Contaminantes orgánicos (PAHs) derivados de la escombrera de la Central Térmica de Aliaga (Teruel)

The aim of this study was to determine if the soils, waters and plants from the Aliaga dump contained polycyclic aromatic hydrocarbons (PAHs) and their quantification.The results showed that PAHs concentrations in soils are in general higher than the reference levels from the Spanish legislation. Waters and plants contained PAHs but in low concentrations. The possible actions for remediation (photodegradation and bioremediation) seem to be unviable here because of the large volume of materials involved, although its use as an additive for the cement industry and derivatives can be considered. It is proposed that fluorantene in waters, and phenanthrene and benzo[ghi]perilene in soils be considered as pollutants as well as to study the incorporation of PAHs to plants. Key-words: Polycyclic aromatic hydrocarbons, soil, plant and water contamination, fly- ash, power plant. RESUMEN: El objetivo de este estudio fue determinar y cuantificar los hidrocarburos policíclicos aromáticos (PAHs) en los suelos, plantas y aguas de la Escombrera de Aliaga. La concentración de PAHs en las cenizas supera, en general, los valores establecidos en la legislación española.Las aguas y plantas contienen PAHs, aunque en concentraciones bajas. La remoción de los materiales para someterlos a fotodegradación y biorremediación es inviable debido al gran volumen de la escombrera, aunque se plantea su uso como aditivo en la fabricación de productos derivados del cemento. Se propone incluir el fenantreno y benzo[ghi]perileno en la normativa de suelos, así como el naftaleno en la de aguas y la elaboración de una legislación sobre la incorporación de estos compuestos a las plantas.

Plant development effects of biochars from different raw materials

Biochar can provide multiple benefits in the ecosystem. However, the presence of phytotoxic compounds in some biochars is an important concern that needs to be addressed and that depends on the raw material and the pyrolysis conditions used in biochar production. For example, sewage sludge biochars can have elevated heavy metal con- tents as they were present in the feedstock and were enriched during pyrolysis. Also during carbonization, some phytotoxic compounds such as polycyclic aromatic hydrocarbons (PAHs), polyphenols or volatile organic com- pounds (VOCs) could be formed representing a risk of contamination to soils and crops. In this work we report the results from seed germination and plant development for three biochars prepared from wood, paper sludge plus wheat husks and sewage sludge. Five higher plant species (cress, lentils, cucumber, tomato and lettuce) were studied. Biochar from wood shows seed inhibition in several species and the paper sludge biochar on lettuce. For the rest, the effect on seed germination was positive. No inhibition of root growth was detected, but in some cases leaves and stems growth were inhibited. Our results are significant in terms of advancing or current understanding on the impacts of biochar on vegetative growth and linking those effects to biochar properties.

Origen y distribución de los hidrocarburos policíclicos aromáticos en sedimentos actuales de la Laguna de El Hito (España central)

Se llevó a cabo la evaluación ambiental y el estudio del estado actual de la cuenca de la Laguna de El Hito referido a 18 hidrocarburos policíclicos aromáticos (PAHs) de 2 a 6 anillos bencénicos. Se determinó su origen a partir de diversos índices (%naftaleno, Fen/Ant y Flu/Pir), interpretándose tanto fuentes no antropogénicas (petrogénica) como antropogénicas (pirogénica). Se obtuvieron los mapas de distribución de las concentraciones de PAHs y de sus índices para localizar los puntos de concentraciones más elevadas. Ningún PAH superó las concentraciones marcadas por los Niveles Genéricos de Referencia (NGR) para la salud humana en los distintos usos del suelo del R.D.09/2005. Los PAHs con las mayores concentraciones fueron el naftaleno y el fenantreno.Environmental evaluation and analysis of the current state of El Hito Lake Basin referred to 18 polycyclic aromatic hydrocarbons (PAHs) with 2 to 6 benzene rings was carried out. Different indexes were used to determine the source of PAHs (% naftalene, Phe/Ant and Flu/Pyr). Both non anthropogenic (petrogenic) and anthropogenic (pyrogenic) sources were interpreted. Distribution maps for PAHs and indexes were plotted to locate the position of the higher concentrations and, therefore, their possible sources. None of these compounds showed concentrations above the Soil Screening Levels (SSL) for human health in the different uses of soil as is established in R.D.09/2005. The ones that reached the highest concentrations were naphthalene and phenanthrene.

