Poised to gain insight into nitrate adsorption and removal processes from water through employment of modified surfaces, a well-defined inorganic manganese species was used in connection with hydrophobic mesoporous silica. To this end, the surface of hydrophobic mesoporous silica was modified by coating silica with a manganese oxychloride (Mn₈O₁₀Cl₃) nanoparticle layer. A sol–gel method was utilized for the synthesis of hydrophobic silica, using tetraethyl orthosilicate–methyl triethoxysilane (TEOS–MTES) as precursors. Subsequent coating with Mn₈O₁₀Cl₃ took place by mixing MnCl₂ and NaOH with hydrophobic silica. Physicochemical characterization of the Mn₈O₁₀Cl₃-coated silica was carried out by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N₂ sorption. The achieved surface modification reduced remarkably the specific surface area by 80.7 % and influenced the ability of nitrates to adsorb on Mn-modified silica. Nitrate adsorption kinetics on Mn₈O₁₀Cl₃-coated silica was studied by a batch reactor. Process parameters including pH, temperature, and initial nitrate concentration were examined thoroughly. The experimental adsorption data were fitted satisfactorily through Langmuir isotherm equations and were found to be well-represented by a pseudo-second-order kinetic model. The collective data emphasize the significance of well-defined inorganic manganese phases, coating hydrophobic silica, in optimally influencing water decontamination from pollutant nitrates.

The present paper examines the phosphate adsorption from aqueous solutions onto goethite, bentonite, and bentonite–goethite system. The properties of the materials were studied by X-ray diffraction (XRD), attenuated total reflectance (ATR), and NMR spectra and by the measurement of the specific surface area, the point of zero charge (p.z.c.) and the pore-specific volume. ATR and NMR spectra of bentonite and bentonite–goethite system show peaks which correspond to tetrahedrally and octahedrally coordinated Al. The specific surface area of the system differs according to the appropriate method used, while system’s p.z.c. is higher than bentonite and lower than goethite. The pore-specific volume of bentonite–goethite system is higher than that of bentonite or goethite. According to XRD spectrum of bentonite–goethite system, goethite coats the (001) spacing of bentonite while the coating of (010) plane of bentonite is limited. The crystallinity of the system decreases and the negative permanent charge increases. Phosphate adsorption experiments took place at different pH (3.8–9.0) and concentrations (40.3–443.5 μmol L⁻¹) and constant capacitance model was applied to describe adsorption. A ligand exchange mechanism characterizes the model because the charge is divided among adsorbate and adsorbent. The constant capacitance model describes the adsorption mechanism in all examined pH. This model can be utilized in such systems using the surface protonation-dissociation constant of goethite and showing the exact shape of the adsorption isotherms for different pH values. Τhe produced low-cost bentonite–goethite system presents the highest adsorption of P per kilogram of goethite.

This study examined the potential for regrowth of Escherichia coli in laboratory-incubated microcosms spiked with ultraviolet (UV)-disinfected sewage effluent and extracts derived from turfgrass or leaf litter. A second part of the study examined the potential of nutrients for predicting E. coli in two urban streams with point source effluent. Microcosms containing effluent and vegetation extracts were incubated for 72 h, samples were withdrawn over six time periods for measurement of E. coli. Streams were sampled every 2 weeks and E. coli and nutrients measured. E. coli counts in the microcosms exceeded the Texas state secondary contact recreation standard for surface water quality within 12 h for the turfgrass and within 18 h for leaf litter extracts. Univariate analysis of variance found that the interaction between vegetation extract source and concentration was more important than source of vegetation or concentration of extract alone. In the two streams sampled downstream of a point source effluent discharge, between 82 and 92 % of the variance in annual E. coli during high stream flow and between 55 and 57 % of the variance in annual E. coli during low stream flow was described by stream water-dissolved organic carbon (DOC) and dissolved organic nitrogen (DON), NH₄-N, NO₃-N, or PO₄-P. Once effluent is discharged to surface water, particularly during high flow conditions, DOC and DON derived from the landscape and nitrogen and PO₄-P derived from the effluent will provide ideal conditions for E. coli regrowth in surface waters downstream of the point source discharge.

