A simple flow-based method was developed for the selective separation of arsenic species (+3 and +5) using a macrocycle-immobilized solid phase extraction (SPE) system, commonly known as molecular recognition technology (MRT) gel. Arsenic species in solution or in the eluent were subsequently quantified with graphite furnace atomic absorption spectrometry. The separation behaviors of As(III) and As(V) on MRT–SPE were investigated. It was found that As(V) can be selectively collected on the SPE system within the range of pH 4 to 9, while As(III) was passed through the MRT–SPE. The retention capacity of the MRT–SPE material for As(V) was found to be 0.25 ± 0.04 mmol g⁻¹. The detection limit of the method for As(V) was 0.06 μg L⁻¹, and the relative standard deviation was 2.9 % (n = 10, C = 1 μmol L⁻¹). Interference from the matrix ions was studied. In order to validate the developed method, certified reference materials of effluent wastewater and groundwater samples were analyzed, and the determined values were in good agreement with the certified values. The proposed method was successfully applied to the speciation analysis of tri- and pentavalent arsenic in natural water samples showing satisfactory recoveries (≥ 98.7 %).

This study investigates the potential impact of OSPW (oil sands processed water) in terms of naphthenic acids (NAs) in the event that OSPW which contain NAs were discharged to a stretch of the Athabasca River of Alberta, Canada. A one-dimensional model WASP7 (water quality analysis simulation programme) was hydro-dynamically calibrated and validated for the data 1999-2008. The model represented the field data quite well except frozen seasons. The sensitivity analysis showed that the concentrations of NAs in the Athabasca River due to OSPW discharged to the river will be most sensitive to changes in the discharge rate of OSPW and concentrations of NAs in the OSPW. The WASP7 was applied to investigate how to achieve acceptable concentrations of NAs (≤0.15 mg/L) along the river, assuming NAs are degraded by natural dilution, biodegradation, sorption, photodegradation or combinations of these processes. If only the dilution effect is considered for an OSPW discharged at 1.5, 3.0 and 4.5 m 3/s (initial NAs concentration of 120 mg/L) to the river, respectively, all the NAs concentrations simulated would exceed an allowable limit of ≤0.15 mg/L, which indicates that dilution effect alone is not sufficient to decrease the concentration of NAs in the river. Similarly, by only considering a photodegradation rate of 0.005/day, the concentrations of NAs would decrease by approximately 0.1-3 %. However, by only considering a maximum biodegradation rate of 0.4/day, NAs discharged to the river can be decreased by 5-90 %. If a more moderate biodegradation rate of 0.2/day is assumed but photodegradation is also considered at 0.0025/day, then for the same three discharge rates of OSPW to the river, the allowable OSPW NAs have to be limited to 8.02, 4.09 and 2.77 mg/L to limit NAs at 0.15 mg/L. This implies that high biodegradation itself is more effective than a combination of moderate biodegradation and photodegradation in degrading NAs. Through multiple numerical experiments with WASP7, it seems that to limit the concentrations of the final NAs in the Athabasca River within 0.15 mg/L, it will be crucial to limit the OSPW NAs and the OSPW discharge rate to the river. © 2013 Springer Science+Business Media Dordrecht.

Chlorine is the most commonly used chemical for water and wastewater disinfection worldwide, and it reacts with both ammonia and dissolved organic nitrogen. Using the salicylate spectrophotometric method, effects of glycine on the classic breakpoint chlorination are studied using glycine as a surrogate for dissolved organic nitrogen. The results show that the shape of the breakpoint chlorination curve with glycine was analogous to that of water without glycine. Increasing the glycine concentration moves the chlorination breakpoint curve to the right, demonstrating that more chlorine must be added to replace the chlorine consumed by glycine and yield the desired residual active chlorine concentration. At the peak of the chlorination breakpoint curve, both NH₂Cl and mono-chlorinated organic chloramine reach their maximum. The Cl₂/N ratio of the peak is linearly related to the glycine concentration, and our calculations indicate that the maximum of mono-chlorinated organic chloramine formation by glycine chlorination occurs at a stoichiometric ratio of 1:1; the same as that for chlorinating ammonia to NH₂Cl. The distribution of NH₂Cl and organic chloramines is controlled by [Gly]/[NH₃-N]. At the breakpoint, ammonia and glycine are completely oxidized by chlorine, which leads to chlorine depletion. The stoichiometric ratio for the complete oxidation of glycine was 3:1, larger than that for complete oxidation of ammonia (2:1). For the different stoichiometric ratio in reaction of oxidation of ammonia and glycine, the sum of ammonia and glycine cannot be used as a chlorine dosage control parameter. The chlorine control method involving ammonia and glycine for chlorine and chloramination process is established.