Multiresidue Analysis of Insecticides and Other Selected Environmental Contaminants in Poultry Manure by Gas Chromatography/Mass Spectrometry

An analytical method was developed for the simultaneous determination in poultry manure of 41 organic contaminants belonging to different chemical classes: pesticides, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, and polybrominated diphenyl ethers. Poultry manure was extracted with a modified QuEChERS method, and the extracts were analyzed by isotope dilution GC/MS. Recovery of these contaminants from samples spiked at levels ranging from 25 to 100 ng/g was satisfactory for all the compounds. The developed procedure provided LODs from 0.8 to 9.6 ng/g. The analysis of poultry manure samples collected on different farms confirmed the presence of some of the studied contaminants. Pyrethroids and polycyclic aromatic hydrocarbons were the main contaminants detected.

Formation of stable adducts and absence of depurinating DNA adducts in cells and DNA treated with the potent carcinogen dibenzo[a,l]pyrene or its diol epoxides

Polycyclic aromatic hydrocarbons (PAH) are widespread environmental contaminants, and some are potent carcinogens in rodents. Carcinogenic PAH are activated in cells to metabolites that react with DNA to form stable covalent DNA adducts. It has been proposed [Cavalieri, E. L. & Roger, E. G. (1995) Xenobiotica 25, 677–688] that unstable DNA adducts are also formed and that apurinic sites in the DNA resulting from unstable PAH adducts play a key role in the initiation of cancer. The potent carcinogen dibenzo[a,l]pyrene (DB[a,l]P) is activated in cells to (+)-syn- and (−)-anti-DB[a,l]P-11,12-diol-13,14-epoxide (DB[a,l]PDE), which have been shown to form stable adducts with DNA. To evaluate the importance of unstable PAH adducts, we compared stable adduct formation to apurinic site formation. Stable DB[a,l]PDE adducts were determined by 33P-postlabeling and HPLC. To measure apurinic sites they were converted to strand breaks, and these were monitored by examining the integrity of a particular restriction fragment of the dihydrofolate reductase gene. The method easily detected apurinic sites resulting from methylation by treatment of cells or DNA with dimethyl sulfate or from reaction of DNA with DB[a,l]P in the presence of horseradish peroxidase. We estimate the method could detect 0.1 apurinic site in the 14-kb fragment examined. However, apurinic sites were below our limit of detection in DNA treated directly with (+)-syn- or (−)-anti-DB[a,l]PDE or in DNA from Chinese hamster ovary B11 cells so treated, although in these samples the frequency of stable adducts ranged from 3 to 10 per 14 kb. We also treated the human mammary carcinoma cell line MCF-7 with DB[a,l]P and again could not detect significant amounts of unstable adducts. These results indicate that the proportion of stable adducts formed by DB[a,l]P activated in cells and its diol epoxides is greater than 99% and suggest a predominant role for stable DNA adducts in the carcinogenic activity of DB[a,l]P.

Health impacts of domestic coal use in China

Domestic coal combustion has had profound adverse effects on the health of millions of people worldwide. In China alone several hundred million people commonly burn raw coal in unvented stoves that permeate their homes with high levels of toxic metals and organic compounds. At least 3,000 people in Guizhou Province in southwest China are suffering from severe arsenic poisoning. The primary source of the arsenic appears to be consumption of chili peppers dried over fires fueled with high-arsenic coal. Coal samples in the region were found to contain up to 35,000 ppm arsenic. Chili peppers dried over high-arsenic coal fires adsorb 500 ppm arsenic on average. More than 10 million people in Guizhou Province and surrounding areas suffer from dental and skeletal fluorosis. The excess fluorine is caused by eating corn dried over burning briquettes made from high-fluorine coals and high-fluorine clay binders. Polycyclic aromatic hydrocarbons formed during coal combustion are believed to cause or contribute to the high incidence of esophageal and lung cancers in parts of China. Domestic coal combustion also has caused selenium poisoning and possibly mercury poisoning. Better knowledge of coal quality parameters may help to reduce some of these health problems. For example, information on concentrations and distributions of potentially toxic elements in coal may help delineate areas of a coal deposit to be avoided. Information on the modes of occurrence of these elements and the textural relations of the minerals and macerals in coal may help predict the behavior of the potentially toxic components during coal combustion.

Multilocus DNA fingerprinting reveals high rate of heritable genetic mutation in herring gulls nesting in an industrialized urban site.

