Comparison of five integrative samplers in laboratory for the monitoring of indicator and dioxin-like polychlorinated biphenyls in water.

This study aimed at evaluating and comparing five integrative samplers for the monitoring of indicator and dioxin-like polychlorinated biphenyls (PCBs) in water: semi-permeable membrane device (SPMD), silicone rubber, low-density polyethylene (LDPE) strip, Chemcatcher and a continuous-flow integrative sampler (CFIS). These samplers were spiked with performance reference compounds (PRCs) and then simultaneously exposed under constant agitation and temperature in a 200 L stainless steel tank for periods ranging from one day to three months. A constant PCB concentration of about 1 ng·L(-1) was achieved by immersing a large amount of silicone rubber sheets ("dosing sheets") spiked with the target PCBs. The uptake of PCBs in the five samplers showed overall good repeatability and their accumulation was linear with time. The samplers SPMD, silicone rubber and LDPE strip were the most promising in terms of achieving low limits of quantification. Time-weighted average (TWA) concentrations of PCBs in water were estimated from uptake of PCBs using the sampling rates calculated from the release of PRCs. Except for Chemcatcher, a good agreement was found between the different samplers and TWA concentrations ranged between 0.4 and 2.8 times the nominal water concentration. Finally, the influence of calculation methods (sampler-water partition coefficients, selected PRCs, models) on final TWA concentrations was studied.

Assessment of odour and H(2)S impact in WWTPs by cryo-condensation.

Stability of gaseous samples is a major concern when dealing with odours and airborne pollutants sampling. In terms of odours, the representativeness of the sample can be very seriously compromised, despite the rigorous application of the maximum storage time established by EN-13725. The present paper is focused on the use of the cryo-condensation technique (Cryocore) for time-weighted-average (TWA) sampling in waste water treatment plants (WWTPs), with the aim of comparing the values of TWA odour and H(2)S concentration when using the Cryocore system and other well established sampling methods, such as those described in EN-13725 and passive sampling. The study showed comparable results when comparing all the methodologies tested.

Analysis of chlorophenols, bisphenol-A, 4-tert-octylphenol and 4-nonylphenols in soil by means of ultrasonic solvent extraction and stir bar sorptive extraction with in situ derivatisation.

A novel method based on ultrasonic solvent extraction and stir bar sorptive extraction for the analysis of phenolic organic pollutants including chlorophenols, bisphenol-A, 4-tert-octylphenol and 4-nonylphenol in soil samples was developed. The different parameters that affect both the extraction of analytes from the soil samples, such as solvent selection, extraction time, and the partitioning from the solvent/water mix to poly(dimethylsiloxane) (PDMS) were studied. The final selected conditions consisted of the extraction of 1g of soil with 15 mL methanol by sonication for 30 min. The methanol extract was mixed with 85 mL of Milli-Q water and extracted by means of stir bar sorptive extraction with in situ derivatisation. The stir bars were analyzed by thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). The effects of the matrix on the recovery of the various pollutants under the developed method were studied using two soils with very different physicochemical properties. Method sensitivity, linearity, repeatability, and reproducibility were also studied. Validation and accuracy of the method were conducted by analyzing two commercial certified reference materials and by comparing the analysis of real samples with the proposed method and a classical method using pressurized solvent extraction (PSE)-GC-MS. The main advantage of this method is a substantial solvent reduction. For the extraction of only 1g of solid sample allowing limits of detection ranging from 0.2 to 1.7 microg kg(-1) dw. Repeatability and reproducibility variation were lower than 20% for all investigated compounds. Results of the certified reference materials and the real samples verify the high accuracy of this method.

Constantly stirred sorbent and continuous flow integrative sampler: new integrative samplers for the time weighted average water monitoring.

Two innovative integrative samplers have been developed enabling high sampling rates unaffected by turbulences (thus avoiding the use of performance reference compounds) and with negligible lag time values. The first, called the constantly stirred sorbent (CSS) consists of a rotator head that holds the sorbent. The rotation speed given to the head generates a constant turbulence around the sorbent making it independent of the external hydrodynamics. The second, called the continuous flow integrative sampler (CFIS) consists of a small peristaltic pump which produces a constant flow through a glass cell. The sorbent is located inside this cell. Although different sorbents can be used, poly(dimethylsiloxane) PDMS under the commercial twister format (typically used for stir bar sorptive extraction) was evaluated for the sampling of six polycyclic aromatic hydrocarbons and three organochlorine pesticides. These new devices have many analogies with passive samplers but cannot truly be defined as such since they need a small energy supply of around 0.5 W supplied by a battery. Sampling rates from 181 x 10(-3) to 791 x 10(-3) L/day were obtained with CSS and 18 x 10(-3) to 53 x 10(-3) with CFIS. Limits of detection for these devices are in the range from 0.3 to 544 pg/L with a precision below 20%. An in field evaluation for both devices was carried out for a 5 days sampling period in the outlet of a waste water treatment plant with comparable results to those obtained with a classical sampling method.

