PLA and Organoclays Nanocomposites: Degradation Process and Evaluation of ecotoxicity Using Allium cepa as Test Organism

In this study, nanocomposites of PLA and organoclays Cloisite 20A and Cloisite 30B were prepared by the melt intercalation method and the obtained samples were characterized by transmission electron microscopy (TEM). Since composting is an important proposal to the final disposal of biopolymers, the influence of clays on the hydrolytic degradation process of PLA was evaluated by visual analysis and monitoring of molecular weight after periods of 15 and 30 days of degradation in compost. After degradation of the materials in composting environment, the evaluation of cytotoxic, genotoxic and mutagenic effects of compost aqueous extract was carried out using a bioassay with Allium cepa as test organism. The TEM micrographs permitted the observation of different levels of dispersion, including exfoliated regions. In the evaluation of hydrolytic degradation it was noted that the presence of organoclays can decrease the rate of degradation possibly due to the barrier effect of clay layers and/or the higher degree of crystallinity in the nanocomposite samples. Nevertheless, even in the case of nanocomposites, the molecular weight reduction was significant, indicating that the composting process is favorable to the chain scission of PLA in studied materials. In the analysis performed by the bioassay using A. cepa as test organism, it was found that after degradation of the PLA and its nanocomposites the aqueous extract of compost samples induced a decreasing in the mitotic index and an increasing in the induction of chromosomal abnormalities. These results were statistically significant in relation to the negative control (distilled water). By comparing the results obtained for the nanocomposites in relative to pure polymer, there were no statistically significant differences. The types of the observed chromosomal aberrations indicated a possible genotoxic effect of the materials, which may be related to an aneugenic action of PLA degradation products.     

Electrokinetic remediation of organochlorines in soil: enhancement techniques and integration with other remediation technologies

Electrokinetic remediation has been increasingly used in soils and other matrices for numerous contaminants such as inorganic, organic, radionuclides, explosives and their mixtures. Several strategies were tested to improve this technology effectiveness, namely techniques to solubilize contaminants, control soil pH and also couple electrokinetics with other remediation technologies. This review focus in the experimental work carried out in organochlorines soil electroremediation, aiming to systemize useful information to researchers in this field. It is not possible to clearly state what technique is the best, since experimental approaches and targeted contaminants are different. Further research is needed in the application of some of the reviewed techniques. Also a number of technical and environmental issues will require evaluation for full-scale application. Removal efficiencies reported in real contaminated soils are much lower than the ones obtained with spiked kaolinite, showing the influence of other factors like aging of the contamination and adsorption to soil particles, resulting in important challenges when transferring technologies into the field.     

Spatially valid data of atmospheric deposition of heavy metals and nitrogen derived by moss surveys for pollution risk assessments of ecosystems

For analysing element input into ecosystems and associated risks due to atmospheric deposition, element concentrations in moss provide complementary and time-integrated data at high spatial resolution every 5 years since 1990. The paper reviews (1) minimum sample sizes needed for reliable, statistical estimation of mean values at four different spatial scales (European and national level as well as landscape-specific level covering Europe and single countries); (2) trends of heavy metal (HM) and nitrogen (N) concentrations in moss in Europe (1990–2010); (3) correlations between concentrations of HM in moss and soil specimens collected across Norway (1990–2010); and (4) canopy drip-induced site-specific variation of N concentration in moss sampled in seven European countries (1990–2013). While the minimum sample sizes on the European and national level were achieved without exception, for some ecological land classes and elements, the coverage with sampling sites should be improved. The decline in emission and subsequent atmospheric deposition of HM across Europe has resulted in decreasing HM concentrations in moss between 1990 and 2010. In contrast, hardly any changes were observed for N in moss between 2005, when N was included into the survey for the first time, and 2010. In Norway, both, the moss and the soil survey data sets, were correlated, indicating a decrease of HM concentrations in moss and soil. At the site level, the average N deposition inside of forests was almost three times higher than the average N deposition outside of forests.     

