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.     

Fall fertilization timing effects on nitrate leaching and turfgrass color and growth

Fall season fertilization is a widely recommended practice for turfgrass. Fertilizer applied in the fall, however, may be subject to substantial leaching losses. A field study was conducted in Connecticut to determine the timing effects of fall fertilization on nitrate N (NO3-N) leaching, turf color, shoot density, and root mass of a 90% Kentucky bluegrass (Poa pratensis L.), 10% creeping red fescue (Festuca rubra L.) lawn. Treatments consisted of the date of fall fertilization: 15 September, 15 October, 15 November, 15 December, or control which received no fall fertilizer. Percolate water was collected weekly with soil monolith lysimeters. Mean log(10) NO3-N concentrations in percolate were higher for fall fertilized treatments than for the control. Mean NO3-N mass collected in percolate water was linearly related to the date of fertilizer application, with higher NO3-N loss for later application dates. Applying fall fertilizer improved turf color and density but there were no differences in color or density among applications made between 15 October and 15 December. These findings suggest that the current recommendation of applying N in mid- to late November in southern New England may not be compatible with water quality goals.     

Effects of calibration on L-THIA GIS runoff and pollutant estimation

Urbanization can result in alteration of a watershed's hydrologic response and water quality. To simulate hydrologic and water quality impacts of land use changes, the Long-Term Hydrologic Impact Assessment (L-THIA) system has been used. The L-THIA system estimates pollutant loading based on direct runoff quantity and land use based pollutant coefficients. The accurate estimation of direct runoff is important in assessing water quality impacts of land use changes. An automated program was developed to calibrate the L-THIA model using the millions of curve number (CN) combinations associated with land uses and hydrologic soil groups. L-THIA calibration for the Little Eagle Creek (LEC) watershed near Indianapolis, Indiana was performed using land use data for 1991 and daily rainfall data for six months of 1991 (January 1-June 30) to minimize errors associated with use of different temporal land use data and rainfall data. For the calibration period, the Nash-Sutcliffe coefficient was 0.60 for estimated and observed direct runoff. The calibrated CN values were used for validation of the model for the same year (July 1-December 31), and the Nash-Sutcliffe coefficient was 0.60 for estimated and observed direct runoff. The Nash-Sutcliffe coefficient was 0.52 for January 1, 1991 to December 31, 1991 using uncalibrated CN values. As shown in this study, the use of better input parameters for the L-THIA model can improve accuracy. The effects on direct runoff and pollutant estimation of the calibrated CN values in the L-THIA model were investigated for the LEC. Following calibration, the estimated average annual direct runoff for the LEC watershed increased by 34%, total nitrogen by 24%, total phosphorus by 22%, and total lead by 43%. This study demonstrates that the L-THIA model should be calibrated and validated prior to application in a particular watershed to more accurately assess the effects of land use changes on hydrology and water quality.     

Changes in soil characteristics and plant species composition along a moisture gradient in a Mediterranean pasture

Soil physicochemical characteristics, total aboveground biomass, number of species and relative abundance of groups and individual species were measured along a moisture gradient in a pasture, flooded in part during winter through early summer, adjacent to Pamvotis lake in Ioannina, Greece. Soil and vegetation measurements were conducted in 39 quadrats arranged in four zones perpendicular to the moisture gradient. The zone closest to the lake, recently separated from the lake, became part of the pasture and its soil texture was quite different from that of the other zones with a substrate containing 91% sand. Except for pH, this zone had the lowest values in the other five soil physicochemical characteristics measured (organic matter, total and extracted inorganic nitrogen, Olsen extracted phosphorus and extractable potassium); in the other zones organic matter, total nitrogen, phosphorus and potassium tended to increase from the driest to the wettest zone. Total aboveground biomass, ranging from 280 to 840 gm-2, is high for herbaceous pastures in the conditions of Mediterranean climate and it was not related to distance from the lake's shoreline, although the highest values were measured at intermediate distances, or to any of the various soil characteristics measured. Also, the number of species/0.25 m2 was not related to any of the various soil characteristics, but it was highest at the intermediate distances from the lake's shoreline. Species composition varied along the moisture gradient. Forbs as well as annual grasses and legumes declined in abundance from the driest to the wettest places; the reverse was the case for sedges and perennial grasses and legumes. These results indicate that the soil moisture gradient was the principal factor affecting soil characteristics and plant species composition. Since most species were recorded in all the four zones of the pasture, indicating that these can tolerate all variations in abiotic conditions of pasture, the vegetation zonation seems to be influenced by competition. Each functional group of species tends to dominate in a particular range of the soil moisture gradient where it is better suited and tends to exclude competitively other species. Management practices (mowing and grazing) affect the kinds of processes which maintain the observed community structure either by preventing the establishment of later successional species, like reeds and woody species, or by moderating the shoot competition, especially in the wetter zones, and thus permitting the creeping species to grow successfully.     

