Photocatalytic activities of tin(IV) oxide surface-modified titanium(IV) dioxide show a strong sensitivity to the TiO 2 crystal form

Surface modification of rutile TiO2 with extremely small SnO2 clusters gives rise to a great increase in its UV light activity for degradation of model organic water pollutants, while the effect is much smaller for anatase TiO2. This crystal form sensitivity is rationalized in terms of the difference in the electronic modification of TiO2 through the interfacial Sn−O−Ti bonds. The increase in the density of states near the conduction band minimum of rutile by hybridization with the SnO2 cluster levels intensifies the light absorption, but this is not seen with modified anatase. The electronic transition from the valence band to the conduction band causes the bulk-to-surface interfacial electron transfer to enhance charge separation. Further, electrons relaxed to the conduction minimum are smoothly transferred to O2 due to the action of the SnO2 species as an electron transfer promoter.

Bisphenol A sorption by organo-montmorillonite: Implications for the removal of organic contaminants from water

Remediation of bisphenol A (BPA) from aqueous solutions by adsorption using organoclays synthesized from montmorillonite (MMT) with different types of organic surfactant molecules was demonstrated. High adsorption capacities of the organoclays for the uptake of BPA were observed and these demonstrated their potential application as strong adsorbents for noxious organic water contaminants. The adsorption of BPA was significantly influenced by pH, with increased adsorption of BPA in acidic pH range. However, the organoclays intercalated with highly loaded surfactants and/or large surfactant molecules were less influenced by the pH of the environment and this was thought to be due to the shielding the negative charge from surfactant molecules and the development of more positive charge on the clay surface, which leads to the attraction of anionic BPA even at alkaline pH. The hydrophobic phase created by loaded surfactant molecules contributed to a partitioning phase, interacting with BPA molecules strongly through hydrophobic interaction. Pseudo-second order kinetic model and Langmuir isotherm provided the best fit for the adsorption of BPA onto the organoclays. In addition, the adsorption process was spontaneous and exothermic with lower temperature facilitating the adsorption of BPA onto the organoclays. The described process provides a potential pathway for the removal of BPA from contaminated waters.

Effects of biochar prepared from organic waste on soil properties

Biochar is a carbon-rich solid obtained by the thermal decomposition of organic matter under a limited supply of oxygen and at relatively low temperatures. Biochar can be prepared from the pyrolysis of different organic feed- stocks, such as wood and biomass crops, agricultural by-products, different types of waste or paper industry waste materials . The pyrolysis procedure of waste, i.e. sewage sludge, has mainly two advantages, firstly, it removes pathogens from waste and, secondly, biochar can reduce the leaching of heavy metals present in raw sewage sludge. This trend of the use of waste material as feedstocks to the preparation of biochar is increasing in the last years due to industrial development and economic growth imply an increase in waste generation. The application of biochar may have positive effects on soil physical properties as water holding capacity and structure or on soil biological activity and soil quality. Also, biochar can be used to remove water pollutants and can be used in multiple ways in soil remediation due to its adsorption of pesticides or metals. Also, biochar contribute to carbon sequestration due to carbon stability of biochar materials. The objective of this presentation is to review the positive effects of the biochar prepared from organic waste on soil properties.

Identifying the Structure and Fate of Wastewater Derived Organic Micropollutants by High-resolution Mass Spectrometry

Human activities represent a significant burden on the global water cycle, with large and increasing demands placed on limited water resources by manufacturing, energy production and domestic water use. In addition to changing the quantity of available water resources, human activities lead to changes in water quality by introducing a large and often poorly-characterized array of chemical pollutants, which may negatively impact biodiversity in aquatic ecosystems, leading to impairment of valuable ecosystem functions and services. Domestic and industrial wastewaters represent a significant source of pollution to the aquatic environment due to inadequate or incomplete removal of chemicals introduced into waters by human activities. Currently, incomplete chemical characterization of treated wastewaters limits comprehensive risk assessment of this ubiquitous impact to water. In particular, a significant fraction of the organic chemical composition of treated industrial and domestic wastewaters remains uncharacterized at the molecular level. Efforts aimed at reducing the impacts of water pollution on aquatic ecosystems critically require knowledge of the composition of wastewaters to develop interventions capable of protecting our precious natural water resources.

