Accumulation, responses and genotoxicity of trace elements in octopus vulgaris

Dissertação apresentada para obtenção do Grau de Doutor em Bioquímica pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Behaviour and fate of metals in urban wastewater treatment plants: a review

The concerns on metals in urban wastewater treatment plants (WWTPs) are mainly related to its contents in discharges to environment, namely in the final effluent and in the sludge produced. In the near future, more restrictive limits will be imposed to final effluents, due to the recent guidelines of the European Water Framework Directive (EUWFD). Concerning the sludge, at least seven metals (Cd, Cr, Cu, Hg, Ni, Pb and Zn) have been regulated in different countries, four of which were classified by EUWFD as priority substances and two of which were also classified as hazardous substances. Although WWTPs are not designed to remove metals, the study of metals behaviour in these systems is a crucial issue to develop predictive models that can help more effectively the regulation of pre-treatment requirements and contribute to optimize the systems to get more acceptable metal concentrations in its discharges. Relevant data have been published in the literature in recent decades concerning the occurrence/fate/behaviour of metals in WWTPs. However, the information is dispersed and not standardized in terms of parameters for comparing results. This work provides a critical review on this issue through a careful systematization, in tables and graphs, of the results reported in the literature, which allows its comparison and so its analysis, in order to conclude about the state of the art in this field. A summary of the main consensus, divergences and constraints found, as well as some recommendations, is presented as conclusions, aiming to contribute to a more concerted action of future research. © 2015, Islamic Azad University (IAU).

Investigation into the potential for establishing a self-sustainable wetland ecosystem over pyritic mine tailings

Research was conducted to investigate the potential for ecologically engineering a sustainable wetland ecosystem over pyritic mine tailings to prevent the generation of acid mine drainage. Ecological engineering is technology with the primary goal being the creation of self-sustainable ecological systems. Work involved the design and construction of a pilot-scale wetland system comprising three wetland cells, each covering 100 m2. Approximately forty tonnes of pyritic mine tailings were deposited on the base of the first cell above a synthetic liner, covered with peat, flooded and planted with emergent wetland macrophytes Typha latifolia, Phragmites australis, and Juncus effusus. The second cell was constructed as a conventional free water surface wetland, planted identically, and used as a reference wetland/experimental control. Wetland monitoring to determine long-term sustainability focused on indicators of ecosystem health including ecological, hydrological, physico-chemical, geochemical, and biotic metrics. An integrated assessment was conducted that involved field ecology in addition to ecological risk assessment. The objective of the field ecology study was to use vegetative parameters as ecological indicators for documenting wetlands success or degradation. The goal of the risk assessment was to determine if heavy-metal contamination of the wetland sediments occurred through metal mobilisation from the underlying tailings, and to evaluate if subsequent water column chemistry and biotic metal concentrations were significantly correlated with adverse wetland ecosystem impacts. Data were used to assess heavy metal bioavailability within the system as a function of metal speciation in the wetland sediments. Results indicate hydrology is the most important variable in the design and establishment of the tailings wetland and suggest a wetland cover is an ecologically viable alternative for pyritic tailings which are feasible to flood. Ecological data indicate that in terms of species richness and diversity, the tailings-wetland was exhibiting the ecological characteristics of natural wetlands within two years. Ata indicate that pH and conductivity in the tailings-wetland were not adversely impacted by the acid-generating potential or sulphate concentration of the tailings substrate and its porewater. Similarly, no enhanced seasonal impacts from sulphate or metals in the water column, nor adverse impacts on the final water quality of the outflows, were detected. Mean total metal concentrations in the sediments of the tailings-wetland indicate no significant adverse mobilisation of metals into the peat substrate from the tailings. Correlation analyses indicate a general increase in sediment metal concentration in this wetland with increasing water depth and pH, and a corresponding decrease in the metal concentrations of the water column. Sediment extractions also showed enrichment of Cd, Fe, Pb and Zn in the oxidisable fraction (including sulphides and organic matter) of the tailings-wetland sediments. These data suggest that adsorption and coprecipitation of metals is occurring from the water column of the tailings wetland with organic material at increasing depths under reducing conditions. The long-term control of metal bioavailability in the tailings wetland will likely be related to the presence and continual build-up of organic carbon binding sites in the developing wetland above the tailings. Metal speciation including free-metal ion concentration and the impact of physico-chemical parameters particularly pH and organic matter, were investigated to assess ecotoxicological risk. Results indicate that potentially bioavailable metals (the sum of the exchangeable and reducible fractions) within the tailings wetland are similar to values cited for natural wetlands. Estimated free-metal ion concentrations calculated from geochemical regression models indicate lower free-metal ion concentrations of Cd in the tailings wetland than natural wetlands and slightly higher free-metal ion concentrations of Pb and Zn. Increased concentrations of metals in roots, rhizomes and stems of emergent macrophytes did not occur in the tailings wetland. Even though a substantial number of Typha latifolia plants were found rooting directly into tailings, elevated metals were not found in these plant tissues. Phragmites also did not exhibit elevated metal concentrations in any plant tissues. Typha and Phragmites populations appear to be exhibiting metal-tolerant behaviour. The chemistry of the water column and sediments in Silvermines wetland were also investigated and were much more indicative of a wetland system impacted by heavy metal contamination than the tailings-wetland. Mean Dc, Fe, Mn, Pb and Zn concentrations in the water column and sediments of Silvermines wetlands were substantially higher than in the pilot wetlands and closely approximate concentrations in these matrices contaminated with metals from mining. In addition, mean sulphate concentration in Silvermines wetland was substantially higher and is closer to sulphate concentrations in waters associated with mining. Potentially bioavailable metals were substantially elevated in Silvermines wetland in comparison to the pilot wetlands and higher than those calculated for natural rive sediments. However, Fe oxy-hydroxide concentrations in Silvermines sediments are also much higher than in the pilot wetlands and this significantly impacts the concentration of free-metal ions in the sediment porewater. The free-metal ion concentrations for Pb and Zn indicate that Silvermines wetland is retaining metals and acting as a treatment wetland for drainage emanating from Silvermines tailings dam.

