Submitted by Jorge Silva (jorgelmsilva@ufrrj.br) on 2017-04-11T21:39:47Z No. of bitstreams: 1 2016 - Tatiana de Oliveira Pinto.pdf: 3500914 bytes, checksum: faf0cbd627200d0ed657530e3be59be3 (MD5) / Made available in DSpace on 2017-04-11T21:39:47Z (GMT). No. of bitstreams: 1 2016 - Tatiana de Oliveira Pinto.pdf: 3500914 bytes, checksum: faf0cbd627200d0ed657530e3be59be3 (MD5) Previous issue date: 2016-02-29 / CAPES / Cadmium is a heavy metal and it offers high risks to human health and it can affect ecosystem functioning at trace levels due to high toxicity, persistence time, which transcends decades and the fact that its bioavailability not diminish the long term. Rice (Oryza sativa L.) has the ability to incorporate large amounts of Cd2+ in their tissues and, therefore, today is the cereal that further incorporates this metal in the human diet by ingestion, causing serious health problems like the known disease as "Itai-Itai", whose main symptoms severe pain in bones and frequent fractures. For this reason rice plants were used in this study in combination with natural materials to assess the effects of these Cd2+. Natural materials such derived from organic matter is currently being used in the remediation of soils and effluents, but studies on the risks of its use today are scarce and often controversial. The use of humified organic matter like vermicompost and its derivatives is a sustainable alternative for the remediation of soils and sewage contaminated by heavy metals due to their chemical composition environmentally non-aggressive, low production cost and possible application in various crops. The aim of this study was to investigate the characteristics of biochar, vermicompost (VC), its solid fraction (RVC) and humin for use in the remediation of soil contaminated with Cd2+. For this was performed characterization of the interactions between the metal and the material through Freundlich and Langmuir adsorption isotherms, spectroscopic techniques CP MAS 13C-NMR and FTIR was also evaluated the ability of each material to provide Cd2+ to plants rice, by determining the root and leaf development parameters and Cd2+ content in plant tissues and the substrate. The surface morphology of the materials was performed using scanning electron microscopy (SEM). This study demonstrates that biochar used and humin are not effective materials for use in remediation. The biochar, although showing a high retention of Cd2+ allowed the bio availability of Cd2+ increasing the accumulation in tissues of rice plants. VC and RVC resulted materials with high Cd2+ retention capacity with a low availability of the metal. Specifically, the RVC can be an effective material for remediation purposes. We warn the risks of use the materials studied for soil remediation purposes contaminated with Cd2+ and propose the use of a new natural source material for phytoremediation purposes. / O C?dmio constitui um metal pesado que oferece altos riscos ? sa?de humana e que pode afetar o funcionamento do ecossistema em n?veis residuais devido ? sua alta toxicidade, seu tempo de persist?ncia, que excede d?cadas e ao fato de sua biodisponibilidade n?o diminuir a longo prazo. O arroz (Oryza sativa L.) possui a capacidade de incorporar quantidades importantes de Cd2+ em seus tecidos e, por esta raz?o, ? hoje o cereal que mais incorpora este metal na dieta humana por ingest?o, ocasionando s?rios problemas de sa?de como a doen?a conhecida como ?Itai-Itai?, que tem como principais sintomas fortes dores nos ossos e frequentes fraturas. Por esta raz?o plantas de arroz foram utilizadas neste estudo em associa??o com os materiais naturais para avalia??o dos efeitos do Cd2+ nestas. Materiais como os derivados da mat?ria org?nica vem sendo utilizados atualmente na remedia??o de solos e efluentes, por?m estudos sobre os riscos de seu uso s?o hoje escassos e muitas vezes controversos. A utiliza??o de mat?ria org?nica humificada, como Vermicomposto e seus derivados ? uma alternativa sustent?vel na remedia??o de solos e efluentes contaminados por metais pesados, devido ? sua composi??o qu?mica ambientalmente n?o agressiva, baixo custo de produ??o, e poss?vel aplica??o em diversas culturas vegetais. O objetivo deste estudo foi investigar as caracter?sticas do biochar, vermicomposto (VC), sua fra??o s?lida (RVC) e humina para serem usados na remedia??o de solos contaminados com Cd2+. Para tal foi realizada a carateriza??o das intera??es entre o metal e os materiais, atrav?s de isotermas de adsor??o de Freundlich e Langmuir, t?cnicas espectrosc?picas CP MAS 13C-RMN e FTIR, foi tamb?m avaliada a capacidade de cada material para biodisponibilizar o Cd2+ para plantas de arroz, atrav?s da determina??o de par?metros de desenvolvimento radicular e foliar e dos conte?dos