Comparison of instrumental methods for chlorinated dibenzo-p-dioxin (CDD) determination - interim results of a round-robin study involving GC-MS, MS-MS, and high resolution MS

A study was designed to determine the feasibility of using GC-MS-MS techniques for the determination of chlorinated dibenzo-p-dioxins (CDD) and dibenzofurans (CDF) in difficult environmental samples with reduced cleanup. Three fish and three sediment extracts were provided to six different laboratories with GC-MS-MS capability for analysis. In addition, extracts were analysed by GC-low reduction MS (LRMS) and GC-high resolution MS (HRMS). At the time of this report, all participating GC-MS-MS laboratories had not completed their analysis of the supplied samples. All reporting laboratories found the analysis of these very complex samples difficult without extensive cleanup. GC-HRMS determination of some samples was possible with reduced cleanup compared to GC-LRMS.     

Analysis of munitions constituents in groundwater using a field-portable GC-MS

The use of munitions constituents (MCs) at military installations can produce soil and groundwater contamination that requires periodic monitoring even after training or manufacturing activities have ceased. Traditional groundwater monitoring methods require large volumes of aqueous samples (e.g., 2-4 L) to be shipped under chain of custody, to fixed laboratories for analysis. The samples must also be packed on ice and shielded from light to minimize degradation that may occur during transport and storage. The laboratory’s turn-around time for sample analysis and reporting can be as long as 45 d. This process hinders the reporting of data to customers in a timely manner; yields data that are not necessarily representative of current site conditions owing to the lag time between sample collection and reporting; and incurs significant shipping costs for samples.The current work compares a field portable Gas Chromatograph-Mass Spectrometer (GC-MS) for analysis of MCs on-site with traditional laboratory-based analysis using High Performance Liquid Chromatography with UV absorption detection. The field method provides near real-time (within ∼1 h of sampling) concentrations of MCs in groundwater samples. Mass spectrometry provides reliable confirmation of MCs and a means to identify unknown compounds that are potential false positives for methods with UV and other non-selective detectors.     

大气降尘测定中蒸发方式的选择

为了加快大气降尘样品的蒸发速度和报出数据的及时,经过分析总结,得出蒸发样品的步骤为:先电热套蒸发再水浴蒸发最后用电热板蒸发,这样既可以节省时间,又可以节约能耗,避免样品在空气中放置时间过长,空气中的尘粒进入样品中,影响样品测定的结果。     

The occurrence of polybrominated diphenyl ethers in river and coastal biota from Portugal

Throughout this work PBDEs level determination in biota was developed for the first time in Portugal. The data obtained was important to provide a global perspective of Portugal contamination by PBDEs and allows the comparison with studies made in other countries. Environmental levels of fourteen polybrominated diphenyl ethers (PBDEs) were analysed in a number of biota samples (Barbus sp. and Mytilus galloprovincialis) taken over a large geographic range covering five rivers and coastal areas of Portugal. Tetrabromodiphenyl ether (BDE 47) was found in almost all samples ranging from not detected (nd) to 30ngg(-1) dry weight (dw). BDE 47 concentration is correlated with mussels weight indicating the bioaccumulation of this compound. Pentabromodiphenyl ethers (BDE 99 and BDE 100) were detected in several samples, but in lower concentrations.     

Clarification of effects of DDE on shell thickness, size, mass, and shape of avian eggs

Moriarty et al. (1986) used field data to conclude that DDE decreased the size or altered the shape of avian eggs; therefore, they postulated that decreased eggshell thickness was a secondary effect because, as a general rule, thickness and egg size are positively correlated. To further test this relationship, the present authors analyzed data from eggs of captive American kestrels. Falco sparverius given DDT- or DDE-contaminated or clean diets and from wild brown pelicans Pelecanus occidentalis collected both before (pre-1946) and after (post-1945) DDT was introduced into the environment. Pertinent data from other field and laboratory studies were also summarized. DDE was not related to and did not affect size, mass, or shape of eggs of the brown pelican or American kestrel; but the relationship of DDE to eggshell thinning held true. Size and shape of eggs of brown pelicans from the post-1945 era and those of kestrels, on DDT-contaminated diets showed some significant, but inconsistent, changes compared to brown pelican data from the pre-1946 era or kestrels on clean diets. In contrast, nearly all samples of eggs of experimental kestrels given DDT-contaminated diets and those of wild brown pelicans from the post-1945 era exhibited significant eggshell thinning. Pertinent experimental studies with other sensitive avian species indicated no effects of DDE on the size or shape of eggs, even though the high dietary concentrations caused extreme eggshell thinning and mortality of some adult mallards (Anas platyrhynchos) in one study. These findings essentially controvert the argument that decreased eggshell thickness is a secondary effect resulting from the primary effect of DDE-induced changes in the size or shape of eggs.     