Bioaccumulation of butyltins and liver damage in the demersal fish Cathorops spixii (Siluriformes,Ariidae)

The toxicity of butyltin compounds (BTs), mainly tributyltin (TBT), has been reported in different organisms. However, such an analysis in fish after field exposure with reference to the related biomarkers has not been commonly observed in the literature. This study presents the uptake of BTs in the liver of a neotropical marine catfish Cathorops spixii in Paranagua Bay, an important estuarine system located in southern Brazil. Two different areas, close to and distant from the harbor, were used for chemical analysis evaluation of hepatotoxicity through genetic, enzymatic, and histopathological biomarkers. The presence of polycyclic aromatic hydrocarbons in bile was also considered as a biomarker. The results showed a significant relationship between TBT levels and the inhibition of biotransformation enzymes and high occurrence of melanomacrophages in fish collected close to the harbor site. These effects were linked to the absence of TBT metabolites in the liver. In the second site, the presence of DBT was associated with an increase in EROD and GST activity. The larger amount of DNA damage as well as the highest oxidative stress was noted in fish from the less TBT-polluted area, where DBT and bile PAHs occurred. These findings showed different impact levels due to or increased by the chronic exposure of biota to BTs.     

Biodegradable chelating agents for industrial,domestic, and agricultural applications—a review

Aminopolycarboxylates, like ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA), are chelating agents widely used in several industrial, agricultural, and domestic applications. However, the fact that they are not biodegradable leads to the presence of considerable amounts in aquatic systems, with serious environmental consequences. The replacement of these compounds by biodegradable alternatives has been the object of study in the last three decades. This paper reviews the most relevant studies towards the use of environmentally friendly chelating agents in a large number of applications: oxidative bleaching, detergents and cleaning compositions, scale prevention and reduction, remediation of soils, agriculture, electroplating, waste treatment, and biocides. Nitrilotriacetic acid (NTA), ethylenediaminedisuccinic acid (EDDS), and iminodisuccinic acid (IDS) are the most commonly suggested to replace the nonbiodegradable chelating agents. Depending on the application, the requirements for metal complexation might differ. Metal chelation ability of the most promising compounds [NTA, EDDS, IDS, methylglycinediacetic acid (MGDA), l-glutamic acid N,N-diacetic acid (GLDA), ethylenediamine-N,N′-diglutaric acid (EDDG), ethylenediamine-N,N′-dimalonic acid (EDDM), 3-hydroxy-2,2-iminodisuccinic acid (HIDS), 2-hydroxyethyliminodiacetic acid (HEIDA), pyridine-2,6-dicarboxylic acid (PDA)] with Fe, Mn, Cu, Pb, Cd, Zn, Ca, and Mg was simulated by computer calculations. The advantages or disadvantages of each compound for the most important applications were discussed.     

Concentrations of cyclic volatile methylsiloxanes in biosolid amended soil,influent, effluent,receiving water,and sediment of wastewater treatment plants in Canada

