Kinetics and thermodynamic studies of Methyl Orange removal by polyvinylidene fluoride-PEDOT mats

We report the preparation of poly(3,4-ethylene dioxythiophene) (PEDOT)-modified polyvinylidene fluoride electrospun fibers and their use as a novel adsorbent material for the removal of the anionic dye Methyl Orange (MO) from aqueous media. This novel adsorbent material can be used to selectively remove MO on a wide pH range (3.0–10.0), with a maximum capacity of 143.8 mg/g at pH 3.0. When used in a recirculating filtration system, the maximum absorption capacity was reached in a shorter time (20 min) than that observed for batch mode experiments (360 min). Based on the analyses of the kinetics and adsorption isotherm data, one can conclude that the predominant mechanism of interaction between the membrane and the dissolved dye molecules is electrostatic. Besides, considering the estimated values for the Gibbs energy, and entropy and enthalpy changes, it was established that the adsorption process is spontaneous and occurs in an endothermic manner. The good mechanical and environmental stability of these membranes allowed their use in at least 20 consecutive adsorption/desorption cycles, without significant loss of their characteristics. We suggest that the physical-chemical characteristics of PEDOT make these hybrid mats a promising adsorbent material for use in water remediation protocols and effluent treatment systems.     

Definition of Homogeneous Environmental Management Units for the Catalan Coast

Geographical areas constitute the basic implementation locus for integrated coastal zone management strategies and activities. Because the definition of territorial planning objectives may be affected by socioeconomic and environmental characteristics, one of the main steps in the process involves dividing the coast into homogeneous environmental management units (HEMUs). This article presents a general and simple method for regionalizing the landside of a coastal zone into HEMUs and illustrates it through application to the Catalan coast. Socioeconomic and natural (biophysical) subsystems were selected as the most appropriate dimensions of the regionalization process. Dimensions were described using 11 spatial themes, which were managed in a geographic information system environment that proved to be an adequate tool for the purpose. A final coastal zone map of four classes of HEMUs connected to local administrative units was obtained, and because it reflects the current natural and socioeconomic dynamics, it can be considered as an initial step in the planning process for the Catalan coast. Although the proposed method was developed based on the characteristics of the Catalan coast, it is general enough to be adapted and applied to most developed or developing coastal areas.     

Effect of Cadmium on Microbial Activity and a Ryegrass Crop in Two Semiarid Soils

Soil pollution with Cd is an environmental problem common in the world, and it is necessary to establish what Cd concentrations in soil could be dangerous to its fertility from toxicity effects and the risk of transference of this element to plants and other organisms of the food chain. In this study, we assessed Cd toxicity on soil microorganisms and plants in two semiarid soils (uncultivated and cultivated). Soil ATP content, dehydrogenase activity, and plant growth were measured in the two soils spiked with concentrations ranging from 3 to 8000 mg Cd/kg soil and incubated for 3 h, 20 days, and 60 days. The Cd concentrations that produced 5%; 10%;, and 50%; inhibition of each of the two soil microbiological parameter studied (ecological dose, ED, values) were calculated using two different mathematical models. Also, the effect of Cd concentration on plant growth of ryegrass (Lolium perenne, L.) was studied in the two soils. The Cd ED values calculated for soil dehydrogenase activity and ATP content were higher in the agricultural soils than in the bare soil. For ATP inhibition, higher ED values were calculated than for dehydrogenase activity inhibition. The average yields of ryegrass were reduced from 5.03 to 3.56 g in abandoned soil and from 4.21 to 1.15 g in agricultural soil with increasing concentrations of Cd in the soil. Plant growth was totally inhibited in abandoned and agricultural soils at Cd concentrations above 2000 and 5000 mg/kg soil, respectively. There was a positive correlation between the concentration of Cd in the plants and the total or DTPA-extractable concentrations of Cd in the soil.     

Upflow reactors for riparian zone denitrification

We used permeable reactive subsurface barriers consisting of a C source (wood particles), with very high hydraulic conductivities ( approximately 0.1-1 cm s(-1)), to provide high rates of riparian zone NO3-N removal at two field sites in an agricultural area of southwestern Ontario. At one site, a 0.73-m3 reactor containing fine wood particles was monitored for a 20-mo period and achieved a 33% reduction in mean influent NO3-N concentration of 11.5 mg L(-1) and a mean removal rate of 4.5 mg L(-1) d(-1) (0.7 g m(-2) d(-1)). At the second site, four smaller reactors (0.21 m3 each), two containing fine wood particles and two containing coarse wood particles, were monitored for a 4-mo period and were successful in attenuating mean influent NO3-N concentrations of 23.7 to 35.1 mg L(-1) by 41 to 63%. Mean reaction rates for the two coarse-particle reactors (3.2 and 7.8 mg L(-1) d(-1), or 1.5 and 3.4 g m(-2) d(-1)) were not significantly different (p > 0.2) than the rates observed in the two fine-particle reactors (5.0 and 9.9 mg L(-1) d(-1), or 1.8-3.5 g m(-2) d(-1)). A two-dimensional ground water flow model is used to illustrate how permeable reactive barriers such as these can be used to redirect ground water flow within riparian zones, potentially augmenting NO3- removal in this environment.     

