Oxalate determination in urine using an immobilized enzyme on Sorghum vulgare seeds in a flow injection conductimetric system

A flow-injection (FI) method was developed for the determination of oxalate in urine. It was based on the use of oxalate oxidase (E.C. 1.2.3.4) immobilized on ground seeds of the BR-303 Sorghum vulgare variety. A reactor was filled with this activated material, and the samples (200 μL) containing oxalate were passed through it, carried by a deionized water flow. The carbon dioxide produced by the enzyme reaction permeated through a microporous PTFE membrane, and was received in a water acceptor stream, promoting conductivity changes proportional to the oxalate concentration in the sample. The results obtained showed a useful linear range from 0.05 to 0.50 mmol dm-3. The proposed method, when compared with the Sigma enzymatic procedure, showed good correlation (Y = 0.006(±0.016) + 0.98(±0.019)X; r = 0.9995, Y = conductivity in μS, and X = concentration in mmol dm-3), selectivity, and sensitivity. The new immobilization approach promotes greater stability, allowing oxalate determination for 6 months. About 13 determinations can be performed per hour. The precision of the proposed method is about ± 3.2 % (r.s.d).

Detection of circulating Paracoccidioides brasiliensis antigen in urine of paracoccidioidomycosis patients before and during treatment

For the diagnosis and follow-up of paracoccidioidomycosis patients undergoing therapy, we evaluated two methods (immunoblotting and competition enzyme immunoassay) for the detection of circulating antigen in urine samples. A complex pattern of reactivity was observed in the immunoblot test. Bands of 70 and 43 kDa were detected more often in urine samples from patients before treatment. The immunoblot method detected gp43 and gp70 separately or concurrently in 11 (91.7%) of 12 patients, whereas the competition enzyme immunoassay detected antigenuria in 9 (75%) of 12 patients. Both tests appeared to be highly specific (100%), considering that neither fraction detectable by immunoblotting was present in urine samples from the control group. gp43 remained present in the urine samples collected during the treatment period, with a significant decrease in reactivity in samples collected during clinical recovery and increased reactivity in samples collected during relapses. Reactivity of some bands was also detected in urine specimens from patients with 'apparent cure.' The detection of Paracoccidioides brasiliensis antigens in urine appears to be a promising method for diagnosing infection, for evaluating the efficacy of treatment, and for detecting relapse.

Determination of vanadium in urine by electrothermal atomic absorption spectrometry using hot injection and preconcentration into the graphite tube

In this work it was developed a procedure for the determination of vanadium in urine samples by electrothermal atomic absorption spectrometry using successive injections for preconcentration into a preheated graphite tube. Three 60 μL volumes were sequentially injected into the atomizer preheated to a temperature of 110°C. Drying and pyrolysis steps were carried out after each injection. A chemical modifier, barium difluoride (100 mg L-1), and a surfactant, Triton X-100 (0.3% v v-1), were added to the urine sample. When injecting into a hot graphite tube, the sample flow-rate was 0.5 μL s-1. The limits of detection and quantification were 0.54 and 1.82 without preconcentration, and 0.11 and 0.37 μg L-1 with preconcentration, respectively. The accuracy of the procedure was evaluated by an addition-recovery experiment employing urine samples. Recoveries varied from 96.0 to 103% for additions ranging from 0.8 to 3.5 μg L-1 V. The developed procedure allows the determination of vanadium in urine without any sample pretreatment and with minimal dilution of the sample.

Non-nutrient heavy metals in tomato plants cultivated in soil amended with biosolid and sugar-cane bagasse compost

In this study, non-nutrient heavy metal concentrations (Cd, Cr, Ni and Pb) were measured in composts during the composting process, in compost/Red-yellow Latosol mixtures, and in tomato plants. Composts were produced using sugar-cane bagasse, biosolids and cattle manure in the proportions 75-0-25, 75-12.5-12.5, 75-25-0, 50-50-0 or 0-100-0 (composts with 0, 12.5, 25, 50 and 100% biosolids). The composts were applied to the soil, in 6 treatments and a control (mineral fertilization). Control and the 0% biosolids treatments received inorganic nitrogen and all the treatments received the same amount of N, P and K. Tomato plants were cultivated in 24-L pots, in a green house in Jaboticabal, SP, Brazil. The experiment had a split plot design, in randomized blocks. Cadmium, Cr, Ni and Pb concentrations were determined during the composting process (7, 27, 57, 97 and 127 days after compost mounting), in soil (0 and 164 days after mixing) and plants. The samples were subjected to digestion with HNO 3, H2O2 and HCl and the metals were determined by AAS. Negative correlations were observed between Cd, Cr and Pb in the compost and Cd, Cr and Pb plant uptake, as well as Ni in the compost and Ni concentration in the plants. The concentrations of Cd, Cr, Ni and Pb increased during composting. Only Cd levels increased when compost was applied to the soil. The roots accumulated Cr, Ni and Pb, the stems and leaves, Cd and Ni and the fruits did not accumulate any of the metals studied. The composts with biosolids did not increase Cd, Cr, Ni and Pb uptake by plants.

