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.

Transformation to "high grade" neuroendocrine carcinoma as an acquired drug resistance mechanism in EGFR-mutant lung adenocarcinoma.

Several different acquired resistance mechanisms of EGFR mutant lung adenocarcinoma to EGFR-tyrosine kinase inhibitor (TKI) therapy have been described, most recently transformation to small cell lung carcinoma (SCLC). We describe the case of a 46-year-old female with relapsed EGFR exon 19 deletion lung adenocarcinoma treated with erlotinib, and on resistance, cisplatin-pemetrexed. Liver rebiopsy identified an afatinib-resistant combined SCLC and non-small cell carcinoma with neuroendocrine morphology, retaining the EGFR exon 19 deletion. This case highlights acquired EGFR-TKI resistance through transformation to the high-grade neuroendocrine carcinoma spectrum and that that such transformation may not be evident at time of progression on TKI therapy.

Nitrogen use efficiency and optimization of nitrogen fertilizer application for stable yields and high quality of cereals grown in conservation agriculture

In most agroecosystems, nitrogen (N) is the most important nutrient limiting plant growth. One management strategy that affects N cycling and N use efficiency (NUE) is conservation agriculture (CA), an agricultural system based on a combination of minimum tillage, crop residue retention and crop rotation. Available results on the optimization of NUE in CA are inconsistent and studies that cover all three components of CA are scarce. Presently, CA is promoted in the Yaqui Valley in Northern Mexico, the country´s major wheat-producing area in which from 1968 to 1995, fertilizer application rates for the cultivation of irrigated durum wheat (Triticum durum L.) at 6 t ha-1 increased from 80 to 250 kg ha-1, demonstrating the high intensification potential in this region. Given major knowledge gaps on N availability in CA this thesis summarizes the current knowledge of N management in CA and provides insights in the effects of tillage practice, residue management and crop rotation on wheat grain quality and N cycling. Major aims of the study were to identify N fertilizer application strategies that improve N use efficiency and reduce N immobilization in CA with the ultimate goal to stabilize cereal yields, maintain grain quality, minimize N losses into the environment and reduce farmers’ input costs. Soil physical and chemical properties in CA were measured and compared with those in conventional systems and permanent beds with residue burning focusing on their relationship to plant N uptake and N cycling in the soil and how they are affected by tillage and N fertilizer timing, method and doses. For N fertilizer management, we analyzed how placement, time and amount of N fertilizer influenced yield and quality parameters of durum and bread wheat in CA systems. Overall, grain quality parameters, in particular grain protein concentration decreased with zero-tillage and increasing amount of residues left on the field compared with conventional systems. The second part of the dissertation provides an overview of applied methodologies to measure NUE and its components. We evaluated the methodology of ion exchange resin cartridges under irrigated, intensive agricultural cropping systems on Vertisols to measure nitrate leaching losses which through drainage channels ultimately end up in the Sea of Cortez where they lead to algae blooming. A throughout analysis of N inputs and outputs was conducted to calculate N balances in three different tillage-straw systems. As fertilizer inputs are high, N balances were positive in all treatments indicating the risk of N leaching or volatilization during or in subsequent cropping seasons and during heavy rain fall in summer. Contrary to common belief, we did not find negative effects of residue burning on soil nutrient status, yield or N uptake. A labeled fertilizer experiment with urea 15N was implemented in micro-plots to measure N fertilizer recovery and the effects of residual fertilizer N in the soil from summer maize on the following winter crop wheat. Obtained N fertilizer recovery rates for maize grain were with an average of 11% very low for all treatments.

Efficiency of low versus high airline pressure on stunning cattle with penetrating captive bolt guns.

2016

Obesogenic Environment By Excess Of Dietary Fats In Different Phases Of Development Reduces Spermatic Efficiency Of Wistar Rats At Adulthood: Correlations With Metabolic Status.