A comprehensive surveillance program was conducted to determine the occurrence of three cyclic volatile methylsiloxanes (cVMS) octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in environmental compartments impacted by wastewater effluent discharges. Eleven wastewater treatment plants (WWTPs), representative of those found in Southern Ontario and Southern Quebec, Canada, were investigated to determine levels of cVMS in their influents and effluents. In addition, receiving water and sediment impacted by WWTP effluents, and biosolid-amended soil from agricultural fields were also analyzed for a preliminary evaluation of the environmental exposure of cVMS in media impacted by wastewater effluent and solids. A newly-developed large volume injection (septumless head adapter and cooled injection system) gas chromatography – mass spectrometry method was used to avoid contamination originating from instrumental analysis. Concentrations of D4, D5, and D6 in influents to the 11 WWTPs were in the range 0.282–6.69 μg L⁻¹, 7.75–135 μg L⁻¹, and 1.53–26.9 μg L⁻¹, respectively. In general, wastewater treatment showed cVMS removal rates of greater than 92%, regardless of treatment type. The D4, D5, and D6 concentration ranges in effluent were <0.009–0.045 μg L⁻¹, <0.027–1.56 μg L⁻¹, and <0.022–0.093 μg L⁻¹, respectively. The concentrations in receiving water influenced by effluent, were lower compared to those in effluent in most cases, with the ranges <0.009–0.023 μg L⁻¹, <0.027–1.48 μg L⁻¹, and <0.022–0.151 μg L⁻¹ for D4, D5, and D6, respectively. Sediment concentrations ranged from <0.003–0.049 μg g⁻¹ dw, 0.011–5.84 μg g⁻¹ dw, and 0.004–0.371 μg g⁻¹ dw for D4, D5, and D6, respectively. The concentrations in biosolid-amended soil, having values of <0.008–0.017 μg g⁻¹ dw, <0.007–0.221 μg g⁻¹ dw, and <0.009–0.711 μg g⁻¹ dw for D4, D5, and D6, respectively, were lower than those in sediment impacted by wastewater effluent in most cases. In comparison with the no-observed-effected concentrations (NOEC) and IC50 (concentration that causes 50% inhibition of the response) values, the potential risks to aquatic, sediment-dwelling, and terrestrial organisms from these reported concentrations are low.     

Phytoextraction of heavy metal polluted soils using Sedum plumbizincicola inoculated with metal mobilizing Phyllobacterium myrsinacearum RC6b

The aim of this study was to investigate the effects of metal mobilizing plant-growth beneficial bacterium Phyllobacterium myrsinacearum RC6b on plant growth and Cd, Zn and Pb uptake by Sedum plumbizincicola under laboratory conditions. Among a collection of metal-resistant bacteria, P. myrsinacearum RC6b was specifically chosen as a most favorable metal mobilizer based on its capability of mobilizing high concentrations of Cd, Zn and Pb in soils. P. myrsinacearum RC6b exhibited a high degree of resistance to Cd (350 mg L⁻¹), Zn (1000 mg L⁻¹) and Pb (1200 mg L⁻¹). Furthermore, P. myrsinacearum RC6b showed multiple plant growth beneficial features including the production of 1-aminocyclopropane-1-carboxylic acid deaminase, indole-3-acetic acid, siderophore and solubilization of insoluble phosphate. Inoculation of P. myrsinacearum RC6b significantly increased S. plumbizincicola growth and organ metal concentrations except Pb, which concentration was lower in root and stem of inoculated plants. The results suggest that the metal mobilizing P. myrsinacearum RC6b could be used as an effective inoculant for the improvement of phytoremediation in multi-metal polluted soils.     

Chromium (VI) remediation in aqueous solution by waste products (peel and seed) of mango (Mangifera indica L.) cultivars

The surface group characteristics of mango cultivar peels and seeds were evaluated by infrared spectra, PZC, and functional group composition. The adsorption/reduction of chromium (VI) in aqueous solutions was investigated by varying pH, contact time, initial Cr(VI) concentration, and adsorbent amount. The results show that both peel and seed powders of the mango cultivars showed significant adsorption/reduction capacity for Cr(VI) and that the desorption process obeys pseudo-second-order kinetics. Optimal adsorption occurred at pH 1.0, using a Cr(VI) concentration of 100 mg/L. On average, at pH 1.0, and a concentration of 3 g/L, the maximum adsorption/reduction capacity of Cr(VI) was 83% (peels 76%, seeds 90%). Of the mango powders tested, the most efficient were Tommy seed (100%) and Coite peel (98%) followed by Coite seed (96%) and Tommy peel powders (95%). The adsorption/reduction of Cr(VI) was complete (100%) by the mango seed, in comparison to the peel powders (97%) after 180 min. The data indicates that mango waste products, such as seed and peel powders, are both excellent candidates for the remediation of Cr(VI) from aqueous systems and due to the higher concentration of gallates and galloyl glucosides, the mango seed powders should be the powders of choice for future remediation projects.

