Geological and hydrogeological features affecting migration, multi-phase partitioning and degradation of chlorinated hydrocarbons through unconsolidated porous media.

Chlorinated solvents are the most ubiquitous organic contaminants found in groundwater since the last five decades. They generally reach groundwater as Dense Non-Aqueous Phase Liquid (DNAPL). This phase can migrate through aquifers, and also through aquitards, in ways that aqueous contaminants cannot. The complex phase partitioning to which chlorinated solvent DNAPLs can undergo (i.e. to the dissolved, vapor or sorbed phase), as well as their transformations (e.g. degradation), depend on the physico-chemical properties of the contaminants themselves and on features of the hydrogeological system. The main goal of the thesis is to provide new knowledge for the future investigations of sites contaminated by DNAPLs in alluvial settings, proposing innovative investigative approaches and emphasizing some of the key issues and main criticalities of this kind of contaminants in such a setting. To achieve this goal, the hydrogeologic setting below the city of Ferrara (Po plain, northern Italy), which is affected by scattered contamination by chlorinated solvents, has been investigated at different scales (regional and site specific), both from an intrinsic (i.e. groundwater flow systems) and specific (i.e. chlorinated solvent DNAPL behavior) point of view. Detailed investigations were carried out in particular in one selected test-site, known as “Caretti site”, where high-resolution vertical profiling of different kind of data were collected by means of multilevel monitoring systems and other innovative sampling and analytical techniques. This allowed to achieve a deep geological and hydrogeological knowledge of the system and to reconstruct in detail the architecture of contaminants in relationship to the features of the hosting porous medium. The results achieved in this thesis are useful not only at local scale, e.g. employable to interpret the origin of contamination in other sites of the Ferrara area, but also at global scale, in order to address future remediation and protection actions of similar hydrogeologic settings.

Transport of volatile chlorinated hydrocarbons in unsaturated aggregated media

Transport of volatile hydrocarbons in soils is largely controlled by interactions of vapours with the liquid and solid phase. Sorption on solids of gaseous or dissolved comPounds may be important. Since the contact time between a chemical and a specific sorption site can be rather short, kinetic or mass-transfer resistance effects may be relevant. An existing mathematical model describing advection and diffusion in the gas phase and diffusional transport from the gaseous phase into an intra-aggregate water phase is modified to include linear kinetic sorption on ps-solid and water-solid interfaces. The model accounts for kinetic mass transfer between all three phases in a soil. The solution of the Laplace-transformed equations is inverted numerically. We performed transient column experiments with 1,1,2-Trichloroethane, Trichloroethylene, and Tetrachloroethylene using air-dry solid and water-saturated porous glass beads. The breakthrough curves were calculated based on independently estimated parameters. The model calculations agree well with experimental data. The different transport behaviour of the three compounds in our system primarily depends on Henry's constants.

Concentrations of aliphatic hydrocarbons and hexachlorocyclohexane isomers in under-ice water, snow, and sea ice from the Greenland Sea

Data on concentrations of aliphatic hydrocarbons and isomers of hexachlorocyclohexane in specimens of various natural environments (water, snow, and ice) of the Greenland Sea obtained during field studies on the ice breaker Otto Shmidt are presented. Analyses were carried out with gas chromatographs using capillary and packed columns. Concentrations of aliphatic and chlorinated hydrocarbons were higher in snow and ice specimens than in sea water and were also higher in less saline water beneath ice. It is concluded that pollutants in this ocean area are at the background level.

Influence of ventilation type in volatile organic compounds exposure: poultry case

Agricultural workers especially poultry farmers are at increased risk of occupational respiratory diseases. Epidemiological studies showed increased prevalence of respiratory symptoms and adverse changes in pulmonary function parameters in poultry workers. In poultry production volatile organic compounds (VOCs) presence can be due to some compounds produced by molds that are volatile and are released directly into the air. These are known as microbial volatile organic compounds (MVOCs). Because these compounds often have strong and/or unpleasant odors, they can be the source of odors associated with molds. MVOC's are products of the microorganisms primary and secondary metabolism and are composed of low molecular weight alcohols, aldehydes, amines, ketones, terpenes, aromatic and chlorinated hydrocarbons, and sulfur-based compounds, all of which are variations of carbon-based molecules.

