Environmental and anthropic variabilities at Guanabara Bay (Brazil): A comparative perspective of metal depositions in different time scales during the last 5,500 yrs.

The determination of age-dated metal sediment accumulation rates in a representative South American bay is able to portray the dimension of human impacts during the colonial occupation and industrial periods. Many studies have assessed metal distribution and chronology at Guanabara Bay, in Brazil. However, understanding natural variabilities associated to paleoclimatic changes and comparing these natural variabilities to anthropogenic processes are not well established to date. Accurate geochronological control integrating ages determined by 210Pb and 14C chronologies through an exponential spline fit model allowed for a precise definition of changes associated to the holocene marine transgression, as well as the colonial period, leading to intense land use changes, and the industrial period. The reference values of the system were defined based on their concentrations and the accumulation rates of ecotoxicologically important metals. Al, Ba, Fe, Cd, Cu, Cr, Li, Ni, Mn, Pb, Si, Ti, V, and Zn distributions were determined in a Guanabara Bay core (BG-28) by the EPA 3051 method. Elemental distribution profile assessment allowed for the identification of variabilities associated to weathering processes, predominantly of lithogenic origin, mainly for Al, Ba, Fe, Li, Si, and V. Weathering processes occurred simultaneously to land use changes in the drainage basin since the colonial period, at 400 cal yr BP, and during the industrial period, mainly after the 1960s, denoted by Cd, Cr, Cu, Mn, Pb and Zn increases. The highest average metal enrichment values metals associated to industrial processes reached 5.95, with 119.1-fold higher accumulation rates than the background accumulation values observed between 4200 and 500 cal yr BP.

Sediment metal enrichment and ecological risk assessment of ten ports and estuaries in the World Harbours Project.

Ten global harbours were assessed for sediment quality by quantifying the magnitude of anthropogenic change and ecological risk. Anthropogenic change (enrichment) was high for Derwent River and Sydney estuary, moderate for Santander Harbour, Rio de Janeiro and Dublin Port, slight for Hong Kong, minimal for Darwin. All 10 enrichment indices used showed similar results. Derwent River sediment was rated at high ecological risk, followed by Sydney and Santander estuaries with moderate risk. Auckland and Darwin sediments exhibited minimal ecological risk and sediment in the remaining harbours (Dublin, Hong Kong, Ravenna, Ria de Vigo and Rio de Janeiro) were assessed at slight ecological risk. The extraordinary variety of environments and types/quantities/qualities of data investigated resulted in as much a critique and development of methodology, as an assessment of human impact, including unique techniques for elemental normalisation and contaminant classification. Recommendations for an improved technical framework for sediment quality assessment are provided.

Metal-Associated Biomarker Responses in Crabs from a Marine Protected Area in Southeastern Brazil.

The environmental quality of a Ramsar wetland site located at the Cananéia-Iguape-Peruíbe Protected Area (CIP-PA), in São Paulo, Brazil, was assessed by geochemical analyses and biomarker assessments (GPx, GST, GSH, GST, MT, LPO, DNA damage) performed in swimming crab Callinectes danae Smith, 1869 organs (posterior and anterior gills and hepatopancreas) to estimate sediment contaminant bioavailability. The results indicated that two sampling stations, PT and PM, exhibited the worst environmental conditions, as sediments collected at both points contained metal contamination, while crabs exhibited significant responses for GPx, GST, and LPO (mostly during winter). Sediment contamination tended to be associated to fine sediments (both seasons) and organic matter (winter). During the summer survey, Pb concentrations in sediments of station PT exceeded the Brazilian Sediment Quality Guidelines (SQGs) and the Canadian Interim Marine Sediment Quality Guidelines. Metal concentrations in sediments sampled in winter were higher compared with summer, with Co, Ni, and Pb exceeding SQGs levels at PT, whereas Co, Ni, Hg, Zn, and Pb exceeded SQGs at PM. Biomarker induction during summer appeared to be caused by natural variables (water salinity and temperature, and molting cycle), whereas oxidative stress and tissue damage during winter appeared to be more clearly linked to metal contamination. Anterior gills presented the clearest signs of seasonal variability, being more responsive to sediment contamination. The results suggest that metals originated from the upper Ribeira de Iguape River are transported toward the estuarine system, causing effects on C. danae individuals. Additionally, seasonality is a strong factor concerning CIP-PA toxicity, since the rainfall regime significantly modifies the freshwater flow and, consequently, estuarine water salinity, suspended particle and metal inputs, as well as the location of depositional areas. Thus, efforts to mitigate CIP-PA contamination should be based on the control of upstream pollution sources.