The goal of this dissertation was to develop a robust, extensible and high-throughput framework for the comprehensive characterization of organic micropollutants in wastewaters by high-resolution accurate-mass mass spectrometry. High-resolution mass spectrometry provides the most powerful analytical technique available for assessing the occurrence and fate of organic pollutants in the water cycle. However, significant limitations in data processing, analysis and interpretation have limited this technique in achieving comprehensive characterization of organic pollutants occurring in natural and built environments. My work aimed to address these challenges by development of automated workflows for the structural characterization of organic pollutants in wastewater and wastewater impacted environments by high-resolution mass spectrometry, and to apply these methods in combination with novel data handling routines to conduct detailed fate studies of wastewater-derived organic micropollutants in the aquatic environment.

In Chapter 2, chemoinformatic tools were implemented along with novel non-targeted mass spectrometric analytical methods to characterize, map, and explore an environmentally-relevant “chemical space” in municipal wastewater. This was accomplished by characterizing the molecular composition of known wastewater-derived organic pollutants and substances that are prioritized as potential wastewater contaminants, using these databases to evaluate the pollutant-likeness of structures postulated for unknown organic compounds that I detected in wastewater extracts using high-resolution mass spectrometry approaches. Results showed that application of multiple computational mass spectrometric tools to structural elucidation of unknown organic pollutants arising in wastewaters improved the efficiency and veracity of screening approaches based on high-resolution mass spectrometry. Furthermore, structural similarity searching was essential for prioritizing substances sharing structural features with known organic pollutants or industrial and consumer chemicals that could enter the environment through use or disposal.

I then applied this comprehensive methodological and computational non-targeted analysis workflow to micropollutant fate analysis in domestic wastewaters (Chapter 3), surface waters impacted by water reuse activities (Chapter 4) and effluents of wastewater treatment facilities receiving wastewater from oil and gas extraction activities (Chapter 5). In Chapter 3, I showed that application of chemometric tools aided in the prioritization of non-targeted compounds arising at various stages of conventional wastewater treatment by partitioning high dimensional data into rational chemical categories based on knowledge of organic chemical fate processes, resulting in the classification of organic micropollutants based on their occurrence and/or removal during treatment. Similarly, in Chapter 4, high-resolution sampling and broad-spectrum targeted and non-targeted chemical analysis were applied to assess the occurrence and fate of organic micropollutants in a water reuse application, wherein reclaimed wastewater was applied for irrigation of turf grass. Results showed that organic micropollutant composition of surface waters receiving runoff from wastewater irrigated areas appeared to be minimally impacted by wastewater-derived organic micropollutants. Finally, Chapter 5 presents results of the comprehensive organic chemical composition of oil and gas wastewaters treated for surface water discharge. Concurrent analysis of effluent samples by complementary, broad-spectrum analytical techniques, revealed that low-levels of hydrophobic organic contaminants, but elevated concentrations of polymeric surfactants, which may effect the fate and analysis of contaminants of concern in oil and gas wastewaters.

Taken together, my work represents significant progress in the characterization of polar organic chemical pollutants associated with wastewater-impacted environments by high-resolution mass spectrometry. Application of these comprehensive methods to examine micropollutant fate processes in wastewater treatment systems, water reuse environments, and water applications in oil/gas exploration yielded new insights into the factors that influence transport, transformation, and persistence of organic micropollutants in these systems across an unprecedented breadth of chemical space.

Brief for GSDR - Emerging Contaminants in urban stormwater: Challenges and perspectives for sustainable water use

Emerging contaminants (ECs) are chemical compounds commonly present in water. It is only recently that this family of compounds is being recognized as significant water pollutants (. ECs include a wide variety of chemicals such as pharmaceutical and personal care products (PPCPs), pesticides, hydrocarbons and hormones, among others, that once released into the environment exert adverse impacts on the human and wildlife endocrine system. Natural attenuation and conventional treatment processes are not capable of removing these micro-pollutants detected in wastewater influent and effluent and surface and drinking water. The main challenges related with presence of ECs in stormwater in the context of reuse are: a) Development of suitable laboratory test methodologies and protocols for ECs identification and quantification b) Identification of the sources of ECs in the urban environment; c) Understanding their impacts on human and/or ecosystem health; and d). Development of cost-effective removal technologies which are appropriate for large as well as small-scale application.

