Evaluating the degradation of the herbicides picloram and 2,4-D in a compartmentalized reactive biobarrier with internal liquid recirculation

Tordon is a widely used herbicide formulation of 2,4-dichlorophenoxyacetic acid (2,4-D) and 4-amino-3,5,6-trichloropicolinic acid (picloram), and it is considered a toxic herbicide. The purposes of this work were to assess the feasibility of a microbial consortium inoculated in a lab-scale compartmentalized biobarrier, to remove these herbicides, and isolate, identify, and evaluate their predominant microbial constituents. Volumetric loading rates of herbicides ranging from 31.2 to 143.9 g m^?3 day^?1, for 2,4-D, and 12.8 to 59.3 g m^?3 day^?1 for picloram were probed; however, the top operational limit of the biobarrier, detected by a decay in the removal efficiency, was not reached. At the highest loading rates probed, high average removal efficiencies of 2,4-D, 99.56?±?0.44; picloram, 94.58?±?2.62; and chemical oxygen demand (COD), 89.42?±?3.68, were obtained. It was found that the lab-scale biofilm reactor efficiently removed both herbicides at dilution rates ranging from 0.92 to 4.23 day^?1, corresponding to hydraulic retention times from 1.087 to 0.236 days. On the other hand, few microbial strains able to degrade picloram are reported in the literature. In this work, three of the nine bacterial strains isolated cometabolically degrade picloram. They were identified as Hydrocarboniphaga sp., Tsukamurella sp., and Cupriavidus sp.     

A real-time,dynamic early-warning model based on uncertainty analysis and risk assessment for sudden water pollution accidents

A real-time, dynamic, early-warning model (EP-risk model) is proposed to cope with sudden water quality pollution accidents affecting downstream areas with raw-water intakes (denoted as EPs). The EP-risk model outputs the risk level of water pollution at the EP by calculating the likelihood of pollution and evaluating the impact of pollution. A generalized form of the EP-risk model for river pollution accidents based on Monte Carlo simulation, the analytic hierarchy process (AHP) method, and the risk matrix method is proposed. The likelihood of water pollution at the EP is calculated by the Monte Carlo method, which is used for uncertainty analysis of pollutants’ transport in rivers. The impact of water pollution at the EP is evaluated by expert knowledge and the results of Monte Carlo simulation based on the analytic hierarchy process. The final risk level of water pollution at the EP is determined by the risk matrix method. A case study of the proposed method is illustrated with a phenol spill accident in China.     

Water quality assessment of the Tubarão River through chemical analysis and biomarkers in the Neotropical fish Geophagus brasiliensis

The Tubarão River rises in Santa Catarina, Brazil, and has been historically affected by coal mining activities around its springhead. To evaluate its water conditions, an investigation regarding a possible decontamination gradient associated with the increased river flow toward the estuary, as well as the influence of seasonality over this gradient was performed through a series of biomarkers (vitellogenin, comet assay, lipid peroxidation, protein carbonylation, gluthatione, gluthatione S-transferase, acetylcholinesterase, light microscopy in liver, and scanning electron microscopy in gills) and chemical analysis (polycyclic aromatic hydrocarbons (PAHs) in bile and metal analysis in sediment) in the cichlid Geophagus brasiliensis. Two collections (summer and winter) were made in four distinct sites along the river, while sediments were sampled between those seasons. As expected, the contamination linked exclusively to mining activities was not observed, possibly due to punctual inputs of contaminants. The decontamination gradient was not observed, although seasonality seemed to have a critical role in the responses of biomarkers and availability of contaminants. In the summer, the fish presented higher histopathological damages and lower concentrations of PAHs, while in the winter they showed both higher genetic damage and accumulation of PAHs. The Tubarão suffers impacts from diverse activities, representing health risks for wild and human populations.     

A new bioseed for determination of wastewater biodegradability: analysis of the experimental procedure

A new bioassay proposed in the patent P201300029 was applied to a pre-treated wastewater containing a mixture of commercial pesticides to simulate a recalcitrant industrial wastewater in order to determine its biodegradability. The test uses a mixture of standardized inoculum of the lyophilized bacteria Pseudomonas putida with the proper proportion of salts and minerals. The results highlight that biodegradation efficiency can be calculated using a gross parameter (chemical oxygen demand (COD)) which facilitates the biodegradability determination for routine water biodegradability analysis. The same trend was observed throughout the assay with the dehydrated and fresh inoculums, and only a difference of 5 % in biodegradation efficiency (E _f) was observed. The obtained results showed that the P. putida biodegradability assay can be used as a commercial test with a lyophilized inoculum in order to monitor the ready biodegradability of an organic pollutant or a WWTP influent. Moreover, a combination of the BOD₅/COD ratio and the P. putida biodegradability test is an attractive alternative in order to evaluate the biodegradability enhancement in water pre-treated with advanced oxidation processes (AOPs).     

