmental contaminants primarily due to long-range atmospheric transport. Blood sampling and contaminant biomonitoring was conducted as part of the International Polar Year Inuit Health Survey in 2007-2008. The body burden of metals (e.g. Cd, Pb) and persistent organic pollutants (e.g. PCBs, DDT & DDE, toxaphene, chlordane, PBDEs) were measured for Inuit participants (n=2172) from 36 communities in Nunavut, Nunatsiavut, and the Inuvialuit Settlement Region, in Canada. The geometric mean of blood concentrations for Cd, Pb, PCBs, DDE & DDT, toxaphene, and chlordane were higher than those in the Canadian general population. A total of 9% of study participants exceeded the intervention guideline of 100µgL(-1) for Pb, 11% of participants exceeded the trigger guideline of 5µgL(-1) for Cd, and 1% exceeded the intervention guideline of 100µgL(-1) for PCBs. Also, 3% of women of child-bearing age exceeded blood Pb of 100µgL(-1) while 28% of women of child-bearing age exceeded 5µgL(-1) of PCBs. This work showed that most Inuit Health Survey participants were below blood contaminant guidelines set by Health Canada but that metal and POP body burdens commonly exceed exposures observed in the general population of Canada.

Using conditional inference trees and random forests to predict the bioaccumulation potential of organic chemicals.

The present study presents a data-oriented, tiered approach to assessing the bioaccumulation potential of chemicals according to the European chemicals regulation on Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH). The authors compiled data for eight physicochemical descriptors (partition coefficients, degradation half-lives, polarity, and so forth) for a set of 713 organic chemicals for which experimental values of the bioconcentration factor (BCF) are available. The authors employed supervised machine learning methods (conditional inference trees and random forests) to derive relationships between the physicochemical descriptors and the BCF values. In a first tier, the authors established rules for classifying a chemical as bioaccumulative (B) or nonbioaccumulative (non-B). In a second tier, the authors developed a new tool for estimating numerical BCF values. For both cases the optimal set of relevant descriptors was determined; these are biotransformation half-life and octanol-water distribution coefficient (log D) for the classification rules and log D, biotransformation half-life, and topological polar surface area for the BCF estimation tool. The uncertainty of the BCF estimates obtained with the new estimation tool was quantified by comparing the estimated and experimental BCF values of the 713 chemicals. Comparison with existing BCF estimation methods indicates that the performance of this new BCF estimation tool is at least as high as that of existing methods. The authors recommend the present study's classification rules and BCF estimation tool for a consensus application in combination with existing BCF estimation methods.

Estimation of Abraham solvation equation coefficients for hydrogen bond formation from Abraham solvation parameters for solute acidity and basicity.

Abraham solvation equations find widespread use in environmental chemistry and pharmaco-chemistry. The coefficients in these equations, which are solvent (system) descriptors, are usually determined by fitting experimental data. To simplify the determination of these coefficients in Abraham solvation equations, this study derives equations, based on Abraham solvation parameters for hydrogen acidity and basicity of the solvents involved, to estimate the value of the coefficients for hydrogen bond formation. These equations were applied to calculate Abraham solvation parameters for hydrogen acidity and basicity for polyoxymethylene, polyacrylate, sodium dodecylsulfate, some ionic liquids, alkanoyl phosphatidyl cholines, and lipids for which fitted values for Abraham coefficients for hydrogen bond formation were available.

Screening organic chemicals in commerce for emissions in the context of environmental and human exposure.

Quantitative knowledge of organic chemical release into the environment is essential to understand and predict human exposure as well as to develop rational control strategies for any substances of concern. While significant efforts have been invested to characterize and screen organic chemicals for hazardous properties, relatively less effort has been directed toward estimating emissions and hence also risks. Here, a rapid throughput method to estimate emissions of discrete organic chemicals in commerce has been developed, applied and evaluated to support screening studies aimed at ranking and identifying chemicals of potential concern. The method builds upon information in the European Union Technical Guidance Document and utilizes information on quantities in commerce (production and/or import rates), chemical function (use patterns) and physical-chemical properties to estimate emissions to air, soil and water within the OECD for five stages of the chemical life-cycle. The method is applied to 16,029 discrete substances (identified by CAS numbers) from five national and international high production volume lists. As access to consistent input data remains fragmented or even impossible, particular attention is given to estimating, evaluating and discussing uncertainties in the resulting emission scenarios. The uncertainty for individual substances typically spans 3 to 4 orders of magnitude for this initial tier screening method. Information on uncertainties in emissions is useful as any screening or categorization methods which solely rely on threshold values are at risk of leading to a significant number of either false positives or false negatives. A limited evaluation of the screening method's estimates for a sub-set of about 100 substances, compared against independent and more detailed emission scenarios presented in various European Risk Assessment Reports, highlights that up-to-date and accurate information on quantities in commerce as well as a detailed breakdown on chemical function are critically needed for developing more realistic emission scenarios.

Freshwater DOM quantity and quality from a two-component model of UV absorbance.

We present a model that considers UV-absorbing dissolved organic matter (DOM) to consist of two components (A and B), each with a distinct and constant spectrum. Component A absorbs UV light strongly, and is therefore presumed to possess aromatic chromophores and hydrophobic character, whereas B absorbs weakly and can be assumed hydrophilic. We parameterised the model with dissolved organic carbon concentrations [DOC] and corresponding UV spectra for c. 1700 filtered surface water samples from North America and the United Kingdom, by optimising extinction coefficients for A and B, together with a small constant concentration of non-absorbing DOM (0.80 mg DOCL⁻¹). Good unbiased predictions of [DOC] from absorbance data at 270 and 350 nm were obtained (r² = 0.98), the sum of squared residuals in [DOC] being reduced by 66% compared to a regression model fitted to absorbance at 270 nm alone. The parameterised model can use measured optical absorbance values at any pair of suitable wavelengths to calculate both [DOC] and the relative amounts of A and B in a water sample, i.e. measures of quantity and quality. Blind prediction of [DOC] was satisfactory for 9 of 11 independent data sets (181 of 213 individual samples).

