The potential of solid phase microextraction (SPME) for the recovery of explosives followed by gas and liquid chromatographic analysis

The potential of solid phase microextraction (SPME) in the analysis of explosives is demonstrated. A sensitive, rapid, solventless and inexpensive method for the analysis of explosives and explosive odors from solid and liquid samples has been optimized using SPME followed by HPLC and GC/ECD. SPME involves the extraction of the organic components in debris samples into sorbent-coated silica fibers, which can be transferred directly to the injector of a gas chromatograph. SPME/HPLC requires a special desorption apparatus to elute the extracted analyte onto the column at high pressure. Results for use of GC/ECD is presented and compared to the results gathered by using HPLC analysis. The relative effects of controllable variables including fiber chemistry, adsorption and desorption temperature, extraction time, and desorption time have been optimized for various high explosives. ^

Variables affecting the collection and preservation of human scent components through instrumental and biological evaluations

In certain European countries and the United States of America, canines have been successfully used in human scent identification. There is however, limited scientific knowledge on the composition of human scent and the detection mechanism that produces an alert from canines. This lack of information has resulted in successful legal challenges to human scent evidence in the courts of law. ^ The main objective of this research was to utilize science to validate the current practices of using human scent evidence in criminal cases. The goals of this study were to utilize Headspace Solid Phase Micro Extraction Gas Chromatography Mass Spectrometry (HS-SPME-GC/MS) to determine the optimum collection and storage conditions for human scent samples, to investigate whether the amount of DNA deposited upon contact with an object affects the alerts produced by human scent identification canines, and to create a prototype pseudo human scent which could be used for training purposes. ^ Hand odor samples which were collected on different sorbent materials and exposed to various environmental conditions showed that human scent samples should be stored without prolonged exposure to UVA/UVB light to allow minimal changes to the overall scent profile. Various methods of collecting human scent from objects were also investigated and it was determined that passive collection methods yields ten times more VOCs by mass than active collection methods. ^ Through the use of polymerase chain reaction (PCR) no correlation was found between the amount of DNA that was deposited upon contact with an object and the alerts that were produced by human scent identification canines. Preliminary studies conducted to create a prototype pseudo human scent showed that it is possible to produce fractions of a human scent sample which can be presented to the canines to determine whether specific fractions or the entire sample is needed to produce alerts by the human scent identification canines. ^

Evaluation of contact and non-contact trapping efficiencies of human scent chemical profiles and their stabilities under different environmental conditions

Establishing an association between the scent a perpetrator left at a crime scene to the odor of the suspect of that crime is the basis for the use of human scent identification evidence in a court of law. Law enforcement agencies gather evidence through the collection of scent from the objects that a perpetrator may have handled during the execution of the criminal act. The collected scent evidence is consequently presented to the canines for identification line-up procedures with the apprehended suspects. Presently, canine scent identification is admitted as expert witness testimony, however, the accurate behavior of the dogs and the scent collection methods used are often challenged by the court system. The primary focus of this research project entailed an evaluation of contact and non-contact scent collection techniques with an emphasis on the optimization of collection materials of different fiber chemistries to evaluate the chemical odor profiles obtained using varying environment conditions to provide a better scientific understanding of human scent as a discriminative tool in the identification of suspects. The collection of hand odor from female and male subjects through both contact and non-contact sampling approaches yielded new insights into the types of VOCs collected when different materials are utilized, which had never been instrumentally performed. Furthermore, the collected scent mass was shown to be obtained in the highest amounts for both gender hand odor samples on cotton sorbent materials. Compared to non-contact sampling, the contact sampling methods yielded a higher number of volatiles, an enhancement of up to 3 times, as well as a higher scent mass than non-contact methods by more than an order of magnitude. The evaluation of the STU-100 as a non-contact methodology highlighted strong instrumental drawbacks that need to be targeted for enhanced scientific validation of current field practices. These results demonstrated that an individual's human scent components vary considerably depending on the method used to collect scent from the same body region. This study demonstrated the importance of collection medium selection as well as the collection method employed in providing a reproducible human scent sample that can be used to differentiate individuals.

