Spectrophotometric determination of Sudan Blue II in environmental samples after dispersive liquid-liquid microextraction

A dispersive liquid-liquid microextraction procedure coupled to spectrophotometry is described for the determination of the trace levels of Sudan Blue II. Analytical parameters, such as pH, volume of extraction solvent (carbon tetrachloride), volume of dispersant (ethanol), volume of sample, and extraction time, were optimized. Matrix effects were also investigated. Preconcentration factor was found to be 200. Detection limit and relative standard deviation (RSD) were 0.55 µg L-1 and 3.9%, respectively. The procedure was successfully used for the determination of trace levels of Sudan Blue II in food, ink, antifreeze, and industrial waste-water samples.

Analysis of llicit and illicit drugs in waste, surface and lake water samples using large volume direct injection high performance liquid chromatography – Electrospray tandem mass spectrometry (HPLC–MS/MS)

http://www.sciencedirect.com/science/article/pii/S0045653510008891

List of publications pertaining to water supply and purification, sewage and industrial waste treatment, water pollution control, milk and food sanitation, and other selected environmental health subjects.

Cover title.

Removal of BrO3 − from drinking water samples using newly developed agricultural waste-based activated carbon and its determination by ultra-performance liquid chromatography-mass spectrometry

Activated carbon was prepared from date pits via chemical activation with H3PO4. The effects of activating agent concentration and activation temperature on the yield and surface area were studied. The optimal activated carbon was prepared at 450 °C using 55 % H3PO4. The prepared activated carbon was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric-differential thermal analysis, and Brunauer, Emmett, and Teller (BET) surface area. The prepared date pit-based activated carbon (DAC) was used for the removal of bromate (BrO3 −). The concentration of BrO3 − was determined by ultra-performance liquid chromatography-mass tandem spectrometry (UPLC-MS/MS). The experimental equilibrium data for BrO3 − adsorption onto DAC was well fitted to the Langmuir isotherm model and showed maximum monolayer adsorption capacity of 25.64 mg g−1. The adsorption kinetics of BrO3 − adsorption was very well represented by the pseudo-first-order equation. The analytical application of DAC for the analysis of real water samples was studied with very promising results.

Application of fourier transform infrared spectroscopy, chemical and chemometrics analyses to the characterization of agro-industrial waste

Agroindustrial waste in general presents significant levels of nutrients and organic matter and has therefore been frequently put to agricultural use. In this context, the objective of this study was to determine the chemical composition, nitrogen, phosphorus, potassium, calcium, magnesium and carbon content, as well as the qualitative characteristics through Fourier transform infrared spectroscopy of four samples of poultry litter and one sample of cattle manure, from the southwestern region of Paraná, Brazil. Results revealed that, in general, the poultry litter presented higher amount of nutrients and carbon than the cattle manure. The infrared spectra allowed identification of the functional groups present and the differences in degree of sample humification. The statistical treatment confirmed the quantitative and qualitative differences revealed.

Evaluation of antioxidant activity of agro-industrial waste of acerola (Malpighia emarginata D.C.) fruit extracts

This study was carried out to evaluate the antioxidant capacity of the agro-industrial waste from acerola. Hydroacetone, hydroethanolic, and hydromethanolic extracts were obtained using the sequential extraction process, and they were screened for their free radical DPPH• (1,1-diphenyl-2-picrilhidrazil) and ABTS•+ (2,2'-azino-bis-(3-etilbenzotiazolin 6-sulfonic acid) scavenging activity and their effect on the linoleic acid peroxidation by the ferric thiocyanate method. Soybean oil with the addition of the extracts (200 ppm) was submitted to Schaal oven test (60 °C, 28 days), in which the samples were analyzed for peroxide value and conjugated dienes. Hydroethanolic and hydromethanolic extracts exhibited good DPPH scavenging activity (low value of EC50 and TEC50 and high value of AE), good ABTS scavenging capacity (1445.1 and 1145.5 µMol TEAC.g-1, respectively), and high percentage inhibition of peroxidation of linoleic acid (96.12 and 91.84%, respectively) and showed the ability to retard the formation of peroxides and conjugated dienes.