Pienten yksiköiden talousveden laatuvaatimukset ja - suositukset

Talousvesi sisältää paljon erilaisia yhdisteitä, joista osa on ihmiselle haitallisia, tällaisia yhdisteitä ovat muun muassa klooratut hiilivedyt. Haitallisten yhdisteiden määrän minimoimiseksi talousvedessä talousveden vieraille aineille on määrätty asetuksissa enimmäispitoisuuksia sekä – tiheyksiä. Näitä laatuvaatimuksia sekä – suosituksia noudattamalla talousvesi on käyttökelpoista. Talousvedellä ei tällöin ole haitallisia terveysvaikutuksia eikä se vahingoita vesilinjastoja. Kirjallisuusosassa selvitetään pienten yksiköiden talousveteen liittyvän sosiaali- ja terveysministeriön asetuksen sisältöä. Mitä asetus pitää sisällään, keitä asetus koskee ja miksi asetukseen kirjatut yhdisteet ja aineet ovat ihmiselle haitallisia sekä mitä terveysvaikutuksia kyseisillä aineilla on. Kokeellisessa osiossa analysoitiin kolmesta näytteestä osa sosiaali- ja terveysministeriön asettamista vaatimuksista. Pääsääntöisesti mitattiin epäorgaanisia aineita sekä ioneja. Mittaukset suoritettiin ionikromatografilla, liekki-atomiabsorptiospektrometrillä, TOC-analysaattorilla, COD-putkilla, pH-, johtokyky- sekä sameusmittarilla.

Physiological effects of copper (II) on sunetta scripta L.

In India industrial pollution has become a subject of increasing concern.Incidents of industrial pollution have been reported from many parts of the country. Cochin, the collection site of the present study, being the industrial capital of Kerela is also a harbour, is vulnerable to pollution by trace metal contaminants. In the recent times, pollutants of greatest concern in the aquatic environment are those which are persistent such as toxic heavy metals and the chlorinated hydrocarbons which include insecticides and pesticides.The animals collected from the clam bed situated on the northern side af Cochin bermouth are subject to wide fluctuations in salinity both seasonal and tidal. also; salinity is considered as an important parameter influencing the.-physiological functioning of an organism. Hence, the salinity tolerance of the animal is worked out. Considering the potential vulnerability of Cochin backwaters to heavy metal pollution, the impact of heavy metal copper (II) on the bivalve Sunetta sripta was conceived. Static bioassays were conducted for the determination of the sublethal concentrations of the metal as a preliminary step towards the toxicity studies. Oxygen consumption and filtration rate which are considered as reliable sublethal toxicity indices were employed for investigating the toxic effects of the metal. Bioaccumulation, a physiological phenomenon which can be of importance from the public health point of view, and also in the assessment of environmental quality is also dealt with.

Compromiso neurológico periférico y exposición a plaguicidas en cultivadores de arroz en una zona rural, Colombia.

Objetivos Mediante un estudio descriptivo transversal, establecer la presencia de una relación entre los niveles de exposición a plaguicidas con la presencia de hallazgos clínicos neurológicos periféricos en personas expuestas ocupacionalmente a estos. Resultados La muestra poblacional fue de 59 trabajadores, en el área rural del municipio del Espinal, Tolima. El 52% de la población refirió usar organofosforados, 32 % carbamatos, 16% organoclorados, y 66% otros grupos de plaguicidas. Los niveles sanguíneos de carbamatos estuvieron presentes en el 7% de la población, organofosforados en el 66% y organoclorados en el 100%. En el 42% de la población se estableció sospecha de neuropatía a partir de los síntomas y en el 92% a partir de los signos. Se estableció asociación estadísticamente significativa entre los niveles sanguíneos de determinados organoclorados con la sospecha de neuropatía periférica a partir de síntomas; la presencia de sensación de pérdida de la fuerza en extremidades y la presencia de alteraciones en los reflejos osteotendinosos. Conclusiones El presente estudio permitió identificar los plaguicidas a los cuales está expuesta la población agrícola del municipio del Espinal así como corrobora el efecto de bioacumulación y biomagnificación de los organoclorados. Adicionalmente, se detectó la presencia de hallazgos sugestivos de compromiso neurológico periférico, con asociaciones significativas entre ciertas anormalidades y determinados organoclorados. Este estudio es una aproximación a la relación entre la exposición a plaguicidas de la población agrícola de la zona rural del municipio del Espinal con la secuelas neurológicos periféricas asociadas a esta.

One-pot synthesis and characterization of soluble poly(aryl ether-ketone)s having pendant carboxyl groups