Methane contamination of drinking water accompanying gas-well drilling and hydraulic fracturing.

Directional drilling and hydraulic-fracturing technologies are dramatically increasing natural-gas extraction. In aquifers overlying the Marcellus and Utica shale formations of northeastern Pennsylvania and upstate New York, we document systematic evidence for methane contamination of drinking water associated with shale-gas extraction. In active gas-extraction areas (one or more gas wells within 1 km), average and maximum methane concentrations in drinking-water wells increased with proximity to the nearest gas well and were 19.2 and 64 mg CH(4) L(-1) (n = 26), a potential explosion hazard; in contrast, dissolved methane samples in neighboring nonextraction sites (no gas wells within 1 km) within similar geologic formations and hydrogeologic regimes averaged only 1.1 mg L(-1) (P < 0.05; n = 34). Average δ(13)C-CH(4) values of dissolved methane in shallow groundwater were significantly less negative for active than for nonactive sites (-37 ± 7‰ and -54 ± 11‰, respectively; P < 0.0001). These δ(13)C-CH(4) data, coupled with the ratios of methane-to-higher-chain hydrocarbons, and δ(2)H-CH(4) values, are consistent with deeper thermogenic methane sources such as the Marcellus and Utica shales at the active sites and matched gas geochemistry from gas wells nearby. In contrast, lower-concentration samples from shallow groundwater at nonactive sites had isotopic signatures reflecting a more biogenic or mixed biogenic/thermogenic methane source. We found no evidence for contamination of drinking-water samples with deep saline brines or fracturing fluids. We conclude that greater stewardship, data, and-possibly-regulation are needed to ensure the sustainable future of shale-gas extraction and to improve public confidence in its use.

Uso de macroalgas para avaliação da Poluição orgânica no Rio Preto, noroeste do estado de São Paulo.

The Preto River, located in the northwest of São Paulo State, receives a total wastewater load of 15.150 kg DBO day-1, from which 13.685 kg DBO day-1 (90.5%) corresponds to domestic sewage, and the city of São José do Rio Preto contributes with 12.400 kg DBO day-1 (90% of domestic sewage). During the period from August 1990 through January 1991, monthly sampling was carried out to evaluate the use of macroalgae as bioindicator of organic pollution. Five sampling sites were established along the main river and the following variables were analised: temperature, conductance, turbidity, dissolved oxygen, BOD, COD, total and fecal coliforms, and composition and abundance of macroalgal communities. Data were submitted to analysis of variance, correlation coefficient, cluster analysis (four different approaches) and converted to biological indices (species deficit, relative pollution, saprobity, diversity and uniformity indices). A wide range in water quality was found (particularly for conductance, oxygen, BOD and COD) among the sampling sites, which were classified into three groups (polluted, moderately polluted and unpolluted/weakly polluted). As regards the occurrence and abundance of macroalgae the Rhodophyta were found only in unpolluted or weakly polluted sites, whereas Cyanophyta occurred mostly under high pollution load; the Chlorophyta species were observed under a wide range of conditions. Among the biological indices, saprobity was the most sensitive and correlated to all water variables and the other indices. Cluster analyses showed that the composition of macroalgal communities was consistent with the levels of organic pollution in the Preto River.

Evaluation of the combined solar TiO2/photo-Fenton process using multivariate analysis

The effect of combining the photocatalytic processes using TiO 2 and the photo-Fenton reaction with Fe3+ or ferrioxalate as a source of Fe2+ was investigated in the degradation of 4-chlorophenol (4CP) and dichloroacetic acid (DCA) using solar irradiation. Multivariate analysis was used to evaluate the role of three variables: iron, H2O2 and TiO2 concentrations. The results show that TiO2 plays a minor role when compared to iron and H2O2 in the solar degradation of 4CP and DCA in the studied conditions. However, its presence can improve TOC removal when H2O2 is totally consumed. Iron and peroxide play major roles, especially when Fe(NO3)3 used in the degradation of 4CP. No significant synergistic effect was observed by the addition of TiO 2 in this process. On the other hand, synergistic effects were observed between FeOx and TiO2 and between H 2O2 and TiO2 in the degradation of DCA. © IWA Publishing 2004.