Waste Water Treatment Using Low Cost Natural Adsorbents

Heavy metals are major toxic pollutants with severe health effects on humans. They are released into the environment from a variety of industrial activities. Cadmium, lead, zinc, chromium and copper are the most toxic metals of widespread use in industries such as tanning, electroplating, electronic equipment manufacturing and chemical processing plants. Heavy metals contribute to a variety of adverse health environmental effects due to their acute and chronic exposure through air, water and food chain. Conventional treatment methods of metal removal are often limited by their cost and ineffectiveness at low concentrations. Adsorption, the use of inactivated biomass as adsorbents offers an attractive potential alternative to their conventional methods. Mango peel and Alisma plantago aquatica are naturally occurring and abundant biomass can offer an economical solution for metal removal.The Cd(II), Pb(II), Zn(II), Cr(III) and Cu(II) adsorption by milled adsorbents of mango peel and Alisma plantago aquatica were evaluated in batches.

Organochlorine pesticides and polychlorinated biphenyls in soil and water samples in the northeastern part of São Paulo State, Brazil

Detailed analyses of persistent organic pollutants (POPs) such as organochlorine pesticides (OCPs), hexachlorocyclohexane (HCH) isomers (HCHs), dichlorodiphenyltrichloro ethane (DDT) and its metabolites (DDTs) and congeners of polychlorinated biphenyls (PCBs) in soil and surface water from the northeastern São Paulo, Brazil allowed the evaluation of the contamination status, distribution and possible pollution sources. The pesticides and PCBs demonstrated markedly different distributions, reflecting different agricultural, domestic and industrial usage in each region studied. The ranges of HCH, DDT, and PCBs concentrations in the soil samples were 0.05-0.92, 0.12-11.01, 0.02-0.25 ng g(-1) dry wt, respectively, and in the surface water samples were 0.02-0.6, 0.02-0.58 and 0.02-0.5 ng l(-1), respectively. Overall elevated levels of DDT and PCB were recorded in region 2, a site very close to melting, automotive batteries industries, and agricultural practice regions. High ratios of metabolites of DDT to DDT isomers revealed the recent use of DDT in this environment. The sources of contamination are closely related to human activities, such as domestic and industrial discharge, street runoff, agricultural pesticides and soil erosion, due to deforestation as well as atmospheric transport. (c) 2006 Elsevier Ltd. All rights reserved.

Genotoxicity and mutagenicity of water samples from the Monjolinho River (Brazil) after receiving untreated effluents

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

On Site Stripping Voltammetric Determination of Zn(II), Cd(II) and Pb(II) in Water Samples of the Cananeia-Iguape Estuarine-Lagoon Complex in Sao Paulo State, Brazil

Estuarine systems play an important role in the retention of toxic trace elements owing to the affinity of these elements with particles dissolved in water. This work presents the use of a voltammetric sensor to monitor heavy metal (Zn (II), Cd(II) and Pb (II)) concentrations in the Cananeia-Iguape Estuarine-Lagoon region (Sao Paulo State, Brazil). Lower concentrations were found in the Southern estuarine system (Cananeia City) and increased concentrations observed in the Northern sector (Iguape City) were promoted by anthropogenic activities, with particular influence from the historical introduction of mining wastes and inputs from agricultural, industrial and domestic effluents. The proposed method is reliable, inexpensive and fast, can simultaneously provide information on the concentration of these metallic ions and can be easily used for field measurements aboard oceanographic ships.

On site stripping voltammetric determination of Zn(II), Cd(II) and Pb(II) in water samples of the Cananéia-Iguape Estuarine-Lagoon complex in São Paulo state, Brazil

Estuarine systems play an important role in the retention of toxic trace elements owing to the affinity of these elements with particles dissolved in water. This work presents the use of a voltammetric sensor to monitor heavy metal (Zn (II), Cd(II) and Pb (II)) concentrations in the Cananéia-Iguape Estuarine-Lagoon region (São Paulo State, Brazil). Lower concentrations were found in the Southern estuarine system (Cananéia City) and increased concentrations observed in the Northern sector (Iguape City) were promoted by anthropogenic activities, with particular influence from the historical introduction of mining wastes and inputs from agricultural, industrial and domestic effluents. The proposed method is reliable, inexpensive and fast, can simultaneously provide information on the concentration of these metallic ions and can be easily used for field measurements aboard oceanographic ships.

