Compositional changes of crude oil SARA fractions due to biodegradation and adsorption on colloidal support such as clays using Iatroscan

The compositional changes of saturates, aromatics, resins and asphaltenes (SARA) fractions in aqueous clay/oil microcosm experiments with a hydrocarbon-degrading microorganism community were analysed using Iatroscan. The clay mineral samples used in this study were organomontmorillonite, acid-activated montmorillonite and K, Ca, Zn and Cr montmorillonites produced by modifying the original montmorillonite sample. The evaluation and quantification of biodegradation and adsorption were carried out using a combination of the Iatroscan and gravimetric analysis. The SARA compositions in the presence of organomontmorillonite and acid-activated montmorillonite after incubation follow the same pattern in which the aromatic fraction is higher than the other fractions unlike in the presence of unmodified, K, Ca and Zn montmorillonites, where the saturates fraction is higher than the other fractions. Changes in SARA fractions due to biodegradation seemed to occur most in the presence of unmodified and calcium montmorillonites; hence, the removal of SARA fractions due to biodegradation was significant and enhanced in the presence of these two clay samples. However, biodegradation in the presence of organomontmorillonite and acid-activated and Cr montmorillonites was hindered. The study indicated that Cr montmorillonite adsorbed resins most, whereas Zn and K montmorillonites adsorbed aromatics most after incubation.     

Partitioning, sources and variability of regional and local oxidant (OX = O3 + NO2) in a coastal rural area in the southwest of Iberian Peninsula

The purpose of this work is to investigate the behaviour and variability of oxidant levels (OX?=?NO₂?+?O₃), for the first time, in a rural coastal area in the southwest of the Iberian Peninsula, affected by several air masses types. Detailed database (built-up over the years 2008 to 2011, and containing around 500,000 data) from the Atmospheric Sounding Station “El Arenosillo” was used. The observed daily cycles of NO _x and OX were influenced by air masses coming from industrial and urban area. It can be seen that the concentration of OX is made up of a NO _x -independent ‘regional’ contribution (i.e. the O₃ background), and a linearly NO _x -dependent ‘local’ contribution from primary emissions, such as traffic. The local emission is very low in this area. Also, the regional contribution is similar to unpolluted sites and presents seasonal variation, being higher in May. However, our measurements showed that the proportion of OX in the form of NO₂ increases with the increase in NO _x concentration during the day. The higher proportion of NO₂ observed at night must be due to the conversion of NO to NO₂ by the NO?+?O₃ reaction. With regards to the source of the local NO _x -dependent contribution, it may be attributed to industrial emission, or the termolecular reaction 2NO?+?O₂?=?2NO₂, at high-NO _x levels and stagnant air during several days. Finally, we estimated the photolysis rate of NO₂, J _NO2, an important key atmospheric reaction coupled with ozone. We also present surface plots of annual variation of the daily mean NO _x and OX levels, which indicate that oxidants come from transport processes instead of local emissions associated as local photochemistry.     

On-farm measurement of electrical conductivity for the estimation of ammonium nitrogen concentration in pig slurry

Pig (Sus scrofa domesticus) slurry (PS) is commonly applied as fertilizer to agricultural fields. Knowledge of PS nitrogen content is essential for good management, but PS nitrogen content is highly variable, not only between farms but also within a farm. Laboratory analysis of animal slurries is often expensive and impractical for routine farmer use. Therefore, when slurry is spread on land, its fertilizer value is generally unknown, resulting in the risk of pollution. In this work, two rapid and suitable for field use methods for determining PS ammonium N (NH(4)+-N) concentration (Quantofix and conductimetry) are evaluated. The electrical conductivity of a dilution 1 PS:9 distilled water had better results than Quantofix, did not need reagents, and gave a direct value of NH(4)+-N concentrations (range, 1.0-7.6 kg NH(4)+-N m(-3)). The conductimetry method allows the use of alternative waters with EC <1.9 dS m(-1) for dilution. This method is being introduced to farmers in northeast Spain to improve PS management and has been well received due to its low cost and ease of use.     