This study compares the impact of obesogenic environment (OE) in six different periods of development on sperm parameters and the testicular structure of adult rats and their correlations with sex steroid and metabolic scenario. Wistar rats were exposed to OE during gestation (O1), during gestation/lactation (O2), from weaning to adulthood (O3), from lactation to adulthood (O4), from gestation to sexual maturity (O5), and after sexual maturation (O6). OE was induced by a 20% fat diet, and control groups were fed a balanced diet (4% fat). Serum leptin levels and adiposity index indicate that all groups were obese, except for O1. Three progressive levels of impaired metabolic status were observed: O1 presented insulin resistance, O2 were insulin resistant and obese, and groups O3, O4, and O5 were insulin resistant, obese, and diabetic. These three levels of metabolic damage were proportional to the increase of leptin and decreased circulating testosterone. The impairment in the daily sperm production (DSP) paralleled these three levels of metabolic and hormonal damage being marginal in O1, increasing in O2, and being higher in groups O3, O4, O5, and O6. None of the OE periods affected the sperm transit time in the epididymis, and the lower sperm reserves were caused mainly by impaired DSP. In conclusion, OE during sexual maturation markedly reduces the DSP at adulthood in the rat. A severe reduction in the DSP also occurs in OE exposure during gestation/lactation but not in gestation, indicating that breast-feeding is a critical period for spermatogenic impairment under obesogenic conditions.

Leaf Manganese Accumulation And Phosphorus-acquisition Efficiency.

Plants that deploy a phosphorus (P)-mobilising strategy based on the release of carboxylates tend to have high leaf manganese concentrations ([Mn]). This occurs because the carboxylates mobilise not only soil inorganic and organic P, but also a range of micronutrients, including Mn. Concentrations of most other micronutrients increase to a small extent, but Mn accumulates to significant levels, even when plants grow in soil with low concentrations of exchangeable Mn availability. Here, we propose that leaf [Mn] can be used to select for genotypes that are more efficient at acquiring P when soil P availability is low. Likewise, leaf [Mn] can be used to screen for belowground functional traits related to nutrient-acquisition strategies among species in low-P habitats.

The Rg1 allele as a valuable tool for genetic transformation of the tomato 'Micro-Tom' model system

Background: The cultivar Micro-Tom (MT) is regarded as a model system for tomato genetics due to its short life cycle and miniature size. However, efforts to improve tomato genetic transformation have led to protocols dependent on the costly hormone zeatin, combined with an excessive number of steps. Results: Here we report the development of a MT near-isogenic genotype harboring the allele Rg1 (MT-Rg1), which greatly improves tomato in vitro regeneration. Regeneration was further improved in MT by including a two-day incubation of cotyledonary explants onto medium containing 0.4 mu M 1-naphthaleneacetic acid (NAA) before cytokinin treatment. Both strategies allowed the use of 5 mu M 6-benzylaminopurine (BAP), a cytokinin 100 times less expensive than zeatin. The use of MT-Rg1 and NAA pre-incubation, followed by BAP regeneration, resulted in high transformation frequencies (near 40%), in a shorter protocol with fewer steps, spanning approximately 40 days from Agrobacterium infection to transgenic plant acclimatization. Conclusions: The genetic resource and the protocol presented here represent invaluable tools for routine gene expression manipulation and high throughput functional genomics by insertional mutagenesis in tomato.

Phase transformation and residual stress probed by Raman spectroscopy in diamond-turned single crystal silicon

Single-point diamond turning of monocrystalline semiconductors is an important field of research within brittle materials machining. Monocrystalline silicon samples with a (100) orientation have been diamond turned under different cutting conditions (feed rate and depth of cut). Micro-Raman spectroscopy and atomic force microscopy have been used to assess structural alterations and surface finish of the samples diamond turned under ductile and brittle modes. It was found that silicon undergoes a phase transformation when machined in the ductile mode. This phase transformation is evidenced by the creation of an amorphous surface layer after machining which has been probed by Raman scattering. Compressive residual stresses are estimated for the machined surface and it is observed that they decrease with an increase in the feed rate and depth of cut. This behaviour has been attributed to the formation of subsurface cracks when the feed rate is higher than or equal to 2.5 mu m/rev. The surface roughness was observed to vary with the feed rate and the depth of cut. An increase in the surface roughness was influenced by microcrack formation when the feed rate reached 5.0 mu m/rev. Furthermore, a high-pressure phase transformation induced by the tool/material interaction and responsible for the ductile response of this typical brittle material is discussed based upon the presented Raman spectra. The application of this machining technology finds use for a wide range of high quality components, for example the creation of a micrometre-range channel for microfluidic devices as well as microlenses used in the infrared spectrum range.