Aromatic poly(ether-ketone)s having pendant carboxyl groups have been obtained by direct, one-pot, Friedel-Crafts copolycondensation of 4,4'-diphenoxybenzophenone with a mixture of terephthaloyl chloride (TC) and trimellitic anhydride acid chloride (TAAC), over a wide range of TAAC/TC molar ratios, in the presence of anhydrous aluminum chloride. The syntheses were performed as precipitation-polycondensations, and the polymers were obtained in particulate form. Besides globular particles of polymer, small quantities of elongated, needlelike particles were observed when the mole ratio TAAC/TC was less than 1. Use of X-ray microdiffraction with synchrotron radiation has revealed that the needlelike material consists of a cyclic compound containing 10 phenylene units, i.e., the crystals are of a [2 + 2] macrocyclic dimer. The polymers obtained are soluble in strong acids and in mixtures of methanesulfonic acid or trifluoroacetic acid with chlorinated hydrocarbons. The molecular structures of the polymers were confirmed by H-1 and C-13 NMR spectroscopy. Reaction of TAAC with 4,4'-diphenoxybenzophenone produced mainly meta-orientation of the resulting ketone linkages. The size of the polymer particles, their molecular weights, and the melting behavior of the products obtained depend on the TAAC/TC ratio used. Ortho-keto acid residues, formed during reaction of anhydride groups of TAAC with 4,4'-diphenoxybenzophenone, exhibit ring-chain tautomerism. A carboxyl-containing aromatic polyketone derived from p-terphenyl, and thus having with no ether linkages in the main chain, was prepared by analogous chemistry, and functional derivatives of carboxy-substituted polyketones were also obtained and characterized.

Levels of persistent organic pollutants and residual pattern of DDTs in small cetaceans from the coast of São Paulo, Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Accumulation of semivolatile organic compounds in Antarctic vegetation: A case study of polybrominated diphenyl ethers

Antarctic plant communities are dominated by lichens and mosses which accumulate semivolatile organic compounds (SOCs) such as polybrominated diphenyl ethers (PBDEs) directly from the atmosphere. Differences in the levels of PBDEs observed in lichens and mosses collected at King George Island in the austral summers 2004-05 and 2005-06 are probably explained by environmental and/or plant parameters. Contamination of lichens showed a positive correlation with local precipitation, suggesting that wet deposition processes are a major mechanism controlling the uptake of most PBDE congeners. These findings are in agreement with physical-chemical data supporting that tetra- through hepta-BDEs in the Antarctic atmosphere are basically bound to aerosols. Conversely, accumulation of PBDEs in mosses appears to be controlled by other environmental factors and/or plant-specific characteristics. Model simulations demonstrated that an ocean-atmosphere coupling may have played a role in the long-range transport of less volatile SOCs such as PBDEs to Antarctica. According to simulations, the atmosphere is the most important transport medium for PBDEs while the surface ocean serves as a temporary storage compartment, boosting the deposition/volatilization ""hopping"" effect similarly to vegetation on continents. (C) 2011 Elsevier B.V. All rights reserved.

Levels of persistent organic pollutants and residual pattern of DDTs in small cetaceans from the coast of Sao Paulo, Brazil

The State of Sao Paulo is the most developed area in Brazil and was impacted by persistent organic pollutants for several decades. This study investigated organochlorines in five species of small cetaceans (Pontoporia blainvillei, Stenella frontalis, Sotalia guianensis, Tursiops truncatus and Steno bredanensis) found dead along the coast of Sao Paulo between 1997 and 2003. DDTs (15.9 mu g g(-1) lipid: mean for all pooled individuals) and PCBs (8.08 mu g g(-1)) exhibited the highest concentrations in the animals, reflecting large amounts formerly used in Brazil. Lower levels of mirex (0.149 mu g g(-1)), HCB (0.051 mu g g(-1)), CHLs (0.008 mu g g(-1)) and HCHs (0.007 mu g g(-1)) were detected in all species. Residual pattern of DDTs in dolphins suggests that o,p`-DDT is more recalcitrant than p,p`-DDT in the body of the animals and/or the environment. In contrast to p,p`-DDT, residues of o,p`-DDT seem to be preferentially converted into o,p`-DDD rather than op-DDE. (C) 2010 Elsevier Ltd. All rights reserved.

Organochlorine contaminants in albatrosses and petrels during migration in South Atlantic Ocean

Albatrosses and petrels (Procellariiformes) are migratory oceanic birds of considerable conservational interest. Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed in the subcutaneous fat, liver and muscle of 100 birds belonging to eight species of Procellariiformes collected during their migration period in southern Brazil, one of the most important feeding areas for these species. Although the profiles of PCBs and OCPs were similar among the individuals, with predominance of penta, hexa and heptachlorobiphenyls and p'p-DDE, organochlorine concentrations exhibited a high degree of intra-species variability. The influence of body condition during the migration period in the distribution of organochlorine contaminants was also evaluated, showing that it is a significant factor in the variation and redistribution of these compounds in the tissues of these birds. The intense use of lipid reserves associated to the contamination from organochlorine compounds could be a troubling factor for seabirds with extended breeding periods and that spend most of their lives at sea migrating long distances, such as most of Procellariiformes. Studies on contamination are necessary to improve the knowledge of the threats to these birds and their populations as well as to contribute with information about persistent organic pollutants in the South Atlantic marine environment.