Improved dynamic headspace sampling and detection using capillary microextraction of volatiles coupled to gas chromatography mass spectrometry

Sampling and preconcentration techniques play a critical role in headspace analysis in analytical chemistry. My dissertation presents a novel sampling design, capillary microextraction of volatiles (CMV), that improves the preconcentration of volatiles and semivolatiles in a headspace with high throughput, near quantitative analysis, high recovery and unambiguous identification of compounds when coupled to mass spectrometry. The CMV devices use sol-gel polydimethylsiloxane (PDMS) coated microglass fibers as the sampling/preconcentration sorbent when these fibers are stacked into open-ended capillary tubes. The design allows for dynamic headspace sampling by connecting the device to a hand-held vacuum pump. The inexpensive device can be fitted into a thermal desorption probe for thermal desorption of the extracted volatile compounds into a gas chromatography-mass spectrometer (GC-MS). The performance of the CMV devices was compared with two other existing preconcentration techniques, solid phase microextraction (SPME) and planar solid phase microextraction (PSPME). Compared to SPME fibers, the CMV devices have an improved surface area and phase volume of 5000 times and 80 times, respectively. One (1) minute dynamic CMV air sampling resulted in similar performance as a 30 min static extraction using a SPME fiber. The PSPME devices have been fashioned to easily interface with ion mobility spectrometers (IMS) for explosives or drugs detection. The CMV devices are shown to offer dynamic sampling and can now be coupled to COTS GC-MS instruments. Several compound classes representing explosives have been analyzed with minimum breakthrough even after a 60 min. sampling time. The extracted volatile compounds were retained in the CMV devices when preserved in aluminum foils after sampling. Finally, the CMV sampling device were used for several different headspace profiling applications which involved sampling a shipping facility, six illicit drugs, seven military explosives and eighteen different bacteria strains. Successful detection of the target analytes at ng levels of the target signature volatile compounds in these applications suggests that the CMV devices can provide high throughput qualitative and quantitative analysis with high recovery and unambiguous identification of analytes.

Evaluation of non-contact sampling and detection of explosives using receiver operating characteristic curves

The growing need for fast sampling of explosives in high throughput areas has increased the demand for improved technology for the trace detection of illicit compounds. Detection of the volatiles associated with the presence of the illicit compounds offer a different approach for sensitive trace detection of these compounds without increasing the false positive alarm rate. This study evaluated the performance of non-contact sampling and detection systems using statistical analysis through the construction of Receiver Operating Characteristic (ROC) curves in real-world scenarios for the detection of volatiles in the headspace of smokeless powder, used as the model system for generalizing explosives detection. A novel sorbent coated disk coined planar solid phase microextraction (PSPME) was previously used for rapid, non-contact sampling of the headspace containers. The limits of detection for the PSPME coupled to IMS detection was determined to be 0.5-24 ng for vapor sampling of volatile chemical compounds associated with illicit compounds and demonstrated an extraction efficiency of three times greater than other commercially available substrates, retaining >50% of the analyte after 30 minutes sampling of an analyte spike in comparison to a non-detect for the unmodified filters. Both static and dynamic PSPME sampling was used coupled with two ion mobility spectrometer (IMS) detection systems in which 10-500 mg quantities of smokeless powders were detected within 5-10 minutes of static sampling and 1 minute of dynamic sampling time in 1-45 L closed systems, resulting in faster sampling and analysis times in comparison to conventional solid phase microextraction-gas chromatography-mass spectrometry (SPME-GC-MS) analysis. Similar real-world scenarios were sampled in low and high clutter environments with zero false positive rates. Excellent PSPME-IMS detection of the volatile analytes were visualized from the ROC curves, resulting with areas under the curves (AUC) of 0.85-1.0 and 0.81-1.0 for portable and bench-top IMS systems, respectively. Construction of ROC curves were also developed for SPME-GC-MS resulting with AUC of 0.95-1.0, comparable with PSPME-IMS detection. The PSPME-IMS technique provides less false positive results for non-contact vapor sampling, cutting the cost and providing an effective sampling and detection needed in high-throughput scenarios, resulting in similar performance in comparison to well-established techniques with the added advantage of fast detection in the field.