An apparatus for in situ spectroscopy of radiation damage of polymers by bombardment with high-energy heavy ions

A new target station providing Fourier transform infrared (FT-IR) spectroscopy and residual gas analysis (RGA) for in situ observation of ion-induced changes in polymers has been installed at the GSI Helmholtz Centre for Heavy Ion Research. The installations as well as first in situ measurements at room temperature are presented here. A foil of polyimide Kapton HN (R) was irradiated with 1.1 GeV Au ions. During irradiation several in situ FT-IR spectra were recorded. Simultaneously outgassing degradation products were detected with the RGA. In the IR spectra nearly all bands decrease due to the degradation of the molecular structure. In the region from 3000 to 2700 cm(-1) vibration bands of saturated hydrocarbons not reported in literature so far became visible. The outgassing experiments show a mixture of C(2)H(4), CO, and N(2) as the main outgassing components of polyimide. The ability to combine both analytical methods and the opportunity to measure a whole fluence series within a single experiment show the efficiency of the new setup. (C) 2011 American Institute of Physics. [doi:10.1063/1.3571301]

Biomass burning in Brazil`s Amazonian ""arc of deforestation"": Burning efficiency and charcoal formation in a fire after mechanized clearing at Feliz Natal, Mato Grosso

Estimates of greenhouse-gas emissions from deforestation are highly uncertain because of high variability in key parameters and because of the limited number of studies providing field measurements of these parameters. One such parameter is burning efficiency, which determines how much of the original forest`s aboveground carbon stock will be released in the burn, as well as how much will later be released by decay and how much will remain as charcoal. In this paper we examined the fate of biomass from a semideciduous tropical forest in the ""arc of deforestation,"" where clearing activity is concentrated along the southern edge of the Amazon forest. We estimated carbon content, charcoal formation and burning efficiency by direct measurements (cutting and weighing) and by line-intersect sampling (LIS) done along the axis of each plot before and after burning of felled vegetation. The total aboveground dry biomass found here (219.3 Mg ha(-1)) is lower than the values found in studies that have been done in other parts of the Amazon region. Values for burning efficiency (65%) and charcoal formation (6.0%, or 5.98 Mg C ha(-1)) were much higher than those found in past studies in tropical areas. The percentage of trunk biomass lost in burning (49%) was substantially higher than has been found in previous studies. This difference may be explained by the concentration of more stems in the smaller diameter classes and the low humidity of the fuel (the dry season was unusually long in 2007, the year of the burn). This study provides the first measurements of forest burning parameters for a group of forest types that is now undergoing rapid deforestation. The burning parameters estimated here indicate substantially higher burning efficiency than has been found in other Amazonian forest types. Quantification of burning efficiency is critical to estimates of trace-gas emissions from deforestation. (C) 2009 Elsevier B.V. All rights reserved.

High-yield kraft pulping of Eucalyptus grandis Hill ex Maiden biotreated by Ceriporiopsis subvermispora under two different culture conditions

In the present study, it was evaluated how two different culture conditions for the biotreatment of Eucalyptus grandis by Ceriporiopsis subvermispora affect a subsequent high-yield kraft pulping process. Under the varied culture conditions investigated, different extracellular enzyme activities were observed. Manganese-peroxidase (MnP) secretion was 3.7 times higher in cultures supplemented with glucose plus corn-steep liquor (glucose/CSL) as compared to non-supplemented (NS) cultures. The biotreated samples underwent diverse levels of wood component degradation as losses of weight and lignin were increased in glucose/CSL cultures. Mass balances for lignin removal during kraft pulping showed that delignification was facilitated when both biotreated wood samples were cooked. Delignification efficiency did not correlate positively with MnP levels in the cultures. On the other hand, biopulps from NS and glucose/CSL cultures saved 27% and 38% beating time to achieve 288 Schopper-Riegler freeness during refining, respectively. Biopulps disposed of decreased tensile and tear resistances, thus easier refining of the biokraft pulps seems to be a consequence of less resistant fiber walls. Improved beatability of biopulps was tentatively related to short fibers and fines formation during refining. We suggest that to some extent polysaccharide depolymerization occurred during the biotreatment, which also resulted in diminished pulp yields in the case of glucose/CSL cultures.