Microextraction techniques coupled to liquid chromatography with mass spectrometry for the determination of organic micropollutants in environmental water samples

[EN]Until recently, sample preparation was carried out using traditional techniques, such as liquid–liquid extraction (LLE), that use large volumes of organic solvents. Solid-phase extraction (SPE) uses much less solvent than LLE, although the volume can still be significant. These preparation methods are expensive, time-consuming and environmentally unfriendly. Recently, a great effort has been made to develop new analytical methodologies able to perform direct analyses using miniaturised equipment, thereby achieving high enrichment factors, minimising solvent consumption and reducing waste. These microextraction techniques improve the performance during sample preparation, particularly in complex water environmental samples, such as wastewaters, surface and ground waters, tap waters, sea and river waters. Liquid chromatography coupled to tandem mass spectrometry (LC/MS/MS) and time-of-flight mass spectrometric (TOF/MS) techniques can be used when analysing a broad range of organic micropollutants. Before separating and detecting these compounds in environmental samples, the target analytes must be extracted and pre-concentrated to make them detectable. In this work, we review the most recent applications of microextraction preparation techniques in different water environmental matrices to determine organic micropollutants: solid-phase microextraction SPME, in-tube solid-phase microextraction (IT-SPME), stir bar sorptive extraction (SBSE) and liquid-phase microextraction (LPME). Several groups of compounds are considered organic micropollutants because these are being released continuously into the environment. Many of these compounds are considered emerging contaminants. These analytes are generally compounds that are not covered by the existing regulations and are now detected more frequently in different environmental compartments. Pharmaceuticals, surfactants, personal care products and other chemicals are considered micropollutants. These compounds must be monitored because, although they are detected in low concentrations, they might be harmful toward ecosystems.

THE POTENTIAL OF INDUSTRIAL WASTE AND AGRICULTURAL FEEDSTOCK TOWARDS SUSTAINABLE BIOFUELS PRODUCTION: TECHNO-ECONOMIC AND ENVIRONMENTAL IMPACT PERSPECTIVES

