Determination of gaseous polycyclic aromatic hydrocarbons by a simple direct method using thermal desorption–gas chromatography–mass spectrometry

In the last decade, the development of novel analytical methodologies enabled the identification of several environmental pollutants responsible for health problems associated with indoor exposure. Polycyclic aromatic hydrocarbons (PAHs) are among the potential hazardous chemicals present in ambient air. Due to their bioaccumulation potential and carcinogenic/mutagenic effects, 16 PAHs are currently listed as priority air pollutants. The main goal of this work was to implement a new and simple method for sampling and determination of PAHs in air by using a thermal desorption (TD) technique followed by gas chromatography coupled with mass spectrometry analysis. A detailed study was carried out to optimise the experimental method in each of its phases, including (active) sampling, TD and chromatographic analysis. The results demonstrate that this approach allowed the detection and quantification of the six more volatile PAHs, namely, naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, and anthracene. Acceptable precision and good linearity over the explored range were obtained. No carry-over was observed during experimental tests and the method provided a reproducible answer. The applicability of the novel methodology was tested in real environment, namely, on the roof of a building in an urban area, in a domestic kitchen and in a collective car garage. The method enabled the identification of two PAHs in the field samples, specifically, naphthalene (two rings) and phenanthrene (three rings). With regard to PAHs sample composition, the most abundant PAH found, in the three different locations, was naphthalene, accounting for about 84–100 % of the total PAH mass detected.     

Assessment of contamination by heavy metals and petroleum hydrocarbons in sediments of Montevideo Harbour (Uruguay)

As part of the first environmental assessment within Montevideo Harbour, in summer and winter of 1998, sediments samples were collected at eight locations to determine the spatial distribution of anthropogenic pollutants. Muddy sediments with high organic matter content dominate the study area. Heavy metal levels indicated that sediments were highly polluted with Zn (overall mean: 312+/-102 microg g(-1) dry sediment), Pb (85+/-31), Cu (89+/-25), Cr (162+/-62), and Hg (0.63+/-0.3) and moderately with Ni (30+/-2) and Ag (1.2+/-0.4). Depending on location and season, aliphatic hydrocarbons reached from 21 to 120 microg g(-1), while the unresolved complex mixture represented up to 76% of the total aliphatic fraction. Total PAH concentrations ranged from 1.56 to 90.44 microg g(-1); except at one location, petroleum derivatives were identified as main local source. The results pointed out that almost all the harbour area presented some substances that can cause adverse biological effects, especially in the inner region where all metals are above PEL levels. Principal components analysis confirmed that the inner harbour region is most severely affected by the pollutants and it was possible to differentiate three regions according to their environmental quality.     

QuEChERS: a sample preparation for extraction of carbaryl from rat feces

Carbamate compounds are an important group of cholinesterase inhibitors. There is a need for creating awareness regarding the risks of the inadequate carbamate use in the residential areas due to potential adverse human effects. Carbaryl is a commonly used pesticide worldwide. A simple, fast, and high-throughput method was developed employing liquid chromatography with fluorescence detector to determine carbaryl residues in rat feces. The extraction was performed by using a rapid, easy, cheap, effective, reliable, and safe (QuEChERS) method, using acetonitrile as the extracting solvent. The parameters for the performance of the extraction method were optimized, such as ratio of mass of sample per volume of extraction solvent, QuEChERS content, and cleanup columns. Linear response was obtained for all calibration curves (solvent and matrix-matched) over the established concentration range (5–500 μg/L) with a correlation coefficients higher than 0.999. The achieved recovery was 97.9% with relative standard deviation values of 1.1% (n = 4) at 167 μg/kg fortified concentration level and the limits of detection and quantification were 27.7 and 92.3 µg/kg, respectively.     

Dosing low-level ferrous iron in coagulation enhances the removal of micropollutants, chlorite and chlorate during advanced water treatment

Drinking water utilities are interested in upgrading their treatment facilities to enhance micropollutant removal and byproduct control. Pre-oxidation by chlorine dioxide (ClO₂) followed by coagulation-flocculation-sedimentation and advanced oxidation processes (AOPs) is one of the promising solutions. However, the chlorite (ClO₂^–) formed from the ClO₂ pre-oxidation stage cannot be removed by the conventional coagulation process using aluminum sulfate. ClO₂^– negatively affects the post-UV/chlorine process due to its strong radical scavenging effect, and it also enhances the formation of chlorate (ClO₃^–). In this study, dosing micromolar-level ferrous iron (Fe(II)) into aluminum-based coagulants was proposed to eliminate the ClO₂^– generated from ClO₂ pre-oxidation and benefit the post-UV/chlorine process in radical production and ClO₃^– reduction. Results showed that the addition of 52.1-µmol/L FeSO₄ effectively eliminated the ClO₂^– generated from the pre-oxidation using 1.0 mg/L (14.8 µmol/L) of ClO₂. Reduction of ClO₂^– increased the degradation rate constant of a model micropollutant (carbamazepine) by 55.0% in the post-UV/chlorine process. The enhanced degradation was verified to be attributed to the increased steady-state concentrations of HO^· and ClO^· by Fe(II) addition. Moreover, Fe(II) addition also decreased the ClO₃^– formation by 53.8% in the UV/chlorine process and its impact on the formation of chloro-organic byproducts was rather minor. The findings demonstrated a promising strategy to improve the drinking water quality and safety by adding low-level Fe(II) in coagulation in an advanced drinking water treatment train.     

Biotoxizit?tstests mit PAK Die Nodulation in der Leguminosen-Rhizobien-Symbiose als sensibler Wirkungsparameter

Im Zusammenhang mit der Umweltchemikalienprüfung und der Untersuchung und Kontrolle kontaminierter B?den besteht gro?er Bedarf an Testverfahren mit h?heren Pflanzen, die schnell, einfach und preisgünstig durchzuführen sind und bereits bestehende Testverfahren nach OECD- und BBA-Richtlinien sinnvoll erg?nzen k?nnen. Dieser Beitrag stellt einen Biotoxizit?tstest vor, der die Nodulation in der Leguminosen-Kn?llchen-Symbiose als sensiblen Wirkungsparameter für die Belastung mit polyzyklischen aromatischen Kohlenwasserstoffen (PAK) benutzt. Fremdstoff, Pflanze und Mikroorganismus werden dabei auf einer festen Matrix in Kontakt miteinander gebracht; das axenische System erlaubt die Untersuchung der Fremdstoffwirkung sowohl auf den Gesamtorganismus Pflanze, als auch auf die Interaktion von Pflanze und Mikroorganismus (Kn?llchenbildung). In Dose-Response-Versuchen zeigte sich der Wirkungsparameter Nodulation, gemessen als Anzahl Wurzelkn?llchen pro Pflanze, sensibler als andere pflanzliche Wachstumsparameter. There is great need for toxicity tests with higher plants for the investigation and monitoring of chemicals in the environment — especially for tests which are quick, easy, and inexpensive. Such tests should add to and improve current guidelines, e.g., OECD- and BBA-Guidelines. This article describes the nodulation of leguminous plants withRhizobium bacteria used in a bioassay with polycyclic aromatic hydrocarbons (PAH). Plants growing on a solid medium were exposed simultaneously to bacteria and PAH. This axenic culture system allows to observe the impact of PAH on plant growth and the interaction between plant and bacteria (nodulation). Dose-response-experiments indicated that nodulation measured as number of nodules per plant, was more sensitive to the inhibition by PAH than other plant growth parameters.