Mercury determination in urine samples by gold nanostructured screen-printed carbon electrodes after vortex-assisted ionic liquid dispersive liquid–liquid microextraction

A novel approach is presented to determine mercury in urine samples, employing vortex-assisted ionic liquid dispersive liquid–liquid microextraction and microvolume back-extraction to prepare samples, and screen-printed electrodes modified with gold nanoparticles for voltammetric analysis. Mercury was extracted directly from non-digested urine samples in a water-immiscible ionic liquid, being back-extracted into an acidic aqueous solution. Subsequently, it was determined using gold nanoparticle-modified screen-printed electrodes. Under optimized microextraction conditions, standard addition calibration was applied to urine samples containing 5, 10 and 15 μg L−1 of mercury. Standard addition calibration curves using standards between 0 and 20 μg L−1 gave a high level of linearity with correlation coefficients ranging from 0.990 to 0.999 (N = 5). The limit of detection was empirical and statistically evaluated, obtaining values that ranged from 0.5 to 1.5 μg L−1, and from 1.1 to 1.3 μg L−1, respectively, which are significantly lower than the threshold level established by the World Health Organization for normal mercury content in urine (i.e., 10–20 μg L−1). A certified reference material (REC-8848/Level II) was analyzed to assess method accuracy finding 87% and 3 μg L−1 as the recovery (trueness) and standard deviation values, respectively. Finally, the method was used to analyze spiked urine samples, obtaining good agreement between spiked and found concentrations (recovery ranged from 97 to 100%).

Screen-printed electrode-based electrochemical detector coupled with in-situ ionic-liquid-assisted dispersive liquid–liquid microextraction for determination of 2,4,6-trinitrotoluene

A novel method is reported, whereby screen-printed electrodes (SPELs) are combined with dispersive liquid–liquid microextraction. In-situ ionic liquid (IL) formation was used as an extractant phase in the microextraction technique and proved to be a simple, fast and inexpensive analytical method. This approach uses miniaturized systems both in sample preparation and in the detection stage, helping to develop environmentally friendly analytical methods and portable devices to enable rapid and onsite measurement. The microextraction method is based on a simple metathesis reaction, in which a water-immiscible IL (1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [Hmim][NTf2]) is formed from a water-miscible IL (1-hexyl-3-methylimidazolium chloride, [Hmim][Cl]) and an ion-exchange reagent (lithium bis[(trifluoromethyl)sulfonyl]imide, LiNTf2) in sample solutions. The explosive 2,4,6-trinitrotoluene (TNT) was used as a model analyte to develop the method. The electrochemical behavior of TNT in [Hmim][NTf2] has been studied in SPELs. The extraction method was first optimized by use of a two-step multivariate optimization strategy, using Plackett–Burman and central composite designs. The method was then evaluated under optimum conditions and a good level of linearity was obtained, with a correlation coefficient of 0.9990. Limits of detection and quantification were 7 μg L−1 and 9 μg L−1, respectively. The repeatability of the proposed method was evaluated at two different spiking levels (20 and 50 μg L−1), and coefficients of variation of 7 % and 5 % (n = 5) were obtained. Tap water and industrial wastewater were selected as real-world water samples to assess the applicability of the method.

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.

Dispersive liquid–liquid microextraction for metals enrichment: A useful strategy for improving sensitivity of laser-induced breakdown spectroscopy in liquid samples analysis

A rapid and efficient Dispersive Liquid–Liquid Microextraction (DLLME) followed by Laser-Induced Breakdown Spectroscopy detection (LIBS) was evaluated for simultaneous determination of Cr, Cu, Mn, Ni and Zn in water samples. Metals in the samples were extracted with tetrachloromethane as pyrrolidinedithiocarbamate (APDC) complexes, using vortex agitation to achieve dispersion of the extractant solvent. Several DLLME experimental factors affecting extraction efficiency were optimized with a multivariate approach. Under optimum DLLME conditions, DLLME-LIBS method was found to be of about 4.0–5.5 times more sensitive than LIBS, achieving limits of detection of about 3.7–5.6 times lower. To assess accuracy of the proposed DLLME-LIBS procedure, a certified reference material of estuarine water was analyzed.

