Experimental and theoretical studies on physico-chemical parameters affecting the solubility of phosphogypsum

Phosphogypsum is a waste by-product of the phosphate fertilizer industry, which is usually disposed in the environment because of its restricted use in industrial applications. Physico-chemical conditions existing in stack fluids and leachates are of major importance and determine solubility and redox stability of phosphogypsum, as well as radionuclide release from stacks to terrestrial environments. The aim of this study is to assess the effect of key parameters (e.g. ionic strength, temperature, pH) on the solubility of phosphogypsum. Phosphogypsum sampling and in-situ measurements were carried out at a coastal stack in Cyprus, solubility experiments were performed in simulated laboratory systems and thermodynamic calculations by means of MINTEQA2, an equilibrium speciation model. Generally, increasing ionic strength and temperature leads to increased phosphogypsum solubility, with the former being much more effective. The increased solubility of phosphogypsum in saline solutions is attributed solely to ionic strength effects on the activity of ionic species in solution and no solid phase transformations could be observed. The effect of pH on phosphogypsum solubility seems to be insignificant at least in a pH range between 4 and 8. Regarding uranium levels, there is a strong correlation between salinity and uranium concentration and linear correlation between phosphogypsum solubility and uranium levels in stack solutions, indicating the incorporation of uranium into the gypsum lattice and the formation of a solid solution.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

Improving lake riparian source area management using surface and subsurface runoff indices

Sensitivity indices, which rank factors pertinent to surface and subsurface runoff pathways, were used to identify phosphorus source areas in riparian zones of 15 northern Minnesota lakes. Watershed models were first developed using a geographic information system (GIS). Empirical models were then developed correlating water quality with land use, lake morphometry, and riparian sensitivity. Base models of forested, cultivated, pasture/open, wetland and residential land use within 100, 200, 400, and 2000 m of the study lakes were regressed on total phosphorus and chlorophyll-a. Area-weighted groundwater and surface runoff sensitivity indices were then incorporated into each model and tested for significance. Within the 200-m buffer, the total phosphorus base model was improved by including the groundwater index alone. The chlorophyll-a base model at 200 m was improved by including: (1) the groundwater index alone, and (2) both the groundwater and surface runoff sensitivity indices. Results suggest that surface and subsurface runoff analysis of potential source areas can improve decision making for lake riparian management.     

FACTORS INFLUENCING ACUTE TOXICfrY OF COAL ASH TO RAINBOW TROUT (SALMO GAIRDNERI) AND BLUEGILL SUNFISH (LEPOMIS MACROCHIRUS)1

ABSTRACT: The potentially toxic components in coal ash (ash particles, heavy metals) were evaluated in laboratory static, acute (96 hr) bioassays, both separately and in various combinations with extreme pH (5.0 and 8.5), using rainbow trout (Salmo gairdneri) and bluegifi sunfish (Lepomis macrochirus). Ash particle morphology and metal distribution anlaysis, using electron microscopy and surface-subsurface analysis by ion microscopy, showed that metals could be either clumped or evenly distributed on the surface of fly ash. Surface enrichment on fly ash particles from electrostatic precipitators, as measured by ion microscopy, was found for cadmium, copper, chromium, nickel, lead, mercury, titanium, arsenic, and selenium. Bottom (heavy) ash was not acutely toxic to either fish species at concentrations of up to 1500 mg/l total suspended solids (TSS) at pH 5.0, 7.5, or 8.5. Fly ash particles were not acutely toxic to blue-gill at levels up to 1360 mg/l TSS. Rainbow trout were highly sensitive to fly ash (25 to 60 percent mortality) at concentrations of 4.3 to 20.5 mg/I TSS when dissolved metal availability was high but were not sensitive at higher particulate concentrations (58 to 638 mg/I TSS) when dissolved metals were low. When metals were acid-leached from fly ash prior to testing, no rainbow trout mortality occurred at TSS concentrations of up to 2,350 mg/l TSS. When the percent of dissolved metal was high (e.g., 50–90 percent of the total), fish mortality was increased. Rainbow trout were nearly two orders of magnitude more sensitive than bluegill when subjected to a blend of cadmium, chromium, copper, nickel, lead, and zinc. The two species were similar in their acute sensitivity to acidic pH at levels at or below 4.0 and alkaline pH of 9.1. If the pH of coal ash effluent is contained within the range 6.0 to 9.0, acute toxicity to fish can be attributed to trace element availability from fly ash but not heavy ash. Control of holding pond and effluent pH and maximizing pond residence time are important strategies for minimizing effects of ash pond discharges on fish.     

Restoration ecology of riverine wetlands: II. An example in a former channel of the Rhône River

Riverine wetlands, which provide numerous valuable functions, are disappearing in floodplains of a channelized European river. A restoration project has been proposed by scientists to restore a former braided channel of the Rhône River by the removal of fine organic sediments in order to enhance groundwater supply. A precise and intensive prerestoration monitoring program during one year (including comparison with a reference channel) has taken into account several variables and ecological performance indicators measured at various spatial and temporal scales. Three restoration techniques were then suggested, taking into account two characteristics of ecosystem functions for increasing restoration success and self-sustainability: (1) the riparian forest as well as the shores must be preserved or disturbed as little as possible; and (2) the upstream alluvial plug must be preserved to prevent direct supply of nutrientrich water from the Rhône River. Among the three restoration options proposed, it was not possible to carry out the less ecologically disturbing one as it was considered too expensive, time consuming, and difficult to realize. A precise and intensive postrestoration monitoring program, conducted over two years, demonstrated restoration success but also unpredicted problems, such as a locally thick layer of fine organic sediment. As long as a self-sustainable state is not achieved, this monitoring should be continued. Afterwards, a less precise and less intensive long-term monitoring should enable the detection of future events that may influence ecosystem changes.     

