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The pH of the growth medium influences Cu speciation in solution, the negativity of plasma membrane (PM) surface potential, and hence the rhizotoxicity of Cu. Solution culture experiments were conducted with wheat (Triticum aestivum L.) seedlings to examine the toxicity of various Cu species at pH values ranging from 4.50 to 8.25. The toxic species of Cu was identified, giving particular consideration to the electrical properties at the plant cell membrane and ion activities at the PM surface. The solution culture studies showed that at pH 95 % of total Cu), the addition of cations (Ca2+ or H+) decreased the toxic effects of Cu by decreasing the negativity of the PM surface potential (and hence decreasing the activity of Cu2+ at the PM surface). For solutions with pH values from 7.50 to 8.25 (CuCO 3 0 >50 % of total Cu), an increase in pH significantly enhanced the toxicity of Cu, whilst the addition of Ca had negligible influence on toxicity. Root growth in solution cultures was influenced primarily by the surface activities of free Cu2+ and CuCO 3 0 . Across all experiments, the data indicate that it was CuCO 3 0 , rather than CuOH+, that contributed Cu toxicity over pH > 7.00. Although our data do not explore the mechanism of toxicity, we propose that CuCO 3 0 has an important role in Cu rhizotoxicity in alkaline growth media.

In acid soil, low pH, reduced availability of nutrients, and toxicity of Al and Mn limit plant growth and the survival and effectiveness of rhizobia. The symbiosis between legumes and rhizobia is particularly sensitive to acid soil stress. A pot experiment evaluated whether Bradyrhizobium japonicum strain growth on acidic agar media would predict ability to colonize the rhizosphere and form effective nodules in acidic soils. Three Indonesian strains of B. japonicum with similar effectiveness at neutral pH in sand culture but with different tolerance of acid soil stress factors in agar media, and an acid-tolerant commercial strain (CB1809) of comparable effectiveness, were tested in three acid soils using the Al tolerant soybean (Glycine max cv PI 416937). At 7 days after inoculation all strains had achieved large rhizosphere populations, but by day 14 the rhizosphere population of the acid-sensitive strain had decreased, while the more acid-tolerant strains increased. The acid-tolerant strains had significantly greater nodulation and symbiotic effectiveness than plants inoculated with the acid-sensitive strain. Laboratory prescreening of B. japonicum for acid, Al and Mn tolerance in acid media successfully identified strains which were symbiotically competent in low pH soils.

Cations, such as Ca and Mg, are generally thought to alleviate toxicities of trace metals through site-specific competition (as incorporated in the biotic ligand model, BLM). Short-term experiments were conducted with cowpea (Vigna unguiculata L. Walp.) seedlings in simple nutrient solutions to examine the alleviation of Cu and Pb toxicities by Al, Ca, H, Mg, and Na. For Cu, the cations depolarized the plasma membrane (PM) and reduced the negativity of ψ(0)(o) (electrical potential at the outer surface of the PM) and thereby decreased {Cu(2+)}(0)(o) (activity of Cu(2+) at the outer surface of the PM). For Pb, root elongation was generally better correlated to the activity of Pb(2+) in the bulk solution than to {Pb(2+)}(0)(o). However, we propose that the addition of cations resulted in a decrease in {Pb(2+)}(0)(o) but a simultaneous increase in the rate of Pb uptake (due to an increase in the negativity of E(m,surf), the difference in potential between the inner and outer surfaces of the PM) thus offsetting the decrease in {Pb(2+)}(0)(o). In addition, Ca was found to alleviate Pb toxicity through a specific effect. Although our data do not preclude site-specific competition (as incorporated in the BLM), we suggest that electrostatic effects have an important role.

Total ionic strength buffers based on citrate at pH 7.5 and cyclohexylenediaminetetra‐acetic acid (CDTA) at pH 5.2 were evaluated for use when determining fluoride (F) concentration in soil solutions. Both buffers achieved acceptable recoveries of F added to ultra‐filtered (0.025 μm) solutions. Recovery of F added to unflltered and 0.22 μm filtered solution was low when the CDTA buffer was used. This effect was attributed to the adsorption of F by micro‐particulate materials present in these samples. The use of this buffer would need to be restricted to samples in which micro‐particulates were not present. The performance of the citrate buffer was not affected by the presence of microparticulates; however, electrode response times, and departure from Nernstian response at low F concentrations, were greater when this buffer was employed. Fluoride was found to be present at low concentrations in the soil solution of the 60 virgin highly weathered soils tested. The F concentration in 75% of the surf...