A pilot-scale anaerobic bioreactor with high levels of microbial sulfate reduction, known to be capable of removing cationic metals from a metal- and acid-contaminated waste stream, was utilized to determine if the system would be effective in removing metals in the form of oxyanions such as arsenate and chromate. The system removed 90 % to >99 % of the arsenic and between 86 % and 94 % of the chromium from a waste stream containing 5 mg/L of each. Cadmium, copper, iron, lead, and zinc also were removed. An equilibrium geochemistry computer modeling code, MINTEQAK, modified from MINTEQA2, was used for the chemical modeling of processes in the bioreactor. Experimental evidence on the chemical and biological reduction of arsenic and chromium and fluorescent diffraction analysis of precipitates support the following hypotheses: the primary removal process for chromium was the reduction of Cr(VI) to Cr(III) by sulfides, followed by precipitation of chromium hydroxide [Cr(OH) 3(s)]; removal of arsenic was by direct microbial enzymatic reduction of As(V) to As(III) followed by precipitation of arsenic sulfides (As 2S3 or AsS). Experimental evidence and modeling with MINTEQAK confirmed that 90 % to 95 % of the removal of arsenic and chromium occurred in the first quarter volume of the bioreactor. Additional removal of arsenic and chromium occurred in the remaining volume of the bioreactor. The use of a sulfate reduction-based anaerobic treatment system was effective for metal-laden wastewater with elevated concentrations of arsenic and chromium. © 2013 Springer Science+Business Media Dordrecht.

We investigated the effects of four commercial formulations of herbicides (glyphosate [GLY], metsulfuron-methyl [MET], bispyribac-sodium [BIS], and picloram [PIC]) individually, and in three 50:50 mixtures (GLY–MET, GLY–BIS, GLY–PIC) on the common toad Rhinella arenarum (Anura: Bufonidae) tadpoles. Enzymatic parameters such as, glutathione S-transferase (GST), butyrylcholinesterase (BChE) and acetylcholinesterase (AChE) activities, as well as erythrocyte nuclear abnormalities (ENA) were studied. Interactions between herbicides in mixtures were evaluated and classified as additive, synergistic, or antagonistic. Toxicity results (48-h LC₅₀) showed that PIC was the most toxic herbicide, followed by BIS, GLY, and MET, while GLY–PIC was the most toxic mixture, followed by GLY–BIS, and GLY–MET. All commercial herbicide formulations and their mixtures significantly inhibited BChE activity in exposed tadpoles. The AChE activity was also inhibited by all herbicides and their mixtures, except by GLY–BIS. The inhibition of GST activity was only significant for GLY, MET, PIC, and GLY–MET. A significant increase in the frequency of ENA was found for tadpoles exposed either to commercial herbicide formulations or to mixtures, except for GLY. All the mixtures showed synergism for BChE activity while for AChE only the GLY–MET and GLY–PIC mixtures acted synergistically. GLY–MET showed synergism for GST, whereas for ENA, the mixture GLY–BIS was antagonistic. This study with R. arenarum tadpoles demonstrates that the interactions between three of the most intensively used herbicides in soybean crops results in synergistic effects on mortality and neurotoxicity and synergistic or additive effects in genotoxicity.

Spatial and temporal trends in nutrient concentrations and loads were analyzed for three rivers in the Red River watershed, Manitoba, Canada to determine changes in nutrient export across hydrologic seasons and along river continua in the Great Plains. Annual patterns in all three rivers were strongly influenced by the snowmelt period: 25-89 % of the total annual river volume, 42-92 % of the total annual TP load, and 41-81 % of the total annual TN load were delivered during snowmelt. Concentrations of TP and TN varied among the hydrologic seasons (snowmelt, summer, fall, and winter), but showed more variability and larger values during winter and snowmelt, with peak values reaching 1.960 mg TP L-1 and 16.07 mg TN L-1. Although the flat topography and semi-arid climate of the Red River watershed results in hydrological disconnects along river continua, discharge and nutrient export increased along the three river gradients. In contrast, TP or TN concentrations showed no significant longitudinal change for the two agriculturally dominated watersheds yet increased along the forested stream. Our finding that TP and TN exports from northern Great Plains rivers are strongly influenced by seasonal hydrology, with snowmelt being a critical period for nutrient export has implications for design and implementation of appropriate management practices to minimize nutrient export to proximal and downstream aquatic ecosystems. © 2013 Her Majesty the Queen in Right of Canada.

