Reduced solvent and reagent amounts: effect on carbonyl dinitrophenylhydrazone measurements at low concentrations.

This work aims to advance towards a more affordable laboratory procedure for sample treatment to determine carbonyl compounds by derivatization with 2,4-dinitrophenylhydrazine (DNPH). The proposal is based on reducing the amount of DNPH and solvents. A simple addition of standard carbonyls in a solution containing DNPH to prepare hydrazone standards is described and evaluated. Tedious recrystallization steps are avoided. Formaldehyde, acetaldehyde, acetone, tolualdehyde and hexanal, as carbonyl models, were quantified using a DNPH concentration of 400 µg mL-1 and 3.8 mM H2SO4 and by keeping for 24 hours at room temperature. Analytical coefficients of variation between 10 and 25% were found from the analysis of blanks under intermediate conditions (two different devices, very different concentrations of DNPH and analysis on two days). From these values of relative standard deviations and background levels, quantification limits were estimated between 15 and 40 ng mL-1. The reduction of reagent amounts allows the operator to better control the background levels in the use of DNPH, as well as making the method more cost-effective and easy to use. In short, it leads to a more sustainable adaptation of the classical method. The versatility in analytical application was tested to estimate the levels of formaldehyde, acetaldehyde and acetone in very different types of environmental samples. In particular, outdoor and indoor samples were collected in filters and impregnated cartridges, respectively. Moreover, tars in 2-propanol and particulate matter from gasification processes were also tested.

Characterization of organic aerosol at a rural site influenced by olive waste biomass burning.

Biomass burning is a major air pollution problem all around the world. However, the identification and quantification of its contribution to ambient aerosol levels is a difficult task due to the generalized lack of observations of molecular markers. This paper presents the results of a yearlong study of organic constituents of the atmospheric aerosol at a rural site in southern Spain (Villanueva del Arzobispo, Jaén). Sampling was performed for PM10 and PM2.5, and a total of 116 and 115 samples, respectively, were collected and analyzed by GC/MS, quantifying 77 organic compounds. Higher levels of organic pollutants were recorded from November to March, coinciding with the cold season when domestic combustion is a common practice in rural areas. This jointly with adverse meteorological conditions, e.g. strong atmospheric stability, produced severe pollution episodes with high PMx ambient levels. High daily concentrations of tracers were reached, up to 26 ng m-3 for B(a)P and 6065 ng m-3 for levoglucosan in PM2.5, supporting that biomass burning is a major source of pollution at rural areas. A multivariate statistical study based on factor and cluster analysis, was applied to the data set with the aim to distinguish sources of organic compounds. The main resulting sources were related with biomass combustion, secondary organic aerosol (SOA), biogenic emissions, lubricating oil and soil organic components. A preliminary organic source profile for olive wastes burning was evaluated, based on cluster results, showing anhydrosacharides and xylitol are the main emitted compounds, accounting for more than 85% of the quantified compounds. Other source compounds were fatty acids, diacids, aliphatics, sugars, sugar alcohols, PAHs and quinones.

Organic Analysis of Environmental Samples Using Liquid Chromatography with Diode Array and Fluorescence Detectors: An Overview.

This overview is focused to provide an useful guide of the families of organic pollutants that can be determined by liquid chromatography operating in reverse phase and ultraviolet/fluorescence detection. Eight families have been classified as the main groups to be considered: carbonyls, carboxyls, aromatics, phenols, phthalates, isocyanates, pesticides and emerging. The references have been selected based on analytical methods used in the environmental field, including both the well-established procedures and those more recently developed.

Validating Analytical Protocols to Determine Selected Pesticides and PCBs Using Routine Samples.

This study aims at providing recommendations concerning the validation of analytical protocols by using routine samples. It is intended to provide a case-study on how to validate the analytical methods in different environmental matrices. In order to analyze the selected compounds (pesticides and polychlorinated biphenyls) in two different environmental matrices, the current work has performed and validated two analytical procedures by GC-MS. A description is given of the validation of the two protocols by the analysis of more than 30 samples of water and sediments collected along nine months. The present work also scopes the uncertainty associated with both analytical protocols. In detail, uncertainty of water sample was performed through a conventional approach. However, for the sediments matrices, the estimation of proportional/constant bias is also included due to its inhomogeneity. Results for the sediment matrix are reliable, showing a range 25-35% of analytical variability associated with intermediate conditions. The analytical methodology for the water matrix determines the selected compounds with acceptable recoveries and the combined uncertainty ranges between 20 and 30%. Analyzing routine samples is rarely applied to assess trueness of novel analytical methods and up to now this methodology was not focused on organochlorine compounds in environmental matrices.

Exploring petroleum hydrocarbons in groundwater by double solid phase extraction coupled to gas chromatography-flame ionization detector.

This work proposes an analytical procedure for measuring aliphatic and aromatic hydrocarbons fractions present in groundwater. In this method, hydrocarbons are solid phase extracted (SPE) twice from the groundwater and the resulting fractions are analyzed by gas chromatography with flame ionization detection. The first SPE disposes the hydrocarbons present in groundwater in organic solvents and the second SPE divides them into aliphatic and aromatic hydrocarbons. The validation study is carried out and its uncertainties are discussed. Identifying the main sources of uncertainty is evaluated through applying the bottom-up approach. Limits of detection for hydrocarbons ranges are below 5 µg L(-1), precision is not above of 30%, and acceptable recoveries are reached for aliphatic and aromatic fractions studied. The uncertainty due to volume of the sample, factor of calibration and recovery are the highest contributions. The expanded uncertainty range from 13% to 26% for the aliphatic hydrocarbons ranges and from 14% to 23% for the aromatic hydrocarbons ranges. As application, the proposed method is satisfactorily applied to a set of groundwater samples collected in a polluted area where there is evidence to present a high degree of hydrocarbons. The results have shown the range of aliphatic hydrocarbons >C21-C35 is the most abundant, with values ranging from 215 µg L(-1) to 354 µg L(-1), which it is associated to a contamination due to diesel.