Water quality characteristics of discharge from reforested loose-dumped mine spoil in eastern Kentucky

Surface mining is a common method for extracting coal in the coal fields of eastern Kentucky. Using the Forestry Reclamation Approach (FRA), which emphasizes the use of minimally compacted or loose-dumped spoil as a growth medium for trees, reclamation practitioners are successfully reestablishing forests. Yet, questions remain regarding the effects FRA has on the quality of waters discharged to receiving streams. To examine the effect of FRA on water quality, this study compared waters that were discharged from three types of spoils: predominantly brown, weathered sandstone (BROWN); predominantly gray, unweathered sandstone (GRAY); and an equal mixture of both aforementioned sandstones and shale (MIXED). The water quality parameters pH, EC, Ca, K, Mg, Na, NO-N, NH-N, SO, Cl, TC, suspended sediment concentration (SSC), settleable solids (SS), and turbidity were monitored over a 2-yr period on six 0.4-ha plots (two replications per spoil type). Generally, levels of Cl, SO, Ca, NO-N, NH-N, SS, SSC, and turbidity decreased over time. The pH for all spoils increased from about 7.5 to 8.5. The EC remained relatively level in the BROWN spoil, whereas the GRAY and MIXED spoils had downward trajectories that were approaching 500 μS cm. The value of 500 μS cm has been reported as the apparent threshold at which certain taxa such as Ephemeroptera (e.g., Mayfly) recolonize disturbed headwater streams of eastern Kentucky and adjacent coal-producing Appalachian states.     

A simple model to assess nitrogen and phosphorus contamination in ungauged surface drainage networks: application to the Massaciuccoli Lake Catchment, Italy

Modeling is a common practice to evaluate factors affecting water quality in environmental systems impaired by point and nonpoint losses of N and P. Nevertheless, in situations with inadequate information, such as ungauged basins, a balance between model complexity and data availability is necessary. In this paper, we applied a simplified analytical model to an artificially drained floodplain in central-western Italy to evaluate the importance of different nutrient sources and in-stream retention processes and to identify critical source areas. We first considered only a set of chemical concentrations in water measured from February through May 2008 and from November 2008 through February 2009. We then broadened available data to include water discharge and hydraulic-head measurements to construct a hydrogeological model using MODFLOW-2000 and to evaluate the reliability of the simplified method. The simplified model provided acceptable estimates of discharge (ranging from 0.03-0.75 m s) and diffuse nutrient inputs from water table discharge and in-stream retention phenomena. Estimates of PO-P and total P retention (ranging from 1.0 to 0.6 μg m s and from 1.18 to 0.95 μg m s for PO-P and total P, respectively) were consistent with the range of variability in literature data. In contrast, the higher temporal variability of nitrate concentrations decreased model accuracy, suggesting the need for more intensive monitoring. The model also separated the dynamics of different reaches of the drainage network and identified zones considered critical source areas and buffer zones where pollutant transport is reduced.     

Investigation of an Escherichia coli environmental benchmark for waterborne pathogens in agricultural watersheds in Canada