Highly Sensitive Electrochemical Sensor for Determination of Vitamin D in Mixtures of Water-Ethanol

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

Bioremediation of PCB-contaminated marine sediments: From identification of indigenous dehalorespirers to enhancement of microbial reductive dechlorination

Marine sediments are the main accumulation reservoir of organic recalcitrant pollutants such as polychlorinated biphenyls (PCBs). In the anoxic conditions typical of these sediments, anaerobic bacteria of the phylum Chloroflexi are able to attack these compounds in a process called microbial reductive dechlorination. Such activity and members of this phylum were detected in PCB-impacted sediments of the Venice Lagoon. The aim of this work was to investigate microbial reductive dechlorination and design bioremediation approaches for marine sediments of the area. Three out of six sediment cultures from different sampling areas exhibited dechlorination activities in the same conditions of the site and two phylotypes (VLD-1 and VLD-2) were detected and correlated to this metabolism. Biostimulation was tested on enriched dechlorinating sediment cultures from the same site using five different electron donors, of which lactate was the best biostimulating agent; complementation of microbial and chemical dechlorination catalyzed by biogenic zerovalent Pd nanoparticles was not effective due to sulfide poisoning of the catalyst. A new biosurfactant-producing strain of Shewanella frigidimarina was concomitantly obtained from hydrocarbon-degrading marine cultures and selected because of the low toxicity of its product. All these findings were then exploited to develop bioremediation lab-scale tests in shaken reactors and static microcosms on real sediments and water of the Venice lagoon, testing i) a bioaugmentation approach, with a selected enriched sediment culture from the same area, ii) a biostimulation approach with lactate as electron donor, iii) a bioavailability enhancement with the supplementation of the newly-discovered biosurfactant, and iv) all possible combinations of the afore-mentioned approaches. The best bioremediation approach resulted to be a combination of bioaugmentation and bioremediation and it could be a starting point to design bioremediation process for actual marine sediments of the Venice Lagoon area.

Catchment-specific element signatures in estuarine crocodiles (Crocodylus porosus) from the Alligator Rivers Region, northern Australia

The concentrations of Na, K, Ca, Mg, Ba, Sr, Fe, Al, Mn, Zn, Pb, Cu, Ni, Cr, Co, Se, U and Ti were determined in the osteoderms and/or flesh of estuarine crocodiles (Crocodylus porosus) captured in three adjacent catchments within the Alligator Rivers Region (ARR) of northern Australia. Results from multivariate analysis of variance showed that when all metals were considered simultaneously, catchment effects were significant (P≤0.05). Despite considerable within-catchment variability, linear discriminant analysis (LDA) showed that differences in elemental signatures in the osteoderms and/or flesh of C. porosus amongst the catchments were sufficient to classify individuals accurately to their catchment of occurrence. Using cross-validation, the accuracy of classifying a crocodile to its catchment of occurrence was 76% for osteoderms and 60% for flesh. These data suggest that osteoderms provide better predictive accuracy than flesh for discriminating crocodiles amongst catchments. There was no advantage in combining the osteoderm and flesh results to increase the accuracy of classification (i.e. 67%). Based on the discriminant function coefficients for the osteoderm data, Ca, Co, Mg and U were the most important elements for discriminating amongst the three catchments. For flesh data, Ca, K, Mg, Na, Ni and Pb were the most important metals for discriminating amongst the catchments. Reasons for differences in the elemental signatures of crocodiles between catchments are generally not interpretable, due to limited data on surface water and sediment chemistry of the catchments or chemical composition of dietary items of C. porosus. From a wildlife management perspective, the provenance or source catchment(s) of 'problem' crocodiles captured at settlements or recreational areas along the ARR coastline may be established using catchment-specific elemental signatures. If the incidence of problem crocodiles can be reduced in settled or recreational areas by effective management at their source, then public safety concerns about these predators may be moderated, as well as the cost of their capture and removal. Copyright © 2002 Elsevier Science B.V.