Ultrasound gel causes fine needle aspiration artifact? A clear choice.

OBJECTIVES: Ultrasound-guided fine needle aspiration (FNA) is a commonly employed tool in cytopathologic practice. Artifacts resulting in misinterpretation of specimens have been noted with various ultrasound gel media. Our purpose was to perform a prospective human cadaveric study of this phenomenon to identify a low-cost solution that eliminates the artifact. STUDY DESIGN: Three separate ultrasound-guided FNAs were performed on the thyroid and parotid glands in situ of a fresh human cadaver using three different types of ultrasound gel media. Slides were prepared in standard fashion (Quik-Diff and Papanicolaou stains). Two cytopathologists subsequently analyzed the slides for the presence of any artifact interfering with their ability to visualize and interpret the cellular aspirate material. RESULTS: Two of the three gel media revealed significant artifacts mimicking apoptosis, necrosis or colloid, making it difficult to visualize the cellular components and differentiate the artifact from the thyroid colloid. One gel medium did not show any significant artifact, and there was no discernable difference in its quality with regard to the ultrasound image during FNA procedures. CONCLUSIONS: Ultrasound gels can be associated with a significant artifact in FNA specimens. To eliminate this artifact, which may alter the adequacy, diagnosis or cytologic appearance, we confirm a specific gel type that is useful for ultrasound-guided FNAs.

Relationships between POPs and baseline corticosterone levels in black-legged kittiwakes (Rissa tridactyla) across their breeding cycle.

Chronic exposure to persistent organic pollutants (POPs) in wildlife might alter the response to environmental changes through interference with the regulation of stress hormones. Here, we examined the relationship between blood concentrations of several POPs and baseline plasma corticosterone levels in the black-legged kittiwake (Rissa tridactyla) during three distinct periods in the breeding season. The concentrations of POPs and corticosterone increased, whereas body mass decreased progressively from the pre-laying period to the incubation and the chick rearing period. ∑PCB (polychlorinated biphenyls) correlated positively with the baseline corticosterone levels during the pre-laying period, which might suggest that PCBs affect the regulation of corticosterone. However, this relationship was not found during the incubation or the chick rearing period. Possible explanations are discussed with emphasis on how total stress/allostatic load is handled during different periods and conditions.

First report on development of quantitative interspecies structure-carcinogenicity relationship models and exploring discriminatory features for rodent carcinogenicity of diverse organic chemicals using OECD guidelines.

Different regulatory agencies in food and drug administration and environmental protection worldwide are employing quantitative structure-activity relationship (QSAR) models to fill the data gaps related with properties of chemicals affecting the environment and human health. Carcinogenicity is a toxicity endpoint of major concern in recent times. Interspecies toxicity correlations may provide a tool for estimating sensitivity towards toxic chemical exposure with known levels of uncertainty for a diversity of wildlife species. In this background, we have developed quantitative interspecies structure-carcinogenicity correlation models for rat and mouse [rodent species according to the Organization for Economic Cooperation and Development (OECD) guidelines] based on the carcinogenic potential of 166 organic chemicals with wide diversity of molecular structures, spanning a large number of chemical classes and biological mechanisms. All the developed models have been assessed according to the OECD principles for the validation of QSAR models. Consensus predictions for carcinogenicity of the individual compounds are presented here for any one species when the data for the other species are available. Informative illustrations of the contributing structural fragments of chemicals which are responsible for specific carcinogenicity endpoints are identified by the developed models. The models have also been used to predict mouse carcinogenicities of 247 organic chemicals (for which rat carcinogenicities are present) and rat carcinogenicities of 150 chemicals (for which mouse carcinogenicities are present). Discriminatory features for rat and mouse carcinogenicity values have also been explored.

[Quantitative determination of contents of three components in Brucea javanica by HPLC].

OBJECTIVE: To develop an HPLC method for quantitative determination of three quassinoids in Brucea javanic. METHOD: The determination was carried out on a phenomenex C18 column (4.6 mm x 250 mm, 5 microm) with gradient elution program of methol-water at a flow rate of 1.0 mL x min(-1), and the detection wavelength was 270 nm. RESULT: Linearites of bruceine D, brusatol and bruceine H were good (r = 0.9996, 0.9996, and 0.9998) in ranges of 2.52-12.60, 2.19-10.95, and 2.91-14.55 microg, respectively. The average recoveries of bruceine D, brusatol and bruceine H were 100.01%, 100.95% and 100.43% respectively, and RSD of the above three compounds were 0.31% (n = 6), 1.7% ( n = 6) and 1.7% (n = 6), respectively. CONCLUSION: The determination results of three batch samples showed that the method was simple, accurate and could be used in the quantitative determination of three components in the B. javanica.

Atomic spectrometry methods for wine analysis: a critical evaluation and discussion of recent applications.

The analysis of wine is of great importance since wine components strongly determine its stability, organoleptic or nutrition characteristics. In addition, wine analysis is also important to prevent fraud and to assess toxicological issues. Among the different analytical techniques described in the literature, atomic spectrometry has been traditionally employed for elemental wine analysis due to its simplicity and good analytical figures of merit. The scope of this review is to summarize the main advantages and drawbacks of various atomic spectrometry techniques for elemental wine analysis. Special attention is paid to interferences (i.e. matrix effects) affecting the analysis as well as the strategies available to mitigate them. Finally, latest studies about wine speciation are briefly discussed.