Determinació de la deposició atmosfèrica de metalls pesants a les Muntanyes de Prades (Tarragona) a partir dels bioindicadors Xanthoria parietina i Hypnum cupressiforme

En aquest estudi s’ha determinat la deposició atmosfèrica de metalls pesants a partir dels bioindicadors Xanthoria parietina (liquen) i Hypnum cupressiforme (molsa), en 16 punts de mostreig repartits per la zona on s’ubicarà el futur parc natural de les Muntanyes de Prades (Tarragona). A partir de la comparació de les concentracions obtingudes en aquest treball amb les d’altres estudis de plantejament equiparable, es va comprovar que la majoria de valors de concentració dels metalls eren similars als d’altres zones geogràfiques estudiades, a excepció del crom i el níquel, que presentaven valors clarament més elevats. A partir de proves estadístiques (ANOVA, regressions múltiples) es va determinar que existien diferències significatives entre les concentracions de metalls dels diferents punts de mostreig. També es van detectar correlacions significatives entre les concentracions dels punts de mostreig i la distància d’aquests respecte els focus potencials de contaminació que s’havien considerat prèviament. Amb les dades obtingudes a partir un petit anàlisi de la riquesa liquènica dels punts de mostreig, es va disposar d’informació extra per poder avaluar les fonts i el patró de distribució d’aquests contaminants.

A system to test the toxicity of brake wear particles

Fine particulate matter from traffic increases mortality and morbidity. An important source of traffic particles is brake wear. American studies reported cars to emit break wear particles at a rate of about 11mg/km to 20mg/km of driven distance. A German study estimated that break wear contributes about 12.5% to 21% of the total traffic particle emissions. The goal of this study was to build a system that allows the study of brake wear particle emissions during different braking behaviours of different car and brake types. The particles should be characterize in terms of size, number, metal, and elemental and organic carbon composition. In addition, the influence of different deceleration schemes on the particle composition and size distribution should be studied. Finally, this system should allow exposing human cell cultures to these particles. An exposure-box (0.25 cubic-m volume) was built that can be mounted around a car's braking system. This allows exposing cells to fresh brake wear particles. Concentrations of particle numbers, mass and surface, metals, and carbon compounds were quantified. Tests were conducted with A549 lung epithelial cells. Five different cars and two typical braking behaviours (full stop and normal deceleration) were tested. Particle number and size distribution was analysed for the first six minutes. In this time, two braking events occurred. Full stop produced significantly higher particle concentrations than normal deceleration (average of 23'000 vs. 10'400 #/cm3, p= 0.016). The particle number distribution was bi-modal with one peak at 60 to 100 nm (depending on the tested car and braking behaviour) and a second peak at 200 to 400 nm. Metal concentrations varied depending on the tested car type. Iron (range of 163 to 15'600 μg/m3) and Manganese (range of 0.9 to 135 μg/m3) were present in all samples, while Copper was absent in some samples (<6 to 1220 μg/m3). The overall "fleet" metal ratio was Fe:Cu:Mn = 128:14:1. Temperature and humidity varied little. A549-cells were successfully exposed in the various experimental settings and retained their viability. Culture supernatant was stored and cell culture samples were fixated to test for inflammatory response. Analysis of these samples is ongoing. The established system allowed testing brake wear particle emissions from real-world cars. The large variability of chemical composition and emitted amounts of brake wear particles between car models seems to be related to differences between brake pad compositions of different producers. Initial results suggest that the conditions inside the exposure box allow exposing human lung epithelial cells to freshly produced brake wear particles.