The potential of solid phase microextraction (spme) for the recovery of explosives followed by gas and liquid chromatographic analysis

The potential of solid phase microextraction (SPME) in the analysis of explosives is demonstrated. A sensitive, rapid, solventless and inexpensive method for the analysis of explosives and explosive odors from solid and liquid samples has been optimized using SPME followed by HPLC and GC/ECD. SPME involves the extraction of the organic components in debris samples into sorbent-coated silica fibers, which can be transferred directly to the injector of a gas chromatograph. SPME/HPLC requires a special desorption apparatus to elute the extracted analyte onto the column at high pressure. Re suits for use of GC[ECD is presented and compared to the results gathered by using HPLC analysis. The relative effects of controllable variables including fiber chemistry, adsorption and desorption temperature, extraction time, and desorption time have been optimized for various high explosives.

Parasitos de importância para a caprinocultura e a ovinocultura potiguar

The goat and sheep industry shows up as an agricultural activity of great importance for the semiarid Northeast. However, the sheep and goats production is made with various difficulties. Among them, parasitic infections, particularly helminth infections of the gastrointestinal tract, the eimeriosis and toxoplasmosis; this one related to problems in reproduction. For this reason, the aim of this study is to to make a survey of the occurrence and some determinants of parasitic diseases that affect small ruminant flocks of the microregions Natal, Macaíba, Litoral Sul, Angicos, Vale do Açu and Borborema Potiguar. Thereunto, epidemiological tools were applied with producers, keepers or guardians of herds and also held collections of blood and feces of animals in eight properties located in seven municipalities of these microregions. The parasite load of the animals was determined through eggs and oocysts counting per gram of feces EPG and OPG, respectively. In addition, the recovery of infective larvae was made. Blood samples were used to measure the globular cell volume and the search for anti-Toxoplasma gondii IgG in sheep serum, by Enzyme Linked Immune Sorbent Assay (ELISA). For categorical variables, the statistical analysis was performed using Poisson regression, with significance level of 0.05. The analysis of the instruments showed that ivermectin is the anthelmintic used in 85,71% of properties. From the total of feces samples of the sheep (n = 179), 53,07% were positive for helminth eggs and 48,04% were positive for oocysts of Eimeria. From the samples of faeces of goats (n = 133), 72,18% were positive for helminth eggs and 96,99% for oocysts of Eimeria. The lowest EPG and OPG count was observed in the micro region of Angicos. Most of the EPG count was found in the micro region Litoral Sul and the OPG count in the micro-region Borborema Potiguar. Both cases the difference was statistically significant(p- value0,000)The most prevalent helminth genus found was Haemonchus, present in 49,87% of the sheep and 80,42% of goats. The average of hematocrit ranged from 22,91 to 33,25 in sheep and from 22,62 to 28,25 in goats. The prevalence of anti-Toxoplasma gondii IgG ranged from 63,33% to 100,00%. The goats showed to be more susceptible to infections by parasites of the gastrointestinal tract than the sheep. In all the properties was observed high prevalence of infection by T. gondii, with the lowest percentages recorded in the micro regions Angicos and Borborema Potiguar.

Adição de policloreto de alumínio e remoção de peixes bentívoros como técnicas de restauração de lagos rasos do semiárido brasileiro

Eutrophication is the most common cause of water quality degradation in the world. This process occurs by excessive nutrients inputs, nitrogen and phosphorus, to the aquatic systems resulting in algal and cyanobacterial blooms. In shallow lakes these effects are pronounced due to the higher interaction of the lake with watershed, air and sediment. There are innumerous restoration techniques of eutrophied lakes with a range of successful results but there is only one case of successful lake restoration in Brazil: Paranoá Lake in Brasília city. The Brazilian semiarid region has many artificial lakes, named açudes, which are mostly eutrophic and shallow lakes. The eutrophication in these lakes is reported and the phytoplankton community is dominated by potentially toxic cyanobacteria species, mainly Cylindrospermopsis raciborskii. The aim of this thesis is to test techniques for water quality management which can be easily applied in Brazilian semiarid lakes. Results from a laboratory experiment suggest that the addition of a phosphorus sorbent clay associated with an aluminium based coagulant is an effective technique in removing soluble reactive phosphorus and reducing C. raciborskii growth rate – cyanobacteria potentially toxic dominant in reservoirs of Brazilian semiarid – but this effect is dependent on the biomass in the application moment. Results from a field experiment in mesocosm in a eutrophied lake showed that the addition of aluminium based coagulant and removal of benthivorous fish is more efficient in removing total phosphorus and chlorophyll-a from water column than the isolated application of one of the techniques. Lastly, laboratory tests showed that aluminium based coagulant exhibited good performance in removing turbidity and total phosphorus from water of six reservoirs but the efficiency was reduced by algal biomass and pH. The results of this study showed that the improvement in water quality of eutrophied reservoirs in semiarid region is possible through internal loading control by phosphorus precipitation and inactivation in sediments or inhibition of phosphorus release by benthivorous fishes, and also that these results show are additives in water quality improvement.

