Improving bioavailability of phosphorous from cattle dung by using phosphatase immobilized on natural clay and nanoclay

The high P retention of acidic Andisols makes necessary to increase our technological approaches in pasture management in the animal system production. Here, we evaluated the clay- or nanoclay-acid phosphatase complexes for improving phosphorus mineralization from degraded cattle dung. We implemented an immobilization mechanism of acid phosphatase (AP) using natural clays (allophanic and montmorillonite) and nanoclays as support materials. Also, we evaluated the mineralization of organic P containing in decomposed cattle dung with clay- and nanoclay-AP complexes by incubation studies. Clays and nanoclays were characterized by microscopy techniques as atomic force and confocal-laser scanning microscopy. We found that these support materials stabilized AP by encapsulation. Our results showed that immobilization on allophanic or montmorillonite materials improved both the specific activity (4-48%) and the V_max (28-38%) of AP. Moreover, the enzyme had a better performance when immobilized on clay and nanoclay from Andisol than on montmorillonite materials. Phosphorous mineralization of cattle dung was regulated by water-soluble P present in the dung and P re-adsorption on allophanic materials. However, we were able to detect a potential capacity of AP immobilized on allophanic nanoclays as the best alternative for P mineralization. Further research with initially low water-soluble P containing organic materials is required to quantify the P mineralization potential and bioavailability of P from dung.     

Analytical improvements of hybrid LC-MS/MS techniques for the efficient evaluation of emerging contaminants in river waters: a case study of the Henares River (Madrid, Spain)

Purpose  

Instrumental capabilities and software tools of modern hybrid mass spectrometry (MS) instruments such as high-resolution mass spectrometry (HRMS), quadrupole time-of-flight (QTOF), and quadrupole linear ion trap (QLIT) were experimentally investigated for the study of emerging contaminants in Henares River water samples.     

Phytoremediation of phenol using Vicia sativa L. plants and its antioxidative response

Common vetch (Vicia sativa L.) is a legume species with an extensive agricultural use. However, the phytoremediation potentiality of this species has not been sufficiently explored because little is known about its resistance to inorganic and organic pollutants. In the present work, phenol tolerance of common vetch was assayed at different stages of growth. Germination index and germination rate decreased only at high phenol concentrations (250 and 500 mg L(-1)), whereas 30-day-old plants were able to tolerate this pollutant, with high removal efficiencies. The activities of antioxidative enzymes, such as peroxidase (POD) and ascorbate peroxidase, increased significantly with the highest phenol concentration, whereas superoxide dismutase activity, malondialdehyde, and H(2)O(2) levels remained unaltered. Besides, an increase in two basic isoforms of POD was observed in plants treated with phenol. The results suggested that common vetch has an efficient protection mechanism against phenol-induced oxidative damage. Moreover, it could tolerate and remove high phenol concentrations, avoiding serious phytotoxic effects. Thus, V. sativa could be considered an interesting tool in the field of phytoremediation.     

Polychlorinated biphenyls and their hydroxylated metabolites in placenta from Madrid mothers

Introduction  

Concentrations and congener profiles of polychlorinated biphenyls (PCBs) and their hydroxylated metabolites (OH-PCBs) in placenta samples from a Madrid population (Spain) are reported. Structure dependent retentions of OH-PCBs are known to occur in both humans and wildlife, making it of interest to assess placental transfer of both parent compounds and their metabolites to the developing foetus.     

Air quality impact assessment of multiple open pit coal mines in northern Colombia

The coal mining region in northern Colombia is one of the largest open pit mining regions of the world. In 2009, there were 8 mining companies in operation with an approximate coal production of ～70 Mtons/year. Since 2007, the Colombian air quality monitoring network has reported readings that exceed the daily and annual air quality standards for total suspended particulate (TSP) matter and particles with an equivalent aerodynamic diameter smaller than 10 μm (PM??) in nearby villages. This paper describes work carried out in order to establish an appropriate clean air program for this region, based on the Colombian national environmental authority requirement for modeling of TSP and PM(10) dispersion. A TSP and PM?? emission inventory was initially developed, and topographic and meteorological information for the region was collected and analyzed. Using this information, the dispersion of TSP was modeled in ISC3 and AERMOD using meteorological data collected by 3 local stations during 2008 and 2009. The results obtained were compared to actual values measured by the air quality monitoring network. High correlation coefficients (>0.73) were obtained, indicating that the models accurately described the main factors affecting particle dispersion in the region. The model was then used to forecast concentrations of particulate matter for 2010. Based on results from the model, areas within the modeling region were identified as highly, fairly, moderately and marginally polluted according to local regulations. Additionally, the contribution particulate matter to the pollution at each village was estimated. Using these predicted values, the Colombian environmental authority imposed new decontamination measures on the mining companies operating in the region. These measures included the relocation of three villages financed by the mine companies based on forecasted pollution levels.     

Solids and nutrient removal from flushed swine manure using polyacrylamides

Most of the organic nutrient elements (nitrogen and phosphorus) and carbon compounds in liquid swine are contained in fine suspended particles. Flocculation treatment with polyacrylamide (PAM) followed by screening is one the best methods to separate the liquid fraction from the solid fraction in swine manure, and thus to eliminate nutrient elements associated with solids. In this study, the efficiency of a synthetic polyacrylamide to treat swine manure was evaluated. After polymer treatment samples were sieved and the filtrated liquid was analyzed. TSS, VSS and COD concentrations in the liquid fraction were 2.17, 1.93 and 16.42 g/L respectively, accounting for 94, 94 and 77% removal percentages for TSS, VSS and COD using 30 mg/L of PAM.     