de Cd2+ nos tecidos das plantas e no substrato. A morfologia da superf?cie dos materiais foi avaliada mediante microscopia eletr?nica de varredura (MEV). Este estudo demonstra que o biochar utilizado e a humina n?o s?o materiais eficientes para serem utilizados na remedia??o. O biochar, embora apresentando uma elevada reten??o de Cd2+ permitiu a biodisponibiliza??o do Cd2+ aumentando o ac?mulo nos tecidos das plantas de arroz. O VC e RVC resultaram materiais com elevada capacidade de reten??o de Cd2+ com uma baixa disponibiliza??o do metal. Especificamente o RVC pode constituir um material eficiente para fins de remedia??o. Adverte-se sobres os riscos no uso dos materiais estudados para fins de remedia??o de solos contaminados com Cd2+ e prop?em-se a utiliza??o deste novo material para fins de fitorremedia??o.

Introduction: Sexual hormone-binding globulin (SHBG) is a protein that binds to androgens and oestrogens, especially testosterone. The fraction of testosterone that is not bound to SHBG is the biologically active fraction which makes its determination more relevant than determining the total amount of circulating testosterone. It is difficult to measure the plasma concentration of free testosterone; therefore calculations using the concentrations of testosterone and SHBG are used to estimate the amount of free testosterone. A few calculations include the concentration of albumin because testosterone also binds to albumin. The main aims of this study were to verify a method for the determination of SHBG and to calculate a reference interval for free androgen index (FAI, testosterone/SHBG) in women. Other calculations for determination of the free testosterone fraction were compared. Methods: Testosterone, SHBG and albumin were measured in serum from 20 men and 100 women. Testosterone and SHBG was measured using immunoassays on a Roche Modular E instrument (ECLIA). Albumin was measured with a c8000 Architect instrument. Four calculations, two with only testosterone and SHBG and two with testosterone, SHBG and albumin were compared.  Results/Conclusion: The verification of the SHBG method was successful which means that the method can be taken into routine use. A reference interval for FAI was constructed. It was difficult to show if other estimation of free testosterone would work better than FAI in clinical practice. This is discussed.

Reductive dechlorination is a significant natural attenuation process in chloroethene-contaminated aquifers where organic carbon combined with reducing redox conditions support active dechlorinating microorganisms. At sites where natural organic carbon (NOC) associated with the aquifer matrix provides fermentable organics, the ability to measure the NOC is needed to assess the potential for the long-term sustainability of reductive dechlorination. This study focused on developing a method to measure the potentially bioavailable organic carbon (PBOC) associated with aquifer sediment. To measure NOC and evaluate its biodegradability, liquid extraction techniques on aquifer sediment were investigated. Single extractions with different extracting solutions showed that extractable organic carbon associated with the sediment ranged from 1-38% of the total organic carbon content (TOCs). Bioassay experiments demonstrated that 30-60% of the extractable organic carbon can be utilized by a microbial consortium. Alternating between 0.1% pyrophosphate and base solutions over multiple extractions increased the rate of removal efficiency and targeted two organic carbon pools. The result of the investigation was a laboratory method to quantify organic carbon from the aquifer matrix in terms of the PBOC. In the second part, the extractable PBOC was shown to biodegrade under anaerobic conditions, to produce H2 at levels necessary to maintain reductive dechlorination, and to support reductive dechlorination in enrichment cultures. For the third part of the research, the difference in extractable organic carbon inside and outside of a chloroethene-contaminated plume was examined through the combination of PBOC laboratory data and field parameters. Supported by ground-water constituent data, the PBOC extraction and bioassay studies showed that less extractable organic carbon was present inside than outside of the chloroethene plume. The final part of the research investigated the distribution of PBOC extractions across six contaminated sites. PBOC extractions were directly correlated to the TOCs, soft carbon content, and level of reductive dechlorination activity at the sites. Based on these correlations, a range for organic carbon potentially available to subsurface microorganisms was proposed where the upper bound consisted of the soft carbon and the lower bound consisted of the PBOC. / Ph. D.