Adam Wightwick1,2,3, Robert Walters3, Graeme Allinson3,4, Suzanne Reichman5, and Neal Menzies1,2 1The University of Queensland 2Co-operative Research Centre for Contamination Assessment and Remediation of the Environment (CRC CARE) 3Department of Primary Industries, Victoria 4Victorian Centre for Aquatic Pollution Identification and Management (CAPIM) 5Royal Melbourne Institute of Technology (RMIT) University Australia

• Reductions in plant growth as a result of salinity are of global importance in natural and agricultural landscapes. • Short-term (48-h) solution culture experiments studied 404 treatments with seedlings of cowpea (Vigna unguiculata cv Caloona) to examine the multiple deleterious effects of calcium (Ca), magnesium (Mg), sodium (Na) or potassium (K). • Growth was poorly related to the ion activities in the bulk solution, but was closely related to the calculated activities at the outer surface of the plasma membrane, {I(z)}₀°. The addition of Mg, Na or K may induce Ca deficiency in roots by driving {Ca²+}₀° to1.6 mM. Shoots were more sensitive than roots to osmolarity. Specific ion toxicities reduced root elongation in the order Ca²+Mg²+Na+K+. The addition of K and, to a lesser extent, Ca alleviated the toxic effects of Na. Thus, Ca is essential but may also be intoxicating or ameliorative. • The data demonstrate that the short-term growth of cowpea seedlings in saline solutions may be limited by Ca deficiency, osmotic effects and specific ion toxicities, and K and Ca alleviate Na toxicity. A multiple regression model related root growth to osmolarity and {I(z)}₀° (R²=0.924), allowing the quantification of their effects.

Silver (Ag) is highly toxic to aquatic organisms, including algae, invertebrate animals, and fish, but little information exists on Ag rhizotoxicity in higher plants. In two solution culture experiments with approximately 1,000 mu M Ca(NO(3))(2) and 5 mu M H(3)BO(3) (pH 5.4), 20 to 80% of added Ag (

Hydrolysis of aluminum (Al) in solution increases at pHor= 4 and with an Al concentration. Pectin, an important anionic polysaccharide of plant cell walls, adsorbs Al, but this phenomenon is poorly understood. This study showed that Al(3+) hydrolysis results in binding of Al to pectin in excess of the stoichiometric equivalent, leading to oversaturation of the pectin with Al. However, the degree of pectin methyl-esterification did not affect the extent of Al hydrolysis. Binding of Al to purified cell wall material also resulted in Al hydrolysis in a pH- and soluble Al concentration-dependent manner, but the source of cell wall material had no effect at fixed pH. Staining of Al-treated pectin and cell wall material from wheat ( Triticum aestivum L.) and sunflower ( Helianthus annuus L.) with the Al-specific dye, chrome azurol S (CAS), resulted in the formation of a purple color, with the intensity related to the extent of Al hydrolysis.

Rheology of Ca-pectate gels is widely studied, but the behaviour of pectate gels formed by Cu, Al and La is largely unknown. It is well known that gel strength increases with increasing Ca concentration, and it is hypothesised that this would also be the case for other cations. Pectins are a critical component of plant cell walls, imparting various physicochemical properties. Furthermore, the mechanism of metal toxicity in plants is hypothesised to be, in the short term, related to metal interactions with cell wall pectin. This study investigated the influence of Ca, Cu, Al and La ion concentrations at pH 4 on the storage modulus as a function of frequency for metal-pectin gels prepared from pectin (1%) with a degree of esterification of 30%. Gels were formed in situ over 6d in metal chloride solution adjusted daily to pH 4. Cation concentration was varied to develop a relationship between gel strength and cation concentration. At similar levels of cation saturation, gel strength increased in the order of La

Solution culture has been used extensively to determine the phytotoxic effects of trace metals. A review of the literature from 1975 to 2009 was carried out to evaluate the effects of As(V), Cd(II), Co(II), Cu(II), Hg(II), Mn(II), Ni(II), Pb(II), and Zn(II) on plants grown in solution. A total of 119 studies was selected using criteria that allowed a valid comparison of the results; reported toxic concentrations varied by five orders of magnitude. Across a range of plant species and experimental conditions, the phytotoxicity of the trace metals followed the trend (from most to least toxic): Pb approximately Hg >Cu >Cd approximately As >Co approximately Ni approximately Zn >Mn, with median toxic concentrations of (muM): 0.30 Pb, 0.47 Hg, 2.0 Cu, 5.0 Cd, 9.0 As, 17 Co, 19 Ni, 25 Zn, and 46 Mn. For phytotoxicity studies in solution culture, we suggest (i) plants should be grown in a dilute solution which mimics the soil solution, or that, at a minimum, contains Ca and B, (ii) solution pH should be monitored and reported (as should the concentrations of the trace metal of interest), (iii) assessment should be made of the influence of pH on solution composition and ion speciation, and (iv) both the period of exposure to the trace metal and the plant variable measured should be appropriate. Observing these criteria will potentially lead to reliable data on the relationship between growth depression and the concentration of the toxic metal in solution.

