The effects and extent of 1,1,1-trichloroethane vapor concentration exposure on workers during solvent vapor degreasing

This study attempted to determine if an excessive amount of 1,1,1 - Trichloroethane was released into the air, the acute effects of exposure and the cause(s) of excessive use. The types of degreasing equipments which were tested in this study are straight vapor and the vapor spray machines. The instruments utilized to obtain the data for this study are Gastech Haline Detector, Organic Vapor Monitor Badge and Personal Sampling Pump. Readings were taken on three different tanks. The data accumulated by this study were obtained during actual cleaning operation. During testing, increased exposure was detected due to exceeding the rate of removal, downward drafts were blowing right over the top of a degreaser and, in some cases, poor general ventilation caused solvent vapor to be blown out of the tank and into the workers' breathing zone, affecting excessive vapor drag out and solvent loss. The results show that, since the characteristics of solvent 1,1,1 - Trichloroethane are well suited to vapor degreasing requirements, by using proper procedures and maintenance, 1,1,1 - Trichloroethane emission during vapor degreasing can be controlled at levels well below the industrial hygiene standard established by OSHA for safe and healthful conditions.

Environmental analysis of polar herbicides in complex organic-rich matrices by high performance liquid chromatography atmospheric pressure ionization mass spectrometry (HPLC-API-MS)

A comprehensive forensic investigation of sensitive ecosystems in the Everglades Area is presented. Assessing the background levels of contamination in these ecosystems represents a vital resource to build up forensic evidence required to enforce future environmental crimes within the studied areas. This investigation presents the development and validation of a fractionation and isolation method for two families of herbicides commonly applied in the vicinity of the study area, including phenoxy acids like 2,4-D, MCPA, and silvex; as well as the most common triazine-based herbicides like atrazine, prometyne, simazine and related metabolites like DIA and DEA. Accelerated solvent extraction (ASE) and solid phase extraction (SPE) were used to isolate the analytes from abiotic matrices containing large amounts of organic material. Atmospheric-pressure ionization (API) with electrospray ionization in negative mode (ESP-), and Chemical Ionization in the positive mode (APCI+) were used to perform the characterization of the herbicides of interest.

(Table 1) Low molecular weight hydrocarbon concentrations and organic carbon contents at DSDP Hole 71-511

C2-C8 hydrocarbons (36 compounds identified) from 56 shipboard sealed, deep-frozen core samples of DSDP Leg 71, Site 511, Falkland Plateau, South Atlantic, were analyzed by a combined hydrogen stripping-thermovaporization method. Concentrations, which represent hydrocarbons dissolved in the pore water and adsorbed to the mineral surfaces of the sediment, vary from 24 ng/g of dry weight sediment in Lithologic Unit 4 to 17,400 ng/g in Lithologic Unit 6 ("black shale" unit). Likewise, the organic carbon normalized C2-C8 hydrocarbon concentrations range from 104 to 3.5 x 105 ng/g Corg. The latter value is more than one order of magnitude lower than expected for petroleum source beds in the main phase of oil generation. The low maturity at 600 meters depth is further supported by light hydrocarbon concentration ratios. The change of the kerogen type from Lithologic Unit 5 (Type III) to 6 (Type II) is evidenced by changes in the C6 and C7 hydrocarbon composition. Redistribution phenomena are observed close to the Tertiary-Cretaceous unconformity and at the contact between the "black shale" unit and the overlying Cretaceous chalks and claystones. Otherwise, the low molecular weight hydrocarbons in Hole 511 are formed in situ and remain at their place of formation. The core samples turned out to be contaminated by large quantities of acetone, which is routinely used as a solvent during sampling procedures onboard Glomar Challenger.

Redistribution of Soil Organic Matter by Permafrost Disturbance in the Canadian High Arctic

With increased warming in the Arctic, permafrost thaw may induce localized physical disturbance of slopes. These disturbances, referred to as active layer detachments (ALDs), redistribute soil across the landscape, potentially releasing previously unavailable carbon (C). In 2007–2008, widespread ALD activity was reported at the Cape Bounty Arctic Watershed Observatory in Nunavut, Canada. Our study investigated organic matter (OM) composition in soil profiles from ALD-impacted and undisturbed areas. Solid-state 13C nuclear magnetic resonance (NMR) and solvent-extractable biomarkers were used to characterize soil OM. Throughout the disturbed upslope profile, where surface soils and vegetation had been removed, NMR revealed low O-alkyl C content and biomarker analysis revealed low concentrations of solvent-extractable compounds suggesting enhanced erosion of labile-rich OM by the ALD. In the disturbed downslope region, vegetation remained intact but displaced material from upslope produced lateral compression ridges at the surface. High O-alkyl content in the surface horizon was consistent with enrichment of carbohydrates and peptides, but low concentrations of labile biomarkers (i.e., sugars) suggested the presence of relatively unaltered labile-rich OM. Decreased O-alkyl content and biomarker concentrations below the surface contrasted with the undisturbed profile and may indicate the loss of well-established pre-ALD surface drainage with compression ridge formation. However, pre-ALD profile composition remains unknown and the observed decreases may result from nominal pre-ALD OM inputs. These results are the first to establish OM composition in ALD-impacted soil profiles, suggesting reallocation of permafrost-derived soil C to areas where degradation or erosion may contribute to increased C losses from disturbed Arctic soils.

