P. Loganathan

Sorption of heavy metal ions by a hydrous manganese oxide

Sorption of Co, Zn, Ca and Na by δ-MnO2 was studied at 24.0 ± 0.5°C and pH 4. During the sorption of Co and Zn, Mn was released to the solution phase; however, Mn release was not detected during the sorption of Ca and Na. On the basis of crystal field theory, it is proposed that Zn may interchange with Mn2+ in the δ-MnO2 structure, whereas Co may interchange with both Mn2+ and Mn3+. It is suggested that the interchangeable Mn2+ and Mn3+ sites were in the disordered layers in the δ-MnO2 structure. Sorption of Co, Zn and Ca at pH 4 fitted single-site Langmuir isotherm expressions at all Ca concentrations, but only at concentrations greater than 10−4 M for Co and Zn. Mn release by δ-MnO2 at pH 4 during Co and Zn sorption also fitted single-site Langmuir isotherms. An expression for the case of multisite Langmuir sorption was derived and applied to the cases of Co and Zn sorption and to the case of Mn release during Co sorption. The data of these cases were used to calculate statistically the coefficients of multiple regression equations from which the sum of the capacities of all sites in each case were obtained. From all of these derived capacities, it is proposed that there was only one site where Ca interchanged with surface bound H. Zn was postulated to interchange not only with these bound H sites, but also with another site where it interchanged with structural Mn2+. Co was postulated to interchange with both of these sites, and additionally, with a third site where it interchanged with structural Mn3+. Using a pH-stat set at pH 4, it was determined that approximately 2 moles of H were released per mole of Co or Zn sorbed at bound H sites.

Environmental hazards of fluoride in volcanic ash: a case study from Ruapehu volcano, New Zealand

Abstract The vent-hosted hydrothermal system of Ruapehu volcano is normally covered by a c. 10 million m3 acidic crater lake where volcanic gases accumulate. Through analysis of eruption observations, granulometry, mineralogy and chemistry of volcanic ash from the 1995–1996 Ruapehu eruptions we report on the varying influences on environmental hazards associated with the deposits. All measured parameters are more dependent on the eruptive style than on distance from the vent. Early phreatic and phreatomagmatic eruption phases from crater lakes similar to that on Ruapehu are likely to contain the greatest concentrations of environmentally significant elements, especially sulphur and fluoride. These elements are contained within altered xenolithic material extracted from the hydrothermal system by steam explosions, as well as in residue hydrothermal fluids adsorbed on to particle surfaces. In particular, total F in the ash may be enriched by a factor of 6 relative to original magmatic contents, although immediately soluble F does not show such dramatic increases. Highly soluble NaF and CaSiF6 phases, demonstrated to be the carriers of ‘available’ F in purely magmatic eruptive systems, are probably not dominant in the products of phreatomagmatic eruptions through hydrothermal systems. Instead, slowly soluble compounds such as CaF2, AlF3 and Ca5(PO4)3F dominate. Fluoride in these phases is released over longer periods, where only one third is leached in a single 24-h water extraction. This implies that estimation of soluble F in such ashes based on a single leach leads to underestimation of the F impact, especially of a potential longer-term environmental hazard. In addition, a large proportion of the total F in the ash is apparently soluble in the digestive system of grazing animals. In the Ruapehu case this led to several thousand sheep deaths from fluorosis.

Fluoride: A review of its fate, bioavailability, and risks of fluorosis in grazed‐pasture systems in New Zealand

Abstract Fluoride (F) is an essential element for animal growth, not readily taken up by plants from soils, yet cases of acute fluorosis in grazing animals caused by ingestion of phosphatic fertilisers, volcanic ash, and industrial wastes remind us of its potential hazard. Fluoride concentrations in topsoils slowly increase where annual inputs through atmospheric pollution and phosphatic fertilisers exceed losses. This paper reviews information on the fate of F in grazed pasture systems with the aim of assessing the potential toxicity of accumulating soil F. A preliminary F‐cycling model for grazed pastures, based on the review of international literature and F concentrations in selected New Zealand pasture soils, indicated that grazing sheep and cattle obtain over 50% of their dietary F (and this may be >80% during winter) from soil ingestion. The model suggests that at the extremes of the ranges of the measured winter soil ingestion (143–300 g d‐1 for sheep and 900–1600 g d‐1 for cattle) and dietary F absorptivity (bioavailability) of soil F (20–38%), total topsoil F concentrations in the range of 372–1461 μg F g‐1 could cause chronic fluorosis in sheep and 326–1085 μg F g‐1 in cattle. We recommend that research is undertaken to measure F accumulation rates and soil F dietary absorptivity for a range of intensively managed New Zealand pasture soils.

Defluoridation of drinking water using adsorption processes

Excessive intake of fluoride (F), mainly through drinking water, is a serious health hazard affecting humans worldwide. There are several methods used for the defluoridation of drinking water, of which adsorption processes are generally considered attractive because of their effectiveness, convenience, ease of operation, simplicity of design, and for economic and environmental reasons. In this paper, we present a comprehensive and a critical literature review on various adsorbents used for defluoridation, their relative effectiveness, mechanisms and thermodynamics of adsorption, and suggestions are made on choice of adsorbents for various circumstances. Effects of pH, temperature, kinetics and co-existing anions on F adsorption are also reviewed. Because the adsorption is very weak in extremely low or high pHs, depending on the adsorbent, acids or alkalis are used to desorb F and regenerate the adsorbents. However, adsorption capacity generally decreases with repeated use of the regenerated adsorbent. Future research needs to explore highly efficient, low cost adsorbents that can be easily regenerated for reuse over several cycles of operations without significant loss of adsorptive capacity and which have good hydraulic conductivity to prevent filter clogging during the fixed-bed treatment process.