Adição de policloreto de alumínio e remoção de peixes bentívoros como técnicas de restauração de lagos rasos do semiárido brasileiro

Eutrophication is the most common cause of water quality degradation in the world. This process occurs by excessive nutrients inputs, nitrogen and phosphorus, to the aquatic systems resulting in algal and cyanobacterial blooms. In shallow lakes these effects are pronounced due to the higher interaction of the lake with watershed, air and sediment. There are innumerous restoration techniques of eutrophied lakes with a range of successful results but there is only one case of successful lake restoration in Brazil: Paranoá Lake in Brasília city. The Brazilian semiarid region has many artificial lakes, named açudes, which are mostly eutrophic and shallow lakes. The eutrophication in these lakes is reported and the phytoplankton community is dominated by potentially toxic cyanobacteria species, mainly Cylindrospermopsis raciborskii. The aim of this thesis is to test techniques for water quality management which can be easily applied in Brazilian semiarid lakes. Results from a laboratory experiment suggest that the addition of a phosphorus sorbent clay associated with an aluminium based coagulant is an effective technique in removing soluble reactive phosphorus and reducing C. raciborskii growth rate – cyanobacteria potentially toxic dominant in reservoirs of Brazilian semiarid – but this effect is dependent on the biomass in the application moment. Results from a field experiment in mesocosm in a eutrophied lake showed that the addition of aluminium based coagulant and removal of benthivorous fish is more efficient in removing total phosphorus and chlorophyll-a from water column than the isolated application of one of the techniques. Lastly, laboratory tests showed that aluminium based coagulant exhibited good performance in removing turbidity and total phosphorus from water of six reservoirs but the efficiency was reduced by algal biomass and pH. The results of this study showed that the improvement in water quality of eutrophied reservoirs in semiarid region is possible through internal loading control by phosphorus precipitation and inactivation in sediments or inhibition of phosphorus release by benthivorous fishes, and also that these results show are additives in water quality improvement.

A study of methods used to analyze total oil and polycyclic aromatic hydrocarbons in produced water: steps towards the validation of molecularly imprinted polymers for use in marine environmetns

Produced water is a by-product of offshore oil and gas production, and is released in large volumes when platforms are actively processing crude oil. Some pollutants are not typically removed by conventional oil/water separation methods and are discharged with produced water. Oil and grease can be found dispersed in produced water in the form of tiny droplets, and polycyclic aromatic hydrocarbons (PAHs) are commonly found dissolved in produced water. Both can have acute and chronic toxic effects in marine environments even at low exposure levels. The analysis of the dissolved and dispersed phases are a priority, but effort is required to meet the necessary detection limits. There are several methods for the analysis of produced water for dispersed oil and dissolved PAHs, all of which have advantages and disadvantages. In this work, EPA Method 1664 and APHA Method 5520 C for the determination of oil and grease will be examined and compared. For the detection of PAHs, EPA Method 525 and PAH MIPs will be compared, and results evaluated. APHA Method 5520 C Partition-Infrared Method is a liquid-liquid extraction procedure with IR determination of oil and grease. For analysis on spiked samples of artificial seawater, extraction efficiency ranged from 85 – 97%. Linearity was achieved in the range of 5 – 500 mg/L. This is a single-wavelength method and is unsuitable for quantification of aromatics and other compounds that lack sp³-hybridized carbon atoms. EPA Method 1664 is the liquid-liquid extraction of oil and grease from water samples followed by gravimetric determination. When distilled water spiked with reference oil was extracted by this procedure, extraction efficiency ranged from 28.4 – 86.2%, and %RSD ranged from 7.68 – 38.0%. EPA Method 525 uses solid phase extraction with analysis by GC-MS, and was performed on distilled water and water from St. John’s Harbour, all spiked with naphthalene, fluorene, phenanthrene, and pyrene. The limits of detection in harbour water were 0.144, 3.82, 0.119, and 0.153 g/L respectively. Linearity was obtained in the range of 0.5-10 g/L, and %RSD ranged from 0.36% (fluorene) to 46% (pyrene). Molecularly imprinted polymers (MIPs) are sorbent materials made selective by polymerizing functional monomers and crosslinkers in the presence of a template molecule, usually the analytes of interest or related compounds. They can adsorb and concentrate PAHs from aqueous environments and are combined with methods of analysis including GC-MS, LC-UV-Vis, and desorption electrospray ionization (DESI)- MS. This work examines MIP-based methods as well as those methods previously mentioned which are currently used by the oil and gas industry and government environmental agencies. MIPs are shown to give results consistent with other methods, and are a low-cost alternative improving ease, throughput, and sensitivity. PAH MIPs were used to determine naphthalene spiked into ASTM artificial seawater, as well as produced water from an offshore oil and gas operation. Linearity was achieved in the range studied (0.5 – 5 mg/L) for both matrices, with R² = 0.936 for seawater and R² = 0.819 for produced water. The %RSD for seawater ranged from 6.58 – 50.5% and for produced water, from 8.19 – 79.6%.