Characterization of lead-recycling facility emissions at various workplaces : major insights for sanitary risks assessment

Most available studies on lead smelter emissions deal with the environmental impact of outdoor particles, but only a few focus on air quality at workplaces. The objective of this study is to physically and chemically characterize the Pb-rich particles emitted at different workplaces in a lead recycling plant. A multi-scale characterization was conducted from bulk analysis to the level of individual particles, to assess the particles properties in relation with Pb speciation and availability. Process PM from various origins were sampled and then compared; namely Furnace and Refining PM respectively present in the smelter and at refinery workplaces, Emissions PM present in channeled emissions.These particles first differed by their morphology and size distribution, with finer particles found in emissions. Differences observed in chemical composition could be explained by the industrial processes. All PM contained the same major phases (Pb, PbS, PbO, PbSO4 and PbO·PbSO4) but differed on the nature and amount of minor phases. Due to high content in PM, Pb concentrations in the CaCl2 extractant reached relatively high values (40 mg.L-1). However, the ratios (soluble/total) of CaCl2 exchangeable Pb were relatively low (< 0.02%) in comparison with Cd (up to 18%). These results highlight the interest to assess the soluble fractions of all metals (minor and major) and discuss both total metal concentrations and ratios for risk evaluations. In most cases metal extractability increased with decreasing size of particles, in particular, lead exchangeability was highest for channeled emissions. Such type of study could help in the choice of targeted sanitary protection procedures and for further toxicological investigations. In the present context, particular attention is given to Emissions and Furnace PM. Moreover, exposure to other metals than Pb should be considered. [Authors]

Genetics of cadmium hyperaccumulation variance in Thlaspi caerulescens natural populations from Switzerland