Low concentrations of some trace metals markedly reduce root elongation rate and cause ruptures to root rhizodermal and outer cortical cells in the elongation zone. The interactions between the trace metals and plant components responsible for these effects are not well understood but may be linked to changes in water uptake, cell turgor and cell wall extensibility. An experiment was conducted to investigate the effects of Al, La, Cu, Gd, Sc and Ru on the saturated hydraulic conductivity of bacterial cellulose (BC)-pectin composites, used as plant cell wall analogs. Hydraulic conductivity was reduced to approximately 30% of the initial flow rate by 39 microM Al and 0.6 microM Cu, approximately 40% by 4.6 microM La, 3 microM Sc and 4.4 microM Ru and approximately 55% by 3.4 microM Gd. Scanning electron microscopy (SEM) revealed changes in the ultrastructure of the composites. The results suggest that trace metal binding decreases the hydraulic conductivity through changes in pectin porosity. The experiment illustrates the importance of metal interactions with pectin, and the implications of such an interaction in plant metal toxicity and in normal cell wall processes.

Soil contamination is defined as the accumulation of hazardous compounds within the soil environment. Among the various technologies developed for soil remediation and rehabilitation, plant-based approaches have attracted attention for several years in view of their potential benefits in terms of cost, ability to improve soil conditions and public acceptance. This chapter reviews the application of plant-based approaches, their potential and drawbacks in the context of various contamination scenarios. The plant-based approaches described phytoextraction, phytostabilization, phytovolatilization, and plant-assisted biodegradation (sometimes termed phytodegradation).

The determination of the Al concentration in soil solution is an important diagnostic tool in studies of Al toxicity in acid soils. Where organic residues have been applied as ameliorants of Al toxicity, it is necessary to measure both the total soluble and monomeric Al concentrations in order to estimate the degree of Al complexation. Determination by ICPAES provides a measure of total Al without discrimination between chemical forms, and thus may include solid-phase Al present as micro-particulates that have passed through a 0.22 pm filter. Colorimetric methods, which do not include an acidification step, discriminate against micro-particulates, but do not measure all Al present as soluble organic forms and thus underestimate total soluble Al. Acidification of soil solutions to decomplex organically bound Al, and thus permit its measurement by colorimetric methods, results in dissolution of micro-particulates and overestimation of total soluble Al. Filtering to 0.025 pm eliminated microparticulates, thereby removing a source of error. However, this process is time consuming and thus unsuitable for routine use.

This study determined the environmental availability of copper (Cu) in Australian vineyard soils contaminated with fungicide derived Cu residues, and investigated the soil characteristics correlated with differences in Cu availability between regions. Concentrations of 0.01 M calcium chloride extractable Cu, measured in surface soils collected from 98 vineyards in 10 different grape-growing regions of Australia, ranged from

Processing of bauxite to extract alumina produces a strongly alkaline waste, bauxite refining residue, which is commonly stored in engineered structures. Once full, these waste dumps must be revegetated. In many alumina refineries, the waste is separated into fine-textured red mud and coarse-textured residue sand (RS). The sand component has physical characteristics that make it a suitable plant growth medium, provided the adverse chemical characteristics can be addressed. Neutralization of the highly saline-sodic RS with sea water lowers pH, reduces Na saturation, and adds plant nutrients. However, sea water-neutralized RS remains saline sodic and needs fresh water leaching before use as a plant growth medium. Columns containing sea water-neutralized RS were leached with 30 m depth-equivalent of fresh water to evaluate the effects of rainfall on the RS and its leachate. Entrained cations were rapidly displaced by the fresh water, lowering salinity to non-plant-limiting levels (< or =0.3 dS m(-1)). The percentage of the effective cation exchange capacity (ECEC) saturated by Na decreased from 71 to 62% due to a reduction in soil solution ionic strength (causing a decrease in the ECEC) and the preferential displacement of Na(+) (and K(+)) from the exchange. Fresh water leaching increased pH (leachate pH increased from 8.0 to 10.1). This pH increase is attributed to the slow dissolution of the Na-containing mineral sodalite. Under the current experimental conditions, the application of 30 m depth-equivalent of leaching reduced the total RS sodalite content by

Potential vitiative effects of Millipore 0.45‐, 0.22‐, 0.05‐ and 0.025‐pm filter elements on aqueous samples were investigated. All the filter elements evaluated exhibited a cation exchange capacity (CEC); in the case of 0.025‐pm filter elements, the CEC increased with pH. Filtration of 20 μM AlCl/1.65 mM CaCl, solutions (I∼0.005 M) to 0.45, 0.22 and 0.05 pm resulted in no significant change in solution A1 concentration. Filtration through 0.025‐μm filter elements significantly reduced the total A1 present in solutions adjusted to pH 4.5 and 5.0; the A1 concentration of solution adjusted to pH 4.0 was not altered. The removal of A1 from pH 4.5 and pH 5.0 solutions was attributed to the retention of A1 hydroxide micro‐particulates formed during pH adjustment of the AlCl/CaCI, solution. Adsorption of A1 by the filter element was not significant. Soil solutions were analysed without filtering and after filtration to 0.45,0.22,0.05 and 0.025 pm. Filtration had no effect on the concentration of the major anions (Cl, SO ‐, NO) or cations (Ca, Mg, Na, K). However, filtration to 0.05 and 0.025 pm resulted in significant reductions in the concentration of Al, Fe, Si and organic C in some samples. In soil solutions for which filtration resulted in the removal of large amounts of particulate material, the solution appeared less coloured after filtration and exhibited lower absorbance in the visible spectrum (4O(MOO nm). However, the absence of colour did not preclude the presence of colloidal particles.