Genotoxins, such as polycyclic aromatic compounds, are ubiquitous in urban and industrial environments. Our understanding of the role that these chemicals play in generating DNA sequence mutations is predominantly derived from laboratory studies with specific genotoxins or extracts of contaminants from environmental media. Most assays are not indicative of the germinal effects of exposure in situ to complex mixtures of common environmental mutagens. Using multilocus DNA fingerprinting, we found the mutation rate in herring gulls inhabiting a heavily industrialized urban harbor (Hamilton Harbour, Ontario) to be more than twice as high as three rural sites: Kent Island, Bay of Fundy; Chantry Island, Lake Huron; and Presqu'ile Provincial Park in Lake Ontario. Overall we found a mutation rate of 0.017 +/- 0.004 per offspring band in Hamilton, 0.006 +/- 0.002 at Kent Island, 0.002 +/- 0.002 from Chantry Island, and 0.004 +/- 0.002 from Presqu'ile Provincial Park. The mutation rate from the rural sites (pooled) was significantly lower than the rate observed in Hamilton Harbour (Fisher's exact test, two-tailed; P = 0.0006). These minisatellite DNA mutations may be important biomarkers for heritable genetic changes resulting from in situ exposure to environmental genotoxins in a free-living vertebrate species.

Targeted overexpression of androgen receptor with a liver-specific promoter in transgenic mice.

The rodent liver displays marked age- and sex-dependent changes in androgen sensitivity due to the sexually dimorphic and temporally programmed expression of the androgen receptor (AR) gene. We have altered this normal phenotype by constitutive overexpression of the rat AR transgene in the mouse liver by targeting it via the human phenylalanine hydroxylase (hPAH) gene promoter. These transgenic animals in their heterozygous state produce an approximately 30-fold higher level of the AR in the liver as compared with the nontransgenic control. Androgen inactivation via sulfonation of the hormone by dehydroepiandrosterone sulfotransferase (DST), an androgen-repressible enzyme, also contributes to the age- and sex-dependent regulation of hepatic androgen sensitivity. DST has a broad range of substrate specificity and is responsible for the age- and sex-specific activation of certain polycyclic aromatic hepatocarcinogens as well, by converting them to electrophilic sulfonated derivatives. In the transgenic female, the hepatic expression of DST was approximately 4-fold lower than in normal females, a level comparable to that in normal males. The hPAH-AR mice will serve as a valuable model for studying the sex- and age-invariant expression of liver-specific genes, particularly those involved in the activation of environmental hepatocarcinogens such as the aromatic hydrocarbons.

Caracterização de valores de referência de qualidade de sedimentos para compostos orgânicos no sistema estuarino da baixada santista, São Paulo

Em regiões altamente contaminadas como a região da Baixada Santista, é importante estabelecer metas para a recuperação do ambiente. Apesar da ausência da contaminação ser a meta ideal, as implicações e os custos associados a esse objetivo, demanda o estabelecimento de metas de recuperação realistas em relação aos contaminantes presentes na região. Com o objetivo de caracterizar valores de referência de qualidade de sedimentos para compostos orgânicos na região da Baixada Santista, o Canal de Bertioga foi escolhido como local de referência por ser uma região sem fontes industrais ou outras fontes pontuais relativas aos compostos analisados. Amostras de água, sedimento e ostras foram coletadas e os hidrocarbonetos policíclicos aromáticos (PAHs), bifenilos policlorados (PCBs) e pesticidas organoclorados (OCPs) foram determinados por técnicas cromatográficas. A avaliação dos resultados de análises de PAHs, permite afirmar com alguma segurança, que os valores da somatória de PAHs das amostras sedimentos são, na sua grande maioria, inferiores a 1.000 µg/kg, não superando 1.600 µg/kg, concentrações abaixo dos limites estabelecidos na Resolução CONAMA 344/04 e abaixo dos valores que possam causar algum efeito adverso à biota, conforme valores descritos na literatura. Resultados de análise de PCBs, OCPs, compostos fenólicos e compostos orgânicos voláteis (VOCs) em amostras de sedimento, indicaram concentrações destes compostos abaixo dos limites de quantificação, exceto DDE (5,30 g/kg) e HCB (2,34 g/kg), que foram detectados em apenas um ii sítio de amostragem. Não houve evidências de possíveis fontes de emissão próximas à região de referência para PCBs, OCPs, compostos fenólicos e VOCs. Finalizando, espera-se que os resultados obtidos neste estudo possam fornecer subsídios para futuramente estabelecer uma área de referência para qualidade de sedimento na região da Baixada Santista, ou ainda serem utilizados em conjunto com as avaliações de contaminantes inorgânicos, testes ecotoxicológicos e indicadores biológicos, como ferramenta para avaliação da qualidade de sedimento e/ou para a classificação de material a ser dragado na região da Baixada Santista.