Revised Air Quality Surveillance Requirements for State Implementation Plans

The National Ambient Air Quality Monitoring Program is carried out by state and local air pollution control agencies in support of their State Implementation Plans (SIP’s). The current EPA regulations which specify the characteristics of these state monitoring programs are undergoing change as a result of a comprehensive review by an independent work group. These revised regulations, which are described in the paper, are intended to improve the quality, timeliness, and usability of the data generated by the states for all data users. In addition, the revised regulations seek to bring about; (a) national consistency in monitoring site locations through standardized siting procedures; (b) improved network operations by means of a minimum quality assurance program; (c) reduced network inflexibility through an annual network review process; and (d) reduced data reporting through changed data reporting procedures.     

Multivariate optimization of solid-phase extraction applied to iron determination in finished waters

In this work, Amberlite XAD-4 resin functionalized with salicylic acid was synthetized, characterized and applied as a new packing material for an on-line system to iron determination in aqueous samples. The detection method is based on the sorption of Fe(III) ions in a minicolumn containing the synthesized resin, followed by a desorption step using an acid solution and measurement of iron by vis-spectrophotometry (CAS method). The optimization of the solid-phase extraction system was performed using factorial design and Doehlert matrix considering six variables: sample percolation rate (0.5-9 ml min(-1)), sample metal concentration (20-200 microg l(-1)), flow-through sample volume (0-5 ml) (all three directly linked to the extraction step), elution flow-rate (0.5-9 ml min(-1)), concentration and volume of eluent (HCl 0.1-0.5M) (all three directly linked to the elution step). The aim of this study was to obtain a set of operating ranges for the six variables tested in order to obtain--by means of a mathematical function allowing maximisation of each response (desirability function)--at least 90% of iron recovery rates. Using the experimental conditions defined in the optimization, the method allowed iron determination with achieved detection limit of 2.3 microgl(-1) and precision (assessed as the relative standard deviation) of 9.3-2.8% for iron solutions of 10.0-150 microgl(-1). Real samples (coming from a water treatment unit) were used successfully when evaluating potentialities of the developed SPE procedure coupled to a spectrophotometric determination.     

Levels of dioxins, dibenzofurans and selected other chlorinated organic compounds in food from Russia

Food is considered to be the main source of dioxins (PCDDs) and dibenzofurans (PCDFs) for human intake, but there are relatively few publications reporting the levels of dioxins and furans in food samples.^(1–4) Food samples from western to eastern Russia were collected during three recent trips by one of us (AS), and tested for dioxins and dibenzofurans to provide some indication of environmental contamination. The results show that in specific food samples there are more dioxins present than dibenzofurans, but in fish samples the opposite is true. We compare the levels found in Russian food with levels found in samples from other countries, on both wet weight and lipid basis. These Russian samples show ranges similar to but slightly lower than those seen in other industrial countries.     

Estimation of measurement uncertainty associated to the determination of pesticide residues: a case study

In the analytical analysis the measurement uncertainty is a quantitative indicator of the confidence describing the range around a reported or experimental result within which the true value can be expected. Several approaches can be used to estimate the measurement uncertainty associated to the analysis of pesticide residues: a) the top-down, the estimation can be referred to default values; b) the bottom-up the estimation is related to the uncertainty sources. Concerning the bottom-up approach, the following contributions have been investigated: weight of sample, calibration solutions, final volume of sample and intermediate repeatability studies. The commodity/residue combination selected in this study was celery/tau-fluvalinate pesticide. Tau-fluvalinate is a broad-spectrum insecticide in the pyrethroid class of pesticides. The Maximum Residue Limit (MRL) of tau-fluvalinate in celery has been set at 0.01 mg/kg. The tau- Fluvalinate showed two chromatographic peaks. Since the individual standards are not available, the two peaks were integrated separately and the instrumental responses were added. The total residue was calculated on the basis of resulted peaks. The present work aims to compare the uncertainty estimated by experimental data using repeated analysis (n = 12) of a real sample and a spiked sample. The relative expanded uncertainty for two data set, incurred and spiked, was 22 % and 20 %, respectively. No differences were observed from repeated determinations of real samples and spiked samples.     