Quantification of free auxins in semi-hardwood plant cuttings and microshoots by dispersive liquid–liquid microextraction/microwave derivatization and GC/MS analysis

Several studies have suggested that differences in the natural rooting ability of plant cuttings could be attributed to differences in endogenous auxin levels. Hence, during rooting experiments, it is important to be able to routinely monitor the evolution of endogenous levels of plant hormones. This work reports the development of a new method for the quantification of free auxins in auxin-treated Olea europaea (L.) explants, using dispersive liquid–liquid microextraction (DLLME) and microwave assisted derivatization (MAD) followed by gas chromatography/mass spectrometry (GC/MS) analysis. Linear ranges of 0.5–500 ng mL 1 and 1–500 mg mL 1 were used for the quantification of indole-3-acetic acid (IAA) and indole-3-butyric acid (IBA), respectively. Determined by serial dilutions, the limits of detection (LOD) and quantification (LOQ) were 0.05 ng mL 1 and 0.25 ng mL 1, respectively for both compounds. When using the calibration curve for determination, the LOQ corresponded to 0.5 ng mL 1 (IAA) and 0.5 mg mL 1 (IBA). The proposed method proved to be substantially faster than other alternatives, and allowed free auxin quantification in real samples of semi-hardwood cuttings and microshoots of two olive cultivars. The concentrations found in the analyzed samples are in the range of 0.131–0.342 mg g 1 (IAA) and 20–264 mg g 1 (IBA).

Tungsten coil atomic emission spectrometry combined with dispersive liquid–liquid microextraction: A synergistic association for chromium determination in water samples

A novel and environment friendly analytical method is reported for total chromium determination and chromium speciation in water samples, whereby tungsten coil atomic emission spectrometry (WCAES) is combined with in situ ionic liquid formation dispersive liquid–liquid microextraction (in situ IL-DLLME). A two stage multivariate optimization approach has been developed employing a Plackett–Burman design for screening and selection of the significant factor involved in the in situ IL-DLLME procedure, which was later optimized by means of a circumscribed central composite design. The optimum conditions were complexant concentration: 0.5% (or 0.1%); complexant type: DDTC; IL anion: View the MathML sourcePF6−; [Hmim][Cl] IL amount: 60 mg; ionic strength: 0% NaCl; pH: 5 (or 2); centrifugation time: 10 min; and centrifugation speed: 1000 rpm. Under the optimized experimental conditions the method was evaluated and proper linearity was obtained with a correlation coefficient of 0.991 (5 calibration standards). Limits of detection and quantification for both chromium species were 3 and 10 µg L−1, respectively. This is a 233-fold improvement when compared with chromium determination by WCAES without using preconcentration. The repeatability of the proposed method was evaluated at two different spiking levels (10 and 50 µg L−1) obtaining coefficients of variation of 11.4% and 3.6% (n=3), respectively. A certified reference material (SRM-1643e NIST) was analyzed in order to determine the accuracy of the method for total chromium determination and 112.3% and 2.5 µg L−1 were the recovery (trueness) and standard deviation values, respectively. Tap, bottled mineral and natural mineral water samples were analyzed at 60 µg L−1 spiking level of total Cr content at two Cr(VI)/Cr(III) ratios, and relative recovery values ranged between 88% and 112% showing that the matrix has a negligible effect. To our knowledge, this is the first time that combines in situ IL-DLLME and WCAES.

Determination of cyclic and linear siloxanes in wastewater samples by ultrasound-assisted dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry

A fast, simple and environmentally friendly ultrasound-assisted dispersive liquid-liquid microextraction (USA-DLLME) procedure has been developed to preconcentrate eight cyclic and linear siloxanes from wastewater samples prior to quantification by gas chromatography-mass spectrometry (GC-MS). A two-stage multivariate optimization approach has been developed employing a Plackett-Burman design for screening and selecting the significant factors involved in the USA-DLLME procedure, which was later optimized by means of a circumscribed central composite design. The optimum conditions were: extractant solvent volume, 13 µL; solvent type, chlorobenzene; sample volume, 13 mL; centrifugation speed, 2300 rpm; centrifugation time, 5 min; and sonication time, 2 min. Under the optimized experimental conditions the method gave levels of repeatability with coefficients of variation between 10 and 24% (n=7). Limits of detection were between 0.002 and 1.4 µg L−1. Calculated calibration curves gave high levels of linearity with correlation coefficient values between 0.991 and 0.9997. Finally, the proposed method was applied for the analysis of wastewater samples. Relative recovery values ranged between 71–116% showing that the matrix had a negligible effect upon extraction. To our knowledge, this is the first time that combines LLME and GC-MS for the analysis of methylsiloxanes in wastewater samples.