Quantitative analysis of potentially toxic metals in alginates for dental use

Alginate is one the materials most employed in practice to make dental impressions. Substances like zinc, cadmium and lead silicate, which are included in several alginate brands with the aim of improving their physical, chemical and mechanical properties, are a source of serious concern as regards their toxicity. The most serious chronic effect of oral exposure to cadmium is renal toxicity. Assimilation of lead has deleterious effects on the gastrointestinal tract, hematopoietic system, cardiovascular system, central and peripheral nervous systems, kidneys, immune system, and reproductive system. Chronic oral exposures to zinc have resulted in hypochromic and microcyte anemia in some individuals. The aim of the present study was to measure the cadmium, lead and zinc contents of seven brands of alginate for dental use on sale in Brazil. The samples were weighed and placed in the Teflon cups of a closed-system microwave oven. Aqua regia (4mL concentrated HCI:HNO3, 3:1 v/v) and hydrofluoric acid (2mL concentrated HF) were added to the samples, which were then subjected to heating. The samples were then cooled to room temperature and diluted to 25 mL in deionized water in a volumetric glass flask. The samples were diluted in duplicate and analyzed against a reagent blank. The analyses were performed in an atomic absorption flame spectrophotometer. Neither lead nor cadmium was detected. Zinc contents ranged from 0.001% to 1.36% by weight. The alginates exhibited low contents of the metals under study and gave no cause for concern regarding toxicity; even so, it is advisable to monitor potentially toxic materials continually and to analyze their plasmatic levels in the professionals working with them.

In vitro and in vivo inhibition of acetylcholinesterase and carboxylesterase by metals in zebrafish (Danio rerio)

Metals are natural components in ecosystems; however, if these elements are in excess, they can have adverse effects on living organisms. This study analyzes the interference of copper, lead, iron and cadmium in acetylcholinesterase (AChE) and carboxylesterase (CbE) activities in zebrafish. AChE was significantly inhibited in vitro by copper, iron, lead and cadmium at higher concentrations (10 and 20 mmol/L), whereas CbE was inhibited only at a concentration of 20 mmol/L. In vivo, only lead and cadmium were able to cause AChE inhibition at higher concentrations, while iron didn't cause any changes, and copper promoted an increase in AChE activity at a concentration of 0.06 mg/L. CbE activity did not change at any of the times (two and seven days) and concentrations tested, except in the case of copper exposure, which resulted in a decrease in CbE activity. Indeed, iodoacetamide treatment didn't changed AChE neither CbE activities, results which indicate that the metal inhibiting effect is probably not due to its biding to thiol groups close the active site of the enzyme. This outcome reveals that metals are important esterase inhibitors in zebrafish, and should be considered in environmental monitoring studies that use esterase inhibition as exposure biomarkers of organophosphate and carbamate pesticides. © 2012 Elsevier Ltd. All rights reserved.

Evaluation of metals in water and sediments of micro-basins in the city of Americana, São Paulo state, Brazil

Water pollution found in major rivers in Brazil has its origin from urban sewage discharges and industrial effluent, carried out by small streams and rivers crossing cities. Therefore, studies related to hydrographic micro-basins offer the opportunity to establish environmental management strategies for restoring water resources, based on diagnosis of the water quality. Despite this understanding, few studies in urban and rural areas have been performed in a systematic manner in Brazilian micro-basins. The main goal of this research was to diagnose the water resources in micro-basins in the region of the district of Americana, São Paulo state, Brazil, through the quantification of metals in water and sediment. The methodology was based on the investigation of metals (Ba, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Zn), in four micro-basins, determined by inductively coupled plasma optical emission spectrometry (ICP-OES). The most significant result showed high concentration levels of chromium (969 μg L-1), downstream of the discharge of sewage from the city of Nova Odessa. This concentration in the river was above the allowed limit of Brazilian regulation agency (50 μg L-1 for Cr). Also high levels of Cr were found in the sediment (98.9 μg g-1) collected at the same monitored site. These results are important indicators of environmental performance and anthropogenic activities to help the government establish environmental management strategies aimed at the reduction of water pollution. © 2013 WIT Press.

