Simultaneous determination of As, Cu, Mn, Sb, and Se in drinking water by GRAS with transversely heated graphite atomizer and longitudinal Zeeman-effect background correction

A method has been developed for the direct and simultaneous determination of As, Cu, Mn, Sb, and Se in drinking water by electrothermal atomic absorption spectrometry (ETAAS) using a transversely heated graphite tube atomizer (THGA) with longitudinal Zeeman-effect back- ground correction. The thermal behavior of analytes during the pyrolysis and atomization stages was investigated in 0.028 mol L-1 HNO3, 0.14 mol L-1 HNO3 and 1 + 1 (v/v) diluted water using mixtures of Pd(NO3)(2) + Mg(NO3)(2) as the chemical modifier, With 5 mug Pd + 3 mug Mg as the modifier, the pyrolysis and atomization temperatures of the heating program of the atomizer were fixed at 1400degreesC and 2100degreesC, respectively, and 20 muL of the water sample (sample + 0.28 mol L-1 HNO3, 1 + 1, v/v), dispensed into the graphite tube, analytical curves were established ranging from 5.00 - 50.0 mug L-1 for As, Sb, Se; 10.0 - 100 mug L-1 for Cu; and 20.0 - 200 mug L-1 for Mn. The characteristic masses were around 39 pg As, 17 pg Cu, 60 pg Mn, 43 pg Sb, and 45 pg Se, and the lifetime of the tube was around 500 firings. The limits of detection (LOD) based on integrated absorbance (0.7 mug L-1 As, 0.2 mug L-1 Cu, 0.6 mug L-1 Mn, 0.3 mug L-1 Sb, 0.9 mug L-1 Se) exceeded the requirements of the Brazilian Food Regulations (decree # 310-ANVS from the Health Department), which established the maximum permissible level for As, Cu, Mn, Sb, and Se at 50 mug L-1, 1000 mug L-1, 2000 mug L-1, 5 mug L-1, and 50 mug L-1, respectively. The relative standard deviations (n = 12) were typically < 5.3% for As, < 0.5% for Cu, < 2.1% for Mn, < 11.7% for Sb, and < 9.2% for Se. The recoveries of As, Cu, Mn, Sb, and Se added to the mineral water samples varied from 102-111%, 91-107%, 92-109%, 89-97%, and 101-109%, respectively. Accuracy for the determination of As, Cu, Mu Sb and Se was checked using standard reference materials NIST SRM 1640 - Trace Elements in Natural Water, NIST SRM 1643d - Trace Elements in Water, and 10 mineral water samples. A paired t-test showed that the results were in agreement with the certified values of the standard reference materials at the 95% confidence level.

Chronopotentiometric stripping analysis using gold electrodes, an efficient technique for mercury quantification in natural waters

This paper proposes a simple methodology for mercury quantification in natural water by stripping chronopotentiometry at constant current, using gold (film) electrodes constructed from recordable CDs in stationary cell. The proposed method allows the direct measurement of labile mercury in natural waters. To quantify total mercury, a robust and low cost UV irradiation system was developed for the degradation of organic constituents of water. The proposed system presents such advantages as excellent sensitivity, low cost, versatility, and smaller dimensions (portability for on-field applications) when compared with other techniques (ICP, GFAAS, fluorimetry) traditionally utilized for mercury quantification. A large linear region of responses was observed, situated over the range 0.02 - 200 μ g L-1. Various experimental parameters were optimized and the system allowed quantifications in natural samples, with detection limit of 8 ng L-1 and excellent reproducibility (RSD of 1.4% for 48 repetitive measurements using a 10 μ g L-1 mercury solution). Different metal ions were evaluated, including copper, as possible interferences on stripping mercury signals. Applications of the new method were demonstrated for the analysis of certified and groundwater samples spiked with a known amount of mercury and for the quantification of methylmercury in synthetic oceanic water, originally utilized for fishes contamination experiment.