The effect of the drug colchicine on the early life of fish

The alkaloid drug colchicine is a mitotic inhibitor. The results of this study show that colchicine influence the normal functioning of the mitotic process in Sarotherodon galilaeus, S. melanotheron and the hybrid S. galilaeus, X S. melanotheron leading to the production of unusual chromosomal events such as anaphase bridges, laggards and polyploid cells. These unusual events could have serious genetic implications in the area of variability of the chromosome number. The use of colchicine also produces results with consistent karyotypes and better morphology as well as providing detailed information on the behaviour of the chromosome of the early life of fish. The knowledge of such information will be of great use in cytotaxonomy, fish breeding and in studying the effects of sub-lethal levels of water pollutants on fish

Potential impacts of leakage from deep CO2 geosequestration on overlying freshwater aquifers.

Carbon Capture and Storage may use deep saline aquifers for CO(2) sequestration, but small CO(2) leakage could pose a risk to overlying fresh groundwater. We performed laboratory incubations of CO(2) infiltration under oxidizing conditions for >300 days on samples from four freshwater aquifers to 1) understand how CO(2) leakage affects freshwater quality; 2) develop selection criteria for deep sequestration sites based on inorganic metal contamination caused by CO(2) leaks to shallow aquifers; and 3) identify geochemical signatures for early detection criteria. After exposure to CO(2), water pH declines of 1-2 units were apparent in all aquifer samples. CO(2) caused concentrations of the alkali and alkaline earths and manganese, cobalt, nickel, and iron to increase by more than 2 orders of magnitude. Potentially dangerous uranium and barium increased throughout the entire experiment in some samples. Solid-phase metal mobility, carbonate buffering capacity, and redox state in the shallow overlying aquifers influence the impact of CO(2) leakage and should be considered when selecting deep geosequestration sites. Manganese, iron, calcium, and pH could be used as geochemical markers of a CO(2) leak, as their concentrations increase within 2 weeks of exposure to CO(2).

Environmental impacts of the coal ash spill in Kingston, Tennessee: an 18-month survey.

An 18 month investigation of the environmental impacts of the Tennessee Valley Authority (TVA) coal ash spill in Kingston, Tennessee combined with leaching experiments on the spilled TVA coal ash have revealed that leachable coal ash contaminants (LCACs), particularly arsenic, selenium, boron, strontium, and barium, have different effects on the quality of impacted environments. While LCACs levels in the downstream river water are relatively low and below the EPA drinking water and ecological thresholds, elevated levels were found in surface water with restricted water exchange and in pore water extracted from the river sediments downstream from the spill. The high concentration of arsenic (up to 2000 μg/L) is associated with some degree of anoxic conditions and predominance of the reduced arsenic species (arsenite) in the pore waters. Laboratory leaching simulations show that the pH and ash/water ratio control the LCACs' abundance and geochemical composition of the impacted water. These results have important implications for the prediction of the fate and migration of LCACs in the environment, particularly for the storage of coal combustion residues (CCRs) in holding ponds and landfills, and any potential CCRs effluents leakage into lakes, rivers, and other aquatic systems.

Survey of the potential environmental and health impacts in the immediate aftermath of the coal ash spill in Kingston, Tennessee.

An investigation of the potential environmental and health impacts in the immediate aftermath of one of the largest coal ash spills in U.S. history at the Tennessee Valley Authority (TVA) Kingston coal-burning power plant has revealed three major findings. First the surface release of coal ash with high levels of toxic elements (As = 75 mg/kg; Hg = 150 microg/kg) and radioactivity (226Ra + 228Ra = 8 pCi/g) to the environment has the potential to generate resuspended ambient fine particles (< 10 microm) containing these toxics into the atmosphere that may pose a health risk to local communities. Second, leaching of contaminants from the coal ash caused contamination of surface waters in areas of restricted water exchange, but only trace levels were found in the downstream Emory and Clinch Rivers due to river dilution. Third, the accumulation of Hg- and As-rich coal ash in river sediments has the potential to have an impact on the ecological system in the downstream rivers by fish poisoning and methylmercury formation in anaerobic river sediments.