A positive pressure filtration apparatus is described which employs compressed gas to provide the differential pressure required to permit the ultrafiltration of soil solution. The apparatus uses low‐cost membrane filter elements and is suitable for use with small volume samples, as there is little retention of solution within the filtration cells. Initial flow rates of‐5 and 25 mL/min were achieved through 0.025 and 0.05 μm pore‐diameter filter elements, respectively. Compressed nitrogen is the preferred gas source as exposure of solutions of pH 6 or higher to compressed air resulted in a lowering of pH levels.

Lead (Pb) contamination of soils is of global importance but little is known regarding Pb uptake, localization, or the chemical forms in which Pb is found within plants, or indeed how some plants tolerate elevated Pb in the environment. Two grasses, signal grass (Brachiaria decumbens Stapf) (Pb-resistant) and Rhodes grass (Chloris gayana Kunth)(Pb-sensitive), were grown for 14 d in dilute nutrient solutions before examination of roots using transmission electron microscopy (TEM) to determine the distribution and speciation of Pb in situ. In both grasses, Pb was initially present primarily in the cytoplasm of rhizodermal and cortical cells before being sequestered within vacuoles as the highly insoluble (and presumably nontoxic) chloropyromorphite (Pb5(PO4)3Cl). In signal grass, Pb also accumulated within membranous structures (perhaps the Golgi apparatus), prior to apoplastic sequestration as chloropyromorphite. These findings suggest that the ability of signal grass to sequester insoluble Pb in the cell wall represents an additional and potentially important mechanism of Pb tolerance not possessed by the Pb-sensitive Rhodes grass.

A concentration as low as 1 microM lead (Pb) is highly toxic to plants, but previous studies have typically related plant growth to the total amount of Pb added to a solution. In the present experiment, the relative fresh mass of cowpea (Vigna unguiculata) was reduced by 10% at a Pb2+ activity of 0.2 microM for the shoots and at a Pb2+ activity of 0.06 microM for the roots. The primary site of Pb2+ toxicity was the root, causing severe reductions in root growth, loss of apical dominance (shown by an increase in branching per unit root length), the formation of localized swellings behind the root tips (due to the initiation of lateral roots), and the bending of some root tips. In the root, Pb was found to accumulate primarily within the cell walls and intercellular spaces.

Although Cu is phytotoxic at Cu(2+) activities as low as 1-2 microM, the effect of Cu(2+) on the nodulation of legumes has received little attention. The effect of Cu(2+) on nodulation of cowpea (Vigna unguiculata (L.) Walp. cv. Caloona) was examined in a dilute solution culture system utilising a cation exchange resin to buffer solution Cu(2+). The nodulation process was more sensitive to increasing Cu(2+) activities than both shoot and root growth; whilst a Cu(2+) activity of 1.0 microM corresponded to a 10% reduction in the relative yield of the shoots and roots, a Cu(2+) activity of 0.2 microM corresponded to a 10% reduction in nodulation. This reduction in nodulation with increasing Cu(2+) activity was associated with an inhibition of root hair formation in treatments containing > or =0.77 microM Cu(2+), rather than to a reduction in the size of the Rhizobium population.

Metal mining frequently results in substrates for rehabilitation which have elevated levels of metals. In Australia, the objective of many rehabilitation programs is to re-establish native plant communities, and yet, very little is known of the responses of Australian plants to elevated levels of metals. Eucalyptus camaldulensis (river red gum) has a wide distribution across the Australian continent. The species is often used successfully in the revegetation programs of mining. Through knowledge of the responses of E. camaldulensis to high metal concentrations, the potential value of this species for use in revegetation of a broader range of mineral waste materials can be identified.

Environmental context.High concentrations of Ni in soil may occur either naturally or as a result of human activities. We used a sand culture system to investigate the suitability of seven perennial grasses for the revegetation of Ni-contaminated sites. This study provides information on the toxic effects of Ni on plant growth and gives consideration to the health of animals consuming these plants, thereby increasing the accuracy of risk assessments. Abstract.Although grasses are commonly used to revegetate disturbed areas, comparatively little is known regarding the tolerance of perennial grasses to toxic levels of trace metals. A sand culture experiment was conducted to investigate the tolerance of seven perennial grasses to high concentrations of Ni. The activity of Ni2+ in solution that resulted in a 50% reduction in shoot growth ranged from 50 µM for Sabi grass (Urochloa mosambicensis (Hack.) Dandy cv. Saraji) to 13 µM for curly Mitchell grass (Astrebla lappacea (Lindl.) Domin). In most grasses, growth in the high-Ni2+ treatments resulted in shoot Ni concentrations at or above the toxicity threshold for consumption by cattle (100 µg Ni g–1). Based upon their tolerance to Ni, and the extent to which they translocate Ni to the shoots, Sabi grass, signal grass (Brachiaria decumbens Stapf. cv. Basilisk) and buffel grass (Cenchrus ciliaris (L.) cv. Biloela) appear well suited for the phytostabilisation of Ni-contaminated sites in subtropical and tropical regions.