Greener Alternatives to Selected Organic Oxidation Reactions

The study of green chemistry is dedicated to eliminating or reducing toxic waste. One route to accomplish this goal is to explore alternative reaction conditions and parameters resulting in the development of more benign synthetic routes and reagents. The primary focus of this research is to find optimal reaction conditions for the oxidation of a primary alcohol to an aldehyde. As a case study, the oxidation of benzyl alcohol to benzaldehyde, a common industrial process, was examined. Traditionally carried out using the Jones Reagent, commonly referred to as chromium (IV) oxide or chromium trioxide (CrO3) in sulphuric acid, a great deal of research went into utilizing less toxic reagents, such as MnO2 or KMnO4 supported on a clay base. This research has led to an improvement on these alternatives, using a lithium chloride (LiCl) catalyst in a montmorillonite K10 clay solid phase, together with the oxidizing agent hydrogen peroxide, as even greener alternatives to these traditional oxidizing agents. Experiments were carried out to determine the lifetime of this LiCl/clay system as compared to MnO2 and KMnO4, to investigate its ability to catalyze the oxidation of other aromatic alcohols (such as 4-methoxybenzyl alcohol and diphenylmethanol), and to further improve the system’s adherence to green chemistry principles. Green solvent alternatives were examined by replacing the toluene solvent with dimethylcarbonate (DMC), and reaction conditions were optimized to improve product yield. It was determined that the LiCl/H2O2 system was, in most cases, equally as effective at catalyzing the oxidation of benzyl alcohol to benzaldehyde. Although the catalyst and oxidizing agent eliminated the toxic waste generated from chromium reagents, it offered significant challenges in product isolation, because of an aqueous-organic phase separation.

Microwave-assisted solvent extraction and analysis of shikimic acid from plant tissues.

A better method for determination of shikimate in plant tissues is needed to monitor exposure of plants to the herbicide glyphosate [N-(phosphonomethyl)glycine] and to screen the plant kingdom for high levels of this valuable phytochemical precursor to the pharmaceutical oseltamivir. A simple, rapid, and efficient method using microwave-assisted extraction (MWAE) with water as the extraction solvent was developed for the determination of shikimic acid in plant tissues. High performance liquid chromatography was used for the separation of shikimic acid, and chromatographic data were acquired using photodiode array detection. This MWAE technique was successful in recovering shikimic acid from a series of fortified plant tissues at more than 90% efficiency with an interference-free chromatogram. This allowed the use of lower amounts of reagents and organic solvents, reducing the use of toxic and/or hazardous chemicals, as compared to currently used methodologies. The method was used to determine the level of endogenous shikimic acid in several species of Brachiaria and sugarcane (Saccharum officinarum) and on B. decumbens and soybean (Glycine max) after treatment with glyphosate. The method was sensitive, rapid and reliable in all cases.

Study of the absorption of organic compounds on biopolymers

This work has been conducted in order to determine the solubility and diffusion coefficients of different aromatic substances in two different grades of polylactic acid (PLA), Amorphous (PDLLA) and Crystalline (PLLA); in particular the focus is on the following terpenes: Linalool, α-Pinene, β-Citronellol and L-Linalool. Moreover, further analyses have been carried out with the aim to verify if the use of neat crystalline PLA, (PLLA), a chiral substrate, may lead to an enantioenrichment of absorbed species in order to use it as membrane in enantioselective processes. The other possible applications of PLA, which has aroused interest in carry out the above-mentioned work, concerns its use in food packaging. Therefore, it is interesting and also very important, to evaluate the barrier properties of PLA, focusing in particular on the transport and absorption of terpenes, by the packaging and, hence, by the PLA. PLA films/slabs of one-millimeter thickness and with square shape, were prepared through the Injection Molding process. On the resulting PLA films heat pretreatment processes of normalizing were then performed to enhance the properties of the material. In order to evaluate solubility and diffusion coefficient of the different penetrating species, the absorption kinetics of various terpenes, in the two different types of PLA, were determined by gravimetric methods. Subsequently, the absorbed liquid was extracted with methanol (MeOH), non- solvent for PLA, and the extract analyzed by the use of High Performance Liquid Chromatography (HPLC), in order to evaluate its possible enantiomeric excess. Moreover, PLA films used were subjected to differential scanning calorimetry (DSC) which allowed to measure the glass transition temperature (Tg) and to determine the degree of crystallinity of the polymer (Xc).

