K. Martínez

Part-per-trillion level determination of antifouling pesticides and their byproducts in seawater samples by off-line solid-phase extraction followed by high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry

A new method for the simultaneous determination of antifouling pesticides and some of their byproducts such as dichlofluanid, diuron and its byproducts [demethyldiuron and 1-(3,4-dichlorophenyl)urea], (2-thiocyanomethylthio)ben: zothiazole, chlorothalonil, Sea-nine 211, Irgarol 1051 and one of its byproducts (2-methylthio-4-tert.-butylamino-s-triazine) in seawater was developed. The extraction of these compounds from the filtered seawater samples was performed off-line with different solid-phase extraction sorbents using (I) a 500 mg graphitized carbon black cartridge (ENVI-Carb) and (II) 200 mg polymeric cartridges (LiChrolut EN and Isolute ENV+) and passing 500 ml of the sample through these cartridges. The detection was carried out by reversed-phase high-performance liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometry both in the negative and positive ion modes. The recovery ranged from 76 to 96% for the whole antifouling group with the ENVI-Carb cartridges and the detection limit was at the part-per-trillion level except for TCMTB. The method utilizing the polymeric cartridge proved to be very useful, time saving and with good recoveries when only Irgarol and its byproduct, Sea-nine 211 and diuron and its byproducts, have to be analyzed. The different cartridges were applied to the analysis of these pesticides in different marinas of the Catalan coast; diuron, dichlofluanid, Sea-nine 211, Irgarol as well as demethyldiuron and the Irgarol byproduct being the must ubiquitous pollutants. Maximum concentration levels were 2-3.5 microg/l of diuron and Sea-nine 211, respectively.

Occurrence of Antifouling Biocides in the Spanish Mediterranean Marine Environment

A compilation of the results of a monitoring program of the recently used antifouling pesticides diuron (3-(3,4-dichlorophenyl)-1,1-dimethylurea), Irgarol 1051 (2-methylthio-4-tertiary-butylamino-6-cyclopropylamino-s-teiazine), seanine 211 (4,5-dichloro-2-n-octyl-4-isothazolin-3-one), chlorothalonil (2,4,5,6-tetrachloro-isophthalonitrile), dichlofluanid (N′-dimethyl-N-phenylsulphanamide), TCMTB ((2-thiocyanomethylthio) benzothiazole), and three degradation products demethyldiuron (3-(3,4-dichlorophenyl)-1-methylurea), 3,4-dichlorophenylurea and 2-methylthio-4-tert-butylamino-s-triazine (Irgarol degradation product) that was carried out between April 1996 and February 2000 in enclosed seawaters from Catalonia and Almería (Spanish Mediterranean coast) is reported. Nine points were sampled along the Catalan coast: Barcelona Olympic port, Masnou, Blanes, Sant Carles de la Ràpita, Tarragona, Cambrils and Salou marinas as well as the Cambrils and Tarragona fishing harbors and in marinas and ports from Almeria: Aguadulce port, Almería port, Almerimar fishing harbour and Almerimar marina. The analytical methodologies were based on Solid Phase Extraction followed by liquid chromatography (LC) or gas chromatography (GC) coupled to a mass spectrometry (MS) or -Diode Array Detector. The main pollutants found in the sampled points were diuron and Irgarol 1051 that were detected at concentrations up to 2.19 µg l−1 and 0.33 µg l−1, respectively. On the other hand, seanine 211 was found at the highest concentration (up to 3.7 µg l−1) during the summer of 1999. Low concentrations of dichlofluanid and the above mentioned degradation products were detected for the first time in the Spanish coasts. Chlorothalonil, TCMTB were not found at concentrations higher than 1 and 20 ng l−1 respectively which were the limit of determination (LOD) of the method for these compounds. In general the contamination at the different marinas is higher at the end of spring and in summer where the boating activity is also higher. This paper shows for the first time that the contamination by the new antifouling pesticides in Spanish coastline, basically marinas and fishing harbours, is permanent along the whole calendar year. So, preventive actions by the harbour authorities will be needed in the near future in order to monitor and control the levels and effects of the new antifouling biocides in the marine environment.