Advanced Aerogel Composites for Oil Remediation and Recovery

Oil spills in marine environments often damage marine and coastal life if not remediated rapidly and efficiently. In spite of the strict enforcement of environmental legislations (i.e., Oil Pollution Act 1990) following the Exxon Valdez oil spill (June 1989; the second biggest oil spill in U.S. history), the Macondo well blowout disaster (April 2010) released 18 times more oil. Strikingly, the response methods used to contain and capture spilled oil after both accidents were nearly identical, note that more than two decades separate Exxon Valdez (1989) and Macondo well (2010) accidents.

The goal of this dissertation was to investigate new advanced materials (mechanically strong aerogel composite blankets-Cabot® Thermal Wrap™ (TW) and Aspen Aerogels® Spaceloft® (SL)), and their applications for oil capture and recovery to overcome the current material limitations in oil spill response methods. First, uptake of different solvents and oils were studied to answer the following question: do these blanket aerogel composites have competitive oil uptake compared to state-of-the-art oil sorbents (i.e., polyurethane foam-PUF)? In addition to their competitive mechanical strength (766, 380, 92 kPa for Spaceloft, Thermal Wrap, and PUF, respectively), our results showed that aerogel composites have three critical advantages over PUF: rapid (3-5 min.) and high (more than two times of PUF’s uptake) oil uptake, reusability (over 10 cycles), and oil recoverability (up to 60%) via mechanical extraction. Chemical-specific sorption experiments showed that the dominant uptake mechanism of aerogels is adsorption to the internal surface, with some contribution of absorption into the pore space.

Second, we investigated the potential environmental impacts (energy and chemical burdens) associated with manufacturing, use, and disposal of SL aerogel and PUF to remove the oil (i.e., 1 m3 oil) from a location (i.e., Macondo well). Different use (single and multiple use) and end of life (landfill, incinerator, and waste-to-energy) scenarios were assessed, and our results demonstrated that multiple use, and waste-to-energy choices minimize the energy and material use of SL aerogel. Nevertheless, using SL once and disposing via landfill still offers environmental and cost savings benefits relative to PUF, and so these benefits are preserved irrespective of the oil-spill-response operator choices.

To inform future aerogel manufacture, we investigated the different laboratory-scale aerogel fabrication technologies (rapid supercritical extraction (RSCE), CO2 supercritical extraction (CSCE), alcohol supercritical extraction (ASCE)). Our results from anticipatory LCA for laboratory-scaled aerogel fabrication demonstrated that RSCE method offers lower cumulative energy and ecotoxicity impacts compared to conventional aerogel fabrication methods (CSCE and ASCE).

The final objective of this study was to investigate different surface coating techniques to enhance oil recovery by modifying the existing aerogel surface chemistries to develop chemically responsive materials (switchable hydrophobicity in response to a CO2 stimulus). Our results showed that studied surface coating methods (drop casting, dip coating, and physical vapor deposition) were partially successful to modify surface with CO2 switchable chemical (tributylpentanamidine), likely because of the heterogeneous fiber structure of the aerogel blankets. A possible solution to these non-uniform coatings would be to include switchable chemical as a precursor during the gel preparation to chemically attach the switchable chemical to the pores of the aerogel.