Study and characterization of polymorphs of BTBT derivatives and their application in organic electronics

The perquisites of organic semiconductors (OSCs) in the field of organic electronics have attracted much attention due to the advantages like cost-effectiveness, solution processibility, etc. A key property in OSCs is charge carrier mobility, which depends on molecular packing, as even the slightest changes in the packing of OSC can significantly impact the mobility. Organic molecules are constructed by weak interactions, which makes the OSCs prone to adopt multiple packing arrangements, thus giving rise to polymorphism. Therefore, polymorph screening in bulk and thin films is crucial for material development. This thesis aims to present a systematic study of polymorphism of [1]benzothieno[3,2-b]benzothiophene (BTBT) derivatives functionalized with different side chains. The role of peripheral side chains has been studied since they can promote different packing arrangements. The bulk polymorph screening of OSCs was approached with conventional solution mediated recrystallization experiments like evaporation, slurry maturation, anti-solvent precipitation, etc. Each of the polymorphs were inspected for their relative stability and the kinetics of transformation was evaluated. Polymorphism in thin films was also investigated for selected OSCs. Non-equilibrium methods like, thermal gradient and solution shearing were employed to examine the nucleation, crystal growth and morphology in controlled crystallization conditions. After careful analysis of crystal phases in bulk and thin films, OFETs have been fabricated by optimizing the manufacturing conditions and the hole mobility values were extracted. The charge transport property of the OSCs tested for OFETs was supported by the ionization potential and transfer integrals calculation. An attempt to correlate the solid-state structure to electronic properties was carried out. For some of the molecules, mechanical properties have been also investigated, as the response to mechanical stress is highly susceptible to packing arrangements and the intermolecular interaction energy contributions. Additionally, collaborative research was carried out by solving and analysing the crystal structures of six oligorylene molecules.

Solvent regeneration of activated carbon mixed-matrix membranes for the removal of micropollutants from wastewater

The constantly increasing demand of clean water has become challenging to deal with over the past years, water being an ever more precious resource. In recent times, the existing wastewater treatments had to be integrated with new steps, due to the detection of so-called organic micropollutants (OMPs). These compounds have been shown to adversely affect the environment and possibly human health, even when found in very low concentrations. In order to remove OMPs from wastewater, one possible technique is a hybrid process combining filtration and adsorption. In this work, polyethersulfone multi-channel mixed-matrix membranes with embedded powdered activated carbon (PAC) were tested to investigate the membrane’s adsorption and desorption performance. Micropollutants retention was analyzed using the pharmaceutical compounds diclofenac (DCF), paracetamol (PARA) and carbamazepine (CBZ) in filtration mode, combining the PAC adsorption process with the membrane’s ultrafiltration. Desorption performance was studied through solvent regeneration, using seven different solvents: pure water, pure ethanol, mixture of ethanol and water in different concentration, sodium hydroxide and a mixture of ethanol and sodium hydroxide. Regeneration experiments were carried out in forward-flushing. At first regeneration efficiency was investigated using a single-solute solution (diclofenac in water). The mixture Ethanol/Water (50:50) was found to be the most efficient with long-term retention of 59% after one desorption cycle. It was, therefore, later tested on a membrane previously loaded with a multi-solute solution. Three desorption cycles were performed after which, retention (after 30 min) reached values of 87% for PARA and 72% for CBZ and 55% for DCF, which indicates decent regenerability. A morphological analysis on the membranes confirmed that, in any case, the regeneration cycles did not affect either the membranes’ structure, or the content and distribution of PAC in the matrix.

Engineered Nanoparticles And Organic Matter: A Review Of The State-of-the-art.

Growth in the development and production of engineered nanoparticles (ENPs) in recent years has increased the potential for interactions of these nanomaterials with aquatic and terrestrial environments. Carefully designed studies are therefore required in order to understand the fate, transport, stability, and toxicity of nanoparticles. Natural organic matter (NOM), such as the humic substances found in water, sediment, and soil, is one of the substances capable of interacting with ENPs. This review presents the findings of studies of the interaction of ENPs and NOM, and the possible effects on nanoparticle stability and the toxicity of these materials in the environment. In addition, ENPs and NOM are utilized for many different purposes, including the removal of metals and organic compounds from effluents, and the development of new electronic sensors and other devices for the detection of active substances. Discussion is therefore provided of some of the ways in which NOM can be used in the production of nanoparticles. Although there has been an increase in the number of studies in this area, further progress is needed to improve understanding of the dynamic interactions between ENPs and NOM.

