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.     

Evaluation of a multiresidue method for pesticides in cereals using supercritical fluid extraction and gas chromatographic detection

Supercritical fluid extraction (SFE) was evaluated to be applied for residue analysis of 22 gas chromatography/electron capture detector-nitrogen phosphorus detector (GC/ECD-NPD) amenable pesticides in rice, wild rice and wheat. Samples were extracted with supercritical carbon dioxide at 200 atm pressure and 50°C temperature, using methanol as a static modifier. Mean recoveries obtained with the proposed SFE method at two spiking levels with four replicates per level are compared with those obtained with an ethyl acetate-based solvent extraction/gel permeation chromatography (GPC) clean up method. Both methods gave consistent high recoveries for almost all the pesticides from all the commodities with overall mean recoveries higher than 70% with relative standard deviations lower than 20%. Remarkable exceptions were captafol and dimethoate, for which low and/or non-reproducible recoveries were obtained with the SFE method. Residue levels determined with both methods in nine different incurred samples of wheat, containing some of the studied pesticides, were very similar, but, in all cases, slightly higher levels were determined with the SFE method.     

Sorption and photodegradation of chlorpyrifos on riparian and aquatic macrophytes

Surface water bodies may become contaminated via spray drift following pesticide application. In this investigation, the photodegradation and sorption of chlorpyrifos was studied in four riparian macrophytes representative of Mediterranean flora (Phragmites australis, Iris pseudacorus, Equisetum pratense and Typha latifolia). The results of experiments with both the active ingredient and the formulation DURSBAN 48® EC confirm the ability of these species to interact with chemicals such as chlorpyrifos. The maximum sorption of chlorpyrifos at equilibrium was observed in Phragmites australis (22%). And, the maximum instantaneous sorption of chlorpyrifos was observed in the dried biomass of Phragmites australis (49%). The epicuticular waxes present on leaves influence photodegradation processes, resulting in a decrease in chlorpyrifos persistence depending on the nature of the extract. The half-life of chlorpyrifos residues in leaf waxes decreased from 34 to 99 minutes when irradiated.     

Microalgae biosynthesis of silver nanoparticles for application in the control of agricultural pathogens

The occurrence of diseases in cultivars has caused significant losses in global food production. The advancement of nanobiotechnology makes it possible to obtain new products to be used in the control of pathogens in cultivars. Silver nanoparticles can be synthesized by microalgae and are widely known for their antimicrobial activity. In addition, the biomass produced in microalgal culture for the biosynthesis of the nanoparticles also demonstrates antimicrobial properties, as it can increase the antibacterial and antifungal potential of the silver nanoparticles. In this context, this article addresses the use of microalgae to biosynthesize silver nanoparticles simultaneously with biomass production. In addition, we demonstrate the antimicrobial potential of these nanomaterials, as well as of the microalgal biomass produced in biosynthesis, to use in the control of pathogens in agriculture.     

Application of QuEChERS method and gas chromatography-mass spectrometry for the analysis of cypermethrin residue in milk

Analytical methods for the isolation and determination of cypermethrin in milk, based on the solid-phase microextraction (SPME) and QuEChERS methods (Quick, Easy, Cheap, Effective, Rugged, and Safe) are presented. The SPME technique was not appropriate to analyse cypermethrin in milk, even establishing the best extraction conditions, polydimethylsiloxane fiber, 60 min time extraction, 60 °C temperature extraction, addition of salt (NaCl) and stirring rate. The extraction efficiency was low probably because of the matrix constituents. The QuEChERS method involves the extraction of the analyte with acetonitrile and simultaneous liquid-liquid partitioning formed by adding anhydrous MgSO₄ plus NaCl, followed by the removal of residual water and cleanup using a procedure called dispersive solid-phase extraction, in which anhydrous MgSO₄ plus PSA and C18 are mixed with 1 mL of acetonitrile extract. The detection and quantification limits were 0.01 and 0.04 mg kg^?1, respectively, and the percentage recovery obtained ranged from 92 to 105% with relative standard deviations below 7%.     

Sorption and desorption of sulfentrazone in Brazilian soils

This study was undertaken to obtain information about the behavior of sulfentrazone in soil by evaluating the sorption and desorption of the herbicide in different Brazilian soils. Batch equilibrium method was used and the samples were analyzed by high performance liquid chromatography. Based on the results obtained from the values of Freundlich constants (Kf), we determined the order of sorption (Haplic Planosol < Red-Yellow Latosol < Red Argisol < Humic Cambisol < Regolitic Neosol) and desorption (Regolitic Neosol < Red Argisol < Humic Cambisol < Haplic Planosol < Red-Yellow Latosol) of sulfentrazone in the soils. The process of pesticide sorption in soils was dependent on the levels of organic matter and clay, while desorption was influenced by the organic matter content and soil pH. Thus, the use of sulfentrazone in soils with low clay content and organic matter (low sorption) increases the probability of contaminating future crops.     