A metabolomic approach to study the rhizodeposition in the tritrophic interaction: tomato, Pochonia chlamydosporia and Meloidogyne javanica

A combined chemometrics-metabolomics approach [excitation–emission matrix (EEM) fluorescence spectroscopy, nuclear magnetic resonance (NMR) and high performance liquid chromatography–mass spectrometry (HPLC–MS)] was used to analyse the rhizodeposition of the tritrophic system: tomato, the plant-parasitic nematode Meloidogyne javanica and the nematode-egg parasitic fungus Pochonia chlamydosporia. Exudates from M. javanica roots were sampled at root penetration (early) and gall development (late). EMM indicated that late root exudates from M. javanica treatments contained more aromatic amino acid compounds than the rest (control, P. chlamydosporia or P. chlamydosporia and M. javanica). 1H NMR showed that organic acids (acetate, lactate, malate, succinate and formic acid) and one unassigned aromatic compound (peak no. 22) were the most relevant metabolites in root exudates. Robust principal component analysis (PCA) grouped early exudates for nematode (PC1) or fungus presence (PC3). PCA found (PC1, 73.31 %) increased acetate and reduced lactate and an unassigned peak no. 22 characteristic of M. javanica root exudates resulting from nematode invasion and feeding. An increase of peak no. 22 (PC3, 4.82 %) characteristic of P. chlamydosporia exudates could be a plant “primer” defence. In late ones in PC3 (8.73 %) the presence of the nematode grouped the samples. HPLC–MS determined rhizosphere fingerprints of 16 (early) and 25 (late exudates) m/z signals, respectively. Late signals were exclusive from M. javanica exudates confirming EEM and 1H NMR results. A 235 m/z signal reduced in M. javanica root exudates (early and late) could be a repressed plant defense. This metabolomic approach and other rhizosphere -omics studies could help to improve plant growth and reduce nematode damage sustainably.

Decomposition of two types of electric wires considering the effect of the metal in the production of pollutants

Combustion runs at 700 °C in a horizontal laboratory furnace were carried out on two different electric wires (PVC and halogen-free wire). Tests were performed in the presence and in the absence of the metal conductor of the wires. The analyses of the polycyclic aromatic hydrocarbons (PAHs), chlorobenzenes (CBzs), chlorophenols (CPhs), mono- to octa-chlorodibenzo-p-dioxin and dibenzofurans (PCDD/Fs), and dioxin-like PCBs are shown. Regarding semivolatile compounds, PAHs production decreases in the presence of metal, while a higher amount of chlorinated compounds are emitted. Respect to the PCDD/Fs, the PVC wire in the presence of metal presents the highest emission, with a much more emission of furans than dioxins. The maximum emission is with 2 or 3 chlorine atom PCDD/Fs. PCBs emission correlates with PCDD/F production and represents 3–4% of total toxicity, determined by using WHO2005 factors.

Kinetic Analysis and Pollutant Evolution During Thermal Degradation of Printed Circuit Boards Considering the Effect of Metals

Paper submitted to the 7th International Symposium on Feedstock Recycling of Polymeric Materials (7th ISFR 2013), New Delhi, India, 23-26 October 2013.

Pollutant Formation During the Thermal Decomposition of Electrical and Electronic Wastes

Paper submitted to the 7th International Symposium on Feedstock Recycling of Polymeric Materials (7th ISFR 2013), New Delhi, India, 23-26 October 2013.

Study of the emissions from pyrolytic and oxidative thermal decomposition of PVC

Polyvinyl chloride (PVC) is one of the plastics most extensively used due to its versatility. The demand of PVC resin in Europe during 2012 reached 5000 ktonnes1. PVC waste management is a big problem because of the high volume generated all over the world and its chlorine content. End-of-life PVC is mainly mixed with municipal solid waste (MSW) and one common disposal option for this is waste-to-energy incineration (WtE). The presence of plastics such as PVC in the fuel mix increases the heating value of the fuel. PVC has two times higher energy content than MSW ‒around 20 MJ/kg vs 10 MJ/kg, respectively. However, the high chlorine content in PVC resin, 57 wt.%, may be a source for the formation of hazardous chlorinated organic pollutants in thermal processes. Chlorine present in the feedstock of WtE plants plays an important role in the formation of (i) chlorine (Cl2) and (ii) hydrochloric gas (HCl), both of them responsible for corrosion, and (iii) chlorinated organic pollutants2. In this work, pyrolytic and oxidative thermal degradation of PVC resin were carried out in a laboratory scale reactor at 500 ºC in order to analyze the influence of the reaction atmosphere on the emissions evolved. Special emphasis was put on the analysis of chlorinated organic pollutants such as polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs) and other related compounds like polychlorobenzenes (PCBzs), polychlorophenols (PCPhs) and polycyclic aromatic hydrocarbons (PAHs). Another objective of this work was to compare the results with those of a previous work3 in which emissions at different temperatures in both pyrolysis and combustion of another PVC resin had been studied; in that case, experiments for PCDD/Fs emissions had been performed only at 850 ºC.