Emissions of PCDD/Fs, PBDD/Fs, dioxin like-PCBs and PAHs from a cement plant using a long-term monitoring system

The aim of the present work was to assess the emission of different persistent organic pollutants from a cement plant over a period of one year, under normal operational conditions. Thus, a long-term sampling device was installed in the clinker kiln stack of the cement plant. The factory uses petroleum coke as primary fuel, but also alternative fuels such as solid recovered fuel (SRF), automotive shredder residue (ASR), sewage sludge, waste tires, and meat and bone meal (MBM) wastes, with an energy substitution level of about 40%. Both PCDD/Fs (together with dl-PCBs) and PBDD/Fs were continuously sampled, with a total of ten samples collected in 2–4 week periods. Also, PAHs were sampled during one-week periods, in order to evaluate their emissions in three different samples. The emission levels throughout the year were much lower than the set legal limits in all substances, being < 10 pg I-TEQ/Nm3 in the case of PCDD/Fs. The data obtained allowed calculation of updated emission factors for the cement sector, which were 8.5 ng I-TEQ/ton clinker for PCDD/Fs and 3.2 ng WHO-TEQ/ton clinker for PCBs. With respect to the congener distribution, 2,3,7,8-TCDF accounts for 60 to 68% of the total toxicity for PCDD/Fs, and in PBDD/F emissions, a clear predominance of octa-substituted species (both dioxin and furan) was found.Support for this work was provided by CEMEX ESPAÑA, S.A., a company owned by the CEMEX group (http://www.cemex.com). Authors acknowledge the financial support for this work provided by the following projects: Ministry of Economy and Competitiveness (Spain): CTQ2013-41006-R, Autonomous Community of Valencia Government (Spain): PROMETEOII/2014/007

Emissions of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) from a cement kiln using a continuous monitoring system

Resumen de la comunicación presentada en PIC2015 – the 14th International Congress on Combustion By-Products and Their Health Effects, Umeå, Sweden, 14-17 June 2015.The aim of the present study was to assess the emission of di2erent persistent organic pollutants from a cement plant over a period of one year, under normal operating conditions. In this way, a Dioxin Monitoring System (a long-term sampling device manufactured by Monitoring Systems) was installed in the clinker kiln stack of the cement plant, located in the vicinity of the University of Alicante. The factory has a production capacity of 150 t/h of clinker and uses petroleum coke as primary fuel, but also alternative fuels such as SRF (solid recovered fuel), ASR (automotive shredder residue), sewage sludge, waste tires, and meat and bone meal wastes, with an enerKy substitution level of about 40 %. The study consisted of a total of 13 samples, namely: • Ten samples collected in 3Q4 week periods, for the determination of brominated dioxins and furans (PBDD/Fs). • Three samples collected during one-week periods, for the determination of polycyclic aromatic hydrocarbons (PAHs).Support for this work was provided by the following projects: • Ministry of Science and Innovation (Spain): CTQ2011Q23618. • Ministry of Economy and Competitiveness (Spain): CTQ2013Q41006QR. • Valencian Community Government (Spain): PROMETEOII/2014/007

Estudi de les emissions de PCDD/F i altres contaminants orgànics persistents a l'atmosfera mitjançant l'ús de captadors en continu