Literature survey of on-line spectroscopic methods for lead determination in environmental solid samples

A review is presented where are shown the advantages involved in the use of flow injection (FI) analysis for the determination of lead in environmental solid samples by spectroscopic detectors. The FI methods proposed for the determination of lead in these samples are described and compared according to the detection technique used. Analytical data of interest and interferences are discussed for each technique.     

Analysis of dioxin-like compounds in vegetation and soil samples burned in Catalan forest fires. Comparison with the corresponding unburned material

Only a few data are reported about the formation of polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) in forest fires. However, the inventories of sources undertaken by several European and American countries consider natural fires as a possible source of PCDD/F and, in some cases, as one of the most important. In our work we have analysed vegetation and soil samples burned in four forest fires which happened in Catalonia in the summer of 1998. The concentration of dioxin-like compounds (PCDD/F, non-ortho polychlorinated bi-phenyls (PCB) and mono-ortho PCB) has been compared to the concentration present in the corresponding unburned material collected in places near the fires but not affected. The results of this preliminary study show very low concentrations in all the samples, both burned and unburned. Although a change in the profile (proportional increase of tetrachlorinated congeners in PCDD/F) is observed in burned samples compared to unburned ones, the absolute values of concentration decrease in most samples. Therefore, natural fires seem not to be an important source of dioxin-like compounds. These results will be confirmed with air emissions measurements in future studies.     

In situ experiments for element species-specific environmental reactivity of tin and mercury compounds using isotopic tracers and multiple linear regression

The fate of mercury (Hg) and tin (Sn) compounds in ecosystems is strongly determined by their alkylation/dealkylation pathways. However, the experimental determination of those transformations is still not straightforward and methodologies need to be refined. The purpose of this work is the development of a comprehensive and adaptable tool for an accurate experimental assessment of specific formation/degradation yields and half-lives of elemental species in different aquatic environments. The methodology combines field incubations of coastal waters and surface sediments with the addition of species-specific isotopically enriched tracers and a mathematical approach based on the deconvolution of isotopic patterns. The method has been applied to the study of the environmental reactivity of Hg and Sn compounds in coastal water and surface sediment samples collected in two different coastal ecosystems of the South French Atlantic Coast (Arcachon Bay and Adour Estuary). Both the level of isotopically enriched species and the spiking solution composition were found to alter dibutyltin and monomethylmercury degradation yields, while no significant changes were measurable for tributyltin and Hg(II). For butyltin species, the presence of light was found to be the main source of degradation and removal of these contaminants from surface coastal environments. In contrast, photomediated processes do not significantly influence either the methylation of mercury or the demethylation of methylmercury. The proposed method constitutes an advancement from the previous element-specific isotopic tracers’ approaches, which allows for instance to discriminate the extent of net and oxidative Hg demethylation and to identify which debutylation step is controlling the environmental persistence of butyltin compounds.     

Influence of storage time on toxicity of freshwater sediments to benthic macroinvertebrates