Total Mercury in Carnivorous Fish from Brazilian Southeast.

Total mercury concentrations were determined by atomic absorption spectrometry in muscle tissue of two commercially important species of carnivorous fishes croaker (Micropogonias furnieri) and cutlassfish (Trichiurus lepturus) caught in Itaipu estuary, Rio de Janeiro. In this study, whitemouth croaker presented more mercury than Atlantic cutlassfish. Bioaccumulation differences can be explained by the biological behavior of juveniles whitemouth croaker, that remain in the estuary up to maturity, which makes them good indicators of local environmental impacts (0.110 mg Kg(-1) HgT). It also can be explained by differences in nutritional requirements between the different life stages of two species. The analysis showed the presence of low levels of the metal. However, our results suggest a possible risk to human health, depending on the level of fish consumption.

Metals in water, sediments, and biota of an offshore oil exploration area in the Potiguar Basin, Northeastern Brazil.

Metal concentrations were evaluated in water, bottom sediments, and biota in four field campaigns from 2002 to 2004 in the Potiguar Basin, northeastern Brazil, where offshore oil exploration occurs. Analyses were performed by inductively coupled plasma mass spectrometry and inductively coupled plasma optical emission spectrometry. Total metal concentrations in water (dissolved + particulate) and sediments were in the range expected for coastal and oceanic areas. Abnormally high concentrations in waters were only found for Ba (80 µg l(-1)) and Mn (12 µg l(-1)) at the releasing point of one of the outfalls, and for the other metals, concentrations in water were found in stations closer to shore, suggesting continental inputs. In bottom sediments, only Fe and Mn showed abnormal concentrations closer to the effluent releasing point. Metal spatial distribution in shelf sediments showed the influence of the silt-clay fraction distribution, with deeper stations at the edge of the continental shelf, which are much richer in silt-clay fraction showing higher concentrations than shallower sediments typically dominated by carbonates. Metal concentrations in estuarine (mollusks and crustaceans) and marine (fish) organisms showed highest concentrations in oysters (Crassostrea rhizophorae). Fish tissues metal concentrations were similar between the continental shelf influenced by the oil exploration area and a control site. The results were within the range of concentrations reported for pristine environments without metals contamination. The global results suggest small, if any, alteration in metal concentrations due to the oil exploration activity in the Potiguar Basin. For monitoring purposes, the continental inputs and the distribution of the clay-silt fraction need to be taken into consideration for interpreting environmental monitoring results.

Reactive sulfides relationship with metals in sediments from an eutrophicated estuary in Southeast Brazil.

The potential association of acid-volatile sulfides (AVS) and reactive (HCl soluble) Fe with the distribution of reactive trace metals (Cu, Cd, Ni, Pb and Zn) was investigated in sediment cores collected in the Iguaçu river estuarine system (Guanabara bay, Brazil), within the river (core R) and the bay (core B) areas. Moderate to extremely high AVS concentrations (33-314 micromol g(-1)) were found in the rapidly-accumulated sediments of this eutrophicated estuary. AVS showed significant correlations with Fe, Ni and Pb in core B, whereas no correlation between AVS and metals was observed in core R. Results suggest that the AVS:Fe molar ratio may often reflect the diagenetic conditions controlling the distribution of Cd and Cu in core B better than AVS and Fe levels themselves. A shift in the biogeochemical controls of metal distribution from the river to the open bay sediments is suggested, with a greater association of most metals with AVS and Fe in bay sediments.