Groundwater remediation strategies have advanced toward more effective and economical remedial technologies. Monitored natural attenuation (MNA) has become accepted by federal regulatory agencies as a viable remediation strategy for contaminants under site-specific conditions. At chloroethene contaminated sites where MNA is used as a remediation strategy, microbially-mediated reductive dechlorination is typically the dominant pathway for natural attenuation. The efficacy of reductive dechlorination at sites with no anthropogenic carbon sources is often influenced by the availability of readily-biodegradable natural organic carbon along with favorable geochemical conditions for supporting microbial dehalogenation. Recent research studies have suggested that the pool of labile natural organic carbon, operationally defined as potentially bioavailable organic carbon (PBOC), may be a critical component related to sustaining reductive dechlorination at MNA sites. The objective of this study was to evaluate PBOC as a quantitative measure of the labile organic carbon fraction of aquifer sediments in relation to microbial reductive dechlorination of chlorinated solvents. In the first phase of this study, the variability of PBOC in aquifer sediments was examined among 15 chloroethene contaminated sites. Results showed that PBOC displayed considerable variability among the study sites, ranging over four orders of magnitude. Regression results demonstrated that a positive correlation existed between PBOC, solid phase total organic carbon (TOCs), and reductive dechlorination activity at the sites. Results supported that greater levels of PBOC and TOCs corresponded to higher reductive dechlorination activity at the sites. Composition results showed that 6-86% of PBOC consisted of proteins and amino acids. Results also suggested a positive relationship existed between PBOC, concentrations of potentially bioavailable organic compounds present in the aquifer system, expressed as hydrolyzable amino acids (HAA), and the natural attenuation capacity (NAC) at the sites. Higher PBOC levels were consistently observed at sites with greater NAC and levels of HAA. The results of this study suggested that the variability of PBOC in the aquifer sediments exhibited a reasonable correlation with TOCs, hydrolyzable amino acids, and chloroethene transformation among the selected sites. In the second phase of this study, the relationship between PBOC in aquifer sediments and site specific performance data was evaluated among 12 chloroethene contaminated sites. Results demonstrated that PBOC in aquifer sediments was directly correlated to independent field metrics associated with reductive dechlorination. Levels of PBOC demonstrated direct relationships with hydrogen (H2) and dissolved oxygen (DO) concentrations within the groundwater system at the selected study sites. Results also indicated that PBOC demonstrated positive relationships with reductive dechlorination activity and the natural attenuation capacity of the sites. The findings of this study suggested that the level of PBOC in aquifer sediments may be a key factor in sustaining conditions favorable for microbial reductive dechlorination. In the third phase of this study, the distribution of PBOC was investigated at a chloroethene contaminated site. PBOC was measured in surficial aquifer sediment samples collected at varying depths in the vicinity of a chloroethene plume. Results demonstrated that levels of PBOC were consistently higher in aquifer sediments with minimal chloroethene exposure relative to samples collected in the PCE-contaminated source zone. Regression results demonstrated that a statistically significant inverse correlation existed between PBOC levels and chloroethene concentrations for selected temporary wells in the contaminated source zone at the study site. Consistent with these findings, results also indicated a similar trend of increased PBOC in aquifer sediments outside the chloroethene plume relative to aquifer sediments inside the plume. Results from this study further suggested that differences in extracted carbon levels at the site for surficial aquifer sediment samples in the PCE-contaminated source zone could impact the extent of reductive dechlorination within the hydrographic unit. / Ph. D.