Sol-gel thin-film based mesoporous silica and carbon nanotubes for the determination of dopamine, uric acid and paracetamol in urine

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

Heavy metals in cowpea (Vigna unguiculata L.) after tannery sludge compost amendment

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

False positivity of gamma-glutamyl transpeptidase measurement in urine

Although enzymuria tends to be associated to renal injury, there are no studies that have evaluated the presence of the enzyme gamma-glutamyl transpeptidase (GGT) spectrophotometry in the urine using a non-nephrotoxic agent (Nerium oleander) in order to evaluate the possibility of false positive results. The urinary GGT/urinary creatinine concentration ratio (uGGT/uCr) of 10 healthy dogs was calculated and posteriorly confronted with data from clinical evaluation, hematological and serum biochemical profiles, creatinine clearance (CrC), urinalysis, urine protein/creatinine ratio (UPC), electrocardiogram, systemic blood pressure (SBP) and light and electron microscopy. The results for kidney histology, SBP, UPC and CrC were not significantly different in any of the time-points analyzed. However, uGGT/uCr was significantly higher when measured 4 hours and 24 hours after administration of N. oleander. The measurement of the urinary GGT enzyme, as performed in many studies, yielded false positive results in dogs poisoned by a non-nephrotoxic agent.

Use of Chemometric Tools to Determine the Source of Metals in Sediments of the Rivers of the Turvo/Grande Hydrographical Basin, Sao Paulo State, Brazil

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

NUTRITIONAL STATUS AND LEVELS OF HEAVY METALS IN LETTUCE PLANTS FERTILIZED WITH ORGANIC COMPOUNDS

The use of organic compounds has been a good option to reduce spending on fertilizers, and gain increased productivity in the cultivation of lettuce. However, given the wide variety of raw materials used in the preparation of organic compounds, studies are needed to evaluate its effects on the release of essential nutrients to plants and on the release of contaminants such as heavy metals. The aim of this study was to evaluate the mineral nutrition and heavy metal contamination of lettuce in soils treated with doses and types of compost. The experiment was conducted in a greenhouse in randomized blocks in factorial scheme 5x4, with five types of organic compounds and four nitrogen levels (0, 35, 70 and 140 kg ha(-1) of N), with four replications. In general, the doses of the compounds were not enough to provide the necessary quantity of nutrients to the lettuce, with the exception of nitrogen. There was no increase in levels of heavy metals in the soil above that allowed by Brazilian legislation. Furthermore, compounds based on manure plus grass, and commercial compound caused increases in Zn concentration in plants at levels above the recommended for consumed.

Thermal and spectroscopic study of the 3,4-(methylenedioxy) cinnamate compounds of transition metals in the solid state

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

Use of Cathorops spixii as bioindicator of pollution of trace metals in the Santos Bay, Brazil

In the present study Cathorops spixii, was evaluated as a bioindicator fish for trace metal pollution. Concentrations of cobalt (Co), iron (Fe), selenium (Se) and zinc (Zn) were determined by Instrumental Neutron Activation Analysis in liver. Mercury (Hg) and methyl-mercury (MeHg) were analyzed by Cold Vapor Atomic Absorption Spectrometry in muscles and livers. High concentrations of Co, Fe, Se and Zn were observed in C. spixii from Santos Bay in comparison to fish collected in a non-polluted site in the same Brazilian coast. These trace metal concentrations were out of the permissible levels for human consumption. Although, Hg and MeHg levels were low, the C. spixii could still be used as an effective bioindicator to observe trace metal behaviors in the environment in function of the bioaccumulation process observed mainly by other analyzed trace metals. Thus, the use of this species is strongly recommended to monitor the effects and behavior of trace metal pollution in aquatic ecosystems in Brazil due to its bioaccumulation function.

Metals and semi-metals in street soils of So Paulo city, Brazil

So Paulo is the largest city in Brazil and South America with about 20 million inhabitants in the metropolitan area, more than nine million motor vehicles and intense industrial activity, which are responsible for increasing pollution in the region. Nevertheless, little is known concerning metal and semi-metal content in the soils of this metropolitan region. This type of information could be extremely useful as a fingerprint of environmental pollution. The present study determined the elements As, Ba, Co, Cr, Sb, and Zn concentrations in soils adjacent to avenues of highly dense traffic in So Paulo city to assess their levels and possible sources. The analytical technique employed was Instrumental neutron activation analysis. The results showed, except for Co, concentration levels higher than the reference values for soils of So Paulo, according to the Environmental Protection Agency of the State of So Paulo guidelines. When compared to similar studies in other cities around the world, So Paulo soils presented higher levels, probably due to its high density traffic and industrial activity. The concentrations obtained for As and Cr indicate anthropogenic origin. The high levels of the traffic-related elements Ba, Sb, and Zn in soils nearby high density traffic avenues indicate they may originate from vehicular exhausts.