Flow injection determination of cobalt after its sorption onto polyurethane foam loaded with 2-(2-thiazolylazo)-p-cresol (TAC).

This paper reports the development of a new methodology for determination of cobalt in water samples by using a flow injection system with loaded PUF as solid phase to preconcentrate analytes. Procedure is based on on-line retention of Co(III) ions (generated in alkaline medium by Co(II) oxidation) in a minicolumn packed with a polyether type polyurethane foam loaded with TAC (2-(2-thiazolylazo)-p-cresol) and elution with 2 mol l(-1) HCl directly to the flame atomic absorption spectrometer nebulizer. Several chemical and flow variables that could affect the performance of this system were investigated as well as the possible interferents. For 2 min of preconcentration time (10.0 ml of sample volume) the system achieved a detection limit 3.2 mug l(-1), a R.S.D. 5% at 20 mug l(-1) and an analytical throughput 24 h(-1). Whereas for 3 min of preconcentration time (15.0 ml of sample volume) a detection limit 2.4 mug l(-1), a R.S.D. under 8% at 10 mug l(-1) and a sampling frequency 17 h(-1) were reported.

Flow injection-FTIR determination of dithiocarbamate pesticides.

A flow injection Fourier transform infrared spectrometric procedure has been developed for the determination the dithiocarbamate pesticides Ziram and Thiram in solid samples. All the operations involved, such as extraction, filtration and measurement, were integrated in the experimental set-up in order to avoid excessive manipulation of samples and standards. Ultrasonic assisted and mechanical extraction were evaluated for the solubilization of the analytes and, additionally, the effect of carrier flow rate, sample loop volume and the ratio between sample mass and volume of solvent employed were studied. Quantitative extractions with chloroform were obtained for both Ziram and Thiram, after 5 and 2 min, respectively, of mechanical shaking of sample slurries. Absorbance measurement, in the wavenumber range of 1600-1460 cm-1 for Ziram and 1400-1315 cm-1 for Thiram, was carried out, and the area values of the peaks obtained, as a function of time, were interpolated in external calibration lines prepared from standard solutions of Ziram and Thiram in chloroform. Analyses of commercial formulations and spiked soil samples incubated two weeks were in a good agreement with values found by other methodologies. Absolute detection limits of 400 micrograms for Ziram and 785 micrograms for Thiram and variation coefficients of 6.4% and 2.5% were obtained by use of the aforementioned methodology.

Spectrophotometric determination of carbaryl by on-line elution after its preconcentration onto polyurethane foam.

An analytical methodology has been developed for the UV-spectrophotometric determination of carbaryl in waters after its preconcentration onto a polyether type polyurethane foam followed by on-line elution. The aforementioned strategy offers an easy way for in-field sampling and to improve the analytical sensitivity. Several chemical and flow variables (mass of sorbent, sample flow rate, sample volume and carrier flow rate) were studied to ensure the best performance of the system. Recovery studies, carried out on natural water samples spiked with known amounts of carbaryl at concentration levels between 250 and 500 mug l(-1), provided recovery percentages between 94 and 105%. A detection limit of 12 mug l(-1) was achieved and a variation coefficient of 3.4% was obtained at 0.50 mug ml(-1).

Lead preconcentration onto C-18 minicolumn in continuous flow and its determination in biological and vegetable samples by flame atomic absorption spectrometry.