Chitosan/Hydrophilic Plasticizer-Based Films: Preparation,Physicochemical and Antimicrobial Properties

The addition of plasticizers to biopolymer films is a good method for improving their physicochemical properties. The aim of this study was to evaluate the effect of chitosan (CHI) blended with two hydrophilic plasticizers glycerol (GLY) and sorbitol (SOR), at two concentrations (20 and 40 wt%) on their mechanical, thermal, barrier, structural, morphological and antimicrobial properties. The chitosan was prepared through the alkaline deacetylation of chitin obtained from fermented lactic from shrimp heads. The obtained chitosan had a degree of deacetylation (DA) of 84 ± 2.7 and a molecular weight of 136 kDa, which indicated that a good film had formed. The films composed of CHI and GLY (20 wt%) exhibited the best mechanical properties compared to the neat chitosan film. The percentage of elongation at break increase to over 700 % in the films that contained 40 % GLY, and these films also exhibited the highest values for the water vapor transmission rate (WVTR) of 79.6 ± 1.9 g m² h^?1 and a yellow color (b _o  = 17.9 ± 2.0) compared to the neat chitosan films (b _o  = 8.8 ± 0.8). For the structural properties, the Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analyses revealed an interaction in the acetamide group and changes in the crystallinity of plasticized films. The scanning electron micrographs revealed that all formulations of the chitosan films were smooth, and that they did not contain aggregations, pores or microphase separation. The thermal analysis using differential scanning calorimetry (DSC) revealed a glass transition temperature (Tg) of 130 °C for neat chitosan film, but the addition of SOR or GLY elicited a decrease in the temperature of the peak (120 °C). In addition, the antimicrobial activity of the chitosan films was evaluated against Listeria monocytogenes, and reached a reduction of 2 log after 24 h. The plasticizer concentration of 20 % GLY is sufficient for obtaining flexible chitosan films with good mechanical properties, and it could serve as an alternative as a packaging material to reduce environmental problems associated with synthetic packaging films.     

Physical Properties, Photo- and Bio-degradation of Baked Foams Based on Cassava Starch, Sugarcane Bagasse Fibers and Montmorillonite

The objectives of this work were to develop biodegradable trays from cassava starch, sugarcane fibers and Na-montmorillonite (Na-MMT) using a baking process and to study the effects of these components on the physical properties, photo- and bio-degradation of the trays. The sample F20 (produced with 20 g fiber/100 g formulation) showed the maximum yield production (100 %). All formulations resulted in well-shaped trays with densities between 0.1941 and 0.2966 g/cm³. The addition of fibers and Na-MMT resulted in less dense and less rigid trays compared to control samples (only starch). The studied processing conditions resulted in good nanoclay dispersion, leading to the formation of an exfoliated structure. The evaluation of the photo-degradation stability of the trays under UV exposure for 336 h showed that a sample produced with a specific combination of fiber and nanoclay (20 g fiber and 5 g nanoclay/100 g formulation) had the highest loss in stress at break (91 %). Biodegradation assays showed that Control trays (starch) and F20 (20 g fiber/100 g formulation) lost a greater percentage of their weight after 90 days of incubation in soil, with losses of up to 85.50 and 82.70 %, respectively.     

Preparation and Characterization of Three Different Derivatized Potato Starches

The use of native starch as a thermoplastic polymer is limited by its fragility and high water absorption. Due to the presence of several hydroxyl groups in its structure, water acts as a natural plasticizer of starch, modifying its properties. It is necessary to chemically modify starch molecules by replacing hydroxyl groups with other functional groups to reduce water absorption. Chemical modification of starch granules also alters its swelling and gelatinization behavior. In this contribution we describe the chemical modification of starch and its influence on its hydrophilicity and heat resistance. Acetic acid, maleic anhydride and octanoyl chloride were used as derivatizing reagents. The effectiveness of the treatments was evaluated by means of infrared spectroscopy. Different tests were conducted in order to evaluate the influence of the different chemical modifications on starch structure and properties. Results showed that the treatments effectively reduced starch moisture susceptibility, while substantially altering other properties such as amylose content, swelling power, solubility, and heat resistance. Finally, films were prepared from native and derivatized starch and their surface polarity was evaluated.     

Rapid Cleanup of Chlorinated Solvent Source Zones: Synergies Between Chemical and Biological Degradation

A chlorinated volatile organic compound (cVOC) source area approximately 25 by 100 ft in a heavily industrialized urban area was characterized with groundwater tetrachloroethene (PCE) concentrations up to 9,180 μg/L. This is approximately 6 percent of PCE's aqueous solubility, indicative of the presence of residual dense, nonaqueous phase liquid. The resulting dissolved‐phase plume migrated off‐site. Biotic and abiotic dechlorination using a combination of a food‐grade organic carbon‐based electron donor and zero‐valent iron suspended in a food‐grade emulsifying agent reduced the source area PCE concentrations by 98 percent within 27 weeks, with minimal downgradient migration of daughter products dichloroethene and vinyl chloride. Combining biological dechlorination with iron‐based chemical dechlorination is synergistic, enhancing treatment aggressiveness, balancing pH, and optimizing degradation of both DNAPL and dissolved‐phase cVOCs. © 2013 Wiley Periodicals, Inc.     

Characterization of distribution of pesticide residues in crop units

The characteristic features of distribution of pesticide residues in crop units and single sample increments were studied based on more than 19,000 residue concentrations measured in root vegetables, leafy vegetables, small-, medium- and large-size fruits representing 20 different crops and 46 pesticides. Log-normal, gamma and Weibull distributions were found to provide the best fit for the relative frequency distributions of individual residue data sets. The overall best fit was provided by lognormal distribution. The relative standard deviation of residues (CV) in various crops ranged from 15–170%. The 100–120 residue values being in one data set was too small to identify potential effects of various factors such as the chemical and physical properties of pesticides and the nature of crops. Therefore, the average of CV values, obtained from individual data sets, were calculated and considered to be the best estimate for the likely variability of unit crop residues for treated field (CV = 0.8) and market samples (CV = 1.1), respectively. The larger variation of residues in market samples was attributed to the potential mixing of lots and varying proportion of non-detects. The expectable average variability of residues in composited samples can be calculated from the typical values taking into account the sample size.