     

Airborne polycyclic aromatic hydrocarbons in a medium-sized city affected by preharvest sugarcane burning and inhalation risk for human health

Polycyclic aromatic hydrocarbons (PAHs) in air were measured in a municipality where sugarcane plantations are extensive, at three sites, one in the city center and two in rural localities. Twenty-four-hour sampling was done using PS1 PUF samplers from Andersen Instruments Inc., at least 1 day per month per site, from June 2009 to October 2009. The chemical analyses were performed by gas chromatography–mass spectrometry (GC/MS) for the 16 most toxic PAHs. The incremental lifetime cancer risk (ILTR) by inhalation was determined by the Monte Carlo method for the urban population using Crystal Ball software. The total concentration of the 16 PAHs at all sites varied from 6.2 to 65.7 ng m^?3, with an average of 25.9 ± 18.2 ng m^?3. The average concentrations per site were 14.1 ± 13.0 ng m^?3 at rural site B, 20.7 ± 11.5 ng m^?3 at rural site A, and 36.1 ± 22.7 ng m^?3 at the central site. The cancer risk for infants, children, and adults was approximately 14%, 25%, and 61% of the total IRLT, respectively. The mean (95% upper probability limit [95% UPL]) values were 1.2 × 10^?7 (2.2 × 10^?7) for infants, 2.2 × 10^?7 (4.1 × 10^?7) for children, and 8.9 × 10^?7 (1.1 × 10^?6) for adults. Although the three most abundant PAHs found were phenanthrene, fluoranthene, and pyrene, the three most important contributions to the incremental risk of cancer came from benzo[a]pyrene, benzo[b]fluoranthene, and naphthalene. Compared with the risks in big cities such as São Paulo, this would be low, but not negligible. Analysis of ratios of PAHs according to the literature showed that vehicle exhaust and biomass burning, including sugarcane burning, seem to be the most important contributors to PAH concentrations in the central area of Araraquara City.

Implications:The growth of biofuel use worldwide, especially ethanol, together with preharvesting burning practice, is cause of concern with regard to possible health effects, due to increased air pollution levels in cities in regions where sugarcane plantation and processing are intensive. This paper shows that the risk of cancer from PAH inhalation in an urban area surrounded by sugarcane agriculture was of the same order of magnitude as the tolerable risk value of 10^?6. As other classical and hazardous pollutants are also present, care should be taken to keep pollution as low as possible to protect human health.     

Ecological and biological determinants of methylmercury accumulation in tropical coastal fish

This research investigated whether environmental conditions, biological fish characteristics and anthropogenic impacts influenced mercury (Hg) assimilation into the muscle tissue of two fish species from two Brazilian bays, Ilha Grande Bay and Guanabara Bay. Fish and superficial water were collected in different periods. Hg was determined by CV-AAS. Methylmercury (MeHg) was identified and quantified by ECD-GC. Chlorophyll a concentrations in the water column indicated that Ilha Grande Bay and Guanabara Bay were oligotrophic and eutrophic, respectively. Hg in fish ranged from 2.10 to 870.17 μg kg^?1 dry wt. in Ilha Grande Bay and 40.90 to 809.24 μg kg^?1 dry wt. in Guanabara Bay. Slight differences were found between the length-normalized Hg concentrations and its percent of Hg in a voracious predator from the bays. In Guanabara Bay, where the presence of a chlor-alkali plant causes Hg input, the iliophagous fish species showed the highest length-normalized Hg concentrations and the voracious predator the lowest. Iliophagous fish is consumed by voracious predator and, consequently, acts as their MeHg food supply. Iliophagous fish from Ilha Grande Bay presented a higher percent of MeHg (80.0 %) than specimens from Guanabara Bay (54.5 %). This fact suggests that more MeHg was transferred from iliophagous fish to voracious predator in Ilha Grande Bay. At Guanabara Bay, the bioproduction is greater than that at Ilha Grande Bay, presenting the highest biomass in it ecosystem, which may subsequently dilute Hg and reduce its availability to the biota; i.e., influencing in Hg and MeHg availability throughout the food chain. Consequently, more MeHg is available in the aquatic environment of Ilha Grande Bay.