Environmental context. Copper (Cu) is an essential element for the growth of plants, but various anthropogenic activities such as mining, smelting, disposal of wastes, and the use of Cu-containing fungicides have resulted in substantial Cu contamination at sites throughout the world. We used a sand-culture system to investigate the tolerance of seven perennial grasses to toxic levels of Cu. This study provides information to assist in the selection of grasses for the revegetation and stabilisation of Cu-contaminated sites. Abstract. Although perennial grasses are commonly used to revegetate and stabilise disturbed sites, comparatively little is known of their tolerance to Cu. High Cu in solution reduced growth in all grasses, with the critical solution Cu concentration (corresponding to a 50% reduction in shoot fresh mass) ranging >5-fold, from 1.7 μM in Queensland blue grass (Dichanthium sericeum (R.Br.) A. Camus) to 10 μM in Sabi grass (Urochloa mosambicensis (Hack.) Dandy cv. Saraji). An increase in Cu in solution resulted in elevated Cu concentration in shoots of all but one species, increasing from 6 to 11 μg g–1 at 0 μM Cu to 13 to 25 μg g–1 at 11 μM Cu. The comparatively small magnitude of this increase to a concentration below the animal toxicity threshold suggests that phytotoxicity is likely to be of more environmental concern than is the uptake of Cu into the shoots (and its subsequent consumption by fauna).

Environmental context. Nickel (Ni) may be present in soil at phytotoxic levels as a result of weathering of ultramafic (serpentine) minerals or activities such as mining and metal ore processing. We assessed the tolerance of two grasses to excess Ni and used electron microscopy to examine the distribution of the Ni within the root tissue. This study provides information on the influence of excess Ni on the growth of these two grasses with consideration to their suitability for the revegetation of areas contaminated with Ni. Abstract. Toxic effects of Nickel (Ni) in solution were evaluated in signal grass and Rhodes grass, two species commonly used for the revegetation of contaminated sites in the tropics and sub-tropics. Both grasses had a similar response to Ni, a Ni2+ activity ({Ni2+}) of 14 × 10–6 M, which reduced the fresh mass by 50%. The sub-cellular distribution of Ni in the roots was similar for both species, with Ni accumulating primarily as particles

As observed with many soils, much of the P in the Brown Kandosol soils of Weipa (Australia) is associated with organic matter. However, following bauxite mining, much of this organic matter is either lost due to mineralisation, or is ‘diluted’ by the mixing of the soil profile. Using a sequential P extraction, the partitioning of P following fertiliser application was examined in an ‘undisturbed’ (Surface) soil and a Mixed soil. In addition, the effect of split-P applications on the growth of 2 native Eucalyptus species was examined. Following its addition to the soil, much of the P was converted comparatively rapidly to forms with reduced availability; by the time of the first measurement (4 weeks) only approximately 10% of the added P remained as the readily available AER-P. For the Surface soil, much of this added P was initially converted to organic P (Po) (measured as hydroxide-Po), before progressively moving into the hydroxide-Pi fraction. In comparison, in the mixed soil, competition for P from microbial biomass was lower (due to a lower organic matter content) and the P was rapidly converted to the hydroxide-Pi fraction before moving to unavailable forms (residual P). Although the use of split-P applications was expected to increase plant growth, maximum growth of Eucalyptus tetrodonta and Eucalyptus leptophleba was generally achieved when all P fertiliser was applied in the first few weeks of growth. Indeed, splitting the P application beyond 16 weeks caused a significant reduction in growth.

The treatment and hydraulic mechanisms in a septic tank–soil absorption system (SAS) are highly influenced by the clogging layer or biomat zone which develops on bottom and lower sidewall surfaces within the trench. Flow rates through the biomat and sub-biomat zones are governed largely by the biomat hydraulic properties (resistance and hydraulic conductivity) and the unsaturated hydraulic conductivity of the underlying soil. One- and 2-dimensional models were used to investigate the relative importance of sidewall and vertical flow rates and pathways in SAS. Results of 1-dimensional modelling show that several orders of magnitude variation in saturated hydraulic conductivity (Ks) reduce to a 1 order of magnitude variation in long-term flow rates. To increase the reliability of prediction of septic trench hydrology, HYDRUS-2D was used to model 2-dimensional flow. In the permeable soils, under high trench loading, effluent preferentially flowed in the upper region of the trench where no resistant biomat was present (the exfiltration zone). By comparison, flow was more evenly partitioned between the biomat zones and the exfiltration zones of the low permeability soil. An increase in effluent infiltration corresponded with a greater availability of exfiltration zone, rather than a lower resistance of biomat. Results of modelling simulations demonstrated the important role that a permeable A horizon may play in limiting surface surcharge of effluent under high trench hydraulic loading.