Desenvolvimento de método para determinação de ferro e cobre em vinho por espectrofotometria empregando DLLME

Este trabalho propõe o desenvolvimento de métodos de preparo de amostra empregando a microextração líquido-líquido dispersiva (DLLME) para a extração e pré- concentração de Fe e Cu em vinho, seguido da determinação espectrofotométrica na região do ultravioleta-visível (UV-Vis). Nas extrações por DLLME, a complexação de Fe e Cu foi feita com pirrolidina ditiocarbamato de amônio (APDC) e dietilditiocarbamato de sódio (DDTC), respectivamente. Para a DLLME, foi usada uma mistura apropriada de pequenos volumes de dois solventes, um extrator e outro dispersor, a qual foi rapidamente injetada na amostra aquosa, ocorrendo à formação de uma dispersão e a extração praticamente instantânea dos analitos. Na otimização da DLLME para extração de Fe foram avaliados alguns parâmetros como, tipo de solvente extrator (C2Cl4, 80 µL) e dispersor (acetonitrila, 1300 µL) e seus volumes, pH (3,0), concentração do APDC (1%, m/v), adição de NaCl (0,02 mol L -1 ) e tempo de extração. Para extração de Cu foi aplicado um planejamento fatorial completo 25 para avaliar a influência de cinco variáveis independentes: volume dos solventes dispersor (acetonitrila, 1600 µL) e extrator (CCl4, 60 µL), concentração de DDTC (2%, m/v), pH (3,0) e concentração de NaCl. Após a otimização das condições para Fe, a curva de calibração com adição de analito foi linear entre 0,2 e 2,5 mg L-1 para vinho branco (R2 = 0,9985) e para vinho tinto (R2 = 0,9988). Para Cu, a curva de calibração com adição de analito foi linear entre 0,05 e 1,0 mg L-1 para vinho branco (R2 = 0,9995) e para vinho tinto (R2 = 0,9986). Os limites de quantificação foram de 0,75 e 0,37 mg L-1 para Fe e Cu, respectivamente. A exatidão foi avaliada utilizando ensaio de recuperação, as quais variaram entre 96% e 112%, com desvio padrão relativo inferior a 8%. Os métodos foram aplicados para 5 amostras de vinho branco e 5 amostras de vinho tinto, obtendo-se concentrações entre 1,3 e 5,3 e entre 2,5 e 4,4 mg L-1 para Fe e entre 0,4 e 1,5 e entre 0,9 e 2,5 mg L-1 para Cu, respectivamente. Os métodos desenvolvidos para a extração e pré-concentração de Fe e Cu em vinhos por DLLME e quantificação por UV-Vis mostraram-se adequados, em termos de linearidade, exatidão e precisão.

Otimização e validação de métodos empregando DLLME e DLLME-SFO para a extração simultânea de agrotóxicos multiclasse em água mineral