Previous research demonstrated that nutrient treatment in conventionally drained bioretention cells is dependent upon temperature and varying wetting and drying regimes in the media. This study examines the influence that previous events have on outflow concentrations by analyzing flow-weighted composite samples from four to six consecutive events during three different seasons for two sets of field-monitored bioretention cells in Nashville, NC. The bioretention cells had different media depths (0.6-m versus 0.9-m). As a means to analyze performance from consecutive events, the evolution of cumulative pollutant loads was presented by plotting cumulative load versus cumulative volume. This method of presenting water quality data allows for the direct analysis of event mean concentrations, load reduction, and volume reduction with one graph, as well as describing the seasonal impacts and impacts from consecutive events. Runoff and outflow concentrations were also correlated to media temperature and rainfall characteristics. The overall results of this study showed that conventionally drained bioretention cells mainly convert organic nitrogen, the predominant source of nitrogen in runoff, into nitrate in the aerobic environment present in the media. Nitrate is then exported from the media during subsequent events. The greatest export occurred during the warmer months because higher media temperatures increased microbial activity. Pollen and leaf litter were identified as organic nitrogen and total phosphorus sources because of elevated runoff concentrations that occurred in the spring and autumn. Based on these results, future bioretention studies should strongly consider monitoring consecutive events and this method of data analysis, as they reveal internal processes and allow researchers to draw conclusions that independent event monitoring could not.

The use of reclaimed wastewater in agriculture can be a solution for regions with water shortages or low rainfall periods; besides fulfilling the crop's water needs, it would also promote the recycle of nutrients. However, care should be taken regarding soil salinization, especially in closed environments such as greenhouses for the cultivation of ornamental plants. The domestic effluents are rich in sodium which can accumulate on soil and cause soil sealing. This study evaluated the use of effluents from anaerobic filters and intermittent sand filters in the production of rosebushes (Rosa hybrida "Ambiance"). The crop yield of the rosebushes irrigated with reclaimed wastewater exceeded the one obtained with traditional cultivation, reaching a value 31.8 % higher when employing nitrified effluent originated from intermittent sand filters, with no difference in the product quality. The salinity levels are below the critical limits found in the literature; however, there was a significant increase compared to the irrigation with drinking water. © 2013 The Author(s).

Groundwater contamination caused by petroleum hydrocarbon (PHC) spills mostly from oil industry is a major environmental concern worldwide. However, infiltration into groundwater is decreasing due to the natural attenuation processes of PHCs in vadose zone, which acts as a safeguard of invaluable groundwater resource against contamination. This study was conducted to determine the retardation capacity of vadose zone and its influence factors based on investigations of a petroleum-contaminated site in NE China. Column leaching experiments in homogeneous and heterogeneous soils were utilized to simulate the actual infiltration process, which aimed to understand the variation of PHC compounds in vadose zone and to examine the effects of soil and water properties on the diversification of the compounds by using gas chromatography–mass spectrometry (GC–MS). The results showed that adsorption and biodegradation are dominant processes and 84 %, 76 %, and 66 % of the organic contaminants were entrapped in fine, medium, and coarse sands, respectively. This was mainly caused by the adsorption coefficient (K d ), which was linked with the soil properties; more specifically, smaller soil aggregates mean a higher K d value and such discrimination also exists among petroleum compounds. Real-time polymerase chain reaction (RT-PCR) and culture-based methods were applied to identify the degrading microorganisms. Results demonstrate that these microorganisms could degrade compounds such as chainalkanes (ChA), cycloalkanes (CyA), and aromatic (Ars) into asphaltenes (Asp). The microorganism population increased with biodegradation products and the consequence of biodegrading capacity was (from high to low): ChA, CyA, and Ars; chemical analyses in the heterogeneous soil experiment indicated that concentration of the biodegradation products in leachate was negatively correlated to dissolved oxygen (DO) as a consumption of oxidants but positively correlated to electrical conductivity (EC) and pH of water. Enzyme activities and microorganism population of soil were positively correlated to concentration of biodegradation products.