Colistin is a peptide antibiotic widely used as a food additive in animal farming, specially swine and poultry, and also has recently been applied in human medicine to treat infections caused by multiresistant gram-negative bacteria strains. When orally administered, colistin is eliminated in feces virtually unaltered; thus, it may reach water bodies and wastewater treatment facilities in its active form. Apart from the risks associated with development of antimicrobial resistance and environmental toxicity issues, the presence of antimicrobials in wastewater can, additionally, interfere in biological processes commonly used to treat them. Nitrifying bacteria are among the most sensitive microorganisms to inhibitory compounds, including pharmaceuticals, and are useful as biosensors to access contaminant toxicity information in wastewater treatment plants. Therefore, in order to assess the colistin acute toxicity to the microorganisms involved in the nitrification processes, the nitritation and nitratation kinetics were monitored under different colistin concentrations. The results showed that only ammonia-oxidizing bacteria are sensitive to the antibiotic, presenting an IC50 of 10.8 mg L⁻¹ of colistin when used as a commercial formulation and 67.0 mg L⁻¹ when used as raw colistin sulfate. For nitrite-oxidizing bacteria, even the highest colistin concentration used in the assays (316 mg L⁻¹) was not sufficient to inhibit the process. According to these results, the colistin concentrations expected in animal farming wastewater, when its dosage is used as a growth promoter, would not be enough to keep nitrification from taking place. Nevertheless, when used in higher concentrations, such as for therapeutic purposes, it could endanger the maintenance of the process.

The impact of three commercially available nanoparticles (NPs) on trichloroethylene (TCE) adsorption onto granular activated carbon (GAC) was investigated. TCE adsorption isotherm and column breakthrough experiments were conducted in the presence and absence of silicon dioxide, titanium dioxide, and iron oxide nanoparticles. A rapid small-scale column test (RSSCT) was assessed for its ability to predict TCE adsorption in pilot-scale GAC in the presence and absence of NPs. Zeta potential of the three NPs and the GAC were measured. Particle size distribution of the NP dispersions was analyzed as a function of time. The surface area and the pore size distribution of the virgin and the exhausted GAC were obtained along with transmission electron microscopy and Fourier transform infrared spectroscopy analysis. The effect of NPs was found to be a function of their zeta potential, concentration, and particle size distribution. Due to their electrical charge, NPs attached to the GAC and blocked the pores and thus reduced the access to the internal pore structure. However, due to the fast adsorption kinetics of TCE, no effect from the three NPs was observed in the isotherm and kinetic studies. The RSSCT, on the other hand, accurately predicted the pilot-column TCE breakthrough in the presence of NPs.

In this paper, we report on a field experiment being carried out in a Typic Eutrorthox. The experiment was initiated in the 1997–98 agricultural season as a randomized block design with four treatments (0, 5, 10, and 20 t ha⁻¹) of sewage sludge and five replicates. Compound soil samples were obtained from 20 subsamples collected at depths of 0–0.1 and 0.1–0.2 m. Cu, Fe, Mn, and Zn concentrations were extracted with DTPA pH 7.3; 0.1 mol L⁻¹ HCl, Mehlich-I, Mehlich-III, and 0.01 mol L⁻¹ CaCl₂. Metal concentrations were determined via atomic absorption spectrometry. Diagnostic leaves and the whole above-ground portion of plants were collected to determine Cu, Fe, Mn, and Zn concentrations extracted by nitric–perchloric digestion and later determined via atomic absorption spectrometry. Sewage sludge application caused increases in the concentrations of soil Cu, Fe, and Mn in samples taken from the 0–0.1 m depth evaluated by the extractants Mehlich-I, Mehlich-III, 0.01 mol L⁻¹ HCl and DTPA pH 7.3. None of the extractants provided efficient estimates of changes in Mn concentrations. The acid extractants extracted more Cu, Fe, Mn, and Zn than the saline and chelating solutions. The highest concentrations of Cu, Fe, and Zn were obtained with Mehlich-III, while the highest concentrations of Mn were obtained with HCl. We did not observe a correlation between the extractants and the concentrations of elements in the diagnostic leaves nor in the tissues of the whole maize plant (Zea mays L.).

A pot experiment was conducted in order to study the relationships of soil pollution indices to maize (Zea mays L.) growth characteristics and soil and plant heavy metal content, as well as the metal plant uptake. A completely randomized block design was used, including 11 treatments in three replications. The treatments applied were control (freshwater), four levels of inorganic NPK fertilizer combined with treated municipal wastewater and freshwater and three sludge levels (5, 25 and 50 %, respectively) in the presence of treated wastewater and freshwater, respectively. The mean effect of the applied sludge levels independent of the presence of the freshwater or wastewater contributed to the accumulation of heavy metals Cr, Cu, Zn and Mn in soil and in leaves. The soil pollution indices, i.e., pollution load index (PLI), elemental pollution index (EPI), total concentration factor and heavy metal load, showed that the soil had been polluted with heavy metals to a great extent. The application of sludge treatment affected positively the maize plant height, leaf number and the indices PLI and EPI. All pollution indices studied were positively related to plant leaf number and plant height, as well to heavy metal soil content.