Management of mine spoil for crop productivity with lignite fly ash and biological amendments

Long-term field trials using lignite fly ash (LFA) were carried out in rice crops during the period 1996-2000 at Mine I, Neyveli Lignite Corporation, Tamil Nadu. LFA, being alkaline and endowed with an excellent pozzolanic nature, silt loam texture, and plant nutrients, has the potential to improve the texture, fertility, and crop productivity of mine spoil. The rice crops were the first, third, fifth, and sixth crops in rotation. The other crops, such as green gram (second) and sun hemp (fourth), were grown as green manure. For experimental trials, LFA was applied at various dosages (0, 5, 10, 20, 50, 100, and 200 t/ha), with and without press mud (10 t/ha), before cultivation of the first crop. Repeat applications of LFA were made at the same dosages in treatments of up to 50 t/ha (with and without press mud) before cultivation of the third and fifth crops. Press mud, a lightweight organic waste product from the sugar industry, was used as an organic amendment and source of plant nutrients. Also, a recommended dosage of chemical fertilizer, along with gypsum, humic acid, and biofertilizer as supplementing agents, was applied in all the treatments, including control. With one-time and repeat applications of LFA, from 5 to 20 t/ha (with and without press mud), the crop yield (grain and straw) increased significantly (p < 0.05), in the range from 3.0 to 42.0% over the corresponding control. The maximum yield was obtained with repeat applications of 20 t/ha of LFA with press mud in the third crop. The press mud enhanced the yield in the range of 1.5-10.2% with various dosages of LFA. The optimum dosage of LFA was 20 t/ha for both one-time and repeat applications. Repeat applications of LFA at lower dosages of up to 20 t/ha were more effective in increasing the yield than the corresponding one-time applications of up to 20 t/ha and repeat applications at 50 t/ha. One-time and repeat applications of LFA of up to 20 t/ha (with and without press mud), apart from increasing the yield, evinced improvement in the texture and fertility of mine spoil and the nutrient content of crop produce. Furthermore, some increase in the content of trace and heavy metals and the level of gamma-emitters in the mine spoil and crop produce was observed, but well within the permissible limits. The residual effect of LFA on succeeding crops was also encouraging in terms of eco-friendliness. Beyond 20 t/ha of LFA, the crop yield decreased significantly (p < 0.05), as a result of the formation of hardpan in the mine spoil and possibly the higher concentration of soluble salts in the LFA. However, the adverse effects of soluble salts were annulled progressively during the cultivation of succeeding crops. A plausible mechanism for the improved fertility of mine spoil and the carryover or uptake of toxic trace and heavy metals and gamma-emitters in mine spoil and crop produce is also discussed.     

A comparative analysis of predictors of sense of place dimensions: attachment to, dependence on, and identification with lakeshore properties

Sense of place can be conceived as a multidimensional construct representing beliefs, emotions and behavioural commitments concerning a particular geographic setting. This view, grounded in attitude theory, can better reveal complex relationships between the experience of a place and attributes of that place than approaches that do not differentiate cognitive, affective and conative domains. Shoreline property owners (N=290) in northern Wisconsin were surveyed about their sense of place for their lakeshore properties. A predictive model comprising owners' age, length of ownership, participation in recreational activities, days spent on the property, extent of property development, and perceptions of environmental features, was employed to explain the variation in dimensions of sense of place. In general, the results supported a multidimensional approach to sense of place in a context where there were moderate to high correlations among the three place dimensions. Perceptions of environmental features were the biggest predictors of place dimensions, with owners' perceptions of lake importance varying in explanatory power across place dimensions.     

Choosing policy instruments for controlling ozone depleting substances in a developing context: the case of Chile

Chile ratified the Montreal Protocol in 1990 which sets out an agenda for the reduction and then elimination of ozone depleting substances (ODS); however, by 1998 the country had not yet defined a strategy to encourage greater compliance, so that in the same year the National Environmental Commission decided to examine the policy options available. This paper examines the process followed to develop this strategy. As a first step it was necessary to look at how far the implicit policy of "business as usual" could be stretched without jeopardizing Chile's compliance obligations. A second step included quantifying compliance costs and their impact on different policy instruments and so policy choice. Finally, the attitudes of decision-makers or participants were identified, by interviews with officials of the different public agents involved, in order to weigh their views about policy. A strategy was proposed, based on this information, which the Chilean regulator has used, although not in its entirety. The methodology developed could well be useful for developing-country Protocol signatories building their own appropriate compliance strategy.     

The effects of leachate recirculation with supplemental water addition on methane production and waste decomposition in a simulated tropical landfill

In order to increase methane production efficiency, leachate recirculation is applied in landfills to increase moisture content and circulate organic matter back into the landfill cell. In the case of tropical landfills, where high temperature and evaporation occurs, leachate recirculation may not be enough to maintain the moisture content, therefore supplemental water addition into the cell is an option that could help stabilize moisture levels as well as stimulate biological activity. The objectives of this study were to determine the effects of leachate recirculation and supplemental water addition on municipal solid waste decomposition and methane production in three anaerobic digestion reactors. Anaerobic digestion with leachate recirculation and supplemental water addition showed the highest performance in terms of cumulative methane production and the stabilization period time required. It produced an accumulated methane production of 54.87 l/kg dry weight of MSW at an average rate of 0.58 l/kg dry weight/d and reached the stabilization phase on day 180. The leachate recirculation reactor provided 17.04 l/kg dry weight at a rate of 0.14l/kg dry weight/d and reached the stabilization phase on day 290. The control reactor provided 9.02 l/kg dry weight at a rate of 0.10 l/kg dry weight/d, and reached the stabilization phase on day 270. Increasing the organic loading rate (OLR) after the waste had reached the stabilization phase made it possible to increase the methane content of the gas, the methane production rate, and the COD removal. Comparison of the reactors' efficiencies at maximum OLR (5 kgCOD/m(3)/d) in terms of the methane production rate showed that the reactor using leachate recirculation with supplemental water addition still gave the highest performance (1.56 l/kg dry weight/d), whereas the leachate recirculation reactor and the control reactor provided 0.69 l/kg dry weight/d and 0.43 l/kg dry weight/d, respectively. However, when considering methane composition (average 63.09%) and COD removal (average 90.60%), slight differences were found among these three reactors.