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.

Organoclays possess unique adsorption behaviour towards hydrophobic organic contaminants. They can also remediate ionic contaminants such as heavy metals and metalloids. The objective of the present study was to prepare organoclay and organoclay mixtures efficient to adsorb both cationic and anionic contaminants. The adsorbents were characterised by X-ray diffraction and infrared spectroscopy. Trivalent (Cr3+) and hexavalent (Cr2O 7 2-) chromium were selected as the model contaminants representing cationic and anionic properties. Bentonite modified with cationic surfactant hexadecyl trimethylammonium bromide at double the cation exchange capacity of the clay remarkably improved Cr2O7 2- adsorption capacity (as high as 0.49 mmol g-1). Similarly, its modification with anionic surfactant sodium dodecyl sulphate at the same dosage improved Cr3+ adsorption (as high as 0.36 mmol g -1). When these two organoclays were physically mixed in equal proportions (1:1), the resultant organoclay mixture efficiently adsorbed both Cr3+ (as high as 0.21 mmol g-1) and Cr2O 7 2- (as high as 0.32 mmol g-1) implying that the mixture could remediate both anionic and cationic contaminants simultaneously. The adsorption of Cr3+ by the organoclay and organoclay mixture fitted well to the Langmuir isothermal model whereas the adsorption of Cr2O7 2- fitted well to the Freundlich model. © 2013 Springer Science+Business Media Dordrecht.

Anionic polyacrylamide (PAM) is a linear, water-soluble anionic polymer that is widely used for erosion control and water quality protection. There has been an issue whether this formulation could possibly have negative effects on soil microbial diversity by altering microbial binding to soil particles or to one another and thus restricting their mobility and role in carbon and nutrient cycling. We conducted an 8-year study annually applying ultra-high rates of PAM to soil and then monitored impacts on soil bacterial diversity. In July and August, we measured active soil bacterial and fungal biomass and microbial diversity in soils receiving 0 (control), 2,691, and 5,382 kg active ingredient PAM ha⁻¹. Active microbial biomass in soil was 19–33 % greater in the untreated control than soil treated with 2,691 or 5,382 kg of active ingredient PAM ha⁻¹. Active bacterial biomass in soil was 21–31 % greater in the control treatment than in soil treated with 2,691 or 5,382 kg of active ingredient PAM ha⁻¹ in August, but not July. Active fungal biomass in soils was 38–50 % greater in the control treatment than soil treated with 2,691 or 5,382 kg of active ingredient PAM ha⁻¹ in July, but not August. Molecular methods were used to access the bacterial diversity, richness, and evenness in an agricultural soil that received 0 (control), 2,691, and 5,382 kg of active ingredient PAM ha⁻¹. We found that although soil receiving these massive PAM application rates and prolonged exposure may reduce active bacterial and fungal biomass, PAM application did not substantially or consistently affect bacterial structural diversity, richness, or evenness in this agricultural soil.

Cadmium (Cd) is a non-essential heavy metal, considered a high-priority pollutant. It occurs naturally in the environment but anthropogenic activities may enhance its presence, with consequences to the biota. Metal research has been focused in the crustaceans but knowledge on estuarine isopods has been lacking. The aim of this study was to assess the bioconcentration kinetics in the estuarine key species Cyathura carinata. This isopod was exposed to different treatments of Cd, through aqueous pathway: control, low (I), medium (II) and very high (III) concentrations during 14 days, being collected along seven sampling times. After the end of the exposure period, the mean uptake rates were 0.023, 0.040 and 0.634 μg g⁻¹ day⁻¹ for each treatment, respectively. Statistical differences in accumulated Cd were recorded between treatments, except between control and treatment I. A linear pattern of accumulation through time was detected for all the concentrations, being most perceptible in the treatment III, where measured Cd in C. carinata’s tissues was significantly different between all the sampling times. Cd accumulation in treatments I and II was not so pronounced, being only noticeable at the end of the exposure period. In these treatments, final concentrations were two and almost four times greater than control, respectively, while in treatment III Cd concentration increased 60 times. Survival did not seem to be affected in the various treatments, suggesting the existence of a strategy for preventing toxic activity of Cd that needs further investigation.

A novel dye degrading bacterium capable of decolorizing and mineralizing four different dyes (Methyl red, Orange II, Direct red 80, and Direct blue 71) was isolated from textile industrial wastewater using the selective enrichment technique. The bacterium was identified as Pseudomonas aeruginosa. More than 80 % decolorization of Direct red 80 was obtained under microaerophilic conditions in 48 h, whereas only 10 % color removal was obtained under oxic conditions at the same time. Subsequent aeration of the decolorized medium resulted in the mineralization of the metabolic intermediates generated after azo bond cleavage by P. aeruginosa as confirmed by total organic carbon content and high-performance liquid chromatography analyses. The degradation products were characterized by Fourier transform infrared spectrometer and nuclear magnetic resonance techniques whereas the biotoxicity profile of the samples were evaluated using the brine shrimp lethality test assay. Data from this study provide evidence of dye mineralization and detoxification by a monoculture of P. aeruginosa in successive microaerophilic/oxic stages. © 2013 Springer Science+Business Media Dordrecht.