Mapping ground water vulnerability to pesticide leaching with a process-based metamodel of EuroPEARL

To support EU policy, indicators of pesticide leaching at the European level are required. For this reason, a metamodel of the spatially distributed European pesticide leaching model EuroPEARL was developed. EuroPEARL considers transient flow and solute transport and assumes Freundlich adsorption, first-order degradation and passive plant uptake of pesticides. Physical parameters are depth dependent while (bio)-chemical parameters are depth, temperature, and moisture dependent. The metamodel is based on an analytical expression that describes the mass fraction of pesticide leached. The metamodel ignores vertical parameter variations and assumes steady flow. The calibration dataset was generated with EuroPEARL and consisted of approximately 60,000 simulations done for 56 pesticides with different half-lives and partitioning coefficients. The target variable was the 80th percentile of the annual average leaching concentration at 1-m depth from a time series of 20 yr. The metamodel explains over 90% of the variation of the original model with only four independent spatial attributes. These parameters are available in European soil and climate databases, so that the calibrated metamodel could be applied to generate maps of the predicted leaching concentration in the European Union. Maps generated with the metamodel showed a good similarity with the maps obtained with EuroPEARL, which was confirmed by means of quantitative performance indicators.     

Bioconversion of selenate in methanogenic anaerobic granular sludge

The capacity of anaerobic granular sludge to remove selenate from contaminated wastewater was investigated. The potential of different types of granular sludge to remove selenate from the liquid phase was compared to that of suspended sludge and contaminated soil and sediment samples. The selenate removal rates ranged from 400 to 1500 microg g VSS(-1) h(-1), depending on the source of biomass, electron donor, and the initial selenate concentration. The granular structure protects the microorganisms when exposed to high selenate concentrations (0.1 to 1 mM). Anaerobic granular sludge "Eerbeek," originating from a UASB reactor treating paper mill wastewater, removed about 90, 50, and 36% of 0.1, 0.5, and 1 mM of Se, respectively, from the liquid phase when incubated with 20 mM lactate at 30 degrees C and pH 7.5. Selenite, elemental Se (Se(o)), and metal selenide precipitates were the conversion products. Enrichments from the anaerobic granular sludge "Eerbeek" were able to convert 90% of the 10-mM selenate to Se(o) at a rate of 1505 microg Se(VI) g cells(-1) h(-1), a specific growth rate of 0.0125 g cells h(-1), and a yield of 0.083 g cells mg Se(-1). Both microbial metabolic processes (e.g dissimilatory reduction) as well as microbially mediated physicochemical mechanisms (adsorption and precipitation) contribute to the removal of selenate from the Se-containing medium.     

Tillage and field scale controls on greenhouse gas emissions

There is a lack of understanding of how associations among soil properties and management-induced changes control the variability of greenhouse gas (GHG) emissions from soil. We performed a laboratory investigation to quantify relationships between GHG emissions and soil indicators in an irrigated agricultural field under standard tillage (ST) and a field recently converted (2 yr) to no-tillage (NT). Soil cores (15-cm depth) were incubated at 25 degrees C at field moisture content and 75% water holding capacity. Principal component analysis (PCA) identified that most of the variation of the measured soil properties was related to differences in soil C and N and soil water conditions under ST, but soil texture and bulk density under NT. This trend became more apparent after irrigation. However, principal component regression (PCR) suggested that soil physical properties or total C and N were less important in controlling GHG emissions across tillage systems. The CO2 flux was more strongly determined by microbial biomass under ST and inorganic N content under NT than soil physical properties. Similarly, N2O and CH4 fluxes were predominantly controlled by NO3- content and labile C and N availability in both ST and NT soils at field moisture content, and NH4+ content after irrigation. Our study indicates that the field-scale variability of GHG emissions is controlled primarily by biochemical parameters rather than physical parameters. Differences in the availability and type of C and N sources for microbial activity as affected by tillage and irrigation develop different levels and combinations of field-scale controls on GHG emissions.     