[cat] L’emissió a l’atmosfera de compostos orgànics persistents (COPs) vinculada als processos de combustió susciten un gran interès per la seva possible influència negativa sobre la salut humana i el medi ambient. La legislació europea obliga a les industries a realitzar controls periòdics de les seves emissions a l’atmosfera, amb l’objectiu de reduir-les al màxim. Entre els compostos orgànics que més preocupen per la seva toxicitat, es troben les dioxines i els furans (PCDD/Fs) i els bifenils policlorats (PCBs). La determinació de les emissions d’aquests compostos en fonts estacionàries es basa a Europa en la Norma EN1948, que preveu per a tal efecte, una presa de mostra de 6 a 8 hores i la posterior determinació del seu contingut al laboratori per GC/HRMS. No obstant, existeixen actualment equips de captació en continu que, permanentment instal·lats a la xemeneia, permeten la recol·lecció ininterrompuda de mostra durant llargs períodes de temps, amb la millora en la representativitat dels resultats que se n’obtenen, però manquen encara d’un marc normatiu que els reguli. En la present tesi doctoral s’han realitzat diversos estudis per a la determinació de les emissions de dioxines i furans (PCDD/Fs), bifenils policlorats tipus dioxina (dl-PCBs) i altres contaminants orgànics persistents en fonts estacionàries mitjançant l’ús de captadors en continu. Aquestes tasques s’han dut a terme en el marc de diferents projectes que han fet possible l’aplicació d’aquesta tècnica en diferents tipus de processos industrials. Els treballs han requerit d’una banda l’estudi previ de la aplicabilitat d’aquests sistemes de captació, i d’altra banda la adaptació del mètode d’anàlisi per a emissions puntuals al nou tipus de mostra. A mode de resum, s’ha modificat la metodologia analítica utilitzada anteriorment al nostre laboratori per a la determinació del contingut de PCDD/Fs i dl-PCBs en mostres procedents de captacions puntuals en xemeneia (de 6 a 8 hores), amb l’objectiu d’adaptar-la a l’anàlisi de mostres procedents de captacions en continu (vàries setmanes), molt més concentrades. Així mateix, s’ha procedit a realitzar un estudi de validació de la metodologia proposada i determinar la incertesa dels resultats obtinguts, fent especial èmfasi en els punts de la metodologia en què aquesta es diferencia del mètode convencional. D’altra banda, els extractes analitzats per GC/HRMS han estat també analitzats per un sistema GC-APCI-MS/MS(QqQ), per tal d’avaluar la idoneïtat d’aquesta nova tècnica, recentment acceptada com a mètode de confirmació per a l’anàlisi de COPs en aliments, per a la determinació en aquest cas, en mostres procedents de fonts estacionàries. La metodologia analítica proposada ha permès caracteritzar mostres procedents de diferents tipus d’activitats industrials. Concretament en el sector de la incineració de residus, s’ha realitzat un estudi al llarg de dos anys que ha permès la determinació de les emissions de PCDD/Fs i dl-PCBs amb un captador en continu en una planta incineradora de residus industrials i perillosos. Els altres estudis han estat desenvolupats en el sector de la fabricació del ciment, i han suposat la determinació de nous factors d’emissió per als processos estudiats, així com la caracterització dels perfils o ‘petjada química’ de les seves emissions. Així mateix, un dels estudis ha comportat l’anàlisi complementari d’altres compostos orgànics d’interès, com les dioxines i els furans polibromats (PBDD/Fs) o els hidrocarburs aromàtics policíclics (PAHs). A més, els treballs en el sector de la fabricació del ciment han permès aprofundir en l’estudi de la influència sobre els nivells de les emissions de compostos orgànics persistents dels processos de co-incineració, amb l’ús de diferents combustibles alternatius, arribant-se a la conclusió que aquesta pràctica no té perquè representar un increment de les emissions d’aquests compostos.[eng] The release of Persistent Organic Pollutants (POP) to air from combustion processes is a matter of concern due to their toxic effect on human health and environment. European legislation obliges industrial plants to undertake periodic controls of their emission releases to air, with the aim to reduce them. In Europe, the determination of the mass concentrarion of dioxins and furans (PCDD/Fs) and polychlorinated biphenyls (PCBs) is regulated by Standard EN1948. This standard is based on the GC/HRMS analysis of a sample issued from a manual sampling train and taken in a range of time from 6 to 8 hours. New automatic sampling devices are available nowadays that allow sampling times up to several months. By extending the sampling coverage to the whole operation period, better results are achieved for the assessment of total pollutants emission release. The present thesis work includes several studies for the determination of the mass concentration of PCDD/Fs, PCBs and other POPs in stack gas emissions by means of long-term sampling systems, in different types of industrial plants. For this purpose a preliminary study of the applicability of long-term sampling systems has been necessary, as well as the modification of the analysis scheme applied to short-term samples, in order to adapt it to the characteristics of new samples. In summary, the methodology used for the analysis of PCDD/Fs and dl-PCBs from short-term samples was adapted to the analysis on these more concentrated samples issued from long-term sampling systems. The uncertainty of the method was assessed as well as the validation, with special emphasis on these points where the new methodology differs from the conventional one. On the other hand, the extracts determined by GC/HRMS were also analysed by means of a gas chromatograph coupled to a triple quadrupole with atmospheric pressure ionization (GC-APCI-MS/MS), for the evaluation of this novel technique performance in emission samples analysis. The proposed methodology was used for the determination of POPs emission in different type of industrial activities. From waste incineration field, with a two year project for the determination of POPs emissions in a hazardous waste plant incinerator, to cement plants with and without the use of alternative fuels. The studies contributed to the establishment of new emission factors for these plants and the characterization of the ‘footprint’ of their particular emissions. Moreover, one of the cement plants study included the simultaneous determination with dioxin-like compounds of polybrominated dioxins and furans (PBDD/Fs) and poly aromatic hydrocarbons (PAHs). The results of the studies in cement plants proved that, even if an influence of the ratio usage of alternative fuels results in some cases in changes on the emission profiles, co-incineration is a practice that is not necessarily related to higher persistent organic pollutants emission levels

