Agricultural solid waste for sorption of metal ions: part I—characterization and use of lettuce roots and sugarcane bagasse for Cu(II), Fe(II), Zn(II), and Mn(II) sorption from aqueous medium

Sugarcane bagasse and hydroponic lettuce roots were used as biosorbents for Cu(II), Fe(II), Zn(II), and Mn(II) removal from monoelemental solutions in aqueous medium, at pH 5.5, using batch procedures. These biomasses were studied in natura (lettuce roots, NLR, and sugarcane bagasse, NSB) and modified with HNO₃ (lettuce roots, MLR, and sugarcane bagasse, MSB). Langmuir, Freundlich, and Dubinin-Radushkevich non-linear isotherm models were used to evaluate the data from the metal ion adsorption assessment. The maximum adsorption capacities (q_max) in monoelemental solution, calculated using the Langmuir isothermal model for Cu(II), Fe(II), Zn(II), and Mn(II), were respectively 24.61, 2.64, 23.04, and 5.92 mg/g for NLR; 2.29, 16.89, 1.97, and 2.88 mg/g for MLR; 0.81, 0.06, 0.83, and 0.46 mg/g for NSB; and 1.35, 2.89, 20.76, and 1.56 mg/g for MSB. The Freundlich n parameter indicated that the adsorption process was favorable for Cu(II) uptake by NLR; Fe(II) retention by MLR and MSB; and Zn(II) sorption by NSB, MLR, and NSB and favorable for all biomasses in the accumulation of Mn(II). The Dubinin-Radushkevich isotherm was applied to estimate the energy (E) and type of adsorption process involved, which was found to be a physical one between analytes and adsorbents. Organic groups such as O–H, C–O–C, CH, and C=O were found in the characterization of the biomass by FTIR. In the determination of the biomass surface charges by using blue methylene and red amaranth dyes, there was a predominance of negative charges.     

Agricultural solid waste for sorption of metal ions,part II: competitive assessment in multielemental solution and lake water

Sugarcane bagasse and hydroponic lettuce roots were used as biosorbents for the removal of Cu(II), Fe(II), Mn(II), and Zn(II) from multielemental solutions and lake water, in batch processes. These biomasses were studied in natura (lettuce roots, NLR, and sugarcane bagasse, NSB) and chemically modified with HNO₃ (lettuce roots, MLR, and sugarcane bagasse, MSB). The results showed higher adsorption efficiency for MSB and either NLR or MLR. The maximum adsorption capacities (q_max) in multielemental solution for Cu(II), Fe(II), Mn(II), and Zn(II) were 35.86, 31.42, 3.33, and 24.07 mg/g for NLR; 25.36, 27.95, 14.06, and 6.43 mg/g for MLR; 0.92, 3.94, 0.03, and 0.18 mg/g for NSB; and 54.11, 6.52, 16.7, and 1.26 mg/g for MSB, respectively. The kinetic studies with chemically modified biomasses indicated that sorption was achieved in the first 5 min and reached equilibrium around 30 min. Sorption of Cu(II), Fe(II), Mn(II), and Zn(II) in lake water by chemically modified biomasses was 24.31, 14.50, 8.03, and 8.21 mg/g by MLR, and 13.15, 10.50, 6.10, and 5.14 mg/g by MSB, respectively. These biosorbents are promising and low costs agricultural residues, and as for lettuce roots, these showed great potential even with no chemical modification.     

Impacts of water resources development on flow regimes in the Brazos River

The Brazos River, the second largest basin in Texas, represents one of the most highly developed river systems in the state. Thirty-nine reservoirs with capacities greater than 5,000 acre-feet are currently in operation in the basin. Impacts on stream ecosystems are evidenced by changes in flow regimes and resulting changes in fish assemblages over the past 50 years. These changes have been widely attributed to human impacts, through the construction of dams, diversion of water supplies for agricultural and municipal uses, and land use change. However, streamflow regimes result from a complex mix of drivers that include climate, topography, land cover, land use practices, reservoir management practices, dam releases, and water consumption patterns, making determination of anthropogenic impacts problematic. This study quantifies changes in flow regime and probable historical drivers including precipitation, dam construction, population growth, and changing water demand in the Brazos River basin over the past 100 years. Results indicate that the climate of the basin has been relatively stable over the study period, while large-scale changes in human population densities and intense water resources development are correlated with impacts on flow regimes, decreasing the frequency and magnitude of high flow events and stabilizing low flows. These changes have resulted in an increase of habitat generalist fish species, a decrease of native obligate riverine fishes, and an overall homogenization of species assemblages. The results of this study indicate the importance of combining ecological data with an assessment of social drivers for a greater understanding of the dynamics of river basin systems.     

Assessment of fecal sterols in Barigui River sediments in Curitiba, Brazil

The Barigui River watershed is located in the metropolitan region of Curitiba, southern Brazil, passing through several neighboring counties. In recent years, due to growth and disorderly occupation along the river, in addition to lack of sanitation, the Basin suffered a very large inflow of untreated domestic sewage. Current programs to monitor the watershed use traditional physical-chemical parameters and generally the analysis is performed only with water samples. This study analyzes the presence of fecal sterols in sediment samples. Sediment samples were collected from six points along the river and the stanols were extracted, purified and analyzed by GC-MS. Eight compounds were analyzed, among sterols and ketones. The presence of coprostanol was also identified. Coprostanol is a stanol containing a large amount in human feces. It is found near sources of pollution and can be associated with contamination by domestic sewage. The results showed high concentrations of coprostanol, ranging from 0.25 to 196 mug g( - 1). The ratio of coprostanol and epicoprostanol, was below 0.20 at most stations, indicating that the sewage discharged into the river does not undergo prior treatment. Contamination by untreated sewage was also confirmed by ratios of isomeric forms of sterols and ketones 5beta/(5beta + 5alpha).     