O Rio Grande Sul destaca-se no cenário nacional como grande produtor de diversas culturas, as quais demandam grande quantidade de agrotóxicos das mais diversas classes químicas e toxicidades. No entanto a intensa utilização destes compostos torna-se uma preocupação devido a possíveis contaminações das águas superficiais e subterrâneas. Em virtude da degradação dos mananciais a água mineral passou a ser uma das fontes mais utilizadas para o consumo humano, pois tem-se a percepção de que a mesma possui melhor qualidade que a água tratada, além disso acredita-se que a mesma esta isenta de substâncias orgânicas prejudiciais à saúde humana. Neste trabalho, foi realizada a determinação dos agrotóxicos atrazina, simazina, imazapique, imazetapir, imidacloprido, ciproconazol, tebuconazol e epoxiconazol em água mineral empregando a Microextração Líquido-Líquido Dispersiva (DLLME), Microextração Líquido-Líquido Dispersiva com Solidificação da Gota Orgânica Flutuante (DLLME-SFO) e Cromatografia Líquida acoplada à Espectrometria de Massas em série com fonte de ionização por Eletronebulização (LC-ESI-MS/MS). Para o método empregando DLLME e LC-ESI-MS/MS foram otimizados alguns fatores como o tipo e volume de solvente extrator e dispersor e pH. Após a otimização dos parâmetros de extração, fragmentação dos compostos e separação cromatográfica, o método foi validado avaliando-se curva analítica, linearidade, limites de detecção e quantificação, precisão (repetitividade e precisão intermediária) e exatidão (recuperação). Todas as curvas analíticas apresentaram valores de r maiores que 0,999. Os Limites de Quantificação (LOQs) para o método estiveram na faixa de 5 a 500 ng L-1. Foram obtidas recuperações entre 102 - 120% para a repetibilidade e entre 92 e 110% para a precisão intermediária, com RSD de 2 a 10% para todos os compostos. Para o método empregando DLLME-SFO e LC-ESI-MS/MS foram avaliados alguns parâmetros que afetam a eficiência da extração como, tipo e volume de solvente extrator e dispersor, força iônica e pH. Nas condições ótimas de extração todas as curvas analíticas apresentaram valores de r maiores que 0,997. Os LOQs para o método variaram entre 12,5 - 125 ng L-1. As recuperações foram entre 70 e 118% para a repetitividade e entre 76 e 95% para a precisão intermediária, com RSD de 2 a 18% para todos os compostos. Com relação ao Efeito Matriz (EM) avaliado para todos os compostos pelos dois métodos, foi observado baixo EM. Isso indicou que não é necessário utilizar a curva analítica preparada no extrato branco da matriz para a quantificação destes analitos. Ambos os métodos foram aplicados para a determinação de resíduos de agrotóxicos em amostras de água mineral provenientes de diferentes regiões do estado do Rio Grande do Sul e não foram encontrados resíduos de agrotóxicos nas amostras analisadas. Os métodos validados apresentaram como principais vantagens baixo consumo de solventes orgânicos e amostra, rapidez, altos fatores de concentração e recuperações dentro da faixa aceitável. Os limites de quantificação dos métodos ficaram abaixo dos limites máximos de resíduos permitidos pela legislação brasileira para agrotóxicos em água mineral.

Avaliação da combinação da nebulização discreta e processos de microextração aplicados à determinação de molibdênio por espectrometria de absorção atômica com chama (FAAS)

Simple and sensitive procedures for the extraction/preconcentration of molybdenum based on vortex-assisted solidified floating organic drop microextraction (VA-SFODME) and cloud point combined with flame absorption atomic spectrometry (FAAS) and discrete nebulization were developed. The influence of the discrete nebulization on the sensitivity of the molybdenum preconcentration processes was studied. An injection volume of 200 µL resulted in a lower relative standard deviation with both preconcentration procedures. Enrichment factors of 31 and 67 and limits of detection of 25 and 5 µg L-1 were obtained for cloud point and VA-SFODME, respectively. The developed procedures were applied to the determination of Mo in mineral water and multivitamin samples.

Avaliação da técnica de dispersão da matriz em fase sólida assistida por vórtex para análise de fármacos em peixes

Os fármacos classificados como contaminantes orgânicos emergentes tornaramse tópico de discussão ambiental pois estes são capazes de atingir diferentes matrizes do meio ambiente, como água, solo e organismos aquáticos, e estudos demonstrando a toxicidade tem despertado o interesse científico. Neste estudo um método analítico foi otimizado e validado para determinação de quinze fármacos em amostras de peixes empregando preparo de amostras por dispersão da matriz em fase sólida (MSPD) assistida por vórtex e determinação por cromatografia líquida acoplada a espectrometria de massas sequencial (LC-MS/MS). O estudo ainda focou na aplicação de diferentes suportes sólidos na etapa de dispersão da MSPD, sendo que três (quitina, quitosana e concha de mexilhão dourado) foram utilizados pela primeira vez para esta finalidade, O método otimizado foi validado seguindo os parâmetros do INMETRO, ANVISA, SANCO e FDA. A curva analítica e linearidade foram avaliados através da calibração externa e superposição na matriz. Os compostos demonstraram linearidade dentro da faixa recomendada, com coeficiente de correlação maior do que 0,99. Os limites de detecção do método variaram de 1 a 100 ng g -1 , e os limites de quantificação a variaram de 5 a 1000 ng g -1 . Os valores de recuperação variaram de 68% a 108%, com RSD menores que 13% para todos os compostos. O efeito de matriz foi avaliado e quatro dos quinze compostos apresentaram efeito maior que ±20%. Na aplicabilidade o método demonstrou ser eficiente para extração de fármacos de diferentes espécies de peixe, apresentando exatidão e precisão adequados. Não foram encontrados resíduos de fármacos nas amostras analisadas.