Removal and Recovery of Phosphate From Water Using Sorption

Sorption is an effective, reliable, and environmentally friendly treatment process for the removal of phosphorus from wastewater sources which otherwise can cause eutrophication of receiving waters. Phosphorus in wastewater, if economically recovered, can partly overcome the future scarcity of phosphorus resulting from exhaustion of natural phosphate rock reserves. The authors present a comprehensive and critical review of the literature on the effectiveness of a number of sorbents, especially some novel ones that have recently emerged, in removing and recovering phosphate. Mechanisms and thermodynamics of sorption, as well as regeneration of sorbents for reuse using acids, bases, and salts, are critically examined.

Fertiliser contaminants in New Zealand grazed pasture with special reference to cadmium and fluorine: a review

Phosphorus (P) fertilisers are an essential input for the economic production of legume-based pastures in New Zealand (NZ) and Australia, but they often contain some unwanted elements that can contaminate the soil, thereby creating potential risks to the health of grazing animal, food quality, and soil quality. Fluorine (F) and cadmium (Cd) are considered to be the elements of most concern. Incidences of F toxicity (from direct ingestion of fertiliser), and accumulation of Cd in offal products above the maximum permissible concentration (MPC) set by the food authorities, have been reported in NZ. Similarly, Cd concentrations in some food grains may exceed the newly proposed MPCs by the Australian and New Zealand Food Authority. Cadmium and F continue to accumulate in the topsoils of NZ and Australian pastures as a result of P fertiliser use. The mobility of both these elements in soils is low and is similar to that of P. Risk of ground water contamination from F and Cd applied to most NZ pastures is low. The plant uptake of these elements, especially F, is also low in most pastoral soils. Cadmium accumulates mainly in liver and kidney of grazing animals mostly through herbage ingestion, whereas F accumulates mainly in the bones of these animals, mostly through soil ingestion. Soil ingestion is highest during the wetter winter months and at high stocking rates. Models have been developed to assess the impact of fertiliser use on the potential risks associated with F and Cd accumulation in soils. Measures to control F and Cd accumulation in soils, plants, and grazing animals are presented and future research needs are identified.

Cadmium Sorption and Desorption in Soils: A Review

Cadmium (Cd) is an environmental pollutant that can be readily taken up by plants and may enter the food chain, causing risk to human health. It can also affect soil quality and, if easily leached, has the potential to pollute surface and ground waters. Sorption and desorption are critical processes controlling the phytoavailability and mobility of Cd in soils. The authors present the present knowledge on the mechanisms and hysteresis of Cd sorption and desorption in soils and factors such as pH, ionic strength, index cation, other heavy metal cations, inorganic anions, organic ligands, Cd loading rate, and the type and amounts of organic matter and inorganic colloids influencing these processes. The methods used to determine the nature and magnitude of Cd sorption and desorption are also critically reviewed.

Enhanced removal of nitrate from water using surface modification of adsorbents – A review

Elevated concentration of nitrate results in eutrophication of natural water bodies affecting the aquatic environment and reduces the quality of drinking water. This in turn causes harm to peoples health, especially that of infants and livestock. Adsorbents with the high capacity to selectively adsorb nitrate are required to effectively remove nitrate from water. Surface modifications of adsorbents have been reported to enhance their adsorption of nitrate. The major techniques of surface modification are: protonation, impregnation of metals and metal oxides, grafting of amine groups, organic compounds including surfactant coating of aluminosilicate minerals, and heat treatment. This paper reviews current information on these techniques, compares the enhanced nitrate adsorption capacities achieved by the modifications, and the mechanisms of adsorption, and presents advantages and drawbacks of the techniques. Most studies on this subject have been conducted in batch experiments. These studies need to include continuous mode column trials which have more relevance to real operating systems and pilot-plant trials. Reusability of adsorbents is important for economic reasons and practical treatment applications. However, only limited information is available on the regeneration of surface modified adsorbents.

Fluoride accumulation in pasture forages and soils following long-term applications of phosphorus fertilisers

Ingestion of soils with high fluoride (F) concentration may cause chronic fluorosis in grazing animals. Analysis of New Zealand pasture soils with long-term phosphorus (P) fertilisation histories showed that total surface soil (0-75 mm depth) F concentration increased up to 217-454 mg kg-1 with P fertiliser application. One-third to two-thirds of F applied in fertilisers resides in the top 75 mm soil depth. Pasture forage accumulation of F was low, and therefore, F intake by grazing animals through pasture consumption is expected to be much lower than F intake by soil ingestion. Ten annual applications of single superphosphate (30 and 60 kg P ha-1 year-1) to a Pallic Soil (Aeric Fragiaqualf) significantly increased total F and labile F (0.01 M CaCl2 extract) concentrations to 200 and 120 mm depths, respectively, of the 300 mm depth investigated. The mobility of F in the soil profile was similar to two other elements, P and cadmium derived from the fertiliser.

Progress in selected areas of rhizosphere research on P acquisition

Large reserves of P have accumulated in soils of developed countries because additions of P fertiliser to sustain agricultural production have exceeded crop removal. By contrast, in many developing countries in the tropics and subtropics, soil P reserves are gravely low and large additions are required before maintenance requirements begin to decline. In addition, the cost of P fertiliser will increase as the currently accessible deposits of high-grade phosphate rock (PR) diminish. Developing plants that efficiently tap soil P reserves and low grade PR is therefore a priority for agricultural research. For the 50th anniversary of the New Zealand Soil Science Society, this paper reviews research on P efficiency in plants, conducted by staff, students, and research associates of Massey University, in the context of other research into plant mechanisms that enhance P uptake, including effects of root geometry, mycorrhizal associations, and root-induced changes in the soil. Techniques for fractionation of soil P are highlighted.