The Influence Of The Buffering Capacity On The Production Of Organic Acids And Alcohols From Wastewater In Anaerobic Reactor.

Some bacteria common in anaerobic digestion process can ferment a broad variety of organic compounds to organic acids, alcohols, and hydrogen, which can be used as biofuels. Researches are necessary to control the microbial interactions in favor of the alcohol production, as intermediary products of the anaerobic digestion of organic compounds. This paper reports on the effect of buffering capacity on the production of organic acids and alcohols from wastewater by a natural mixed bacterial culture. The hypothesis tested was that the increase of the buffering capacity by supplementation of sodium bicarbonate in the influent results in benefits for alcohol production by anaerobic fermentation of wastewater. When the influent was not supplemented with sodium bicarbonate, the chemical oxygen demand (COD)-ethanol and COD-methanol detected in the effluent corresponded to 22.5 and 12.7 % of the COD-sucrose consumed. Otherwise, when the reactor was fed with influent containing 0.5 g/L of sodium bicarbonate, the COD-ethanol and COD-methanol were effluents that corresponded to 39.2 and 29.6 % of the COD-sucrose consumed. Therefore, the alcohol production by supplementation of the influent with sodium bicarbonate was 33.6 % higher than the fermentation of the influent without sodium bicarbonate.

Ambiental volatile organic compounds in the megacity of São Paulo

In order to characterize the composition of the main urban air organic compounds in the megacity of Sao Paulo, analysis of samples collected during the winter of 2003 downtown was carried out. The samplings were performed on the roof of a building in the commercial center of São Paulo. Hydrocarbons and carbonyls compounds were collected on August 4, 5 and 6. Comparing to previous data, the concentration of hydrocarbons presented no decrease in the concentration, except for the aldehydes, which decreased when compared to previous data. Among the HCs species analyzed, the highest concentrations observed were those of toluene (7.5 ± 3.4 ppbv), n-decane (3.2 ± 2.0 ppbv), benzene (2.7 ± 1.4 ppbv) and 1,3,5-trimethylbenzene (2.2 ± 1.5 ppbv).

Screening process for activity determination of conductive oxide electrodes for organic oxidation

A modified method for the calculation of the normalized faradaic charge (q fN) is proposed. The method involves the simulation of an oxidation process, by cyclic voltammetry, by employing potentials in the oxygen evolution reaction region. The method is applicable to organic species whose oxidation is not manifested by a defined oxidation peak at conductive oxide electrodes. The variation of q fN for electrodes of nominal composition Ti/RuX Sn1-X O2 (x = 0.3, 0.2 and 0.1), Ti/Ir0.3Ti0.7O2 and Ti/Ru0.3Ti0.7O2 in the presence of various concentrations of formaldehyde was analyzed. It was observed that electrodes containing SnO2 are the most active for formaldehyde oxidation. Subsequently, in order to test the validity of the proposed model, galvanostatic electrolyses (40 mA cm-2) of two different formaldehyde concentrations (0.10 and 0.01 mol dm-3) were performed. The results are in agreement with the proposed model and indicate that this new method can be used to determine the relative activity of conductive oxide electrodes. In agreement with previous studies, it can be concluded that not only the nature of the electrode material, but also the organic species in solution and its concentration are important factors to be considered in the oxidation of organic compounds.

Avaliação de solventes de extração por ultrassom usando-se cromatografia líquida de alta eficiência para a determinação de hidrocarbonetos policíclicos aromáticos em solos contaminados

A method using ultrasonication extraction for the determination of 17 polycyclic aromatic hydrocarbons (PAHs), selected by the USEPA and NIOSH as "consent decree" priority pollutants, in soil by High Performance Liquid Chromatography (HPLC) was studied. Separation and detection were completed in 20 min with a C18 columm, acetonitrile-water gradient elution and ultraviolet absorption and fluorescence detections. The detection limits, for a 10 µL of solution injection, were less than 9,917 ng/g in UV detection and less than 1,866 ng/g in fluorescence detection. Several organic solvents were tested for extraction of the 17 PAHs from soils. Acetone was the best solvent among the three solvents tested, and the order of the extraction efficiencies was: acetone>methanol>acetonitrile. Ultrasonication using acetone as solvent extraction was used to evaluate the biodegradation of those compounds in contaminated soil during a vermicomposting process.