This Ph.D. research is comprised of three major components; (i) Characterization study to analyze the composition of defatted corn syrup (DCS) from a dry corn mill facility (ii) Hydrolysis experiments to optimize the production of fermentable sugars and amino acid platform using DCS and (iii) Sustainability analyses. Analyses of DCS included total solids, ash content, total protein, amino acids, inorganic elements, starch, total carbohydrates, lignin, organic acids, glycerol, and presence of functional groups. Total solids content was 37.4% (± 0.4%) by weight, and the mass balance closure was 101%. Total carbohydrates [27% (± 5%) wt.] comprised of starch (5.6%), soluble monomer carbohydrates (12%) and non-starch carbohydrates (10%). Hemicellulose components (structural and non-structural) were; xylan (6%), xylose (1%), mannan (1%), mannose (0.4%), arabinan (1%), arabinose (0.4%), galatactan (3%) and galactose (0.4%). Based on the measured physical and chemical components, bio-chemical conversion route and subsequent fermentation to value added products was identified as promising. DCS has potential to serve as an important fermentation feedstock for bio-based chemicals production. In the sugar hydrolysis experiments, reaction parameters such as acid concentration and retention time were analyzed to determine the optimal conditions to maximize monomer sugar yields while keeping the inhibitors at minimum. Total fermentable sugars produced can reach approximately 86% of theoretical yield when subjected to dilute acid pretreatment (DAP). DAP followed by subsequent enzymatic hydrolysis was most effective for 0 wt% acid hydrolysate samples and least efficient towards 1 and 2 wt% acid hydrolysate samples. The best hydrolysis scheme DCS from an industry's point of view is standalone 60 minutes dilute acid hydrolysis at 2 wt% acid concentration. The combined effect of hydrolysis reaction time, temperature and ratio of enzyme to substrate ratio to develop hydrolysis process that optimizes the production of amino acids in DCS were studied. Four key hydrolysis pathways were investigated for the production of amino acids using DCS. The first hydrolysis pathway is the amino acid analysis using DAP. The second pathway is DAP of DCS followed by protein hydrolysis using proteases [Trypsin, Pronase E (Streptomyces griseus) and Protex 6L]. The third hydrolysis pathway investigated a standalone experiment using proteases (Trypsin, Pronase E, Protex 6L, and Alcalase) on the DCS without any pretreatment. The final pathway investigated the use of Accellerase 1500® and Protex 6L to simultaneously produce fermentable sugars and amino acids over a 24 hour hydrolysis reaction time. The 3 key objectives of the techno-economic analysis component of this PhD research included; (i) Development of a process design for the production of both the sugar and amino acid platforms with DAP using DCS (ii) A preliminary cost analysis to estimate the initial capital cost and operating cost of this facility (iii) A greenhouse gas analysis to understand the environmental impact of this facility. Using Aspen Plus®, a conceptual process design has been constructed. Finally, both Aspen Plus Economic Analyzer® and Simapro® sofware were employed to conduct the cost analysis as well as the carbon footprint emissions of this process facility respectively. Another section of my PhD research work focused on the life cycle assessment (LCA) of commonly used dairy feeds in the U.S. Greenhouse gas (GHG) emissions analysis was conducted for cultivation, harvesting, and production of common dairy feeds used for the production of dairy milk in the U.S. The goal was to determine the carbon footprint [grams CO2 equivalents (gCO2e)/kg of dry feed] in the U.S. on a regional basis, identify key inputs, and make recommendations for emissions reduction. The final section of my Ph.D. research work was an LCA of a single dairy feed mill located in Michigan, USA. The primary goal was to conduct a preliminary assessment of dairy feed mill operations and ultimately determine the GHG emissions for 1 kilogram of milled dairy feed.

Blending of industrial waste from different sources as partial substitution of Portland cement in pastes and mortars

Binary and ternary combinations of sewage sludge ash (SSA) with marble dust (MD), fly ash (FA) and rice husk ash (RHA) as replacement in Portland cement pastes, were assessed. Several tests were carried out at different curing ages: thermogravimetry, density, water absorption, ultrasonic pulse velocity and mechanical strengths. Pozzolanic effects of the mineral admixtures, densities similar to control sample and improved absorptions when combining waste materials were identified. In general, the compressive strength reaches or exceeds the cement strength class, and blending SSA, FA and RHA (30% cement replacement) increase of strength by 9%, compared to the control sample, was achieved.

Screen-printed electrode based electrochemical detector coupled with ionic liquid dispersive liquid–liquid microextraction and microvolume back-extraction for determination of mercury in water samples

A novel approach is presented, whereby gold nanostructured screen-printed carbon electrodes (SPCnAuEs) are combined with in-situ ionic liquid formation dispersive liquid–liquid microextraction (in-situ IL-DLLME) and microvolume back-extraction for the determination of mercury in water samples. In-situ IL-DLLME is based on a simple metathesis reaction between a water-miscible IL and a salt to form a water-immiscible IL into sample solution. Mercury complex with ammonium pyrrolidinedithiocarbamate is extracted from sample solution into the water-immiscible IL formed in-situ. Then, an ultrasound-assisted procedure is employed to back-extract the mercury into 10 µL of a 4 M HCl aqueous solution, which is finally analyzed using SPCnAuEs. Sample preparation methodology was optimized using a multivariate optimization strategy. Under optimized conditions, a linear range between 0.5 and 10 µg L−1 was obtained with a correlation coefficient of 0.997 for six calibration points. The limit of detection obtained was 0.2 µg L−1, which is lower than the threshold value established by the Environmental Protection Agency and European Union (i.e., 2 µg L−1 and 1 µg L−1, respectively). The repeatability of the proposed method was evaluated at two different spiking levels (3 and 10 µg L−1) and a coefficient of variation of 13% was obtained in both cases. The performance of the proposed methodology was evaluated in real-world water samples including tap water, bottled water, river water and industrial wastewater. Relative recoveries between 95% and 108% were obtained.