Simultaneous determination of As, Cu, Mn, Sb, and Se in drinking water by GFAAS with transversely heated graphite atomizer and longitudinal zeeman-effect background correction

A method has been developed for the direct and simultaneous determination of As, Cu, Mn, Sb, and Se in drinking water by electrothermal atomic absorption spectrometry (ETAAS) using a transversely heated graphite tube atomizer (THGA) with longitudinal Zeeman-effect background correction. The thermal behavior of analytes during the pyrolysis and atomization stages was investigated in 0.028 mol L-1 HNO3, 0.14 mol L-1 HNO3 and 1 + 1 (v/v) diluted water using mixtures of Pd(NO3)2 + Mg(NO3)2 as the chemical modifier. With 5 μg Pd + 3 μg Mg as the modifier, the pyrolysis and atomization temperatures of the heating program of the atomizer were fixed at 1400°C and 2100°C, respectively, and 20 μL of the water sample (sample + 0.28 mol L-1 HNO3, 1 + 1, v/v), dispensed into the graphite tube, analytical curves were established ranging from 5.00 -50.0 μg L-1 for As, Sb, Se; 10.0 - 100 μg L-1 for Cu; and 20.0 - 200 μg L-1 for Mn. The characteristic masses were around 39 pg As, 17 pg Cu, 60 pg Mn, 43 pg Sb, and 45 pg Se, and the lifetime of the tube was around 500 firings. The limits of detection (LOD) based on integrated absorbance (0.7 μg L-1 As, 0.2 μg L-1 Cu, 0.6 μg L-1 Mn, 0.3 μg L-1 Sb, 0.9 μg L-1 Se) exceeded the requirements of the Brazilian Food Regulations (decree # 310-ANVS from the Health Department), which established the maximum permissible level for As, Cu, Mn, Sb, and Se at 50 μg L-1, 1000 μg L-1, 2000 μg L-1, 5 μg L-1, and 50 μg L-1, respectively. The relative standard deviations (n = 12) were typically < 5.3% for As, < 0.5% for Cu, < 2.1% for Mn, < 11.7% for Sb, and < 9.2% for Se. The recoveries of As, Cu, Mn, Sb, and Se added to the mineral water samples varied from 102-111%, 91-107%, 92-109%, 89-97%, and 101-109%, respectively. Accuracy for the determination of As, Cu, Mn, Sb, and Se was checked using standard reference materials NIST SRM 1640 - Trace Elements in Natural Water, NIST SRM 1643d - Trace Elements in Water, and 10 mineral water samples. A paired t-test showed that the results were in agreement with the certified values of the standard reference materials at the 95% confidence level.

Evaluation of the mixtures ammonium phosphate/magnesium nitrate and palladium nitrate/magnesium nitrate as modifiers for simultaneous determination of Cd, Cr, Ni and Pb in mineral water by GFAAS

A method is described for the simultaneous determination of Cd, Cr, Ni and Pb in mineral water samples by graphite furnace atomic absorption spectrometry with a transversely heated graphite atomizer (THGA) and a longitudinal Zeeman-effect background correction system. The electrothermal behavior of analytes during pyrolysis and atomization steps was studied without modifier, in presence of 5 μg Pd and 3 μg Mg(NO3)2 and in presence of 50 μg NH4H2PO4 and 3 μg Mg(NO3)2. A volume of 20 μL of a 0.028 mol L -1 HNO3 solution containing 50 μg L-1 Ni and Pb, 10 μg L-1 Cr and 5 μg L-1 Cd was dispensed into the graphite tube at 20°C. The mixture palladium/magnesium was selected as the optimum modifier. The pyrolysis and atomization temperatures were fixed at 1000°C and 2300°C, respectively. The characteristic masses were calculated as 2.2 pg Cd, 10 pg Cr, 42 pg Ni and 66 pg Pb and the lifetime of the graphite tube was around 600 firings. Limits of detection based on integrated absorbance were 0.02 μg L-1Cd, 0.94 μg L-1 Cr, 0.45 μg L-1 Ni and 0.75 μg L-1 Pb, which exceeded the requirements of Brazilian Food Regulation that establish the maximum permissible level for Cd, Cr, Ni and Pb at 3 μg L-1, 50 μg L-1, 20 μg L-1 and 10 μg L-1, respectively. The recoveries of Cd, Cr, Ni and Pb added to mineral water samples varied within the 93-108%, 96-104%, 87-101% and 98-108% ranges, respectively. Results of analysis of standard reference materials (National Institute of Standards and Technology: 1640-Trace Elements in Natural Water; 1643d-Trace Elements in Water) were in agreement with certified values at the 95% confidence level.