SUMMARY Heavy metal presence in the environment is a serious concern since some of them can be toxic to plants, animals and humans once accumulated along the food chain. Cadmium (Cd) is one of the most toxic heavy metal. It is naturally present in soils at various levels and its concentration can be increased by human activities. Several plants however have naturally developed strategies allowing them to grow on heavy metal enriched soils. One of them consists in the accumulation and sequestration of heavy metals in the above-ground biomass. Some plants present in addition an extreme strategy by which they accumulate a limited number of heavy metals in their shoots in amounts 100 times superior to those expected for a non-accumulating plant in the same conditions. Understanding the genetic basis of the hyperaccumulation trait - particularly for Cd - remains an important challenge which may lead to biotechnological applications in the soil phytoremediation. In this thesis, Thlaspi caerulescens J. & C. Presl (Brassicaceae) was used as a model plant to study the Cd hyperaccumulation trait, owing to its physiological and genetic characteristics. Twenty-four wild populations were sampled in different regions of Switzerland. They were characterized for environmental and soil parameters as well as intrinsic characteristics of plants (i.e. metal concentrations in shoots). They were as well genetically characterized by AFLPs, plastid DNA polymorphism and genes markers (CAPS and microsatellites) mainly developed in this thesis. Some of the investigated genes were putatively linked to the Cd hyperaccumulation trait. Since the study of the Cd hyperaccumulation in the field is important as it allows the identification of patterns of selection, the present work offered a methodology to define the Cd hyperaccumulation capacity of populations from different habitats permitting thus their comparison in the field. We showed that Cd, Zn, Fe and Cu accumulations were linked and that populations with higher Cd hyperaccumulation capacity had higher shoot and reproductive fitness. Using our genetic data, statistical methods (Beaumont & Nichols's procedure, partial Mantel tests) were applied to identify genomic signatures of natural selection related to the Cd hyperaccumulation capacity. A significant genetic difference between populations related to their Cd hyperaccumulation capacity was revealed based on somè specific markers (AFLP and candidate genes). Polymorphism at the gene encoding IRTl (Iron-transporter also participating to the transport of Zn) was suggested as explaining part of the variation in Cd hyperaccumulation capacity of populations supporting previous physiological investigations. RÉSUMÉ La présence de métaux lourds dans l'environnement est un phénomène préoccupant. En effet, certains métaux lourds - comme le cadmium (Cd) -sont toxiques pour les plantes, les animaux et enfin, accumulés le long de la chaîne alimentaire, pour les hommes. Le Cd est naturellement présent dans le sol et sa concentration peut être accrue par différentes activités humaines. Certaines plantes ont cependant développé des stratégies leur permettant de pousser sur des sols contaminés en métaux lourds. Parmi elles, certaines accumulent et séquestrent les métaux lourds dans leurs parties aériennes. D`autres présentent une stratégie encore plus extrême. Elles accumulent un nombre limité de métaux lourds en quantités 100 fois supérieures à celles attendues pour des espèces non-accumulatrices sous de mêmes conditions. La compréhension des bases génétiques de l'hyperaccumulation -particulièrement celle du Cd - représente un défi important avec des applications concrètes en biotechnologies, tout particulièrement dans le but appliqué de la phytoremediation des sols contaminés. Dans cette thèse, Thlaspi caerulescens J. & C. Presl (Brassicaceae) a été utilisé comme modèle pour l'étude de l'hyperaccumulation du Cd de par ses caractéristiques physiologiques et génétiques. Vingt-quatre populations naturelles ont été échantillonnées en Suisse et pour chacune d'elles les paramètres environnementaux, pédologique et les caractéristiques intrinsèques aux plantes (concentrations en métaux lourds) ont été déterminés. Les populations ont été caractérisées génétiquement par des AFLP, des marqueurs chloroplastiques et des marqueurs de gènes spécifiques, particulièrement ceux potentiellement liés à l'hyperaccumulation du Cd (CAPS et microsatellites). La plupart ont été développés au cours de cette thèse. L'étude de l'hyperaccumulation du Cd en conditions naturelles est importante car elle permet d'identifier la marque, éventuelle de sélection naturelle. Ce travail offre ainsi une méthodologie pour définir et comparer la capacité des populations à hyperaccumuler le Cd dans différents habitats. Nous avons montré que les accumulations du Cd, Zn, Fe et Cu sont liées et que les populations ayant une grande capacité d'hyperaccumuler le Cd ont également une meilleure fitness végétative et reproductive. Des méthodes statistiques (l'approche de Beaumont & Nichols, tests de Martel partiels) ont été utilisées sur les données génétiques pour identifier la signature génomique de la sélection naturelle liée à la capacité d'hyperaccumuler le Cd. Une différenciation génétique des populations liée à leur capacité d'hyperaccumuler le Cd a été mise en évidence sur certains marqueurs spécifiques. En accord avec les études physiologiques connues, le polymorphisme au gène codant IRT1 (un transporteur de Fe impliqué dans le transport du Zn) pourrait expliquer une partie de la variance de la capacité des populations à hyperaccumuler le Cd.

Características geoquímicas de sedimentos del perfil Callao, Octubre 2008

Se determinó la tendencia y variabilidad vertical de las características geoquímicas de los sedimentos y del agua intersticial en los primeros 10 cm superficiales de dos testigos de Callao, colectados en dos estaciones del perfil Callao, durante el Crucero Miniox BIC Olaya 0810: (1) E-2, a 8 mn de la costa y 98 m de profundidad, donde la materia orgánica presentó un amplio rango de variabilidad (4,75% a 56,34%) y una tendencia al incremento con la profundización del perfil vertical, al existir condiciones geoquímicas que favorecen una mayor preservación de la materia orgánica y una lenta remineralización; y (2) E-5, a 30 mn de la costa y 178 m de profundidad, donde la materia orgánica presentó una distribución más homogénea en el perfil vertical (30,72% a 36,17%). Las elevadas correlaciones (r > 0,7) de la materia orgánica total con el carbono orgánico total, así como con los fosfatos y los silicatos en sedimentos superficiales indican que la materia orgánica gobierna parcialmente las concentraciones de carbono y fósforo. La variabilidad en la conducta de distribución de las concentraciones de metales Redox sensitivos en los sedimentos recientes, está asociada a condiciones anóxicas y a la intensa actividad sulfato reductora característica en la zona de estudio.