绵阳市大气降水pH值时空分布及酸雨成因研究

通过对绵阳市9个测点1998－1999年大气降水监测数据的统计分析，并结合历史数据，对大气降水pH值的时空分布及酸雨成因进行了研究。结果表明：绵阳市大气降水酸化严重，除主要受本地区大气污染影响外，还受大气中、长距离输送的影响。     

Physiological Age of Host Plant Foliage and Survival of Gypsy Moth Larvae

The pH of leaf homogenates of common birch (Betula verrucosa L.), a food plant of gypsy moth (Lymantria dispar L.) larvae, was measured at different times of day in the course of leaf organogenesis, and midgut pH was measured in gypsy moth larvae phenotypically differing in the color of the hypodermis at the fifth instar. A possible relation between these parameters is discussed.     

Monitoring of eutrophication and nutrient limitation in the Izmir Bay (Turkey) before and after Wastewater Treatment Plant

The distribution of inorganic nutrients and phytoplankton chlorophyll-a was investigated and N/P ratios were determined in Izmir Bay during 1996-2001. The average concentrations showed ranges of 0.01-0.19 and 0.01-10 microM for phosphate-phosphorus; 0.11-1.8 and 0.13-27 microM for (nitrate+nitrite)-nitrogen, 0.30-4.1 and 0.50-39 microM for silicate and 0.02-4.3 and 0.10-26 microg l(-1) for chlorophyll-a in the outer and middle-inner bays, respectively. The results are compared with the values obtained from the relatively unpolluted waters of the Aegean Sea. The N/P ratio is significantly lower than the assimilatory optimal (N/P=15:1) in conformity with Redfield's ratio N/P=16:1. Nitrogen is the limiting element in the Izmir Bay. Phosphate, which originates from detergents, is an important source for eutrophication in the bay, especially in the inner bay. In early 2000, a Wastewater Treatment Plant (WTP) began to treat domestic and industrial wastes. This plant treats the wastes about 60% capacity between 2000 and 2001. The sampling periods cover before and after treatment plant. Although the capacity of wastewater plant is sufficient for removal of nitrogen from the wastes, it is inadequate for removal of phosphate. This is also in accordance with the decreasing N/P ratios observed during 2000-2001 (after WTP) in the middle-inner bays.     

Watershed scale assessment of nitrogen and phosphorus loadings in the Indian River Lagoon basin,Florida

There is a growing evidence that the ecological and biological integrity of the lagoon has declined during the last 50 years, probably due to the decline in water quality. Establishment of a watershed scale seagrass-based nutrient load assessment is the major aim of water quality management in the Indian River Lagoon (IRL). Best estimate loadings incorporate wet and dry deposition, surface water, groundwater, sediment nutrient flux, and point source effluent discharge data. On the average, the IRL is receiving annual external loadings of 832, 645 and 94,476kg of total nitrogen (TN) and total phosphorus (TP), respectively, from stormwater discharges and agricultural runoff. The average internal cycling of TN and TP from sediment deposits in the IRL was about 42,640kg TN and 1050kg TPyr(-1). Indirect evidence suggests that atmospheric deposition has played a role in the ongoing nutrient enrichment in the IRL. The estimated total atmospheric deposition of TN and TP was about 32,940 and 824kgyr(-1), while groundwater contribution was about 84,920 and 24,275kgyr(-1), respectively, to the surface waters of the IRL. The estimated annual contribution of point effluent discharge was about 60,408kg TN and 7248kg TP. In total, the IRL basin is receiving an annual loading of about 1,053,553kg TN and 127,873kg TP. With these results, it is clear that the current rate of nutrient loadings is causing a shift in the primary producers of the IRL from macrophyte to phytoplankton- or algal-based system. The goal is to reverse that shift, to attain and maintain a macrophyte-based estuarine system in the IRL.     

Soil Phosphorus Concentrations in Dane County,Wisconsin, USA: An Evaluation of the Urban–Rural Gradient Paradigm

Understanding the magnitude and location of soil phosphorus (P) accumulation in watersheds is a critical step toward managing runoff of this pollutant to aquatic ecosystems. Here, I examine the usefulness of urban–rural gradients, an emerging experimental design in urban ecology, for predicting extractable soil P concentrations across a rapidly urbanizing agricultural watershed in southern Wisconsin. I compare several measures of an urban–rural gradient to predictors of soil P such as soil type, slope, topography, land use, land cover, and fertilizer and manure use. Most of the factors that were expected to drive differences in soil P concentrations were found to be poor predictors of Bray-1 (extractable) soil P, which ranged from 4 to 660 ppm; while there were several significant relationships, most explained only a small proportion of the variation. A multiple linear regression model captured approximately 37% of the variation in the data using the urban–rural gradient, topography, land use, land cover, manure use, and soil type as predictors. There was a significant relationship between Bray-1 P concentration and each of the urban–rural gradients, but these relationships explained only between 2.6% and 3.3% of the variation in P concentrations. Extractable P concentration in soils, unlike some other ecosystem properties, is not well predicted by urban–rural gradients.