UV filters in water samples: Experimental design on the SPE optimization followed by GC-MS/MS analysis

Esse estudo descreve o desenvolvimento e otimização de um método de extração em fase solida (SPE) para análise dos filtros ultravioletas (UV): benzofenona-3 (BP-3), etilhexil salicilato (ES), etilhexil metoxinamato (EHMC) e octocrileno (OC) em matrizes ambientais. Um planejamento fatorial fracionário (PFF) 25-1 foi empregado na avaliação das variáveis significativas do método de extração. As condições experimentais otimizadas da avaliação estatística foram: capacidade do cartucho de 500 mL, eluente acetato de etila, metanol como solvente de lavagem (10% em água, v/v) and volume do eluente de 3 × 2 mL e pH 3. Os parâmetros analíticos avaliados foram satisfatõrios, apresentando linearidade de 100 a 4000 ng L -1, recuperaç ões para os quatro níveis de fortificação (Limite de Quantificação do Método, 200, 1000 e 2000 ng L-1) entre 62 e 107% com desvio padrão relativo menor que 14%. Os limites de quantificação foram encontrados na faixa de ng L-1, variando entre 10 e 100 ng L-1. O método proposto foi aplicado para a determinação dos quatro filtros UV em amostras de águas naturais. This study describes the development and optimization of a solid-phase extraction (SPE) method for analysis of ultraviolet (UV) filters, benzophenone-3 (BP-3), ethylhexyl methoxycinnamate (EHMC), ethylhexyl salicylate (ES) and octocrylene (OC), in environmental matrices. A 25-1 fractional factorial design (FFD) was used to evaluate the significant variables for the extraction method. The optimized experimental conditions determined from the statistical evaluation were: breakthrough volume of 500 mL, eluent of ethyl acetate, wash solvent of methanol (10% in water, v/v), eluent volume of 3 × 2 mL and pH 3. The evaluated analytical parameters were satisfactory for the analytes and showed linearity between 100 and 4000 ng L-1, recoveries for four fortification levels (Method Quantification Limit, 200, 1000 and 2000 ng L-1) were between 62 and 107% with relative standard deviations less than 14%. Limits of quantification were in the ng L-1 range and were between 10 and 100 ng L-1. The proposed method was used to analyze four UV filters in natural water samples. ©2013 Sociedade Brasileira de Química.

Determination of Tetracycline in Environmental Water Samples at a Graphite-Polyurethane Composite Electrode

A bare graphite-polyurethane composite was evaluated in the tetracycline (TC) determination in natural water samples. Using differential pulse voltammetry (DPV), a linear response was observed in the range of 4.00-40.0 mu mol L-1 with limit of detection of 2.80 mu mol L-1, without the need of surface renewing between successive runs. During the tetracycline determination in water samples, recoveries between 92.6 and 100% were found. The results for TC determination in water samples after a pre-concentration stage agreed with spiked value at a 95% confidence level according to student t-test.

Determination of atenolol in environmental water samples and pharmaceutical formulations at a graphite-epoxy composite electrode

A bare graphite-epoxy composite was evaluated as an electrode material in the determination of atenolol in natural water samples and pharmaceutical formulations for which the analyte was spiked. Using a DPV procedure, a linear response was observed in the 4.45-84.7 mu mol L-1 range with a LOD = 2.23 mu mol L-1, without need of surface renewal between successive runs, and recoveries between 92.5 and 107.5% for pharmaceutical formulations. The results obtained from the proposed procedure agreed with HPLC results within a 95% confidence level. During the determination of atenolol in water samples, recoveries between 96.1 and 102.6% were found.

Determination of tetracycline in environmental water samples at a graphite-polyurethane composite electrode

A bare graphite-polyurethane composite was evaluated in the tetracycline (TC) determination in natural water samples. Using differential pulse voltammetry (DPV), a linear response was observed in the range of 4.00-40.0 µmol L-1 with limit of detection of 2.80 µmol L-1, without the need of surface renewing between successive runs. During the tetracycline determination in water samples, recoveries between 92.6 and 100% were found. The results for TC determination in water samples after a pre-concentration stage agreed with spiked value at a 95% confidence level according to student t-test.

Veterinary drugs in drinking water used for pharmaceutical treatments in breeding farms

Water is susceptible to be used for numerous purposes, including edible, both for humans and animals. In the food animal production, drinking water is frequently used as a way to carry out the most common pharmacological treatments. In these cases, there are many variables which could degrade drugs dissolved in this mean, even when properly arranged pharmaceutical formulations are used. In fact, although a product obtains a Marketing Authorization through appropriate laboratory studies both drug stability and solubility, on the other hand the solubility of the same drug in natural water used as a drinking water is not documented. In the present study has been evaluated the dissolution kinetics (at 0 hours and 24 hours) of products, having oxytetracycline and tylosin as active ingredient, used in drinking water samples in order to see how the different physical and chemical factors that characterize the drinking water may affect therapeutic efficacy. In fact, multiple factors, also of little relevance if individually considered, are able to adversely affect the pharmacological treatment carried out in drinking water.