Copper, zinc and manganese in soils of two watersheds in Santa Catarina with intensive use of pig slurry

Systematic pig slurry application to crop soils may lead to the accumulation of heavy metals in regions with intensive pig raising. The aim of this study was to evaluate the accumulation of Cu, Zn and Mn in soils under systematic pig slurry application. For this purpose, soil samples were collected from two of the most representative watersheds of Santa Catarina where the predominant activity is pig raising. In each watershed, 12 properties were chosen to evaluate the different systems of pig husbandry (complete cycle (CC), farrowing (FaU) and finishing units (FiU)). Based on information of the producers, soil samples were collected in areas with and without systematic manure application. To determine the total Cu, Zn and Mn content in soils and manure, a methodology proposed by the Environmental Protection Agency of the United States (USEPA), method nº 3050B, was used. For the available heavy metal content, Cu and Zn was extracted with HCl 0.1 mol L-1 and Mn with KCl 1 mol L-1. Data were subjected to multivariate analysis, using the canonical discriminant analysis to identify the metals that best differentiate the soils studied within each swine housing system. Successive pig slurry applications cause an increase in Cu, Zn and Mn availability in the soil and this indicates the need for monitoring of the metal concentrations over time. The critical values of Cu in the soil can be reached and exceeded more rapidly than Zn. The results showed that the soil type may be one of the attribute underlying the determination of public policies in pig raising and waste management because soils such as Inceptisols were shown to be more prone to possible contamination since they may more rapidly reach total critical Cu levels.

Heavy metals in soils and plants in mango orchards in Petrolina, Pernambuco, Brazil

The monitoring of heavy metal concentrations in areas under intensive agriculture is essential for the agricultural sustainability and food safety. This paper evaluates the total contents of heavy metals in soils and mango trees in orchards of different ages (6, 7, 8, 9, 10, 11, 14, 16, 17, 19, and 26 years) in Petrolina, Pernambuco, Brazil. Soil samples were taken from the layers 0-20 cm and 20-40 cm, and mango leaves were collected in the growth stage. Areas of native vegetation (Caatinga) adjacent to the cultivated areas were used for comparison. The total concentrations of heavy metals (Cu, Cr, Fe, Zn, Mn, Ni, and Pb) were determined in soils and leaves. In general, mango cultivation led to Cu and Zn accumulation in the soil surface and to a reduction in the contents of Ni, Pb, Mn, and Fe in surface and subsurface. Since contamination by Cu, Zn, and Cr was detected, these areas must be monitored to prevent negative environmental impacts. For instance, the presence of Cr in mango tree leaves indicates the need to investigate the source of the element in these orchards. The management strategies of the different companies led to deficiency or excess of some metals in the evaluated areas. However, the Fe and Mn levels were adequate for the mineral nutrition of mango in all areas.

Genesis, Characterization, and Classification of Mangrove Soils in the Subaé River Basin, Bahia, Brazil

ABSTRACT Preservation of mangroves, a very significant ecosystem from a social, economic, and environmental viewpoint, requires knowledge on soil composition, genesis, morphology, and classification. These aspects are of paramount importance to understand the dynamics of sustainability and preservation of this natural resource. In this study mangrove soils in the Subaé river basin were described and classified and inorganic waste concentrations evaluated. Seven pedons of mangrove soil were chosen, five under fluvial influence and two under marine influence and analyzed for morphology. Samples of horizons and layers were collected for physical and chemical analyses, including heavy metals (Pb, Cd, Mn, Zn, and Fe). The moist soils were suboxidic, with Eh values below 350 mV. The pH level of the pedons under fluvial influence ranged from moderately acid to alkaline, while the pH in pedons under marine influence was around 7.0 throughout the profile. The concentration of cations in the sorting complex for all pedons, independent of fluvial or marine influence, indicated the following order: Na+>Mg2+>Ca2+>K+. Mangrove soils from the Subaé river basin under fluvial and marine influence had different morphological, physical, and chemical characteristics. The highest Pb and Cd concentrations were found in the pedons under fluvial influence, perhaps due to their closeness to the mining company Plumbum, while the concentrations in pedon P7 were lowest, due to greater distance from the factory. For containing at least one metal above the reference levels established by the National Oceanic and Atmospheric Administration (United States Environmental Protection Agency), the pedons were classified as potentially toxic. The soils were classified as Gleissolos Tiomórficos Órticos (sálicos) sódico neofluvissólico in according to the Brazilian Soil Classification System, indicating potential toxicity and very poor drainage, except for pedon P7, which was classified in the same subgroup as the others, but different in that the metal concentrations met acceptable standards.