Taken as a whole, the implications of this work are that mechanical deployment and recovery of aerogel composite blankets is a viable oil spill response strategy that can be deployed today. This will ultimately enable better oil uptake without the uptake of water, potential reuse of the collected oil, reduced material and energy burdens compared to competitive sorbents (e.g., PUF), and reduced occupational exposure to oiled sorbents. In addition, sorbent blankets and booms could be deployed in coastal and open-ocean settings, respectively, which was previously impossible.

Variables Affecting the Collection and Preservation of Human Scent Components through Instrumental and Biological Evaluations

In certain European countries and the United States of America, canines have been successfully used in human scent identification. There is however, limited scientific knowledge on the composition of human scent and the detection mechanism that produces an alert from canines. This lack of information has resulted in successful legal challenges to human scent evidence in the courts of law. The main objective of this research was to utilize science to validate the current practices of using human scent evidence in criminal cases. The goals of this study were to utilize Headspace Solid Phase Micro Extraction Gas Chromatography Mass Spectrometry (HS-SPME-GC/MS) to determine the optimum collection and storage conditions for human scent samples, to investigate whether the amount of DNA deposited upon contact with an object affects the alerts produced by human scent identification canines, and to create a prototype pseudo human scent which could be used for training purposes. Hand odor samples which were collected on different sorbent materials and exposed to various environmental conditions showed that human scent samples should be stored without prolonged exposure to UVA/UVB light to allow minimal changes to the overall scent profile. Various methods of collecting human scent from objects were also investigated and it was determined that passive collection methods yields ten times more VOCs by mass than active collection methods. Through the use of polymerase chain reaction (PCR) no correlation was found between the amount of DNA that was deposited upon contact with an object and the alerts that were produced by human scent identification canines. Preliminary studies conducted to create a prototype pseudo human scent showed that it is possible to produce fractions of a human scent sample which can be presented to the canines to determine whether specific fractions or the entire sample is needed to produce alerts by the human scent identification canines.

Desenvolvimento de método para determinação de resíduos de sedativos e B-bloqueadores em rim por LC-MS/MS

O desenvolvimento de métodos adequados que permitam o monitoramento de resíduos e contaminantes em alimentos é de suma importância pois é a única forma de garantir a segurança dos alimentos evitando danos à saúde do consumidor. Para isso, fazse necessário que estes métodos sejam rápidos, fáceis e de baixo custo, capazes de detectar a presença de resíduos em concentrações baixas e em diferentes matrizes. Este trabalho consistiu no desenvolvimento de método para determinação de 5 sedativos e 14 β-bloqueadores em amostras de rim suíno e posterior análise por Cromatografia Líquida Acoplada à Espectrometria de Massas em Série (LC-MS/MS). O procedimento de extração que melhor se adequou para análise destes compostos consistiu na pesagem de 2 g de amostra e adição de 10 mL de acetonitrila seguida de homogeneização com auxílio de Ultra-Turrax e mesa agitadora. Após extração, as amostras foram submetidas a duas técnicas de clean-up, sendo elas, congelamento do extrato à baixa temperatura e extração em fase sólida dispersiva (d-SPE) utilizando como sorvente Celite® 545. Uma etapa de concentração foi realizada com auxílio de concentrador de amostras sob fluxo de N2 e temperatura controlada. As amostras secas foram retomadas com metanol e analisadas utilizando sistema LC-MS/MS com Ionização por Eletrospray (ESI), operando no modo MRM positivo, coluna Poroshell 120 EC-C18 (3,0 x 50 mm, 2,7 μm) para separação dos analitos, e gradiente de fase móvel composta por (A) solução aquosa acidificada com 0,1% de ácido fórmico (v/v) e (B) metanol 0,1% ácido fórmico (v/v). Os parâmetros de validação avaliados foram linearidade, seletividade, efeito matriz, precisão, veracidade, recuperação, limite de decisão, capacidade de detecção, incerteza da medição, robustez, limite de detecção e de quantificação. Além disso foram observados os critérios de desempenho aplicáveis à detecção por espectrometria de massas e estabilidade dos compostos. A recuperação foi avaliada em 10 μg kg-1 e a veracidade em 5, 10 e 15 μg kg-1 apresentando resultados satisfatórios entre 70 - 85% e 90 - 101%, respectivamente. O limite de quantificação determinado foi de 2,5 μg kg-1 , exceto para carazolol que foi de 1,25 μg kg- 1 . O estudo de linearidade foi realizado entre 0 e 20 μg kg-1 apresentando coeficientes de determinação superiores a 0,98. Estes procedimentos foram realizados através de análise de matriz branca fortificada. Além disso, o presente método foi utilizado para analisar carazolol, azaperone e azaperol em amostras de ensaio colaborativo de rim suíno, apresentando resultados muito próximos aos reais. Portanto, é possível concluir que o método desenvolvido é adequado para análise de sedativos e β-bloqueadores através de extração dos compostos e limpeza do extrato eficientes utilizando procedimentos rápidos, fáceis e de baixo custo, garantindo resultados seguros e confiáveis.