A cation exchange method (Chelex 100) that distinguishes weakly bound and strongly bound copper was investigated for its ability to measure bioavailable copper in estuarine waters. Copper bound to the Chelex 100 resin was operationally defined as bioavailable copper. Varying initial copper concentration from 195 to 495 ug/L at a constant 12.5 mg/L natural organic matter (NOM) did not affect percent bioavailability. There were also no noticeable effects when varying total Cu concentration in the presence of 0, 12, and 24 mg/L NOM. An increase in pH from 4 to 8.5 and NOM from 0 mg/L to 12.5 mg/L reduced percent bioavailability. Using the Chelex 100 resin to measure bioavailable copper, about 20 to 40% of the total copper was bioavailable in the absence of NOM, while about 15 to 20% was bioavailable when either 12 or 24 mg/L NOM was present. Acute toxicity bioassays were performed with mysid shrimp (Americamysis bahia) to evaluate the toxic effects of copper in the presence of Suwannee River Fulvic Acid, which served as a source of NOM. Static or static renewal tests, based on EPA method OPPTS 850.1035 with a minimum of 10 mysid shrimp per test condition, were used to determine the LC50 and EC50 of copper and the effects of NOM. Test solutions consisted of artificial synthetic seawater at 20 parts per thousand containing concentrations of 0, 100, 200, 400, 800 ug/L copper with either 0, 12, 24 mg/L NOM. Forty-eight hour acute toxicity tests were performed on larval (2 to 3 day) mysid shrimp that were fed Artemia (brine shrimp); mortality and immobilization were the endpoints. The 48 hour LC50 was 200 ug/L dissolved Cu and 94 ug/L bioavailable Cu without NOM, 340 ug/L dissolved Cu and 98 ug/L bioavailable Cu when 12 mg/L NOM was present, and 495 ug/L dissolved Cu and 105 ug/L bioavailable Cu at 24 mg/L NOM. The consistency of the LC50 measurement using bioavailable Cu suggest that the Chelex 100 resin is a useful technique for toxicity analysis in saline water. / Master of Science

Chlorinated ethenes are considered one of the most prevalent sources of groundwater contamination in developed countries. Natural attenuation of chlorinated ethenes is possible through the process of microbial reductive dechlorination. Reductive dechlorination can occur in contaminated aquifers where there are sufficient amounts of organic carbon and reducing redox conditions to support dechlorinating microorganisms. Natural organic carbon (NOC) from dissolved aquifer sediment is thought to be the source of fermentable compounds needed to produce molecular hydrogen that functions as the primary electron donor for reductive dechlorination. Therefore, in an anaerobic aquifer, the production of molecular hydrogen from the fermentation of NOC drives the reductive dechlorination process. The variability and distribution of potential bioavailable organic carbon (PBOC) at a site is relatively unknown and any potential relationships between PBOC and the physical properties of the aquifer sediment have not been evaluated. Exploring relationships between the grain size of aquifer sediment PBOC may help to determine the feasibility of natural attenuation as a long-term remediation strategy at chlorinated ethene-contaminated sites. Because hydraulic conductivity is directly related to aquifer sediment grain size, zones of high hydraulic conductivity may promote greater microbial activity or biodegradation because of the increased availability of PBOC and nutrient flux. To determine potential relationships between PBOC and aquifer sediment grain size, two experiments were performed. PBOC was measured for 106 sediment samples impacted by chlorinated solvent contamination from an anaerobic type II site through a multiple liquid extraction process (Rectanus et al. 2007). Grain size distributions for each of the 106 sediment samples were determined by conducting sieve analyses. The results of both experiments were compared to explore relationships between PBOC and sediment grain size and to evaluate spatial distribution of both in the surficial aquifer. / Master of Science