Flux Pinning Optimization of MgB(2) Bulk Samples Prepared Using High-Energy Ball Milling and Addition of TaB(2)

MgB(2) is considered to be an important conductor for applications. Optimizing flux pinning in these conductors can improve their critical currents. Doping can influence flux pinning efficiency and grain connectivity, and also affect the resistivity, upper critical field and critical temperature. This study was designed to attempt the doping of MgB(2) on the Mg sites with metal-diborides using high-energy ball milling. MgB(2) samples were prepared by milling pre-reacted MgB(2) and TaB(2) powders using a Spex 8000M mill with WC jars and balls in a nitrogen-filled glove box. The mixing concentration in (Mg(1-x)Ta(x))B(2) was up to x = 0.10. Samples were removed from the WC jars after milling times up to 4000 minutes and formed into pellets using cold isostatic pressing. The pellets were heat treated in a hot isostatic press (HIP) at 1000 degrees C under a pressure of 30 kpsi for 24 hours. The influence that milling time and TaB(2) addition had on the microstructure and the resulting superconducting properties of TaB(2)-added MgB(2) is discussed. Improvement J(c) of at high magnetic fields and of pinning could be obtained in milled samples with added TaB(2) The sample with added 5at.% TaB(2) and milled for 300 minutes showed values of J(c) similar to 7 x 10(5) A/cm(2) and F(p) similar to 14 GN/m(3) at 2T, 4.2 K. The milled and TaB(2)-mixed samples showed higher values of mu(0)H(irr) than the unmilled-unmixed sample.

Properties of Y-TZP/Al(2)O(3) ceramic nanocomposites obtained by high-energy ball milling

In this work, the synthesis of Y(2)O(3) stabilized tetragonal zirconia polycrystals (Y-TZP)-alumina (Al(2)O(3)) powder mixture was performed by high-energy ball milling and the sintering behavior of this composite was investigated. In order to understand the phase transformations occurring during ball milling, samples were collected after different milling times, from 1 to 60 h. The milled powders were compacted by cold uniaxial pressing and sintered at 1400 and 1600 degrees C. Both powders and sintered samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometry analysis (EDS) and mechanical properties. Fully dense samples were obtained after sintering at 1600 degrees C, while the samples sintered at 1400 degrees C presented a full density for powder mixtures milled for 30 and 60 h. Fracture toughness and Vickers hardnessvalues of the Y-T-ZP/Al(2)O(3) nanocomposite were improved due to dispersed Al(2)O(3) grains and reduced ZrO(2) grain size. Samples sintered at 1400 degrees C, based on powders milled for 60 h, presented high K(IC) and hardness values near to 8.0 Mpan(1/2) and 15 GPa, respectively (C) 2008 Elsevier B.V. All rights reserved

Porous alumina-spinel ceramics for high temperature applications

In order to reduce energy costs, high-temperature insulation porous refractory ceramics have been subjected to increasing demands. Among the techniques used to produce these materials (such as the addition of foaming agents and organic compounds), the pore generation via phase transformation presents key aspects, such as easy processing and the absence of toxic volatiles. In this study, this technique was applied to produce porous ceramics by decomposing an aluminum magnesium hydro-carbonate known as hydrotalcite (Mg(6)Al(2)(CO(3))(OH)(16)center dot 4H(2)O). It was found out that by using this complex compound, a large fraction of pores can be generated and kept at high temperatures (above 1300 degrees C) due to the in situ formation of spinel-like phases (MgAl(2)O(4)). (C) 2011 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Measuring the eco-efficiency of cement use

At present, the cement industry generates approximately 5% of the world`s anthropogenic CO(2) emissions. This share is expected to increase since demand for cement based products is forecast to multiply by a factor of 2.5 within the next 40 years and the traditional strategies to mitigate emissions, focused on the production of cement, will not be capable of compensating such growth. Therefore, additional mitigation strategies are needed, including an increase in the efficiency of cement use. This paper proposes indicators for measuring cement use efficiency, presents a benchmark based on literature data and discusses potential gains in efficiency. The binder intensity (bi) index measures the amount of binder (kg m(-3)) necessary to deliver 1 MPa of mechanical strength, and consequently express the efficiency of using binder materials. The CO(2) intensity index (ci) allows estimating the global warming potential of concrete formulations. Research benchmarks show that bi similar to 5 kg m(-3) MPa(-1) are feasible and have already been achieved for concretes >50 MPa. However, concretes with lower compressive strengths have binder intensities varying between 10 and 20 kg m(-3) MPa(-1). These values can be a result of the minimum cement content established in many standards and reveal a significant potential for performance gains. In addition, combinations of low bi and ci are shown to be feasible. (c) 2010 Elsevier Ltd. All rights reserved.