El control de emisiones de contaminantes persistentes en la utilización de combustibles alternativos en la industria del cemento

8 páginas, 9 figuras, 1 tabla.En la actualidad la medida del nivel de dioxinas emitido por una chimenea se efectúa en Europa por aplicación de la Norma EN 1948 que contemplaba hasta hace poco un tiempo máximo de captación de ocho horas (aproximadamente 10 m3). No obstante, existen hoy día nuevos sistemas de captación que recogen muestra en la chimenea de forma ininterrumpida. Estos sistemas permiten, al integrar un período más largo de captación, obtener muestras más representativas, avanzar en el estudio de la relación entre las condiciones de la planta y los niveles de emisión y adaptarse al futuro desarrollo de la Norma cuya parte 5 relativa a las captaciones en continuo se halla en curso de redacción por el Comité Europeo de Normalización. En este estudio se presenta la primera experiencia del sector cementero en España con captadores en continuo para el control de las emisiones de dioxinas. Los equipos se instalaron en dos hornos de clínker alimentados con coque de petróleo, al tiempo que en uno de ellos se utilizan combustibles alternativos. Los resultados, obtenidos a partir de muestreos entre 7 y 56 días de duración, permiten confirmar que ambas plantas tienen niveles de emisión por debajo del límite legal establecido en el Real Decreto 653/2003 de 0,1ng I-TEQ/Nm3.El estudio ha sido co-financiado por el Ministerio de Medio Ambiente, Marino y Rural (Proyecto 314/2006/3-11.5) y por el Ministerio de Educación y Ciencia (Proyecto CTM2006-04608)Peer reviewe

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.Peer reviewe

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.Peer reviewe

Levels of polychlorinated biphenyls, polychlorinated dibenzo-p-dioxins and dibenzofurans in commercial yoghurt samples in SpainComparison with different dairy products

A method developed previously for the simultaneous analysis of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in powdered full fat milk is now examined for their determination in yoghurt. The results of this study are consistent with those found for PCBs and PCDD/Fs in powdered full fat milk. The methodology is based on the matrix solid-phase dispersion of the freeze dried yoghurt enabling the extraction of the neutral and apolar lipids of the matrix. Mean recoveries were above 94% for the studied coplanar PCB congeners spiked at the typical reported levels for dairy products and above 92% for the spiked 13C12-PCDD/Fs. The validated methodology was applied to the PCB and PCDD/F analysis in full fat and low fat yoghurts form different brands commercialised in Spain. In all cases, levels detected in the low fat yoghurts analysed were several times higher than those found in the full fat yoghurts when reported on a fat basis (between 3.3 and 11 times for PCBs and between 3.3 and 45 times for PCDD and PCDF homologue groups). In general, this discrepancy applied also for the toxic 2,3,7,8-TCDD equivalents (TEQs) calculated in each case. The calculated TEQs (on a fat weight basis) from PCBs and PCDFs in the low fat yoghurts were higher than those reported previously for different Spanish dairy products, including liquid and powdered milk and butter. Nevertheless, the estimated daily intake (DI) for low fat yoghurts was lower than those calculated for the rest of the dairy products investigated. This apparent contradiction showed that the regulation of PCB and PCDD/F contents should be based on DIs rather than on TEQs reported on a fat-adjusted basis. Finally, the feasibility of differentiation among different dairy products, i.e. liquid and powdered milk, butter and yoghurt, on the basis of their respective PCB and PCDD/F patterns by using multivariate methods, has been shown.The authors thank the CSIC and the Comunidad Autónoma of Madrid for project 07M/0600/97.Peer Reviewe

Levels of PCBs, PCDDs and PCDFs in commercial butter samples in Spain

Feasibility of three different extraction methods for the simultaneous determination of polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in butter is discussed. The method based on liquid-liquid extraction with water of the non fatty solids from butter dissolved in hexane was found to be the most efficinent for the determination of the lipid content and the levels of the investigated pollutants. This method was used to evaluate the background levels of PCBs, PCDDs and PCDFs in butters commercially available in Spain. Broad ranges of PCB, specifically, PCDD and PCDF concentrations were found in the different brands analysed. Levels, profiles and patterns of these pollutants in butter were compared with those previously reported for different Spanish dairy products. The toxic tetra-equivalents of 2,3,7,8-TCDD (I-TEQ) averages for PCDDs and PCDFs in the 21 butter samples analysed were 0.41 and 0.70 pg/g fat basis, respectively. These values were similar or lower than those cited in the literature for other countries.Peer reviewe

Levels of pcdds and pcdfs in farm cow's milk located near potential contaminant sources in Asturias (spain). Comparison with levels found in control point and commercial clorinated dioxins and related compounds

Peer Reviewe

Opportunities for ATM The multimedia network of the future

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