Contaminants can exist in a wide range of states in aqueous environments, especially in surface waters. They can be freely dissolved or associated with dissolved or particulate organic matter depending on their chemical and physical characteristics. The freely dissolved fraction represents the most bioavailable fraction to an organism. These freely dissolved contaminants can cross biomembranes, potentially exerting toxic effects. Passive sampling devices (PSDs) have been developed to aid in sampling many of these contaminants by having the ability to distinguish between the freely dissolved and bound fraction of a contaminant. A new PSD, the Lipid-Free Tube (LFT) sampler was developed in response to some of the shortcomings of other current PSD that sample hydrophobic organic contaminants (HOCs). The device and laboratory methods were original modeled after a widely utilized PSD, the semipermeable membrane device (SPMD), and then improved upon. The effectiveness, efficiency, and sensitivity of not only the PSD itself, but also the laboratory methods were investigated. One requirement during LFT development was to ensure LFTs could be coupled with biological analyses without deleterious results. In an embryonic zebrafish developmental toxicity assay, embryos exposed to un-fortified LFT extracts did not show significant adverse biological response as compared to controls. Also, LFT technology lends itself to easy application in monitoring pesticides at remote sampling sites. LFTs were utilized during a series of training exchanges between Oregon State University and the Centre de Recherches en Ecotoxicologie pour le Sahel (CERES)/LOCUSTOX laboratory in Dakar, Senegal that sought to build "in country" analytical capacity. Application of LFTs as biological surrogates for predicting potential human health risk endpoints, such as those in a public health assessment was also investigated. LFT mass and accumulated contaminant masses were used directly, representing the amount of contaminants an organism would be exposed to through partitioning assuming steady state without metabolism. These exposure concentrations allow for calculating potential health risks in a human health risk model. LFT prove to be a robust tool not only for assessing bioavailable water concentrations of HOCs, but also potentially providing many insights into the toxicological significance of aquatic contaminants and mixtures. / Graduation date: 2010

[Truncated abstract] Eleven sites, each with the trio of land uses: Eucalyptus globulus plantation, pasture and natural vegetation, representing from the Mediterranean climate, high rainfall region (<550 mm annually) of south-western Australia were investigated to assess medium-term changes in the P-supplying capacity of soils in eucalypt plantations growing on agricultural land. The natural vegetation soils were a benchmark for comparing soil P change since land clearing and development for agriculture. The experimental framework provided an ideal basis for studying changes in P forms since land clearing and fertilization for agriculture and the ensuing conversion to plantations (on an average 9 years ago). Conventional soil P indices measure plant available P that is more relevant to short duration annual crops and pastures. To predict medium-term P availability, P forms were determined using Hedley et al.’s (1982) fractionation scheme and fractions were grouped using the Guo and Youst (1998) criteria into readily, moderately and sparingly available P. The P species were also determined by 31P NMR spectroscopy of 0.5M NaOH-0.1M EDTA extracts. Hedley et al.’s (1982) inorganic P extracted by anion exchange resin and by NaHCO3 are widely considered to be approximations to the actual plant available P. The availability to plants of other P fractions is less certain and this is examined in an experiment to compare the plant availability of various P fractions in soils from fertilized and unfertilized land uses following exhaustive cropping in the glasshouse. The soil texture for the sites studied included coarse sand, loamy sand, clayey sand, and sandy loam. Surface soils (0-10 cm) have pH(CaCl2) in the acidic range (mean 4.4) and there is no significant difference due to differences in land use (P<0.05). The soils are of low EC (1:5 H2O) - 6 mS m-1. There is an almost 5-fold variation in organic C among sites (from 1.4% to 8%) but organic C values did not show any significant effect (P<0.05) of changes in land use. To evaluate the degree of similarity of soils within each triplet set at a site principal component analysis was carried out on those soil chemical⁄mineralogical characteristics that were least likely to be affected by changes in land use practices. This analysis showed good matching of the triplet of sub-sites on the whole, especially for the duo of pasture and plantation land uses. This degree of matching of the trio of land uses was considered while interpreting the effects of land use on the forms and behaviour of soil P, and variations due to various extents of mismatch were mostly addressed using statistical techniques including regression analysis to interpret sub-site difference

No description available.