Stir bar sorptive extraction for the analysis of short-chain chlorinated paraffins in water.

An optimised method using stir bar sorptive extraction (SBSE) and a thermal desorption-GC-electron capture detector (GC-ECD) for the determination of short-chain chlorinated paraffins from water samples was developed. Recoveries near to 100% were obtained by using 20 mm x 0.5 mm (length x film thickness) PDMS commercial stir bars from 200 mL spiked water samples and 20% methanol addition with an extraction period of 24 h. Method sensitivity, linearity and precision were evaluated for surface water and wastewater spiked samples. A LOD of 0.03 and 0.04 microg/L was calculated for surface and wastewater, respectively. The precision of the method given as an RSD was below 20% for both matrices. The developed method was applied for the analysis of two real samples from a contaminated river and a wastewater treatment plant. Results were in accordance with those obtained using a previously developed method based on solid phase microextraction (SPME).

New universal, portable and cryogenic sampler for time weighted average monitoring of H2S, NH3, benzene, toluene, ethylbenzene, xylenes and dimethylethylamine.

A new cryogenic integrative air sampler (patent application number 08/00669), able to overcome many of the limitations in current volatile organic compounds and odour sampling methodologies is presented. The sample is spontaneously collected in a universal way at 15 mL/min, selectively dried (reaching up to 95% of moisture removal) and stored under cryogenic conditions. The sampler performance was tested under time weighted average (TWA) conditions, sampling 100L of air over 5 days for determination of NH(3), H(2)S, and benzene, toluene, ethylbenzene and xylenes (BTEX) in the ppm(v) range. Recovery was 100% (statistically) for all compounds, with a concentration factor of 5.5. Furthermore, an in-field evaluation was done by monitoring the TWA inmission levels of BTEX and dimethylethylamine (ppb(v) range) in an urban area with the developed technology and comparing the results with those monitored with a commercial graphitised charcoal diffusive sampler. The results obtained showed a good statistical agreement between the two techniques.

Analysis of 51 persistent organic pollutants in soil by means of ultrasonic solvent extraction and stir bar sorptive extraction GC-MS.

A novel method based on ultrasonic solvent extraction and stir bar sorptive extraction (SBSE) for the analysis of 51 persistent organic pollutants including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and polybrominated diphenylethers (PBDEs) in soil samples was developed. The different parameters that affect both the extraction of analytes from the soil samples, such as solvent selection, solvent volume, mass of soil, and extraction time, and the partitioning from the solvent/water mixture to the PDMS were studied. The final selected conditions consisted of the extraction of 1 g of soil with 15 mL methanol by sonication for 30 min. The methanol extract was mixed with 85 mL of Milli-Q water and extracted by means of SBSE for 14 h at 900 rpm. The stir bars were analyzed by thermal desorption-GC-mass spectometry (TD-GC-MS). The effects of the matrix on the recovery of the various pollutants under the developed method were studied using two soils with very different physicochemical properties. Method sensitivity, linearity, repeatability, and reproducibility were also studied. Validation and accuracy of the method were conducted by analyzing two commercial certified reference materials (CRMs). The main advantage of this method resides in the fact that a small amount of a nontoxic solvent (methanol) is needed for the extraction of only 1 g of solid sample allowing LODs ranging from 0.01 to 2.0 microg/kg. Repeatability and reproducibility variations were lower than 20% for all investigated compounds. Results of the CRMs verify the high accuracy of this method.

Ultra trace determination of 31 pesticides in water samples by direct injection-rapid resolution liquid chromatography-electrospray tandem mass spectrometry.

A liquid chromatography-tandem mass spectrometry (LC-MS/MS)-based method for the detection of pesticides in tap and treated wastewater was developed and validated according to the ISO/IEC 17025:1999. Key features of this method include direct injection of 100 microL of sample, an 11 min separation by means of a rapid resolution liquid chromatography system with a 4.6 mm x 50 mm, 1.8 microm particle size reverse phase column and detection by electrospray ionization (ESI) MS-MS. The limits of detection were below 15 ng L(-1) and correlation coefficients for the calibration curves in the range of 30-2000 ng L(-1) were higher than 0.99. Precision was always below 20% and accuracy was confirmed by external evaluation. The main advantages of this method are direct injection of sample without preparative procedures and low limits of detection that fulfill the requirements established by the current European regulations governing pesticide detection.