Fractionation of heavy metals and assessment of contamination of the sediments of Lake Titicaca

Chemical weathering is one of the major geochemical processes that control the mobilization of heavy metals. The present study provides the first report on heavy metal fractionation in sediments (8–156 m) of Lake Titicaca (3,820 m a.s.l.), which is shared by the Republic of Peru and the Plurinational State of Bolivia. Both contents of total Cu, Fe, Ni, Co, Mn, Cd, Pb, and Zn and also the fractionation of these heavy metals associated with four different fractions have been determined following the BCR scheme. The principal component analysis suggests that Co, Ni, and Cd can be attributed to natural sources related to the mineralized geological formations. Moreover, the sources of Cu, Fe, and Mn are effluents and wastes generated from mining activities, while Pb and Zn also suggest that their common source is associated to mining activities. According to the Risk Assessment Code, there is a moderate to high risk related to Zn, Pb, Cd, Mn, Co, and Ni mobilization and/or remobilization from the bottom sediment to the water column. Furthermore, the Geoaccumulation Index and the Enrichment Factor reveal that Zn, Pb, and Cd are enriched in the sediments. The results suggest that the effluents from various traditional mining waste sites in both countries are the main source of heavy metal contamination in the sediments of Lake Titicaca.     

Prediction of the solubility of zinc, copper, nickel, cadmium, and lead in metal-contaminated soils

Risk assessment of metal-contaminated soil depends on how precisely one can predict the solubility of metals in soils. Responses of plants and soil organisms to metal toxicity are explained by the variation in free metal ion activity in soil pore water. This study was undertaken to predict the free ion activity of Zn, Cu, Ni, Cd, and Pb in metal-contaminated soil as a function of pH, soil organic carbon, and extractable metal content. For this purpose, 21 surface soil samples (0–15 cm) were collected from agricultural lands of various locations receiving sewage sludge and industrial effluents for a long period. One soil sample was also collected from agricultural land which has been under intensive cropping and receiving irrigation through tube well water. Soil samples were varied widely in respect of physicochemical properties including metal content. Total Zn, Cu, Ni, Cd, and Pb in experimental soils were 2,015?±?3,373, 236?±?286, 103?±?192, 29.8?±?6.04, and 141?±?270 mg kg^?1, respectively. Free metal ion activity, viz., pZn²⁺, pCu²⁺, pNi²⁺, pCd²⁺, and pPb²⁺, as estimated by the Baker soil test was 9.37?±?1.89, 13.1?±?1.96, 12.8?±?1.89, 11.9?±?2.00, and 11.6?±?1.52, respectively. Free metal ion activity was predicted by pH-dependent Freundlich equation (solubility model) as a function of pH, organic carbon, and extractable metal. Results indicate that solubility model as a function of pH, Walkley–Black carbon (WBC), and ethylenediaminetetraacetic acid (EDTA)-extractable metals could explain the variation in pZn²⁺, pCu²⁺, pNi²⁺, pCd²⁺, and pPb²⁺ to the extent of 59, 56, 46, 52, and 51 %, respectively. Predictability of the solubility model based on pH, KMnO₄-oxidizable carbon, and diethylenetriaminepentaacetic acid-extractable or CaCl₂-extractable metal was inferior compared to that based on EDTA-extractable metals and WBC.     

Biodegradation or simple adsorption to the support material? Development of a simple, fast and low-cost technique

Biofilms are present in several areas and are studied in microbiology, medical sciences, biology and, of course, sanitary engineering. Biofilms are used for the treatment of municipal wastewater, and their application was even before the invention of the activated sludge process. The main objective of this work was to develop a simple, fast and low-cost technique to evaluate the nature of the first decay in the concentration of an organic compound in the presence of a solid material. Though simple, the technique developed has allowed the clarification of whether the initial concentration decay is due to adsorption to the support material or a result of biodegradation. The results show that, with two different support materials, adsorption does not take place, and the biodegradation processes are responsible for the first decay in the organic concentration. The technique used offers a fast and low-cost way of studying the existence of adsorption. Two feed concentration solutions and two different support materials were used.     

Distribution of radionuclides in surface soils, Singhbhum Shear Zone, India and associated dose

Gamma emitters were estimated in surface soils from a mineralized zone in Eastern India using high purity Germanium detector-based high resolution gamma spectrometry system. Activities of ²³⁸U, ²²⁶Ra, ²³²Th, ²³⁵U, ²²⁷Th, ^234mPa, ²¹⁰Pb, ⁴⁰K, and ¹³⁷Cs were 79?±?50, 81?±?53, 65?±?23, 4?±?2, 5?±?4, 92?±?50, 97?±?45, 517?±?201, and 4?±?2 Bq/kg, respectively. Most radionuclides were observed to follow log-normal distribution. The correlation between physicochemical properties of the samples, like pH, organic matter content, particle size, and moisture content were also studied. Activity ratios of ²²⁶Ra/²³⁸U, ²¹⁰Pb/²²⁶Ra, and ²²⁷Th/²³⁵U indicated deviation from secular equilibrium in some samples. The associated annual effective dose ranged from 0.07 to 0.24 mSv and the mean was calculated to be 0.12?±?0.04 mSv for this region, indicating it to be one of normal natural background radiation.     