Effect of manure application timing, crop, and soil type on nitrate leaching

Timing of manure application affects N leaching. This 3-yr study quantified N losses from liquid manure application on two soils, a Muskellunge clay loam and a Stafford loamy sand, as affected by cropping system and timing of application. Dairy manure was applied at an annual rate of 93 800 L ha(-1) on replicated drained plots under continuous maize (Zea mays L.) in early fall, late fall, early spring, and as a split application in early and late spring. Variable rates of supplemental sidedress N fertilizer were applied as needed. Manure was applied on orchardgrass (Dactylis glomerata L.) in split applications in early fall and late spring, and early and late spring, with supplemental N fertilizer topdressed as NH4NO3 in early spring at 75 kg N ha(-1). Drain water was sampled at least weekly when lines were flowing. Three-year FWM (flow-weighted mean) NO3-N concentrations on loamy sand soil averaged 2.5 times higher (12.7 mg L(-1)) than those on clay loam plots (5.2 mg L(-1)), and those for fall applications on maize-cropped land averaged >10 mg L(-1) on the clay loam and >20 mg L(-1) on the loamy sand. Nitrate-N concentrations among application seasons followed the pattern early fall > late fall > early spring = early + late spring. For grass, average NO3-N concentrations from manure application remained well below 10 mg L(-1). Fall manure applications on maize show high NO3-N leaching risks, especially on sandy soils, and manure applications on grass pose minimal leaching concern.     

Experimental oxidative dissolution of sphalerite in the Aznalcollar sludge and other pyritic matrices

After the collapse on 25 Apr. 1998 of the Aznalcóllar mine tailings dike in southwestern Spain, 45 km2 of the Guadiamar valley were covered by a pyritic sludge containing up to 2% sphalerite (ZnS). Later, the sludge was mechanically removed and calcium carbonate was plowed into the soil to immobilize heavy metals. By June 2001 more than 60% of the sulfides in the residual sludge had oxidized and soil Zn contents reached locally phytotoxic levels. Therefore, the oxidative dissolution of sphalerite in the sludge and other pyritic samples was examined. Flow-through oxidation experiments showed that: (i) about 5 and 17% of the sludge Fe and Zn were in soluble form, respectively, because the sludge sample had been partly oxidized in the field; (ii) the oxidation rates of the residual pyrite and sphalerite were similar; (iii) the overall sulfide oxidation rate was relatively unaffected by the addition of calcite; and (iv) poorly crystalline Fe (hydr)oxides containing Zn in occluded form and Zn (hydroxi)carbonates were formed in the presence of calcite. The rate of oxidation of reference sphalerite greatly increased when it was incorporated in the sludge or in a reference pyrite matrix. This enhancement was due to galvanic interaction because pyrite oxidation was depressed in the presence of sphalerite. Oxidation by Fe3+ ions was less important because the oxidation rates of native sphalerite were not greater at low than at high pH. The fast oxidation rate of sphalerite in the Aznalcóllar sludge indicates a need for quick adoption of remediation measures in similar accidents elsewhere. The use of calcite amendments has little influence on the oxidation rate but does result in the accumulation of Zn in relatively insoluble forms.     

Aerating grassland before manure application reduces runoff nutrient loads in a high rainfall environment

The effect of mechanically aerating grassland before liquid manure application in the fall on surface runoff and transport of nutrients and solids was studied in a high rainfall area. The two treatments were control and aeration, the latter receiving one pass with an aerator perpendicular to the slope before fall application of liquid manure (dairy in Years 1-3 and swine in Year 4). Treatments were randomly assigned on 3 to 5% sloping land with a silt loam surface soil (Aquic Dystroxerept) planted in orchardgrass (Dactylis glomerata L.). Runoff from natural rainfall events was sampled for nutrient and solids analysis. Aeration significantly reduced runoff and loads of suspended solids, total Kjeldahl N (TKN), and dissolved reactive P in all years. Annual runoff amounts were reduced by 47 to 81%, suspended and volatile solid loads by 48 to 69% and 42 to 83%, respectively, TKN loads by 56 to 81%, and total P (TP) loads by 25 to 75%. Loads of the soluble nutrient NH4-N, dissolved reactive P, and K were reduced by 41 to 83%. The first three runoff events after manure application accounted for approximately one-third of the annual total runoff and solid and nutrient loads when averaged across treatments, with loads of TKN, K, and NH4-N totaling 4.4, 3.3, and 1.9 kg ha-1, respectively. Aeration slightly increased downward movement of NO3-N, but not other nutrients in the soil. Thus mechanical aeration can be an effective tool for reducing runoff and loads of solids and nutrients after surface application of liquid manure on sloping grassland.