On-site wastewater treatment and dispersal systems (OWTS) are used in non-sewered populated areas in Australia to treat and dispose of household wastewater. The most common OWTS in Australia is the septic tank–soil absorption system (SAS)—which relies on the soil to treat and disperse effluent. The mechanisms governing purification and hydraulic performance of a SAS are complex and have been shown to be highly influenced by the biological zone (biomat) which develops on the soil surface within the trench or bed. Studies suggest that removal mechanisms in the biomat zone, primarily adsorption and filtering, are important processes in the overall purification abilities of a SAS. There is growing concern that poorly functioning OWTS are impacting upon the environment, although to date, only a few investigations have been able to demonstrate pollution of waterways by on-site systems. In this paper we review some key hydrological and biogeochemical mechanisms in SAS, and the processes leading to hydraulic failure. The nutrient and pathogen removal efficiencies in soil absorption systems are also reviewed, and a critical discussion of the evidence of failure and environmental and public health impacts arising from SAS operation is presented. Future research areas identified from the review include the interactions between hydraulic and treatment mechanisms, and the biomat and sub-biomat zone gas composition and its role in effluent treatment.

Nitrate (NO3) accumulations (up to 1880 kg NO3-N/ha for a 12-m profile) in the soils of the Johnstone River catchment (JRC) may pose a serious environmental threat to the Great Barrier Reef lagoon if the NO3 were released. The leaching of artificial rainwater through repacked soil columns was investigated to determine the effect of low NO3/low ionic strength inputs on the NO3 chemistry of the JRC profiles. Repacked soil columns were used to simulate the 11.5-m profiles, and the soil solution anion and cation concentrations were monitored at 10 points throughout the soil column. As the rainwater was applied, NO3 leached down the profile, with substantial quantities exiting the columns. Anion exchange was discounted as the major mechanism of NO3 release due to the substantial net loss of anions from the system (up to 2740 kg NO3-N/ha over the experimental period). As the soils were dominated by variable charge minerals, the effect of changing pH and ionic strength on the surface charge density was investigated in relation to the release of NO3 from the exchange. It was concluded that the equilibration of the soil solution with the low ionic strength rainwater solution resulted in a lessening of both the positive and negative surface charge. Nitrate was released into the soil solution and subsequently leached due to the lessening of the positive surface charge. Loss of NO3 from the soil profile was slow, with equivalent field release times estimated to be tens of years. Although annual release rates were high in absolute terms (up to 175 kg NO3-N/ha.year), they are only slightly greater than the current loss rates from fertilised sugarcane production (up to 50 kg NO3-N/ha.year). In addition to this, the large-scale release of NO3 from the accumulations will only occur until a new equilibrium is established with the input rainwater solution.

Piggery pond sludge (PPS) was applied, as-collected (Wet PPS) and following stockpiling for 12 months (Stockpiled PPS), to a sandy Sodosol and clay Vertosol at sites on the Darling Downs of Queensland. Laboratory measures of N availability were carried out on unamended and PPS-amended soils to investigate their value in estimating supplementary N needs of crops in Australia’s northern grains region. Cumulative net N mineralised from the long-term (30 weeks) leached aerobic incubation was described by a first-order single exponential model. The mineralisation rate constant (0.057/week) was not significantly different between Control and PPS treatments or across soil types, when the amounts of initial mineral N applied in PPS treatments were excluded. Potentially mineralisable N (No) was significantly increased by the application of Wet PPS, and increased with increasing rate of application. Application of Wet PPS significantly increased the total amount of inorganic N leached compared with the Control treatments. Mineral N applied in Wet PPS contributed as much to the total mineral N status of the soil as did that which mineralised over time from organic N. Rates of CO2 evolution during 30 weeks of aerobic leached incubation indicated that the Stockpiled PPS was more stabilised (19–28% of applied organic C mineralised) than the Wet PPS (35–58% of applied organic C mineralised), due to higher lignin content in the former. Net nitrate-N produced following 12 weeks of aerobic non-leached incubation was highly correlated with net nitrate-N leached during 12 weeks of aerobic incubation (R2 = 0.96), although it was