Canada's National Agri-Environmental Standards Initiative sought to develop an environmental benchmark for low-level waterborne pathogen occurrence in agricultural watersheds. A field study collected 902 water samples from 27 sites in four intensive agricultural watersheds across Canada from 2005 to 2007. Four of the sites were selected as reference sites away from livestock and human fecal pollution sources in each watershed. Water samples were analyzed for Campylobacter spp., Salmonella spp., Escherichia coli O157:H7, Cryptosporidium spp., Giardia spp., and the water quality indicator E. coli. The annual mean number of pathogen species was higher at agricultural sites (1.54 ± 0.07 species per water sample) than at reference sites (0.75 ± 0.14 species per water sample). The annual mean concentration of E. coli was also higher at agricultural sites (491 ± 96 colony-forming units [cfu] 100 mL(-1)) than at reference sites (53 ± 18 cfu 100 mL(-1)). The feasibility of adopting existing E. coli water quality guideline values as an environmental benchmark was assessed, but waterborne pathogens were detected at agricultural sites in 80% of water samples with low E. coli concentrations (<100 cfu 100 mL(-1)). Instead, an approach was developed based on using the natural background occurrence of pathogens at reference sites in agricultural watersheds to derive provisional environmental benchmarks for pathogens at agricultural sites. The environmental benchmarks that were derived were found to represent E. coli values lower than geometric mean values typically found in recreational water quality guidelines. Additional research is needed to investigate environmental benchmarks for waterborne pathogens within the context of the "One World, One Health" perspective for protecting human, domestic animal, and wildlife health.     

In vitro methane removal by volcanic pumice soil biofilter columns over one year

Soil methane (CH(4)) biofilters, containing CH(4)-oxidizing bacteria (methanotrophs), are a promising technology for mitigating greenhouse gas emissions. However, little is known about long-term biofilter performance. In this study, volcanic pumice topsoils (0-10 cm) and subsoils (10-50 cm) were tested for their ability to oxidize a range of CH(4) fluxes over 1 yr. The soils were sampled from an 8-yr-old and a 2-yr-old grassed landfill cover and from a nearby undisturbed pasture away from the influence of CH(4) generated by the decomposing refuse. Methane was passed through the soils in laboratory chambers with fluxes ranging from 0.5 g to 24 g CH(4) m(-3) h(-1). All topsoils efficiently oxidized CH(4). The undisturbed pasture topsoil exhibited the highest removal efficiency (24 g CH(4) m(-3) h(-1)), indicating rapid activation of the methanotroph population to the high CH(4) fluxes. The subsoils were less efficient at oxidizing CH(4) than the topsoils, achieving a maximum rate oxidation rate of 7 g CH(4) m(-3) h(-1). The topsoils exhibited higher porosities; moisture contents; surface areas; and total C, N, and available-P concentrations than the subsoils, suggesting that these characteristics strongly influence growth and activity of the CH(4)-oxidizing bacteria. Soil pH values and available-P levels gradually declined during the trial, indicating a need to monitor chemical parameters closely so that adjustments can be made when necessary. However, other key soil physicochemical parameters (moisture, total C, total N) increased over the course of the trial. This study showed that the selected topsoils were capable of continually sustaining high CH(4) removal rates over 1 yr, which is encouraging for the development of biofilters as a low-maintenance greenhouse gas mitigation technology.     

Inputs and losses by surface runoff and subsurface leaching for pastures managed by continuous or rotational stocking

Pasture management practices can affect forage quality and production, animal health and production, and surface and groundwater quality. In a 5-yr study conducted at the North Appalachian Experimental Watershed near Coshocton, Ohio, we compared the effects of two contrasting grazing methods on surface and subsurface water quantity and quality. Four pastures, each including a small, instrumented watershed (0.51-1.09 ha) for surface runoff measurements and a developed spring for subsurface flow collection, received 112 kg N ha(-1) yr(-1) and were grazed at similar stocking rates (1.8-1.9 cows ha(-1)). Two pastures were continuously stocked; two were subdivided so that they were grazed with frequent rotational stocking (5-6 times weekly). In the preceding 5 yr, these pastures received 112 kg N ha(-1) yr(-1) after several years of 0 N fertilizer and were grazed with weekly rotational stocking. Surface runoff losses of N were minimal. During these two periods, some years had precipitation up to 50% greater than the long-term average, which increased subsurface flow and NO(3)-N transport. Average annual NO(3)-N transported in subsurface flow from the four watersheds during the two 5-yr periods ranged from 11.3 to 22.7 kg N ha(-1), which was similar to or less than the mineral-N received in precipitation. Flow and transport variations were greater among seasons than among watersheds. Flow-weighted seasonal NO(3)-N concentrations in subsurface flow did not exceed 7 mg L(-1). Variations in NO(3)-N leached from pastures were primarily due to variable precipitation rather than the effects of continuous, weekly rotational, or frequent rotational stocking practices. This suggests that there was no difference among these grazing practices in terms of NO(3)-N leaching.     