Adsorption of chloridazon from aqueous solution on modified kerolite-rich materials

The adsorption of chloridazon (5-amine-4-chloro-2-phenylpyridazin-3(2H)-one) on kerolite samples heated at 110°C (K-110), 200°C (K-200), 400°C (K-400), 600°C (K-600) and acid-treated with H₂SO₄ solutions of two different concentrations (0.25 and 0.5 M) (K-0.25 and K-0.5, respectively) from pure water at 25°C has been studied by using batch and column experiments. The adsorption experimental data points were fitted to the Freundlich equation in order to calculate the adsorption capacities (K_f) of the samples; K_f values ranged from 184.7 mg kg^?1 (K-0.5) up to 2253 mg kg^?1 (K-600). This indicated that the heat treatment given to the kerolite greatly increases its adsorption capacity for the herbicide whereas the acid treatment produces a clear decrease in the amount of chloridazon adsorbed. The removal efficiency (R) was also calculated; R values ranging from 52.8% (K-0.5) up to 88.3% (K-600). Thus, the results showed that the 600°C heat-treated kerolite was more effective in relation to adsorption of chloridazon and it might be reasonably used in removing this herbicide from water.     

Electro-Fenton degradation of the antibiotic sulfanilamide with Pt/carbon-felt and BDD/carbon-felt cells. Kinetics,reaction intermediates,and toxicity assessment

The degradation of 230 mL of a 0.6-mM sulfanilamide solution in 0.05 M Na₂SO₄ of pH 3.0 has been studied by electro-Fenton process. The electrolytic cell contained either a Pt or boron-doped diamond (BDD) anode and a carbon-felt cathode. Under these conditions, organics are oxidized by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton’s reaction between initially added (and then electrochemically regenerated) Fe²⁺ and cathodically generated H₂O₂. From the decay of sulfanilamide concentration determined by reversed-phase liquid chromatography, an optimum Fe²⁺ concentration of 0.20 mM in both cells was found. The drug disappeared more rapidly using BDD than Pt, and, in both cases, it was more quickly removed with raising applied current. Almost total mineralization was achieved using the BDD/carbon-felt cell, whereas the alternative use of Pt anode led to a slightly lower mineralization degree. In both cells, the degradation rate was accelerated at higher current but with the concomitant fall of mineralization current efficiency due to the greater increase in rate of the parasitic reactions of hydroxyl radicals. Reversed-phase liquid chromatography allowed the identification of catechol, resorcinol, hydroquinone, p-benzoquinone, and 1,2,4-trihydroxybenzene as aromatic intermediates, whereas ion exclusion chromatography revealed the formation of malic, maleic, fumaric, acetic, oxalic, formic, and oxamic acids. NH₄ ⁺, NO₃ ^?, and SO₄ ^2? ions were released during the electro-Fenton process. A plausible reaction sequence for sulfanilamide mineralization involving all detected intermediates has been proposed. The toxicity of the solution was assessed from the Vibrio fischeri bacteria luminescence inhibition. Although it acquired its maximum value at short electrolysis time, the solution was completely detoxified at the end of the electro-Fenton treatment, regardless of the anode used.     

Arsenic, chromium and mercury removal using mussel shell ash or a sludge/ashes waste mixture

Different batches of valued mussel shell and waste mussel shell ash are characterised. Shell ash has pH?>?12 and high electrical conductivities (between 16.01 and 27.27 dS?m^?1), while calcined shell shows pH values up to 10.7 and electrical conductivities between 1.19 and 3.55 dS?m^?1. X-ray fluorescence, nitric acid digestion and water extractions show higher concentrations in shell ash for most parameters. Calcite is the dominant crystalline compound in this ash (95.6 %), followed by aragonite. Adsorption/desorption trials were performed for mussel shell ash and for a waste mixture including shell ash, sewage sludge and wood ash, showing the following percentage adsorptions: Hg(II) >94 %, As(V) >96 % and Cr(VI) between 11 and 30 % for shell ash; Hg(II) >98 %, As(V) >88 % and Cr(VI) between 30 and 88 % for the waste mixture. Hg and As desorption was <5 % for both shell ash and the waste mixture, while Cr desorption was between 92 and 45 % for shell ash, and between 19 and 0 % for the mixture. In view of that, mussel shell ash and the mixture including shell ash, sewage sludge and wood ash could be useful for Hg(II) and As(V) removal.     

New trends in the analytical determination of emerging contaminants and their transformation products in environmental waters

Since the so-called emerging contaminants were established as a new group of pollutants of environmental concern, a great effort has been devoted to the knowledge of their distribution, fate and effects in the environment. After more than 20 years of work, a significant improvement in knowledge about these contaminants has been achieved, but there is still a large gap of information on the growing number of new potential contaminants that are appearing and especially of their unpredictable transformation products. Although the environmental problem arising from emerging contaminants must be addressed from an interdisciplinary point of view, it is obvious that analytical chemistry plays an important role as the first step of the study, as it allows establishing the presence of chemicals in the environment, estimate their concentration levels, identify sources and determine their degradation pathways. These tasks involve serious difficulties requiring different analytical solutions adjusted to purpose. Thus, the complexity of the matrices requires highly selective analytical methods; the large number and variety of compounds potentially present in the samples demands the application of wide scope methods; the low concentrations at which these contaminants are present in the samples require a high detection sensitivity, and high demands on the confirmation and high structural information are needed for the characterisation of unknowns. New developments on analytical instrumentation have been applied to solve these difficulties. Furthermore and not less important has been the development of new specific software packages intended for data acquisition and, in particular, for post-run analysis. Thus, the use of sophisticated software tools has allowed successful screening analysis, determining several hundreds of analytes, and assisted in the structural elucidation of unknown compounds in a timely manner.