Determination of estrogenic mycotoxins in environmental water samples by low-toxicity dispersive liquid-liquid microextraction and liquid chromatography-tandem mass spectrometry

A novel, simple, rapid and eco-friendly method based on dispersive liquid-liquid microextraction using a bromosolvent was developed to determine six estrogenic mycotoxins (zearalenone, zearalanone, alpha-zearalanol, beta-zearalanol, alpha-zearalenol and beta-zearalenol) in water samples by liquid chromatography-electrospray ionization tandem mass spectrometry in the negative mode (LC-ESI-MS/MS). The optimal conditions for this method include the use of 100 mu L bromocyclohexane as an extraction solvent (using a non-dispersion solvent), 10 mL of aqueous sample (adjusted to pH 4), a vortex extraction time of 2 min, centrifugation for 10 min at 3500 rpm and no ionic strength adjustment. The calibration function was linear and was verified by applying the Mandel fitting test with a 95% confidence level. No matrix effect was observed. According to the relative standard deviations (RSDs), the precision was better than 13% for the repeatability and intermediate precision. The average recoveries of the spiked compounds ranged from 81 to 118%. The method limits of detection (LOD) and quantification (LOQ) considering a 125-fold pre-concentration step were 4-20 and 8-40 ng L-1, respectively. Next, the method was applied to the analysis of the environmental aqueous samples, demonstrating the presence of beta-zearalanol and zearalanone in the river water samples. (C) 2015 Elsevier B.V. All rights reserved.

Development and validation of a novel method for the analysis of chlorinated pesticides in soils using microwave-assisted extraction–headspace solid phase microextraction and gas chromatography–tandem mass spectrometry

A new procedure for determining eleven organochlorine pesticides in soils using microwave-assisted extraction (MAE) and headspace solid phase microextraction (HS-SPME) is described. The studied pesticides consisted of mirex, α- and γ-chlordane, p,p’-DDT, heptachlor, heptachlor epoxide isomer A, γ-hexachlorocyclohexane, dieldrin, endrin, aldrine and hexachlorobenzene. The HS-SPME was optimized for the most important parameters such as extraction time, sample volume and temperature. The present analytical procedure requires a reduced volume of organic solvents and avoids the need for extract clean-up steps. For optimized conditions the limits of detection for the method ranged from 0.02 to 3.6 ng/g, intermediate precision ranged from 14 to 36% (as CV%), and the recovery from 8 up to 51%. The proposed methodology can be used in the rapid screening of soil for the presence of the selected pesticides, and was applied to landfill soil samples.

Tandem use of solid-phase extraction and dispersive liquid-liquid microextraction for the determination of mononitrotoluenes in aquatic environment.

Solid-phase extraction (SPE) in tandem with dispersive liquid-liquid microextraction (DLLME) has been developed for the determination of mononitrotoluenes (MNTs) in several aquatic samples using gas chromatography-flame ionization (GC-FID) detection system. In the hyphenated SPE-DLLME, initially MNTs were extracted from a large volume of aqueous samples (100 mL) into a 500-mg octadecyl silane (C(18) ) sorbent. After the elution of analytes from the sorbent with acetonitrile, the obtained solution was put under the DLLME procedure, so that the extra preconcentration factors could be achieved. The parameters influencing the extraction efficiency such as breakthrough volume, type and volume of the elution solvent (disperser solvent) and extracting solvent, as well as the salt addition, were studied and optimized. The calibration curves were linear in the range of 0.5-500 μg/L and the limit of detection for all analytes was found to be 0.2 μg/L. The relative standard deviations (for 0.75 μg/L of MNTs) without internal standard varied from 2.0 to 6.4% (n=5). The relative recoveries of the well, river and sea water samples, spiked at the concentration level of 0.75 μg/L of the analytes, were in the range of 85-118%.

Ion pair-dispersive liquid-liquid microextraction of trace amount of rhodium ion in water and road dust samples prior to flame atomic absorption spectrometry determination

A simple ion pair-dispersive liquid-liquid microextraction method was proposed for preconcentration trace amounts of rhodium. An ion association complex of RhCl4- and tetradecyldimetylbenzylamonium was extracted into cholorobenzene. The volume and the type of extractive and dispersive solvents, the extraction time and the pH of the aqueous solutions were optimized. The calibration curve was linear in the range of 0.6-500 ng mL-1 of rhodium. The limit of detection was 0.10 ng mL-1 in initial solution and preconcentration factor was 40. The proposed method was successfully applied to the extraction and determination of rhodium in road dust and water samples.