Valorisation of forestry waste by pyrolysis in an auger reactor

Pyrolysis of forestry waste has been carried out in an auger reactor to study the influence of operational variables on the reactor performance and the properties of the related products. Pine woodchips were used for the first time as raw material and fed continuously into the reactor. Ten experiments were carried out under inert atmosphere at: (i) different reaction temperature (1073, 973, 873, 823 and 773 K); (ii) different solid residence time (5, 3, 2 and 1.5 min); and (iii) different biomass flow rate (3.9, 4.8 and 6.9 kg/h). Results show that the greatest yields for liquid production (59%) and optimum product characterisation were obtained at the lowest temperature studied (773 K) and applying solid residence times longer than 2 min. Regarding bio-oil properties, GC/MS qualitative identification show that the most abundant compounds are volatile polar compounds, phenols and benzenediols; and very few differences can be observed among the samples regardless of the pyrolysis operating conditions. On the whole, experimental results demonstrate that complete reaction of forest woodchips can be achieved in an auger reactor in most of the experimental conditions tested. Moreover, this study presents the initial steps for the future scaling up of the auger reactor with the aim of converting it into a mobile plant which will be able to remotely process biomass such as energy crops, forestry and agricultural wastes to obtain bio-oil that, in turn, can be used as energy vector to avoid high transport costs.     

Representative measurement of two-dimensional reactive phosphate distributions and co-distributed iron(II) and sulfide in seagrass sediment porewaters

The high degree of heterogeneity within sediments can make interpreting one-dimensional measurements difficult. The recent development and use of in situ techniques that measure two-dimensional distributions of porewater solutes have facilitated investigation of the role of spatial heterogeneity in sediment biogeochemistry. A colourimetric diffusive equilibration in thin films method has been developed that allows two-dimensional, high-resolution measurement of reactive phosphate in sediment porewaters. A method detection limit of 0.22 μM, an effective upper limit of ∼1000 μM and relative standard deviations typically below 5% were achieved. This method was evaluated by deployment in seagrass (Zostera capricorni) colonised sediments, as part of combined probes with similar colourimetric methods for sulfide and iron(II). The two-dimensional, high resolution distributions obtained provide a highly representative measurement of the co-distributions of porewater solutes, allowing heterogeneous features and biogeochemical processes to be observed and interpreted. Microniches of high phosphate concentration >100 μM were observed throughout the distributions and were interpreted to be due to localised zones of rapid organic matter mineralisation, possibly using electron acceptors other than iron(III) oxyhydroxides (e.g. aerobic respiration) as often they did not correspond with microniches of higher Fe(II) concentration.     

Modelling a recovery network for WEEE: a case study in Portugal

The European Union directive for electric and electronic waste, published in 2003, enforced all European countries to meet some targets concerning the recycling and recovery of these products. This directive was transposed to the Portuguese legislation in 2004. Following this, a group of EEE producers set up an organization (Amb3e) whose mission was to design and manage a nationwide recovery network for WEEE, which will be the subject matter of this work. A generic MILP model is proposed to represent this network, which is applied to its design and planning, where the best locations for collection and sorting centres are chosen simultaneously with the definition of a tactical network planning. Several analyses are performed to provide further insights regarding the selection of these alternative locations. The results gave support to the company strategic expansion plans for a high number of centres to be opened and to their location near the major WEEE sources.     

Comparison of waste prevention behaviors among three Japanese megacity regions in the context of local measures and socio-demographics

Waste prevention behaviors (WPBs) should be investigated separately from recycling behaviors and analyzed in the context of local policies and measures. Previous studies on WPBs have been mainly conducted in the USA and Europe (mainly in the UK), and studies in Japan have remained very limited to date. Moreover, the effects of socio-demographic factors have been rarely described correctly based on appropriate large sampling. In this study, we conducted an on-line questionnaire survey and obtained 8000 respondents in three megacity regions (Tokyo, Osaka, and Aichi) in Japan. Among these three regions, Osaka respondents showed significantly lower practice rates in nine of 18 WPBs. Particularly in My-bag behavior, the charging of plastic shopping bags strongly affects the practice rate. As shown in the results, local policies and measures affect WPBs. Based on the practice rates, latent four factors were extracted by factor analysis. Multiple regression analysis revealed that gender and age significantly affect WPB factors before local policy effects.