The aim of this study was to statistically compare sampling sites identified along the Berg River system to identify the major point sources of metal pollution from June 2004 to May 2005. Three sites were selected [site A—agricultural farming area, site B—Plot 8000 (close to the informal settlement), and site C—the Newton pumping station] representing different sectors which the river services. Aluminium (Al), iron (Fe), manganese (Mn), and lead (Pb) concentrations were determined using Inductively Coupled Plasma Atomic Emission Spectrometry and were statistically compared and analysed with one-way ANOVAs. For all the metals analysed, site C (industrial area) proved to be the site where the highest average metal concentrations were recorded. Generally, the concentrations recorded at site A (site furthest from the industrial area) were significantly (p < 0.05) lower than the concentrations recorded at both sites B and C. While the Al and Fe concentrations were consistently higher than any of the other metals analysed for, site C was identified as the primary source of metal contamination in the Berg River, resulting from the runoff from industrial activities at this particular site.

Chlorpyrifos (O, O-diethyl-O-(3,5,6-trichloro-2-pyridyl) phosphorothioate) is a broad-spectrum organophosphate insecticide and acaricide, widely used in our country. Nowadays, it is the principal insecticide in the market employed for agricultural purposes. A number of studies tending to study the affinity of different pesticides with soil have been performed, but only a few refer to chlorpyrifos. Because of its intensive use, a wide range of terrestrial ecosystems may be contaminated with chlorpyrifos, and there is a need to evaluate its environmental behavior and effects. The aim of our work is to study the interaction and persistence of a commercial formulation of chlorpyrifos on an agricultural soil from Provincia de Buenos Aires, Argentina. In this case, recovery percentages increased with the increase of initial concentration of the pesticide until a concentration of about 25 ppm is reached, and then a decrease was observed. The half-time life was not affected by an increase in chlorpyrifos concentration.

In theory, biological and physical clogging, induced as a result of potentially excessive formation of biomass from degradation of pollutants and retention of inert suspended fine particles, respectively, should result in a decrease of treatment performance. However, some wetlands are not prone to clogging in practice. The aim of this study was to compare the impact of different design (aggregate size) and operational (contact time, empty time and chemical oxygen demand [COD] loading) variables on the treatment efficiency and clogging processes. Different vertical-flow constructed wetlands were constructed and operated from June 2011 until June 2012. Data from June 2011 (setting-up period) were not used. The filter with the highest COD loading performed the worst in terms of outflow COD concentration (120 mg/l) but best in terms of COD load reduction (61 %). The wetland with the largest aggregate size had the lowest mean nitrate-nitrogen outflow concentration of 1.2 mg/l. However, the results were similar regardless of aggregate size (10 versus 20 mm) and resting time (24 versus 48 h) for most water quality variables. However, different COD inflow concentrations (COD of 146 mg/l versus COD of 312 mg/l) had a significant (p < 0.05) impact on the treatment performance for COD, ammonia-nitrogen, ortho-phosphate-phosphorus and suspended solids (SS). Serious clogging phenomena impacting negatively on the treatment performance were not observed for any columns. However, a small aggregate diameter, a short contact time, a long resting time and a low COD inflow concentration were most beneficial in reducing SS accumulation within the wetland filters. © 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.

Lanthanum/aluminum-modified zeolite adsorbent (La/Al-ZA) was prepared and investigated for their ability to remove phosphorus from wastewater. Various batch adsorption conditions, e.g., pH, ionic strength, temperature, contact time, initial phosphorus concentration, and the dosage of adsorbent were tested. The results showed that the adsorption amount increased with the increase of temperature, contact time, and initial phosphorus concentration and decreased with the increase of adsorbent dosage and initial anion concentration. The adsorption amount first increased with increasing pH from 2.0 to 4.0 and reached a plateau over the pH range from 4.0 to 8.0, then significantly decreased from 8.0 to 12.0, and the suitable adsorption was achieved with the pH range 4–9. The phosphorus removal efficiency decreased slightly from 95.86 to 93.39 and 92.53 %, respectively, in the presence of Cl⁻ and SO₄²⁻ at the lower concentration of 0.1 mmol/L, while they decreased significantly from 95.86 % to the ranges of 85.02–88.80 % and 83.77–87.45 %, respectively, in the presence of Cl⁻ and SO₄²⁻ at higher concentrations ranging from 0.5 to 2.0 mmol/L, and the effects on adsorption of La/Al-ZA follow the order: Cl⁻ > SO₄²⁻. Phosphorus adsorption matched with both Langmuir and Freundlich isotherms. The results presented here supported the potential use of the new La/Al-ZA as a material for the treatment of phosphorus in wastewater.