The leaching of N fertilisers has led to the formation of nitrate (NO3) accumulations in deep subsoils (>5 m depth) of the Johnstone River catchment. This paper outlines the chemical mechanism by which these NO3 accumulations are formed and maintained. This was achieved via a series of column experiments designed to investigate NO3 leaching in relation to the soil charge chemistry and the competition of anions for exchange sites. The presence of variable charge minerals has led to the formation positive surface charge within these profiles. An increase in the soil solution ionic strength accompanying the fertiliser leaching front acts to increase the positive (and negative) charge density, thus providing adsorption sites for NO3. A decrease in the soil solution ionic strength occurs after the fertiliser pulse moves past a point in the profile, due to dilution with incoming rainwater. Nitrate is then released from the exchange back into the soil solution, thus buffering the decrease in the soil solution ionic strength. Since NO3 was adsorbed throughout the profile in this experiment it does not effectively explain the situation occurring in the field. Previous observations of the sulfate (SO4) profile distribution indicated that large SO4 accumulations in the upper profile may influence the NO3 distribution through competition for adsorption sites. A subsequent experiment investigating the effect of SO4 additions on NO3 leaching showed that NO3 adsorption was minimal in the upper profile. Adsorption of NO3 did occur, though only in the region of the profile where SO4 occupancy was low, i.e. in the lower profile. Therefore, the formation of the NO3 accumulations is dependent on the variable charge mineralogy, the variation of charge density with soil solution ionic strength, and the effects of SO4 competition for adsorption sites.

The incorporation of organic matter (OM) in soils that are able to rapidly sorb applied phosphorus (P) fertiliser reportedly increases P availability to plants. This effect has commonly been ascribed to competition between the decomposition products of OM and P for soil sorption sites resulting in increased soil solution P concentrations. The evidence for competitive inhibition of P sorption by dissolved organic carbon compounds, derived from the breakdown of OM, includes studies on the competition between P and (i) low molecular weight organic acids (LOAs), (ii) humic and fulvic acids, and (iii) OM leachates in soils with a high P sorption capacity. These studies, however, have often used LOAs at 1–100 mm, concentrations much higher than those in soils (generally

The appropriate use of wastes is a significant issue for the pig industry due to increasing pressure from regulatory authorities to protect the environment from pollution. Nitrogen contained in piggery pond sludge (PPS) is a potential source of supplementary nutrient for crop production. Nitrogen contribution following the application of PPS to soil was obtained from 2 field experiments on the Darling Downs in southern Queensland on contrasting soil types, a cracking clay (Vertosol) and a hardsetting sandy loam (Sodosol), and related to potentially mineralisable N from laboratory incubations conducted under controlled conditions and NO3– accumulation in the field. Piggery pond sludge was applied as-collected (wet PPS) and following stockpiling to dry (stockpiled PPS). Soil NO3– levels increased with increased application rates of wet and stockpiled PPS. Supplementary N supply from PPS estimated by fertiliser equivalence was generally unsatisfactory due to poor precision with this method, and also due to a high level of NO3– in the clay soil before the first assay crop. Also low recoveries of N by subsequent sorghum (Sorghum bicolor) and wheat (Triticum aestivum) assay crops at the 2 sites due to low in-crop rainfall in 1999 resulted in low apparent N availability. Over all, 29% (range 12–47%) of total N from the wet PPS and 19% (range 0–50%) from the stockpiled PPS were estimated to be plant-available N during the assay period. The high concentration of NO3- for the wet PPS application on sandy soil after the first assay crop (1998 barley, Hordeum vulgare) suggests that leaching of NO3– could be of concern when high rates of wet PPS are applied before infrequent periods of high precipitation, due primarily to the mineral N contained in wet PPS. Low yields, grain protein concentrations, and crop N uptake of the sorghum crop following the barley crop grown on the clay soil demonstrated a low residual value of N applied in PPS. NO3– in the sandy soil before sowing accounted for 79% of the variation in plant N uptake and was a better index than anaerobically mineralisable N (19% of variation explained). In clay soil, better prediction of crop N uptake was obtained when both anaerobically mineralisable N (39% of variation explained) and soil profile NO3– were used in combination (R2 = 0.49).

The solubilities and dissolution rates of 3 gypsum sources [analytical grade reagent (AR), phosphogypsum (PG), mined gypsum (MG)] with 6 MG size fractions (>2.0, 1.0–2.0, 0.5–1.0, 0.25–0.5, 0.125–0.25, PG > MG) due to reactivity and surface area differences, with 1 : 20 gypsum : solution suspensions reaching saturation within 15 s (AR) to 30 min (MG >2.0 mm). The ability of bauxite residue to adsorb Ca from solution was also examined. The quantity of the total solution Ca adsorbed was found to be small (5%). These low rates of solution Ca adsorption, combined with the comparatively rapid dissolution rates, preclude the application of gypsum to the residue sand/seawater slurry as a method for residue amelioration. Instead, direct field application to the residue would ensure more efficient gypsum use. In addition, the formation of a sparingly soluble CaCO3 coating around the gypsum particles after mixing in a highly alkaline seawater/supernatant liquor solution greatly reduced the rate of gypsum dissolution.