Passive sampling, as opposed to the conventional spot or bottle water sampling technique, has shown to be reliable and efficient in monitoring the toxicologically relevant, freely dissolved (e.g. bioavaialable) concentrations of a wide range of organic contaminants in water. At the same time, partitioning controlled delivery (passive dosing; PD) techniques promise to overcome many of the challenges associated with toxicity testing of hydrophobic substances that may bias the interpretation of toxicity data. The present study investigated the feasibility of coupling silicone rubber passive sampling devices (SR-PSDs) with bioassay techniques for both chemical and ecotoxicological assessment of complex mixtures of organic contaminants in the aquatic environment. SR-PSDs were deployed in water at various locations within the Ythan catchment (north east, Scotland, UK), Forth estuary and the Firth of Forth (east coast of central Scotland, UK) for 7 to 9 weeks. Following retrieval, extracts from the SR-PSDs were analysed for dissolved concentrations of a variety of organic contaminants including PAHs and PCBs using GC-MS and GC-ECD respectively and were screened for a wide range of pesticides using GC-MS/MS and LC-MS/MS. The extracts were further evaluated for acute cytotoxicity (i.e. neutral red uptake assay) and EROD induction potential using rainbow trout liver cell line (Oncorhynchus mykiss; RTL-W1) and for phytotoxicity and developmental toxicity potential using algal growth inhibition test (with a marine phytoplankton, Diacronema lutheri) and fish embryo toxicity test (with embryos from zebrafish Danio rerio) respectively. Overall, the individual and total dissolved concentrations of PAHs (ΣPAH40; parent and branched) and PCBs (ΣPCB32; ortho and mono-ortho) measured in water from the Ythan, Forth estuary and Firth of Forth were relatively low compared with other studies using PSDs. A number and level of pesticides, including insecticides, herbicides and fungicides of varying hydrophobicity (log KOWs ~2.25 to ~5.31) were detected in the silicone rubber (SR) extracts from the Ythan catchment, the Forth estuary and the Firth of Forth, suggesting input mainly from agricultural run-off and possibly from direct discharges. No statistically significant (p<0.05) acute cytotoxicity was observed following 48 h exposure of RTL-W1 cells to SR extracts from the Ythan catchment. But, on a sublethal level, for every site, statistically significant EROD activity was observed to some degree following 72 h exposure. In addition, developmental and algal toxicities on embryos of D. rerio and D. lutheri respectively, were measured in all the deployed samples compared with the procedural controls (undeployed samples). Interestingly, extracts of SR-PSDs from the Forth estuary and the Firth of Forth exhibited growth inhibitions on D. lutheri that were similar to those of extracts from the Ythan, even though, fewer numbers of pesticides were detected in the Forth estuary and Firth of Forth than the Ythan. This suggests that pesticides were not solely responsible for the observed effects in the Ythan catchment. To further improve data from toxicity testing of hydrophobic substances, the study identified the use of SR O-rings as a suitable passive dosing format in in vitro toxicity tests and was partially validated through their use in dosing RTL-W1 cells with two individual PAHs and subsequently determining cytotoxicity and EROD-activity.