Application of chitosan loaded with metal oxide nano particles to remove lead present from sea water

Chitosan is a natural polymer obtained by deacetylation of chitin. After cellulose chitin is the second most abundant polysaccharide in nature. It is biologically safe, non-toxic, biocompatible and biodegradable polysaccharide. Chitosan loaded with zinc oxide nanoparticles have gained more attention bio sorbent because of their better stability, low toxicity, simple and mild preparation method and high sorption capacity. Chitosan loaded with zinc oxide nanoparticles have been prepared of chitosan. The physicochemical properties of nanoparticles were characterized by Fourier Transform Infrared (FTIR), Scanning Electron Microscope (SEM) Analysis. Its sorption capacity for lead and cadmium ions studied. Factors such as initial concentration of lead ions, cadmium ions sorbent amount, contact time, pH and temperature were investigated. It is found that chitosan loaded with zinc oxide nanoparticles could sorb lead and cadmium ions effectively, this sorption rate was affected significantly by initial concentration of lead and cadmium ions, sorbent amount, contact time, pH of solution. The maximum of percentage of lead sorption was 98 % with initial concentration 3 mg/l and sorbent amount 0.05 g, pH 11 in 45 min and cadmiumwas90 %with initial concentration 3mg/l and sorbent amount 0.05 g, pH 11 in45 min. Consequently chitosan loaded with zinc oxide nanoparticles demonstrated greater fixation ability for lead ions than cadmium ions.

Biosorción en tanque agitado de Cd(+2) y Pb(+2) con cáscara de cacao

En la búsqueda de tecnologías más limpias para el tratamiento de efluentes que contienen metales pesados se ha dirigido la atención hacia la biosorción. Este estudio permitió abordar el proceso de biosorción de 〖Cd〗^(+2)y 〖Pb〗^(+2) en efluentes mineros a través de la cáscara de cacao. Se determinó las características físico-químicas del biosorbente y el resultado obtenido fue: la cáscara de cacao tiene una superficie neutra, compuesta principalmente por grupos ésteres alifáticos; además se estudió los factores que afectan este proceso como son: pH, tamaño de partícula, tiempo de contacto, Temperatura, y la concentración inicial del metal. El pH óptimo para la biosorción de plomo es entre 4 y 5 y para el cadmio fue entre 5 y 6; con respecto al tiempo de contacto necesario para eliminar la mayor cantidad de iones metálicos fue de 10 minutos, siendo el resultado obtenido en la remoción tanto de cadmio como de plomo de 86,92% y 96,74% respectivamente. Se observó que la temperatura no afecta significativamente el proceso de biosorción como el pH y se determinó como óptima 25℃ ; también se analizó que la cáscara de cacao tiene mayor afinidad por el cadmio por tener un radio iónico más pequeño que el plomo permitiéndole alcanzar poros reducidos; además al aumentar la concentración, la eliminación de cadmio disminuyó y para el plomo aumentó pero no de forma significativa. Los datos experimentales de la biosorción de plomo y cadmio en cáscara de cacao, reproducen favorablemente el modelo cinético Pseudo Segundo Orden, con coeficientes de correlación (R^2) para 〖Pb〗^(+2) de 0,999 y 〖Cd〗^(+2) de 1. Finalmente en el estudio de equilibrio el modelo de Langmuir describe el proceso de adsorción para 〖Cd〗^(+2) y el modelo de Fleundlich se ajustó mejor a los datos experimentales para 〖Pb〗^(+2).