Guidance concerning recommended storage times for sediments to be used in toxicity tests generally has not been based upon systematically collected experimental data. The objective of this study was to better define the effects of storage time on toxicity of a series of freshwater sediments. Sixteen sediments with varying types of contaminants were collected, homogenized and stored at 4 degrees C in 1 liter aliquots, which were periodically tested for toxicity to the amphipod Hyalella azteca and the midge Chironomus tentans after storage times of up to 101 weeks. The sediments ranged from non-toxic to extremely toxic (100% mortality) in 10-day assays, with several of the samples displaying an intermediate degree of toxicity (e.g. partial mortality, reduced growth). Biological responses in most of the samples did not vary with time relative to their statistical relationship to control values; samples identified initially as toxic (or non-toxic) tended to remain toxic (or non-toxic) regardless of when they were tested. The variations that were observed in biological responses over time generally were not systematic; that is, there were no apparent trends in samples becoming more (or less) toxic in the 10-day assays. This suggests that the source of at least some of the temporal changes in toxicity were due to inherent biological variability of the assays used to assess the sediments, rather than the effects of storage. In C. tentans tests with the least toxic sediments, among-replicate variability tended to be greater in initial assays than in tests with samples that had been stored for some period of time. This may have been due to the presence of indigenous competitive or predatory organisms that did not survive during prolonged storage.     

Determination of 2,4-Dichlorophenoxyacetic acid in food and water samples using a modified graphene oxide sorbent and high-performance liquid chromatography

Abstract

In the present work, dispersive micro-solid phase extraction (D-μ-SPE) method using magnetic graphene oxide tert-butylamine (GO/Fe₃O₄/TBA) nanocomposite, as an efficient sorbent, was applied for determining 2,4-dichlorophenoxyacetic acid (2,4-D) in water and food samples. Detection was carried out using high-performance liquid chromatography (HPLC) instrument. Influential parameters of D-μ-SPE such as sorbent and its amount, elution solvent and its volume, adsorption and desorption times and pH of sample solution were investigated and optimized. Under the optimized conditions, limit of detection and quantitation values were 0.007 and 0.02?μg/mL, respectively. Recovery data for several real samples were obtained within the range of 88.0–94.0% with a relative standard deviation (RSD) less than 7.5%. The proposed method was successfully applied to quantitative determination of 2,4-D in several vegetables and water samples.     

Influence of indoor transport and mixing time scales on the performance of sensor systems for characterizing contaminant releases

Optimizing real-time sensor systems to detect and identify relevant characteristics of an indoor contaminant event is a challenging task. The interpretation of incoming sensor data is confounded by uncertainties in building operation, in the forces driving contaminant transport, and in the physical parameters governing transport. In addition, simulation tools used by the sensor interpretation algorithm introduce modeling uncertainties. This paper explores how the time scales inherent in contaminant transport influence the information that can be extracted from real-time sensor data. In particular, we identify three time scales (within room mixing, room-to-room transport, and removal from the building) and study how they affect the ability of a Bayesian Monte Carlo (BMC) sensor interpretation algorithm to identify the release location and release mass from a set of experimental data, recorded in a multi-floor building. The research shows that some limitations in the BMC approach do not depend on details of the models or the algorithmic implementation, but rather on the physics of contaminant transport. These inherent constraints have implications for the design of sensor systems.     

A simple spectrophotometric method for the determination of cobalt in industrial, environmental, biological and soil samples using bis(salicylaldehyde)orthophenylenediamine

Bis(salicylaldehyde)orthophenylenediamine (BSOPD) has been proposed as new analytical reagent for the direct non-extractive spectrophotometric determination of cobalt. It reacts with cobalt in slightly acidic (0.0002-0.001 M H(2)SO(4)) 50% 1,4-dioxanic medium to form a red-orange chelate with a molar ratio 1:1. The reaction is instantaneous and the maximum absorbance was obtained at 458 nm and remains constant for over 24h. The average molar absorption coefficient and Sandell's sensitivity were found to be 1.109 x 10(4)l mol(-1)cm(-1) and 20 ng cm(-2) of Co(II), respectively. Linear calibration graph was obtained for 0.1-15 mg l(-1) of Co(II) with a correlation coefficient value of 0.995 for Co-BSOPD complex. Large excess of 44 cations, anions and complexing agents do not interfere in the determination. The method was successfully used in the determination of cobalt(II) from synthetic mixture and certified reference materials for the purpose of validating the method and the results of analyses were found to be excellent agreement with those of actual values. This developed method was also used for determination of cobalt in some environmental waters (potable and polluted), biological (blood and urine) and soil samples and solution containing both cobalt(II) and cobalt(III). The results of the proposed method for biological samples were comparable with AAS and were found to be in good agreement. The method has high precision and accuracy (s=+/-0.01 for 0.5 mg l(-1)).     

