What potential do mosses have as biomonitors of POPs? A comparative study of hexachlorocyclohexane sorption.

Persistent organic pollutants (POPs) pose a significant global threat to human health and the environment, and require continuous monitoring due to their ability to migrate long distances. Active biomonitoring using cloned mosses is an inexpensive but underexplored method to assess POPs, mainly due to the poor understanding of the loading mechanisms of these pollutants in mosses. In this work, Fontinalis antipyretica (aquatic moss) and Sphagnum palustre (terrestrial moss) were evaluated as potential biomonitors of hexachlorocyclohexanes (HCHs: α-, ß-, γ-, δ-HCH), crucial POPs. Moss clones, grown in photobioreactors and subsequently oven-dried, were used. Their lipid composition and distribution were characterized through molecular and histochemical studies. Adsorption experiments were carried out in the aqueous phase using the repeated additions method and in the gas phase using an active air sampling technique based on solid-phase extraction, a pioneering approach in moss research. F. antipyretica exhibited greater lipid content in the walls of most cells and higher adsorption capacity for all HCH isomers in both gaseous and liquid environments. These findings highlight the need for further investigation of POP loading mechanisms in mosses and open the door to explore other species based on their lipid content.

The photochemical behaviour of five household pyrethroid insecticides and a synergist as studied by photo-solid-phase microextraction.

In the present study, solid-phase microextraction in photochemical studies was used to investigate UV light induced photodegradation of five pyrethroids (empenthrin, transfluthrin, allethrin, phenothrin and cyphenothrin) and a synergist (piperonyl butoxide), which are common ingredients of household insecticides. Gas chromatography coupled with mass spectrometry was used to separate and tentatively identify the parent compounds and their corresponding photoproducts generated in the same polydimethylsiloxane fibre. Kinetics curves were obtained and apparent first-order rate constants and half-lives were estimated. Twenty-six photoproducts were tentatively identified and photodegradation pathways for the compounds investigated were proposed. It is a matter of some concern that three of the photoproducts identified [(3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid, 3-phenoxybenzaldehyde and (3-phenoxyphenyl)methanol] have been reported to be endocrine disruptors. There is no record of previous studies of cyphenothrin and empenthrin photodegradation, and therefore the present study represents the first attempt to elucidate the photochemical behaviour of these compounds. Figure Photo-SPME for Pyrethroids.

Alternative sample preparation method for photochemical studies based on solid phase microextraction: synthetic pyrethroid photochemistry.

An alternative sample preparation method for photochemical studies, which overcomes all the disadvantages associated with classical approaches, is proposed. The method is based on Solid Phase Microextraction (SPME) and can be considered as being within the scope of "green photochemistry", especially when it is combined with sunlight irradiation. To demonstrate the potential of the procedure, photochemical studies of synthetic pyrethroids were carried out. Photodegradation pathways for five dihalogenovinyl-substituted pyrethroid pesticides: permethrin, deltamethrin, cyfluthrin, cypermethrin and lambda-cyhalothrin, are proposed, and kinetic curves and parameters provided. This information, obtained by rapidly carried out, green experiments, allows us to corroborate photoproducts reported by other authors and to identify the photoproducts proposed for the first time in the present study.

Low part per trillion determination of reactive alkanethiols in wastewater by in situ derivatization-solid-phase microextraction followed by GC/MS.

A solid-phase microextraction (SPME) procedure for the simultaneous determination of volatile alkanethiols (i.e., methane-, ethane-, propanethiol) and dihydrogen sulfide in aqueous samples as stable thioethers followed by GC/MS determination was developed. Accordingly, N-ethylmaleimide as derivatization reagent in the aqueous phase was used for the first time, improving the analyte stability and method sensitivity in comparison to the determination of free forms. Thus, pH of the aqueous medium, reaction time, and derivatization reagent concentration have been evaluated, and the main parameters affecting the SPME process (i.e., coating selection, extraction mode and time profile, extraction and desorption temperatures) optimized. At the selected derivatization and extraction conditions, the proposed method provided no matrix effect either in the derivatization reaction or in the microextraction steps. RSD values were lower than 11% and LODs from 0.74 to 5.2 ng L(-1). The developed procedure was successfully applied to different water and wastewater samples, where dihydrogen sulfide and some of the target alkanethiols were identified at low-microgram per liter concentrations.

Photochemical studies of a polybrominated diphenyl ethers (PBDES) technical mixture by solid phase microextraction (SPME).

In this work the photochemical behaviour of a technical mixture of polybrominated diphenyl ethers (PBDEs) (BDE-47, BDE-99, BDE-100, BDE-153 and BDE-154) has been studied. The mixture of BDEs was extracted from aqueous solutions using SPME fibers that were subsequently exposed to different UV irradiation times, procedure so-called Photo-SPME. PBDEs photochemical studies in such medium have been accomplished for the first time. Twenty one different photoproducts, all of them generated by successive bromine atoms losses, have been identified, being their photoformation-photodegradation curves easily determined by the Photo-SPME technique.

Further solid-phase microextraction-gas chromatography-mass spectrometry applications: "on-fibre" and aqueous photodegradation of nitro musks.

Photodegradation kinetics of four nitro musks (musk xylene, musk tibetene, musk ketone and musk moskene) in solid-phase microextraction (SPME) fibres ("photo-SPME") and in an aqueous system were studied by means of gas chromatography-mass spectrometry (MS) detection. Musks fragrances were extracted from aqueous solutions using SPME fibres that subsequently were exposed to different UV irradiation times, generating photoproducts easily characterized by their mass spectra. Aqueous photodegradation studies followed by SPME were also performed and compared to photo-SPME. The same fourteen photoproducts have been detected in both media. The potential of this approach to readily calculate apparent rate constants (from 10(-4) to 10(-3) s(-1)), half-life times (from 3 to 32 min) and reaction orders (n = 1) in both media is stated. The main photoreaction determined was photocyclization, but products of photoreduction and photorearrangement have also been detected. Tentative photodegradation pathways for musk moskene and musk tibetene are proposed for the first time.

Development of a solid-phase microextraction gas chromatography/tandem mass spectrometry method for polybrominated diphenyl ethers and polybrominated biphenyls in water samples.

Solid-phase microextraction has been applied for the first time to the determination of trace concentrations of some brominated flame-retardant compounds (BFRs) in water samples. For the development of the method, six polybrominated diphenyl ethers and two polybrominated biphenyls were considered as target analytes. The factors expected to influence the extraction process are fully discussed. Quantification has been performed by gas chromatography/tandem mass spectrometry using an ion trap mass analyzer. This is also the first time that tandem mass spectrometry is applied with these analytes. Unlike conventional methods for BFR analysis, which involve solvent extraction and several cleanup steps before gas chromatography, the proposed method uses headspace extraction and hard contamination of the chromatographic system is prevented. In addition, tandem mass spectrometry provides selectivity and sensitivity in the detection process. The method performs well achieving good linearity (R(2) > 0.997), precision, and detection limits (S/N = 3) ranging from 7.5 to 190 pg/L. The method has been applied to a variety of water samples.