A procedure for the preconcentration and determination of lead in vegetable and biological samples was developed in the continuous mode coupled to a flame atomic absorption spectrometer. Lead is quantitatively preconcentrated in acetic buffer as its diethyldithiocarbamate chelate onto a C-18 minicolumn, placed in the loop of a proportional injector, eluted by a stream of methyl isobutyl ketone and introduced directly into the nebuliser. A detection limit of 3 microg 1(-1) is obtained using a time-based technique for 2 min preconcentration and an RSD of 3.8% was readily achieved for three measurements of 25 microg Pb 1(-1). The sample throughput is 24 h(-1). Using preconcentration times of 10 min an enrichment factor of 189 can be obtained. The continuous flow system was used for some reference sample analysis and the obtained results reveal that the methodology can be easily applied for vegetable and biological sample analysis.

On the spectrophotometric flow injection determination of chromium(VI) in natural waters after on-line preconcentration on activated alumina.

The feasibility of chromium(VI) preconcentration on to activated alumina in a continuous flow system with spectrophotometric detection was investigated. Chemical and flow variables, and the influence of concomitant species were studied both with and without preconcentration systems. The best results were obtained by using a 2.5 cm long, 1.6 mm i.d. alumina minicolumn, and selecting 1 x 10(-4) M nitric acid as the preconcentrating medium and 0.1 M ammonium hydroxide as the eluent. The eluted chromium(VI) was mixed with diphenylcarbazide in acidic medium and the absorbance of the colored complex was measured at 540 nm. Linear calibrations for 5, 25 and 50 ml sample volumes were established over the concentration ranges 10-50 mug 1(-1), 2-10 mug 1(-1) and 1-5 mug 1(-1) with sensitivity enhancements of 44, 196 and 392 and detection limits (3sigma) of 3.0 mug 1(-1), 0.3 mug 1(-1) and 0.2 mug 1(-1), respectively. The methods is relatively fast and cheap. Natural waters were analyzed with use of the developed procedure.

Preconcentration and atomic absorption determination of copper traces in waters by on-line adsorption-elution on an activated carbon minicolumn.

A continuous preconcentration method for the determination of trace copper in waters was developed. Ammonium pyrrolidinedithiocarbamate is used to form a chelate which is adsorbed on an activated carbon minicolumn and desorbed with 200 mul of methyl isobutyl ketone. The organic extract is driven by a water stream to an atomic absorption spectrometer. By using a time-based technique equivalent to from 1.5 to 4.5 ml of sample, preconcentration factors between 35 and 100, respectively, are achieved. The flow system is quite simple and rapid, and provides highly precise results (RSD 1.8-3.5%). The results obtained in the determination of copper in waters show the usefulness of the proposed method.

A flow injection system with ion-exchange for spectrophotometric determination of copper in rocks.

A flow injection system is proposed for the spectrophotometric determination of copper in rocks. Samples are mineralized by treatment with hydrofluoric and perchloric acids and the solutions analysed after iron III precipitation. Copper is preconcentrated in a small CHELEX-100 resin column placed in the flow system, eluted with 2.5M nitric acid and further mixed with diethanoldithiocarbamate (DEDC) in basic medium. The coloured complex was monitored at 410 nm. With the proposed system, about 2-30 samples are run per hour with low reagent consumption. Beer's law is followed within 0.04 and 2.00, microg/ml. Precision and accuracy were assessed by using reference rock standards from USGS and GSJ with copper content as low as 0.4 microg/g with good precision and accuracy.

Determination of bromazepam by coupling a continuous liquid-liquid extractor to an atomic-absorption spectrometer.

Bromazepam, in the form of the ion-pair (bromazepam)(3) Cu(ClO(4))(2), can be extracted into methyl isobutyl ketone, and determined indirectly by atomic-absorption spectrometry with a limit of detection of 0.1 mug/ml bromazepam at the 324.8 nm copper resonance line. The optimum conditions for determining this drug (0.4-4.0 mug/ml) are described. The relative standard deviation achieved is 1.7%. The method is selective and free from the interference of other 1,4-benzodiazepines. It was applied to the determination of bromazepam in pharmaceuticals and was also spiked in plasma samples.