Method for reporting in-use vehicle fuel consumption and carbon dioxide emissions from a fast-pass transient inspection

A method has been developed that allows reporting of the fuel consumption and carbon dioxide (CO2) emissions for in-use vehicles from a fast-pass transient (IM240) inspection. The major technical obstacle to reporting CO2 emission rate and fuel consumption is that inspection and maintenance tests do not all use a standardized test duration or test method. The method is able to project full-duration fuel consumption from IM240 tests that actually fast-passed as early as just 30 sec from starting the test. It is based on basic considerations of the work done in driving the inspection cycle, with additional empirical adjustments. The initial application examined the differences between passing and failing inspections, and this did confirm that there are significant differences.     

Quantification of low levels of organochlorine pesticides using small volumes (<or=100 microl) of plasma of wild birds through gas chromatography negative chemical ionization mass spectrometry

A solid phase extraction and gas chromatography with negative chemical ionization mass spectrometry in scan mode (GC-NCI-MS) method was developed to identify and quantify for the first time low levels of organochlorine pesticides (OCs) in plasma samples of less than 100 microl from wild birds. The method detection limits ranged from 0.012 to 0.102 pg/microl and the method reporting limit from 0.036 to 0.307 pg/microl for alpha, gamma, beta and delta-hexachlorocyclohexane (HCH), heptachlor, aldrin, heptachlor epoxide, endosulfan I, 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p,p'-DDE), dieldrin, endrin, endosulfan-II, endrin-aldehyde and endosulfan-sulfate. Pesticide levels in small serum samples from individual Falco sparverius, Sturnella neglecta, Mimus polyglottos and Columbina passerina were quantified. Concentrations ranged from not detected (n/d) to 204.9 pg/microl for some OC pesticides. All levels in the food web in and around cultivated areas showed the presence of pesticides notwithstanding the small areas for agriculture existing in the desert of Baja California peninsula.     

Determination of the temperature dependence of water solubilities of polycyclic aromatic hydrocarbons by a generator column-on-line solid-phase extraction-liquid chromatographic method

An improved dynamic coupled column liquid chromatographic (DCCLC) technique for determining water solubility data of hydrophobic compounds is presented. The technique is based on pumping water through a thermostated generator column in order to generate emulsion-free, saturated aqueous solutions of the compound under study. Through a switching valve system the solute in the aqueous solution is extracted and concentrated by an on-line solid-phase extraction process and subsequently eluted and analyzed by high performance liquid chromatography (fluorescence detection coupled to photodiode array detection). The improvements carried out to the original DCCLC technique have given rise to savings in time for the experimental work and increased sensitivity during the detection and quantification stage. Applicability of the method for studying highly hydrophobic substances is demonstrated by determining water solubility of anthracene and pyrene in the temperature range of 8.9-49.9 and 8.5-32.2 degrees C, respectively. The measured water solubilities are in good agreement with the best available literature data. The method has also been applied to the determination of water solubility of m-terphenyl, 9, 10-dihydrophenanthrene and guaiazulene, in the temperature range of 4.8-49.9, 4.8-25.0, and 4.5-29.9 degrees C, respectively. The uncertainty in the Sw values determined in this work ranged from 0.7% to 4.6%. The experimental water solubility data, as a function of temperature, are fitted to the equation In Sw = A + B/T; where Sw and T are given in mole fraction and Kelvin, respectively.     

Comparison of different modifications on QuEChERS sample preparation method for PAHs determination in black, green, red and white tea

The aim of this work was the evaluation of QuEChERS extraction method for polycyclic aromatic hydrocarbon (PAH) determination in various types of tea. In the experiment, different kinds of extraction solvents, sorbents and a final method of sample preparation were compared. The final extracts were analysed by gas chromatography-selected ion monitoring-mass spectrometry. The results suggest that acetonitrile extraction, clean up with SAX and final liquid–liquid extraction was the best combination giving the most purified extracts and acceptable compound recoveries for different types of teas. In the study of real samples, compounds belonging to light PAHs were mostly detected, and heavy polycyclic aromatic hydrocarbons, including benzo[a]pyrene, were not identified in any of samples.