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.     

Sand as a relevant fraction in geochemical studies in intertidal environments

Soil and sediment samples from several intertidal environment exposed to different types of contamination were studied to investigate the importance of grain size in relation to the capacity of the substrates to retain trace metals. The unfractionated samples (referred to as bulk samples) were separated into the following grain/size fractions: fine–coarse sand (2?0.100 mm), very fine sand (0.100?0.050 mm), silt (0.050?0.002 mm), and clay (0.002 mm). The sample into its fractions was carried out was in a glove box under high-purity N₂ atmosphere in order to minimize any alterations to the samples. The bulk samples were characterized in terms of physicochemical properties such as pH, redox potential, and grain size. The total organic carbon (TOC), total sulfur (S), iron (Fe) pyrite, Fe, and manganese (Mn), and trace metals lead (Pb), mercury (Hg), chromium (Cr), and nickel (Ni) were analyzed in the bulk samples and in each fraction. The sand fractions were also examined by scanning electron microscopy (SEM). Comparisons of the above parameters were made between fractions and between each fraction and the corresponding bulk sample. The fine–coarse sand fraction contained high levels of the primary elements of the geochemical processes that occur in marine sedimentary environments such as TOC, total Fe, Mn, and S. The net concentrations of these four elements were higher in the fine-coarse sand fraction than in the very fine sand fraction and were similar to the net concentrations in the silt and clay fractions. Detailed SEM analysis of the sand coarse fraction revealed the presence of Fe and aluminum oxyhydroxide coatings in the oxic layers, whereas the framboidal pyrites and coatings observed in the anoxic layers were Fe sulfides. The presence of the various coatings explains why the trace metal concentrations in the sand fine–coarse fraction were similar to those in the clay fraction and higher than those in the very fine sand fraction. The present results highlight the importance of the sand fraction, which is generally disregarded in geochemical and environmental studies of sedimentary layers.     

Changes in the trade in native medicinal plants in Brazilian public markets

Plants continue to be an important source of new bioactive substances. Brazil is one of the world’s mega-diverse countries, with 20 % of the world’s flora. However, the accelerated destruction of botanically rich ecosystems has contributed to a gradual loss of native medicinal species. In previous study, we have observed a fast and intensive change in trade of medicinal plants in an area of Amazon, where human occupation took place. In this study, we surveyed 15 public markets in different parts of Brazil in search of samples of 40 plants used in traditional medicine and present in first edition of Brazilian Official Pharmacopoeia (FBRAS), published in 1926. Samples of plants commercialized as the same vernacular name as in Pharmacopoeia were acquired and submitted to analysis for authentication. A total of 252 plant samples were purchased, but the laboratory analyses showed that only one-half of the samples (126, 50.2 %) were confirmed as the same plant species so named in FBRAS. The high number of unauthenticated samples demonstrates a loss of knowledge of the original native species. The proximity of the market from areas in which the plant occurs does not guarantee that trade of false samples occurs. The impact of the commerce of the substitute species on their conservation and in public health is worrying. Strategies are necessary to promote the better use and conservation of this rich heritage offered by Brazilian biodiversity.     

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.     

Performance evaluation of two commercial chemiluminescence NOx analysers according to European Standard EN 14211

According to Directive 2008/50/EC, all equipment used for NO(x) fixed measurements must comply with the reference method or equivalent by 11 June 2013. Up to that date, non-type-approved equipment can continue to be used in air monitoring networks and will probably also be used in air pollution studies even after that date. In this context, it is advisable to know how these "old" measuring instruments respond to the requirements of European Standard EN 14211: 2005: Ambient Air Quality--Standard method for the measurement of the concentration of nitrogen dioxide and nitrogen monoxide by chemiluminescence. In this work, we carry out a thorough performance evaluation of two commercial NO(x) analysers, both purchased before 2010, according to the mentioned Standard. Results show that water vapour interference is one of the most important disconformities with this Standard. The expanded uncertainty estimation of both analysers was below the quality objective of the above-mentioned Directive (15%); however, this calculation was performed by applying some modifications to the proposed model of Standard EN 14211. These modifications are also discussed in the paper.     

The spatial statistics formalism applied to mapping electromagnetic radiation in urban areas

Determining the electromagnetic radiation levels in urban areas is a complicated task. Various approaches have been taken, including numerical simulations using different models of propagation, sampling campaigns to measure field values with which to validate theoretical models, and the formalism of spatial statistics. In the work, we present here that this latter technique was used to construct maps of electric field and its associated uncertainty from experimental data. For this purpose, a field meter and a broadband probe sensitive in the 100-kHz–3-GHz frequency range were used to take 1,020 measurements around buildings and along the perimeter of the area. The distance between sampling points was 5 m. The results were stored in a geographic information system to facilitate data handling and analysis, in particular, the application of the formalism of spatial statistical to the analysis of the distribution of the field levels over the study area. The spatial structure was analyzed using the variographic technique, with the field levels at non-sampled points being interpolated by kriging. The results indicated that, in the urban area analyzed in the present work, the linear density of sampling points could be reduced to a distance which coincides with the length of the blocks of buildings without the statistical parameters varying significantly and with the field level maps being reproduced qualitatively and quantitatively.     

One-Component Spray Polyurethane Foam from Liquefied Pinewood Polyols: Pursuing Eco-Friendly Materials

The use of petroleum-derived products should be avoided regarding the principles of green and sustainable chemistry. The work reported herein, is aimed at the liquefaction of pine shavings for the production of an environmentally-friendly polyol suitable to be used in the formulations of sprayable polyurethane foams. The biopolyols were obtained in high yield and were used to replace those derived from fossil sources, to produce more “greener” polyurethane foams and therefore, less dependent on petroleum sources, since the polyol component was substituted by products resulting from biomass liquefaction. The partial and fully exchange of the polyols was accomplished, and the results compared with a reference foam. The foams were afterward, chemical, physical, morphological, and mechanically characterized. The complete replacement of polyether polyol and polyol polyester has presented some similar characteristics as that used as a reference, validating that the path chosen for the development of more sustainable materials is on the right track for the contribution to a cleaner world.     

Transfer of Graphene CVD to Surface of Low Density Polyethylene (LDPE) and Poly(butylene adipate-co-terephthalate) (PBAT) Films: Effect on Biodegradation Process

Here, the influence of graphene as a coating on the biodegradation process for two different polymers is investigated, poly(butylene adipate-co-terephthalate) (PBAT) (biodegradable) and low-density polyethylene (LDPE) (non-biodegradable). Chemical vapor deposition graphene was transferred to the surface of two types of polymers using the Direct Dry Transfer technique. Polymer films, coated and uncoated with graphene, were buried in a maturated soil for up to 180 days. The films were analyzed before and after exposure to microorganisms in order to obtain information about the integrity of the graphene (Raman Spectroscopy), the biodegradation mechanism of the polymer (molecular weight and loss of weight), and surface changes of the films (atomic force microscopy and contact angle). The results prove that the graphene coating acted as a material to control the biodegradation process the PBAT underwent, while the LDPE covered by graphene only had changes in the surface properties of the film due to the accumulation of solid particles. Polymer films coated with graphene may allow the production of a material that can control the microbiological degradation, opening new possibilities in biodegradable polymer packaging. Regarding the possibility of graphene functionalization, the coating can also be selective for specific microorganisms attached to the surface.