A chromatographic method to analyze products from photo-oxidation of anthropogenic and biogenic mixtures of volatile organic compounds in smog chambers.

A method for quantifying secondary organic aerosol compounds (SOA) and water soluble secondary organic aerosol compounds (WSOA) produced from photo-oxidation of complex mixtures of volatile organic compounds (VOCs) in smog chambers by gas chromatography/mass spectrometry (GC/MS) has been developed. This method employs a double extraction with water and methanol jointly to a double derivatization with N,O-bis (trimethylsilil) trifluoroacetamide (BSTFA) and O-(2,3,4,5,6)-pentafluorobenzyl-hydroxylamine hydrochloride (PFBHA) followed by an analysis performed by GC/MS. The analytical procedure complements other methodologies because it can analyze SOA and WSOA compounds simultaneously at trace levels. As application, the methodology was employed to quantify the organic composition of aerosols formed in a smog chamber as a result of photo-oxidation of two different mixtures of volatile organic compounds: an anthropogenic mixture and a biogenic mixture. The analytical method allowed us to quantify up to 17 SOA compounds at levels higher than 20 ng m(-3) with reasonable recovery and a precision below 11%. Values found for applicability, selectivity, linearity, precision, recovery, detection limit, quantification limit and sensitivity demonstrated that the methodology can be satisfactorily applied to quantify SOA and WSOA.

An evaluation of uncertainty associated to analytical measurements of selected polycyclic aromatic compounds in ambient air.

This paper presents an evaluation of uncertainty associated to analytical measurement of 18 polycyclic aromatic compounds (PACs) in ambient air by liquid chromatography with fluorescence detection (HPLC/FD). The study was focused on analyses of PM(10), PM(2.5) and gas phase fractions. Main analytical uncertainty was estimated for 11 polycyclic aromatic hydrocarbons (PAHs), four nitro-polycyclic aromatic hydrocarbons (nitro-PAHs) and two hydroxy-polycyclic aromatic hydrocarbons (OH-PAHs) based on the analytical determination, reference material analysis and extraction step. Main contributions reached 15-30% and came from extraction process of real ambient samples, being those for nitro-PAHs the highest (20-30%). Range and mean concentration of selected PACs measured in gas phase and PM(10)/PM(2.5) particle fractions during a full year are also presented. Concentrations of OH-PAHs were about 2-4 orders of magnitude lower than their parent PAHs and comparable to those sparsely reported in literature.

Estimation of measurement uncertainty of pesticides, polychlorinated biphenyls and polyaromatic hydrocarbons in sediments by using gas chromatography-mass spectrometry.

The evaluation of the uncertainty associated to analytical methods is essential in order to demonstrate quality of a result. However, there is often lack of information about uncertainty of methods to estimate persistent organic pollutants concentration in complex matrix. Current work has thoroughly evaluated uncertainty associated to quantification of several organochloride pesticides, PCBs and PAHs in sediments. A discussion of the main contributions to the overall uncertainty is reported, allowing authors to establish the accuracy of results and plan future improvements. Combined uncertainties ranged between 5-9% (pesticides), 4-7% (PCBs) and 5-10% (PAHs), being uncertainty derived of calibration the main contribution. Also, the analytical procedure was validated analysing a standard reference material (IAEA-408).

Sampling of tar from sewage sludge gasification using solid phase adsorption.

Sewage sludge is a residue from wastewater treatment plants which is considered to be harmful to the environment and all living organisms. Gasification technology is a potential source of renewable energy that converts the sewage sludge into gases that can be used to generate energy or as raw material in chemical synthesis processes. But tar produced during gasification is one of the problems for the implementation of the gasification technology. Tar can condense on pipes and filters and may cause blockage and corrosion in the engines and turbines. Consequently, to minimize tar content in syngas, the ability to quantify tar levels in process streams is essential. The aim of this work was to develop an accurate tar sampling and analysis methodology using solid phase adsorption (SPA) in order to apply it to tar sampling from sewage sludge gasification gases. Four types of commercial SPA cartridges have been tested to determine the most suitable one for the sampling of individual tar compounds in such streams. Afterwards, the capacity, breakthrough volume and sample stability of the Supelclean™ ENVI-Carb/NH(2), which is identified as the most suitable, have been determined. Basically, no significant influences from water, H(2)S or NH(3) were detected. The cartridge was used in sampling real samples, and comparable results were obtained with the present and traditional methods.

Assessment uncertainty associated to the analysis of tar from gasification of sewage sludge.

The uncertainty evaluation associated with the quantification of tar from gasification of sewage sludge is present. Each of the sources of uncertainty associated with the wet type sampling method and GC-MS analysis was identified to determine the critical stages of the analytical methodology in order to reduce them. The study shows that major contributions to the overall uncertainty are related to extraction steps. High expanded uncertainties were found for all compounds, due to the segregation of the tar in different samples because of the sampling method. However, the analytical method used was successfully applied for the evaluation of the tar cleaning filter in a real gasification plant.