Switchgrass biochar affects two aridisols

The use of biochar has received growing attention because of its ability to improve the physicochemical properties of highly weathered Ultisols and Oxisols, yet very little research has focused on its effects in Aridisols. We investigated the effect of low or high temperature (250 or 500°C) pyrolyzed switchgrass () biochar on two Aridisols. In a pot study, biochar was added at 2% w/w to a Declo loam (Xeric Haplocalcids) or to a Warden very fine sandy loam (Xeric Haplocambids) and incubated at 15% moisture content (by weight) for 127 d; a control (no biochar) was also included. Soils were leached with 1.2 to 1.3 pore volumes of deionized HO on Days 34, 62, 92, and 127, and cumulative leachate Ca, K, Mg, Na, P, Cu, Fe, Mn, Ni, Zn, NO-N, NO-N, and NH-N concentrations were quantified. On termination of the incubation, soils were destructively sampled for extractable Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Zn, NO-N, and NH-N, total C, inorganic C, organic C, and pH. Compared with 250°C, the 500°C pyrolysis temperature resulted in greater biochar surface area, elevated pH, higher ash content, and minimal total surface charge. For both soils, leachate Ca and Mg decreased with the 250°C switchgrass biochar, likely due to binding by biochar's functional group sites. Both biochars caused an increase in leachate K, whereas the 500°C biochar increased leachate P. Both biochars reduced leachate NO-N concentrations compared with the control; however, the 250°C biochar reduced NO-N concentrations to the greatest extent. Easily degradable C, associated with the 250°C biochar's structural make-up, likely stimulated microbial growth, which caused NO-N immobilization. Soil-extractable K, P, and NO-N followed a pattern similar to the leachate observations. Total soil C content increases were linked to an increase in organic C from the biochars. Cumulative results suggest that the use of switchgrass biochar prepared at 250°C could improve environmental quality in calcareous soil systems by reducing nutrient leaching potential.     

Using flue gas desulfurization gypsum to remove dissolved phosphorus from agricultural drainage waters

High levels of accumulated phosphorus (P) in soils of the Delmarva Peninsula are a major source of dissolved P entering drainage ditches that empty into the Chesapeake Bay. The objective of this study was to design, construct, and monitor a within-ditch filter to remove dissolved P, thereby protecting receiving waters against P losses from upstream areas. In April 2007, 110 Mg of flue gas desulfurization (FGD) gypsum, a low-cost coal combustion product, was used as the reactive ingredient in a ditch filter. The ditch filter was monitored from 2007 to 2010, during which time 29 storm-induced flow events were characterized. For storm-induced flow, the event mean concentration efficiency for total dissolved P (TDP) removal for water passing through the gypsum bed was 73 ± 27% confidence interval (α = 0.05). The removal efficiency for storm-induced flow by the summation of load method was 65 ± 27% confidence interval (α = 0.05). Although chemically effective, the maximum observed hydraulic conductivity of FGD gypsum was 4 L s(-1), but it decreased over time to <1 L s(-1). When bypass flow and base flow were taken into consideration, the ditch filter removed approximately 22% of the TDP load over the 3.6-yr monitoring period. Due to maintenance and clean-out requirements, we conclude that ditch filtration using FGD gypsum is not practical at a farm scale. However, we propose an alternate design consisting of FGD gypsum-filled trenches parallel to the ditch to intercept and treat groundwater before it enters the ditch.