Assessment of the emission of PCDD/Fs and dioxin-like PCBs from an industrial area over a nearby town using a selective wind direction sampling device

The development of new sampling devices or strategies to assess the concentration of persistent organic pollutants (POPs) in the environment has increased in the last two decades. In this study, a selective sampling device was used to evaluate the impact of potential local sources of polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/Fs) and dioxin-like polychlorinated biphenyl (dl-PCBs) emissions on the ambient air levels of such compounds in a town near an important industrial estate. Average concentrations of target compounds of up to 2.5 times for PCDD/Fs and 2 times for dl-PCBs were found to come from the industrial state confirming this area as the main responsible for the majority of such compounds reaching the town. This finding was supported by a PCDD/F and dl-PCB sample profile analysis and a principal component analysis (PCA), which established a direct link between the dioxin-like compounds found in the samples collected in the town and their source.

Assessment of polychlorinated dibenzo-p-dioxin and dibenzofuran emissions from a hazardous waste incineration plant using long-term sampling equipment

The aim of this work is to evaluate the performance of a continuous monitoring system for the analysis of the mass concentration of PCDD/Fs from stationary sources. Data was acquired from a modern, state of the art, hazardous waste thermal treatment plant for a period of more than 2 years using a commercial available continuous monitoring system. The study consisted of a total of 16 samples, collected in periods from 1 week to 2 months resulting in an average of 360 m³ sampled flue gas per sample. The study showed the system was able to confirm that for a period of more than 2 years the plant was complying with the limit of 0.1 ng I-TEQ/Nm(3). In addition, the data showed the typical fingerprint of such installations which is useful for example in impact studies. Long-term samples were compared to five short-term samples (6 h) collected every 6 months during the study period. Principal component analysis was applied to PCDD/Fs obtained data as useful statistical tool to find out trends and similarities between different samples. Improvement in terms of representativeness of data was achieved through continuous assessment since the starts of the project. The obtained data was further used to determine the emission factor for this activity and the total annual PCDD/Fs release to the atmosphere.

Long-term sampling of dioxin-like substances from a clinker kiln stack using alternative fuels

The aim of this work is to characterize atmospheric emissions of polychlorinated dibenzo-p-dioxins (PCDDs)/polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) from a cement production plant where the existing clinker production line was completely replaced by a new state-of-the-art installation. The project started in April 2008 with the installation of a long-term sampling system in the stack of the clinker kiln that used petroleum coke as fuel; PCDD/PCDF and dl-PCB emissions were then evaluated for a two year period. To carry out the second part of the study, in 2010 the sampling system was moved to the new installation in which, apart from conventional fuel, recovered derived fuel (RDF) and WWTP sludge were used as alternative fuels. For both the old and new clinker kilns, PCDD/PCDF emission values were well below the limit established by the European Waste Incineration Directive 2000/76/CE (EWID) of 100 pg I-TEQ/Nm(3); values ranged from 0.43 to 2.02 and from 0.07 to 3.31 pg I-TEQ/Nm(3), respectively. dl-PCBs accounted for approximately 25% of the WHO-TEQ toxicity. These results prove that the installation is capable of reducing PCDD/PCDF and dl-PCB emissions when alternative fuels are integrated into the process. In the case of PCDDs/PCDFs, the major contributions to total TEQ were usually from 2,3,7,8-TCDD (owing to its relative abundance) and 2,3,4,7,8-PeCDF (due to its high I-TEF of 0.5); while for dl-PCBs, the major contribution was from PCB-126. The slight shift in the congener profile between the old and new installations was characterized and a regression model was proposed for dl-PCB emissions depending on the RDF flow rate in the clinker.