Metaldehyde is a selective molluscicide used in the agricultural and residential sector to control slugs and snails for a wide variety of crops. In recent years, some water companies have started monitoring drinking water supply catchments for presence of this compound, with positive and concern results. Conventional techniques are yet to achieve complete efficient and feasible removal of metaldehyde. The aim of this study was to measure the efficiency of nano-sized zinc oxide/laponite composites (NZnC) in the effective removal of metaldehyde (influent concentration of 500 μg dm⁻³) through the interaction of photocatalysis. Reaction time, pH of sample solution and NZnC mass were tested against each other using a rotatable central composite design method of experimentation. Statistical tests showed that linear effects of time, quadratic/linear effects of NZnC mass and the interaction of pH and NZnC mass proved to be the most significant variables for degrading metaldehyde. Optimal values of each variable for the highest removal efficiency were achieved, being pH equal to 10.4 and NZnC mass added equal to 28 g. The rate of reaction was then predicted by non-linear regression of four models. The best fit was provided by the modified first-order with residual kinetic model, with the apparent degradation coefficient k equal to 0.0363 min⁻¹ and the lowest remaining metaldehyde concentration observed among all runs was 278.7 μg dm⁻³. NZnC has shown to be a prominent nanotechnology for metaldehyde removal.

Approximately 1.1 million deer–vehicle collisions occur in the United States each year. The predominant methods of disposing of these carcasses (landfill and burial) have several costly disadvantages, including long travel distances to landfills, increasing landfill restrictions, and lack of viable burial areas. Some states have found static compost windrows to be an easy and cost-effective carcass management technique. This type of composting involves the construction of passively aerated static piles, which do not require the materials turning needed with more traditional composting methods. In this study, deer mortality static compost windrows were monitored for 1 year. Windrows were analyzed for pathogen destruction and the degree to which underlying soil filtered leachate contaminants. In response to high windrow temperatures, indicator pathogens Escherichia coli and Salmonella were reduced by 99.99 % the first sampling day (day 7) and ascarids were deemed non-viable by day 77. Soil filtration of leachate was effective in reducing concentrations of ammonia, chloride, and total organic carbon. Nitrate, a contaminant of particular regulatory concern, had an estimated mass contaminant loss of 2.1 kg/ha, compared to the estimated 9 to 50 kg/ha loss from fertilizer application of common agronomic crops. Results of this study indicate that with properly constructed static compost windrows, (1) high temperatures effectively destroy indicator pathogens; (2) the natural filtration of leachate through soil reduces deer mortality contaminant concentrations; and (3) the low volume of leachate (i.e., two percent of the precipitation that fell on windrows) results in nominal losses of nitrate and other contaminants.

The occurrence, as well as the environmental fate and impact, of vegetable oil spills in freshwater wetlands have until now been unreported. Thus, the largest global vegetable oil spillage in a freshwater wetland, which occurred at the Con Joubert Bird Sanctuary wetland in 2007, presented an ideal opportunity to evaluate these impacts. Five post-spill sampling sites were selected within the wetland from which a variety of abiotic and biotic samples were collected bi-monthly over a period of 12 months. Abiotic variables included the sediment and water column oil concentrations, total nitrogen, total phosphorous, biochemical oxygen demand (BOD), silica, chlorophyll a, as well as in situ measurements of pH, electrical conductivity, and dissolved oxygen. Aquatic macroinvertebrates were chosen as biotic indicators in the study field due to their wide applicability as water quality indicators and were thus collected at each site. Spatial and temporal changes in total nitrogen, total phosphorous, and chlorophyll a concentrations as well as changes in pH were observed. The oil spillage also resulted in an increase in tolerant macroinvertebrate taxa, mainly Chironomidae and Psychodidae, at the sites closest to the source of the spillage. These two taxa, and to a lesser extent, Syrphidae, were identified as potentially useful indicators to determine the extent of vegetable oil contamination within a freshwater wetland. Furthermore, monitoring of these indicator taxa can be a useful management tool to determine the recovery of freshwater wetlands after vegetable oil spills. In the study, a static battery of bioassays of different biotic trophic levels was also employed to determine the adverse effects of the spilled vegetable oil on the biotic environment. It was evident from the result of the static battery of bioassay that adverse effects of the sunflower oil differ between trophic levels. The latter was in relationship with the data obtained from the field macroinvertebrate study, indicating that certain macroinvertebrate families were more tolerant to the adverse effects of sunflower oil than other families. © 2013 Springer Science+Business Media Dordrecht.

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.