Biofilm thickness measurement using an ultrasound method in a liquid phase

In this report, the development of an online, noninvasive, measurement method of the biofilm thickness in a liquid phase is presented. The method is based in the analysis of the ultrasound wave pulse-echo behavior in a liquid phase reproducing the real reactor conditions. It does not imply the removal of the biomass from the support or any kind of intervention in the support (pipes) to detect and perform the measurements (non-invasiveness). The developed method allows for its sensor to be easily and quickly mounted and unmounted in any location along a pipe or reactor wall. Finally, this method is an important innovation because it allows the thickness measurement of a biofilm, in liquid phase conditions that can be used in monitoring programs, to help in scheduling cleaning actions to remove the unwanted biofilm, in several application areas, namely in potable water supply pipes.     

Habitat monitoring and genotoxicity in Ucides cordatus (Crustacea: Ucididae), as tools to manage a mangrove reserve in southeastern Brazil

In Brazil, the state of São Paulo contains both preserved areas (Juréia-Itatins Ecological Station) and extremely impacted ones (Cubatão Municipality). This study evaluated the concentrations of five metals (Cu, Cd, Cr, Pb, and Hg) in two mangroves with different levels of anthropogenic impact and the apparent genotoxicity to Ucides cordatus. Water and sediment samples were obtained, and metal concentrations were determined with an atomic absorption spectrophotometer. The genotoxic impact was quantified based on the number of micronucleated cells per 1,000 analyzed (MN‰), using hemolymph slides stained with Giemsa. Metal concentrations in water were below the detection limit, except for lead, although no significant difference was observed between the areas (P?>?0.05). Sediment from Cubatão had higher concentrations of Cd, Pb, Cr, and Cu than sediment from Juréia-Itatins (P?<?0.05), but no significant differences in metal concentrations were detected among depth strata of the sediment (P?>?0.05). Crabs from Cubatão had a 2.6 times higher mean frequency of micronucleated cells (5.2?±?1.8 MN‰) than those from Juréia-Itatins (2.0?±?1.0 MN‰; P?<?0.0001). The more-polluted conditions found in the mangrove sediments of Cubatão were reflected in the micronucleus assay, demonstrating their genotoxic effect; however, genetic damage should be attributed to a synergistic effect with other kinds of pollutants previously recorded in different environments of Cubatão. U. cordatus proved to be an excellent bioindicator of mangrove pollution. This study established, for the first time, the normal frequency of MN‰ in a population of this species within an ecological station.     

Arsenic and other trace elements in two catfish species from Paranaguá Estuarine Complex, Paraná, Brazil

Concentrations of arsenic and four additional trace elements (Cu, Cr, Ni, and Zn) were determined by inductively coupled plasma–optical emission spectrometry in the muscular tissue of the yellow catfish (Cathorops spixii) and the urutu catfish (Genidens genidens) from Paranaguá Estuarine Complex, Brazil (PEC). The PEC can be characterized by an environment of high ecological and economic importance in which preserved areas of rainforest and mangroves coexist with urban activities as ports and industries. The average concentrations (in milligram per kilogram dry weight) of elements in the muscle tissue of C. spixii are as follows: Zn (31), As (17), Cu (1.17), Cr (0.62), and Ni (0.28). Similar concentrations could be found in G. genidens with exception of As: Zn (36), As (4.78), Cu (1.14), Cr (0.51), and Ni (0.14). Fish from the geographic northern rural region (Guaraqueçaba–Benito) display higher As concentrations in the muscle tissues than fish found in the south-western (urban) part of the PEC. An international comparison of muscle tissue concentrations of trace elements in fish was made. Except for Ni in C. spixii, a tendency of decrease in element concentration with increasing size (age) of the fish could be observed. According to the National Health Surveillance Agency of Brazil, levels of Cr and As exceeded the permissible limits for seafood. An estimation of the provisional tolerable weekly intake of As was calculated with 109 % for C. spixii and with 29 % for G. genidens.     

Adjusting the effect of seasonal variability in the bioassessment of streams

Bioassessment tools should distinguish between the effects of anthropogenic degradation in communities and natural temporal changes. The present study tests the influence of natural seasonal variability on macroinvertebrate stream communities assessed by a predictive model (PORTRIV) and a multimetric index (IPtI) calibrated for spring. The scores of PORTRIV decreased significantly between spring and autumn, and between spring and winter (ca. 37 to 53 %, respectively), while those of IPtI did not change significantly between seasons. For non-reference samples, the results of the predictive model also indicate no significant differences. A correction factor (CF) was calculated to adjust the existing differences in the model assessments between seasons, based on the percentage of variation of reference site scores from spring to autumn and winter. After the application of the CF to the OE50 scores of spring reference samples, the differences were no longer significant. Independent reference validation sites confirmed this tendency. This method has the advantage of avoiding large efforts required for the construction of databases from other seasons and the development of new models to allow the assessment of streams in seasons other than spring. Further tests with models developed in regions with more marked seasonal changes should be done to confirm its wider applicability.     

Validation of atmospheric aerosols parallel sampling in a multifold device

In this work, particulate matter was collected using an active sampling system consisting of a PM₁₀ (<10 μm) inlet coupled to a multifold device containing six channels, connected to a vacuum pump. Each channel was equipped with a filter holder fitted with adequately chosen filters. The system was fixed on a metallic structure, which was placed on the roof of the laboratory building, at the Faculty of Sciences, in Lisbon. Sampling took place under flow-controlled conditions. Aerosols were extracted from the filters with water, in defined conditions, and the water-soluble fraction was quantified by ion chromatography (IC) for the determination of inorganic anions (Cl^?, NO₃ ^? and SO₄ ^2?). Equivalent sampling through the various channels was validated. Validation was based on the metrological compatibility of the content results for the various filters. Ion masses are metrologically equivalent when their absolute difference is smaller than the respective expanded uncertainty. When this condition is verified, the studied multifold device produces equivalent samples.