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.

During this study, we investigated the mineralogical characterization of technogenic magnetic particles (TMPs) contained in alkaline industrial dust and fly ash emitted by coal burning power plants and cement plants. The reaction of tested dust samples varied between values of pH 8 and pH 12. Their magnetic properties were characterized by measurement of magnetic susceptibility (χ), frequency dependence of magnetic susceptibility (χfd), and temperature dependence of magnetic susceptibility. Mineralogical and geochemical analyses included scanning electron microscopy with energy dispersive spectroscopy, microprobe analysis and X-ray diffraction. The TMPs in fly ash from hard coal combustion have the form of typical magnetic spherules with a smooth or corrugated surface as well as a skeletal morphology, composed of iron oxides (magnetite, maghemite, and magnesioferrite) that occurred in the form of incrustation on the surface of mullite, amorphous silica, or aluminosilicate particles. The TMPs observed in fly ash from lignite combustion have a similar morphological form but a different mineralogical composition. Instead of magnetite and magnesioferrite, maghemite and hematite with lower χ values were the prevailing magnetic minerals, which explains the much lower magnetic susceptibility of this kind of ash in comparison with the ash from hard coal combustion, and probably results from the lower temperature of lignite combustion. Morphology and mineralogical composition of TMPs in cement dust is more diverse. The magnetic fraction of cement dust occurs mostly in the form of angular and octahedral grains of a significantly finer granulation (<20 μm); however, spherules are also present. A very characteristic magnetic form for cement dust is calcium ferrite (CaFe₃O₅). The greatest impact on the magnetic susceptibility of cement dust results from iron-bearing additives (often waste materials from other branches of industry), which should be considered the most dangerous to the environment. Stoichiometric analysis of micro-particles confirmed the presence of heavy metals such as Pb, Mn, Cd, and Zn connected with TMPs, which are carriers of magnetic signals in atmospheric dust. Therefore, in some cases, their presence in topsoil when detected by magnetic measurement can be treated as an indicator of inorganic soil contamination.

A laboratory-scale study was conducted to determine the removal efficiencies of nine contaminants from a tannery wastewater using a number of physicochemical processes. Coagulation–flocculation using bittern as coagulant, oxidation-utilizing ozone, and adsorption using activated carbon were applied separately and in different sequences. Jar tests were utilized to conduct the experimental work. Except for arsenic, the highest removal efficiencies were recorded when coagulation/flocculation was conducted on the alkalized samples using a bittern dose of 5 mL/L. Activated carbon adsorption improved removal efficiencies of several contaminants. The coagulation/flocculation–adsorption sequence using the optimum dose of 5 mL/L of bittern resulted in high removal efficiencies for total suspended solids (TSS) (97 % ± 1), apparent color (100 % ± 0), turbidity (97 % ± 1), total nitrogen (86 % ± 1), and chromium (100 % ± 0). On the other hand, the same sequence resulted in moderate removal efficiencies for chemical oxygen demand (COD) (72 % ± 7) and total phosphorus (74 % ± 5) and relatively low removals for biochemical oxygen demand (BOD) (55 % ± 10) and arsenic (42 % ± 14). The removal efficiencies for the different tested sequences demonstrated that each sequence did improve the removal efficiencies for most of the parameters tested and consequently, the quality of tannery effluent. However, no single optimum sequence was capable of attaining high removal efficiencies for all nine parameters.

Natural palygorskite was used as an adsorbent for the removal of copper, cobalt and nickel from an aqueous solution. All assays were performed under controlled conditions to establish the adsorption capacity of the solid. Initially, the clay was characterized by chemical analysis, XRD, infrared spectroscopy and thermogravimetry. Adsorption experiments for the ions in aqueous solution were carried out by a batch method through which the reaction time, initial concentration of cations, temperature and pH of the aqueous solution were systematically varied. First-order, pseudo-second-order and intraparticle diffusion models were used to describe the kinetic data. The results show that the processes were fitted well by the pseudo-second-order model. Moreover, the equilibrium solid–cation systems followed the Langmuir isotherm model. The results indicate that raw palygorskite could be employed as a low-cost material for the removal of heavy metals from aqueous solution.

The remediation of tributyltin (TBT) by adsorption onto nFeO, activated carbon and nFeO/activated carbon composite material as a function of adsorbent dose, contact time, pH, stirring speed, initial TBT concentration and temperature was studied. The effect of temperature on kinetics and equilibrium of TBT sorption on the precursors and the composite was thoroughly examined. The adsorption kinetics is well fitted using a pseudo-second-order kinetic model, and the adsorption isotherm data of nFeO, activated carbon could be described by the Freundlich isotherm model whereas nFeO/activated carbon composite could be described by the Freundlich and Dubinin-Radushkevich isotherm models. Thermodynamic parameters (i.e. change in the free energy (∆ G°), the enthalpy (∆ H°) and the entropy (∆ S°)) were also evaluated. The overall adsorption process was endothermic and spontaneous in nature. The results obtained also showed that 99.9, 99.7 and 80.1 % TBT were removed from contaminated natural seawater by nFeO/activated carbon composite, activated carbon and nFeO, respectively.