Hydrologic and Water Quality Assessment of Miller Run: A Study of Bucknell University’s Impact

Human development causes degradation of stream ecosystems due to impacts on channel morphology, hydrology, and water quality. Urbanization, the second leading cause of stream impairment, increases the amount of impervious surface cover, thus reducing infiltration and increasing surface runoff of precipitation, which ultimately affects stream hydrologic process and aquatic biodiversity. The main objective of this study was to assess the overall health of Miller Run, a small tributary of the Bull Run and Susquehanna River watersheds, through an integrative hydrologic and water quality approach in order to determine the degree of Bucknell University’s impact on the stream. Hydrologic conditions, including stage and discharge, and water quality conditions, including total suspended solids, ion, nutrient, and dissolved metal concentrations, specific conductivity, pH, and temperature, were measured and evaluated at two sampling sites (upstream and downstream of Bucknell’s main campus) during various rain events from September 2007 to March 2008. The primary focus of the stream analysis was based on one main rain event on 26 February 2008. The results provided evidence that Miller Run is impacted by Bucknell’s campus. From a hydrologic perspective, the stream’s hydrograph showed the exact opposite pattern of what would be expected from a ‘normal’ stream. Miller run had a flashier downstream hydrograph and a broader upstream hydrograph, which was more than likely due to the increased amount of impervious surface cover throughout the downstream half of the watershed. From a water quality perspective, sediment loads increased at a faster rate and were significantly higher downstream compared to upstream. These elevated sediment concentrations were probably the combined result of sediment runoff from upstream and downstream construction sites that were being developed over the course of the study. Sodium, chloride, and potassium concentrations, in addition to specific conductivity, also significantly increased downstream of Bucknell’s campus due to the runoff of road salts. Calcium and magnesium concentrations did not appear to be impacted by urbanization, although they did demonstrate a significant dilution effect downstream. The downstream site was not directly affected by elevated nitrate concentrations; however, soluble reactive phosphorus concentrations tended to increase downstream and ammonium concentrations significantly peaked partway through the rain event downstream. These patterns suggest that Miller Run may be impacted by nutrient runoff from the golf course, athletic fields, and/or fertilizers applications on the main campus. Dissolved manganese and iron concentrations also appeared to slightly increase downstream, demonstrating the affect of urban runoff from roads and parking lots. pH and temperature both decreased farther downstream, but neither showed a significant impact of urbanization. More studies are necessary to determine how Miller Run responds to changes in season, climate, precipitation intensity, and land-use. This study represents the base-line analysis of Miller Run’s current hydrologic and water quality conditions; based on these initial findings, Bucknell should strongly consider modifications to improve storm water management practices and to reduce the campus’s overall impact on the stream in order to enhance and preserve the integrity of its natural water resources.

Species of Fusarium isolated from river and sea water of Southeastern Spain and pathogenicity on four plant species

Species of Fusarium were isolated from water samples collected from the Andarax River and coastal sea water of the Mediterranean in Granada and Almería provinces of southeastern Spain. In total, 18 water samples were analyzed from the Andarax River, and 10 species of Fusarium were isolated: Fusarium anthophilum, F. acuminatum, F. chlamydosporum, F. culmorum, F. equiseti, F. verticillioides, F. oxysporum, F. proliferatum, F. solani, and F. solani. When considering the samples by their origins, 77.8% of the river water samples yielded at least one species of Fusarium , with F. oxysporum comprising 72.2% of the total isolates. In the case of marine water, 45.5% of the samples yielded at least one species of Fusarium, with F. solani comprising 36.3% of the total isolates. The pathogenicity of 41 isolates representing nine of the species collected from river an sea water during the study ws evluated on barley, kohlrabe, melon, and tomato. Inoculation with F. acuminatum, F. chlamydosporum, F. culmorum, F. equiseti, F. verticillioides, F. oxysporum, F. proliferatum F. solani, and F. sambucinum resulted in pre-and post-emergence damping off. Pathogenicity of Fusarium isolates did not seem to be related to the origin of the isolates (sea water or fresh water). However, the presence of pathogenic species of Fusarium in river water flowing to the sea could indicate long-distance dispersal in natural water environments

(Table 2) Concentrations of dissolved aluminum in interstitial water from sediments of the Indian Ocean