Distribution of metals exposure and associations with cardiometabolic risk factors in the "Modeling the Epidemiologic Transition Study".

BACKGROUND: Metals are known endocrine disruptors and have been linked to cardiometabolic diseases via multiple potential mechanisms, yet few human studies have both the exposure variability and biologically-relevant phenotype data available. We sought to examine the distribution of metals exposure and potential associations with cardiometabolic risk factors in the "Modeling the Epidemiologic Transition Study" (METS), a prospective cohort study designed to assess energy balance and change in body weight, diabetes and cardiovascular disease risk in five countries at different stages of social and economic development. METHODS: Young adults (25-45 years) of African descent were enrolled (N = 500 from each site) in: Ghana, South Africa, Seychelles, Jamaica and the U.S.A. We randomly selected 150 blood samples (N = 30 from each site) to determine concentrations of selected metals (arsenic, cadmium, lead, mercury) in a subset of participants at baseline and to examine associations with cardiometabolic risk factors. RESULTS: Median (interquartile range) metal concentrations (μg/L) were: arsenic 8.5 (7.7); cadmium 0.01 (0.8); lead 16.6 (16.1); and mercury 1.5 (5.0). There were significant differences in metals concentrations by: site location, paid employment status, education, marital status, smoking, alcohol use, and fish intake. After adjusting for these covariates plus age and sex, arsenic (OR 4.1, 95% C.I. 1.2, 14.6) and lead (OR 4.0, 95% C.I. 1.6, 9.6) above the median values were significantly associated with elevated fasting glucose. These associations increased when models were further adjusted for percent body fat: arsenic (OR 5.6, 95% C.I. 1.5, 21.2) and lead (OR 5.0, 95% C.I. 2.0, 12.7). Cadmium and mercury were also related with increased odds of elevated fasting glucose, but the associations were not statistically significant. Arsenic was significantly associated with increased odds of low HDL cholesterol both with (OR 8.0, 95% C.I. 1.8, 35.0) and without (OR 5.9, 95% C.I. 1.5, 23.1) adjustment for percent body fat. CONCLUSIONS: While not consistent for all cardiometabolic disease markers, these results are suggestive of potentially important associations between metals exposure and cardiometabolic risk. Future studies will examine these associations in the larger cohort over time.

The effects of polycyclic aromatic hydrocarbons and heavy metals on terrestrial annelids in urban soils

The effect of soil contamination by polycyclic aromatic hydrocarbons (PAH) and heavy metals on earthworms and enchytraeids was studied in urban parks, in Brno, Czech Republic. In spring and autumn 2007, annelids were collected and soil samples taken in lawns along transects, at three different distances (1, 5 and 30 m) from streets with heavy traffic. In both seasons, two parks with two transects each were sampled. Earthworms were collected using the electrical octet method. Enchytraeids were extracted by the wet funnel method from soil cores. All collected annelids were counted and identified. Basic chemical parameters and concentrations of 16 PAH, Cd, Cu, Pb, and Zn were analysed from soil from each sampling point. PAH concentrations were rather low, decreasing with the distance from the street in spring but not in autumn. Heavy metal concentrations did not decrease significantly with increasing distance. Annelid densities did not significantly differ between distances, although there was a trend of increase in the number of earthworms with increasing distance. There were no significant correlations between soil content of PAH or heavy metals and earthworm or enchytraeid densities. Earthworm density and biomass were negatively correlated with soil pH; and enchytraeid density was positively correlated with soil phosphorus.