Analytical approach and occurrence for the determination of mass concentration of PCDD/PCDF and dl-PCB in flue gas emissions using long-term sampling devices.

In this work, a reliable methodology for the simultaneous analysis of PCDD/PCDF and dioxin-like PCB (dl-PCB) in flue gas emissions collected using continuous sampling devices is proposed. The analytical scheme followed the minimum requirements described in the EU standard EN-1948:1,2,3,4 according to samples containing large amounts of dioxins and dl-PCBs or samples collected over a long period of time of about 4 weeks. Parameters, such as reproducibility, precision, limits of detection (LOD), limits of quantification (LOQ), extract aliquot size, analytical blanks, extraction efficiency, as well as the amount of internal standards required for an accurate determination, were assessed. The findings demonstrate the suitability of the proposed analytical scheme for the analysis of PCDD/PCDF and PCB in samples collected using long-term sampling devices. The analysis of five different 5% v/v sample aliquots reported %RSD values lower than 10% for all of the 29 congeners at both low and high levels. Similarly, %RSD values were 3.2 and 2.0 for the low level samples and 0.9 and 1.1%RSD for the high level extracts for PCDD/PCDF and dl-PCB, respectively expressed in total TEQ units. Re-extraction provided values less than 3%, expressed in TEQ. Based on blank analyses, LOD values of 100 pg I-TEQ for PCDD/PCDF and 10 pg WHO-TEQ for dl-PCB were achieved when 5% v/v aliquots were analyzed. Finally, the proposed analytical approach was tested with samples from a wide range of combustion processes such as hazardous and municipal waste incinerators, as well as cement kilns (with and without waste co-incineration).

Baseline levels of dioxin and furan emissions from waste thermal treatment in Colombia.

Background data of polychlorinated dibenzodioxin and dibenzofuran (PCDD/Fs) emissions from the incineration sector in Colombia are presented. Monitoring was carried out during a two-year period, 2003-2005. Twelve plants were sampled for stack gas emissions of dioxins and total solid particulate (TSP). Additionally, PCDD/Fs in several fly ash samples were analyzed. Most incinerators burned industrial refuse materials and medical residues. A wide range of PCDD/Fs emission levels were found. In particular, levels ranging from 6.9 to 343.8 ng I-TEQ/N m(3) were determined in plants without any air pollution control system (APCS). In contrast, 0.5-39.2 ng I-TEQ/N m(3) levels were found in plants with APCS while 8.5-67.5 ng I-TEQ/g were measured in fly ash samples. TSP values ranged from 14 to 448 mg/N m(3). This study also evaluated the impact of implementing different control systems in an incinerator. Finally, for comparison purposes several samples were analyzed by both high resolution gas chromatography coupled to high resolution mass spectrometry (HRGC-HRMS) and high resolution gas chromatography coupled to ion-trap low resolution mass spectrometry-mass spectrometry (HRGC-IT LRMS/MS). Overall, I-TEQ values deviated about 20-30% between both techniques.

Analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans in stack gas emissions by gas chromatography-atmospheric pressure chemical ionization-triple-quadrupole mass spectrometry

A gas chromatography coupled to triple-quadrupole mass spectrometry (GC-(QqQ)MS/MS) including a soft-ionization through an atmospheric pressure chemical ionization (APCI) source based method was compared with the high resolution mass spectrometry (HRMS) standard reference method EN1948, for the analysis of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) in stack gas emissions. The stack emission samples were collected, both, by manual method sampling (from 6 to 8h) and by long-term sampling systems (sampling time of several weeks). This work presents the first comparison of GC-(QqQ)MS/MS with APCI source with the European Standard EN1948 technique for stack gas emissions. Sample concentrations ranged from 0.5 to 596pg I-TEQ/Nm3. Comparative results in all investigated samples showed relative errors that were within ±15%. These results make GC-(QqQ)MS/MS with APCI suitable for the quantitative analysis of dioxins in the studied samples and create a real alternative tool to the reference sector GC-HRMS instruments.