Small-scale spatial variability of atrazine and dinoseb adsorption parameters in an alluvial soil

Soil sorption processes largely control the environmental fate of herbicides. Therefore, accuracy of sorption parameters is crucial for accurate prediction of herbicide mobility in agricultural soils. A combined experimental and statistical study was performed to investigate the small-scale spatial variability of sorption parameters for atrazine and dinoseb in soils and to establish the number of samples needed to provide a value of the distribution coefficient (K(d)) next to the mean, with a given precision. The study explored sorption properties of the two herbicides in subsurface samples collected from four pits distributed along a transect of an alluvial soil; two to four samples were taken at about 30 cm apart at each sampling location. When considering all the data, the distribution coefficients were found to be normally and log-normally distributed for atrazine and dinoseb, respectively; the CVs were relatively high (close to 50% for dinoseb and 40% for atrazine). When analyzed horizon by horizon, the data revealed distribution coefficients normally distributed for both herbicides, whatever the soil layer, with lower CVs. The K(d) values were shown to vary considerably between samples collected at very short distance (a few centimeters), suggesting that taking a single soil sample to determine sorption properties through batch experiments can lead to highly unrepresentative results and to poor sorption/mobility predictions.     

Reactivity of the plant growth regulator paclobutrazol (cultar) with two tropical soils of the northeast semiarid region of Brazil

The reactivity of paclobutrazol (PBZ, a plant growth retardant) with a Yellow Ultisol and a Vertisol from the semiarid northeast region of Brazil was evaluated through batch sorption experiments and modeling. Although not instantaneous, the sorption kinetic of PBZ (pure and formulated) was fast (a few hours) in both soils. The sorption kinetics were well described by a second-order (dS(t)/dt=k(2)(S(e2)-S(t))(2)) but not by a first-order model. The sorption isotherms were found to be linear and the calculated K(D) values were 8.8 +/- 0.11 and 7.4 +/- 0.2 L kg(-1) for pure PBZ in the Ultisol and the Vertisol, respectively. The corresponding K(OC) values were 1275 +/- 34 (logK(OC) = 3.11) and 1156 +/- 49 (logK(OC) = 3.06) L kg(-1), respectively. Considering the very different texture of the two soils and the similar K(OC) values determined, these results showed that in both soils, the sorption of PBZ is dominantly controlled by organic matter, although some interactions of PBZ with iron oxides (goethite) were observed in the Ultisol. Based on these sorption parameters a low leachability potential of PBZ in soils is anticipated, as they correspond to a groundwater ubiquity score (GUS) ranging from 2.0 to 2.7, i.e., moderately to not mobile, in contradiction with the actual groundwater situation in Brazil. This work stresses the need to evaluate and predict the risk associated with aquifer contamination by this widely used plant growth regulator.     

Spatial distribution of illicit drugs in surface waters of the natural park of Pego-Oliva Marsh (Valencia,Spain)

Background, aim and scope  

The Pego-Oliva Marsh is the second most important wetland in the Valencian Community (Spain). It is included in the RAMSAR agreement and represents one key point for migratory birds. Emerging contaminants from the human pressure, such as pharmaceuticals, illicit drugs and personal care product, are not included in the list of priority contaminants of the Water Framework Directive yet, and are neither monitored nor controlled. However, pollution of emerging contaminants can threaten the environment and even human health. In order to understand the status of the emerging contamination and recommend future rationalization of countermeasures, the occurrence of illicit drugs was investigated.     

Optimization of artificial neural network models through genetic algorithms for surface ozone concentration forecasting

Introduction

This study proposes three methodologies to define artificial neural network models through genetic algorithms (GAs) to predict the next-day hourly average surface ozone (O₃) concentrations. GAs were applied to define the activation function in hidden layer and the number of hidden neurons.

Methods

Two of the methodologies define threshold models, which assume that the behaviour of the dependent variable (O₃ concentrations) changes when it enters in a different regime (two and four regimes were considered in this study). The change from one regime to another depends on a specific value (threshold value) of an explanatory variable (threshold variable), which is also defined by GAs. The predictor variables were the hourly average concentrations of carbon monoxide (CO), nitrogen oxide, nitrogen dioxide (NO₂), and O₃ (recorded in the previous day at an urban site with traffic influence) and also meteorological data (hourly averages of temperature, solar radiation, relative humidity and wind speed). The study was performed for the period from May to August 2004.

Results and discussion

Several models were achieved and only the best model of each methodology was analysed. In threshold models, the variables selected by GAs to define the O₃ regimes were temperature, CO and NO₂ concentrations, due to their importance in O₃ chemistry in an urban atmosphere.

Conclusion

In the prediction of O₃ concentrations, the threshold model that considers two regimes was the one that fitted the data most efficiently.