Wounding of Arabidopsis halleri leaves enhances cadmium accumulation that acts as a defense against herbivory.

Approximately 0.2 % of all angiosperms are classified as metal hyperaccumulators based on their extraordinarily high leaf metal contents, for example >1 % zinc, >0.1 % nickel or >0.01 % cadmium (Cd) in dry biomass. So far, metal hyperaccumulation has been considered to be a taxon-wide, constitutively expressed trait, the extent of which depends solely on available metal concentrations in the soil. Here we show that in the facultative metallophyte Arabidopsis halleri, both insect herbivory and mechanical wounding of leaves trigger an increase specifically in leaf Cd accumulation. Moreover, the Cd concentrations accumulated in leaves can serve as an elemental defense against herbivory by larvae of the Brassicaceae specialist small white (Pieris rapae), thus allowing the plant to take advantage of this non-essential trace element and toxin. Metal homeostasis genes are overrepresented in the systemic transcriptional response of roots to the wounding of leaves in A. halleri, supporting that leaf Cd accumulation is preceded by systemic signaling events. A similar, but quantitatively less pronounced transcriptional response was observed in A. thaliana, suggesting that the systemically regulated modulation of metal homeostasis in response to leaf wounding also occurs in non-hyperaccumulator plants. This is the first report of an environmental stimulus influencing metal hyperaccumulation.

Lentotuhkan fraktiointi sähkösuodattimella ja Ion Blast -menetelmällä

Diplomityö on osa YTI-tutkimuskeskuksessa vuosina 2002 - 2004 toteutettavaa Jätekompostit rakeiksi tuhkaseostuksella -käyttöarvon parantaminen -projektia. Työssä tutkittiin Etelä-Savon Energia Oy:n Pursialan voimalaitoksen lentotuhkan fraktioimista voimalaitoksen nykyisellä 3-kenttäisellä sähkösuodattimella ja pilot-mittakaavaisella Ion Blast -koelaitteistolla. Sähkösuodattimen koeajojen aikana muuteltiin sen ajotapaa mm. CBO -suhteen ja maksimijänniteasetuksen avulla. Ion Blast -koelaitteistolla tutkittiin mahdollisuuksia voimalaitoksen lentotuhkan puhdistamiseksi raskasmetalleista. Lentotuhkan hyötykäyttöä vaikeuttaa sen raskasmetallipitoisuuksien suuri vaihtelu. Ongelmallisin raskasmetalli puuperäisessä lentotuhkassa on kadmium, jonka lannoitelainsäädännön raja-arvo on tällä hetkellä 3 mg/kg. Sähkösuodattimella tehtyjen fraktiointikokeiden perusteella voidaan todeta raskasmetallipitoisuuksien olevan pienimmillään sähkösuodattimen 1-kentässä ja suurimmillaan 3-kentässä. Tämä johtuu siitä, että 1-kenttään kerääntyy hiukkaskooltaan suurimmat lentotuhkahiukkaset ja 3-kentässä on mukana enemmän pienhiukkasia sisältävää tuhkaa. Lannoitteeksi menevän tuhkan Cd-pitoisuutta voidaan vähentää parhaimmillaan jopa 70 % sähkösuodattimella fraktioimalla. Muiden raskasmetallien pitoisuudet eivät vähene aivan yhtä paljon. Sähkösuodattimella voidaan tulosten perusteella fraktioida lentotuhkaa. Sähkösuodattimella ei kuitenkaan voida varmasti saavuttaa alle 3 mg/kg Cd-pitoisuuksia polttoaineen laadunvaihtelun vuoksi. Ion Blast -koelaitteiston tulokset tukevat sähkösuodattimella tehtyjä kokeita. Erottimen jännitteen kasvaessa raskasmetalleja sisältävien hiukkasten erotusaste kasvaa. Ion Blast -laitteistolla tehdyissä kokeissa myös Cd-pitoisuus oli korkeimmillaan pienimmän raeluokan hiukkasissa ja laski sitten raeluokan suurentuessa. Ion Blast -laitteisto ei kuitenkaan sellaisenaan ole hyvä fraktiointiin. Se on liian tehokas, jolloin se puhdistaa tehokkaasti myös raskasmetalleja sisältävät pienhiukkaset. Jos laitetta aiotaan käyttää fraktiointiin, tulisi sen rakennetta muuttaa.