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.

Arsenic contamination of groundwater and surface water is widespread throughout the world. Considering its carcinogenicity and toxicity to human and animal health, remediation of arsenic-contaminated water has become a high priority. There are several physicochemical-based conventional technologies available for removing arsenic from water. However, these technologies possess a number of limitations such as high cost and generation of toxic by-products, etc. Therefore, research on new sustainable and cost-effective arsenic removal technologies for water has recently become an area of intense research activity. Bioremediation technology offers great potential for possible future application in decontamination of pollutants from the natural environment. It is not only environmentally friendly but cost-effective as well. This review focuses on the state-of-art knowledge of currently available arsenic remediation methods, their prospects, and recent advances with particular emphasis on bioremediation strategies.

DayCent is a biogeochemical model of intermediate complexity widely used to simulate greenhouse gases (GHG), soil organic carbon and nutrients in crop, grassland, forest and savannah ecosystems. Although this model has been applied to a wide range of ecosystems, it is still typically parameterized through a traditional "trial and error" approach and has not been calibrated using statistical inverse modelling (i.e. algorithmic parameter estimation). The aim of this study is to establish and demonstrate a procedure for calibration of DayCent to improve estimation of GHG emissions. We coupled DayCent with the parameter estimation (PEST) software for inverse modelling. The PEST software can be used for calibration through regularized inversion as well as model sensitivity and uncertainty analysis. The DayCent model was analysed and calibrated using N2O flux data collected over 2 years at the Iowa State University Agronomy and Agricultural Engineering Research Farms, Boone, IA. Crop year 2003 data were used for model calibration and 2004 data were used for validation. The optimization of DayCent model parameters using PEST significantly reduced model residuals relative to the default DayCent parameter values. Parameter estimation improved the model performance by reducing the sum of weighted squared residual difference between measured and modelled outputs by up to 67 %. For the calibration period, simulation with the default model parameter values underestimated mean daily N2O flux by 98 %. After parameter estimation, the model underestimated the mean daily fluxes by 35 %. During the validation period, the calibrated model reduced sum of weighted squared residuals by 20 % relative to the default simulation. Sensitivity analysis performed provides important insights into the model structure providing guidance for model improvement. © 2013 Springer Science+Business Media Dordrecht.

Major incidents involving mine waste facilities and poor environmental management practices have left the legacy of thousands of contaminated sites like in the historic mining areas in the Carpathian Basin. Associated environmental risks have triggered the development of new EU environmental legislation to prevent and minimize the effects of such incidents. The Mine Waste Directive requires the risk-based inventory of all mine waste sites in Europe by May 2012. In order to address the mining environmental problems, a standard risk-based pre-selection protocol has been developed by the EU Commission. The protocol consists of 18 simple questions about contamination source, pathway and receptor. This paper evaluates the protocol by applying it to real-life cases, adopting it to local conditions, comparing to the similar method of the European Environmental Agency standard Preliminary Risk Assessment Model (PRAMS) and by carrying out uncertainty analysis. All together, 145 ore mine waste sites have been selected for scientific testing and evaluation using the EU Mining Waste Directive (MWD) Pre-selection Protocol as a case study from Hungary. The proportion of uncertain responses to questions in the protocol for the mine waste site gives an insight of specific and overall uncertainty in the data used. Questions of the EU MWD Pre-selection Protocol are linked to a GIS system, and key parameters such as the topographic slope and distance to the nearest surface and groundwater bodies to settlements and protected areas are calculated and statistically evaluated in order to adjust the RA models to local conditions in Hungary. Results show that the adjustment of threshold values to local conditions is necessary; however, the EU MWD Pre-selection Protocol is robust and is relatively insensitive to threshold values. Results of the EU MWD Pre-selection Protocol are consistent with the pre-screening European Environmental Agency PRAMS model which further confirms that the Protocol delivers reliable selection results that are not sensitive to the selected parameters. An interesting outcome of the study is that the highest uncertainty is associated with the engineering conditions of the waste facilities, such as the heights and size.

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.