Results are presented of application of laser stepwise photoionization of atoms in combination with thermal atomization of matter in vacuum for direct determination of aluminum dissolved in sea and interstitial waters. Dry residue from evaporation of 40 ?l sea water was atomized in a crucible at 1800°C, and aluminum atoms in the beam thus formed were energized into Rydberg state in two steps by two tunable dye laser beams; the atoms were then ionized by an electric pulse and resulting ions were recorded by secondary emission electron multiplier (ion detector). Ionic signal dependence on sample vaporization time was studied. The procedure is suggested for separating out a selective signal in a single measurement. Dissolved aluminum concentrations in interstitial waters of the Indian Ocean and in waters of the river-sea zone were determined using preliminarily plotted calibration characteristics for aluminum solutions in deionized and sea waters. The minimum detectable Al concentration in seawater was 1 ?g/l that corresponds to 40 pg of Al in a sample.

Aquatic invertebrates in final void water bodies at an open-cut coal mine in central Queensland

We describe the diversity of aquatic invertebrates colonising water-filled final voids produced by an open-cut coal mine near Moura, central Queensland. Ten disused pits that had been filled with water from < 1 year to 22 years prior to the survey and three nearby 'natural' water bodies were sampled in December 1998 and again in March 1999. All invertebrates collected were identified to family with the exception of oligochaetes, cladocerans, ostracods and copepods, which were identified to these coarser taxonomic levels. Sixty-two taxa were recorded from > 20 000 individuals. The greatest familial richness was displayed by the Insecta (33 families) followed by the mites (Acari) with 12 families. While natural water bodies held the greatest diversity, several mine pits were almost as rich in families. Classification analyses showed that natural sites tended to cluster together, but the groupings did not clearly exclude pit sites. Mining pits that supported higher diversity tended to be older and had lower salinity (< 2000 mu S/cm); however, salinity in all water bodies varied with rainfall conditions. We conclude that ponds formed in final voids at this mine have the potential to provide habitat for many invertebrate taxa typical of lentic inland water bodies in central Queensland.

Light Effects on Leaf Morphology in Water Hyacinth (Eichhornia crassipes)

Water hyacinth leaves in natural populations vary from being long and thin-petioled to being short with inflated petioles. A variety of factors has been used experimentally to alter water hyacinth leaf shape, but what controls the development of leaf morphology in the field has not been established. We measured photosynthetic photon flux density (PPFD) and spectral distribution of radiation in a natural water hyacinth population. PPFD in the center of the water hyacinth mat was reduced to 2.7% of full sunlight, and the red to far red (R:FR) ratio was reduced to 0.28. When shoot tips of plants were exposed to artificial light environments, only plants in the treatment with a R:FR ratio comparable to that in the natural population produced leaves with long, thin petioles. Shoot tips in full sun or covered with clear plastic bags or bags that reduced light quantity without greatly altering light quality produced shorter leaves with inflated petioles. We hypothesize that the altered light quality inside a mat is a major environmental control of water hyacinth leaf morphology.

Water Quality and Wet Season Diatom Assemblage Characteristics from the Tamiami Trail Pilot Swales Sites (Everglades National Park, Florida, USA)

A pivotal component of hydrological restoration of the Florida Everglades is the improvement of water conveyance to Everglades National Park by the degradation of the current network of canals, roadways and levees. The Tamiami Trail (L29) road/canal complex represents a major barrier to natural water flows into the park and a variety of modification options for flow improvement are currently being explored, including the installation of spreader swales immediately downstream of culverts conveying water under Tamiami Trail from the L29 canal into Everglades National Park. In this study, we evaluated water column chemistry and wet-season diatom community structure to provide baseline information for use in future monitoring activities related to the proposed Tamiami Trail modifications. Water chemistry showed pronounced fluctuations in response to precipitation and anthropogenically mediated hydrological events. Differences in water quality variables among sites were dampened during periods of inundation, and became more pronounced during periods of low canal stage, suggesting the importance of small-scale mechanisms related to isolation of habitat patches. Diatom assemblages were unexpectedly speciose (127 taxa in 40 samples) compared to typical Everglades assemblages, and spatially heterogeneous in sites associated with concentric areas of dense vegetation immediately downstream of culverts. We also observed significant compositional dissimilarities among transects, indicating that culvert pool and north transect assemblages were substantially influenced by propagule input from the canal and areas to the north, while south transect sites were compositionally similar to typical sawgrass prairie diatom communities. Central transect sites were compositionally intermediate to their north and south counterparts. We propose that the position and spatial extent of this “transitional assemblage” is a sensitive indicator of subtle environmental change related to Tamiami Trail modifications.