The chemical properties of deep profile samples (up to 12 m) of Ferrosols from northern Queensland were investigated to provide an understanding of the accumulation of nitrate (NO3) within these soil profiles. The influence of other cations and anions present in the soil solution or on the exchange and the charge chemistry of the profiles were examined with respect to the NO3 accumulations. The major ions in the soil solution were Na, NO3, and chloride (Cl). Distinct regions of anion accumulation were observed; SO4 accumulated in the upper profile of all cores, whereas NO3 and Cl accumulations were restricted to the lower profile of cores with appreciable AEC (>1�cmolc/kg). Gaines-Thomas selectivity coefficients were used to indicate exchange preference for cations and anions, and are as follows: Al > Ca ~ Mg > K > Na and sulfate (SO4) > Cl ~ NO3. The selectivity of SO4 increased and the extractable SO4 decreased in the lower profile of all cores. This has important implications for the adsorption of NO3 and Cl. The NO3 and Cl accumulations were shown to correspond to a region of low SO4 occupancy of the exchange sites in the lower profile. Along with the high SO4 selectivity, this suggests that SO4 may control the positioning of the NO3 accumulations. It was concluded that the NO3 accumulations were relatively stable under current management practices, although the reduction in NO3 inputs would likely see the gradual replacement of NO3 with Cl as a result of their comparable selectivity for exchange sites.

Nitrate leaching below the crop root-zone in variable charge soils may be adsorbed at anion exchange sites, thereby temporarily reducing the risk of contamination of water bodies. The objectives of this study were (i) to investigate whether nitrate adsorption, accumulation, and retention in the Johnstone River Catchment of Far North Queensland wet tropics is widespread; (ii) to assess the capacity of soil in the Johnstone River Catchment to retain nitrate; and (iii) to deduce the consequences of nitrate adsorption/desorption on contamination of water bodies. Soil cores ranging from 8 to 12.5 m depth were taken from 28 sites across the catchment, representing 9 Ferrosol soil types under sugarcane (Saccharum officinarum-S) cultivation for at least 50 years and from rainforest. The cores were segmented at 0.5-m depth increments and subsamples were analysed for nitrate-N, cation and anion exchange capacities, pH, exchangeable cations (Ca, Mg, K, Na), soil organic C, electrical conductivity, sulfate-S, and chloride. Nitrate-N concentration under sugarcane ranged from 0 to 72.5 mg/kg, compared with 0 to 0.31 mg/kg under rainforest, both Pin Gin soils. The average N load in 1–12 m depth across 19 highly oxidic profiles of the Pin Gin soil series was 1550 kg/ha, compared with 185 kg/ha under 8 non-Pin Gin soils and 11 kg/ha in rainforest on a Pin Gin soil. Most of the nitrate retention was observed at depth of 2–12 m, particularly at 4–10 m, indicating that the accumulation was well below the crop root-zone. The average maximum potential nitrate retention capacity was 10.8 t/ha for the Pin Gin and 4.7 t/ha for the non-Pin Gin soil. Compared with the current N load, the soils still possess a large capacity to adsorb and retain nitrate in profiles. Retention of large quantities of the leached nitrate deep in most of the profiles has reduced the risk of contamination of water bodies. However, computations show that substantial quantities of the nitrate leached below the root-zone were not adsorbed and remain unaccounted for. This unaccounted nitrate might have entered both on- and off-site water bodies and/or have been denitrified.

High concentrations of NH4+ (up to 270 kg N/ha) have been observed in a Vertosol below 1 m depth in south-east Queensland. This study examined the possibility that mineralisation associated with the removal of native vegetation (Acacia harpophylla) for cropping was responsible for the production of NH4+. Particularly, the potential contribution of decomposing root material and/or dissolved organic nitrogen (DON) leached into the subsoil after clearing was investigated. The amount of N that was contained within native vegetation root material was determined from an area of native vegetation adjacent to the cleared site containing elevated NH4+ concentrations. In addition, the amount of NH4+ that could be mineralised in the native vegetation soil was determined by monitoring NH4+ concentrations over 360 days in intact cores, and by conducting waterlogged incubations. To determine the rate at which a source of DON leached into the subsoil would mineralise, soil was amended with glutamic acid at a rate of 250 mg N/kg and placed under waterlogged incubation. The possibility that the acidic pH of the subsoil, or the lack of a significant subsoil microbial population, was inhibiting mineralisation was also examined by increasing soil pH from 4.4 to 7.0, and inoculating the subsoil with surface soil microorganisms during waterlogged incubations. Low concentrations of N, approximately 90 kg N/ha between 1.2 and 3 m, were found in the native vegetation root material. In addition, no net N mineralisation was observed in either the extended incubation of intact cores or in the control samples of the waterlogged incubations. Net N mineralisation was also not detected when the subsoil was amended with a source of organic N. Results indicate that this lack of mineralisation is largely due to pH inhibition of the microbial population. It is concluded that the mineralisation of either in situ organic material, or DON transported to the subsoil during leaching events, is unlikely to have significantly contributed to the subsoil NH4 accumulation at the study site.

High concentrations of ammonium (up to 0.1 cmol/kg) have been observed below 1 m depth in a Vertosol soil near Warra in south-eastern Queensland. This study examined whether ammonium leaching could be responsible for the ammonium accumulation observed in the Warra soil. This was done by using quantity/intensity (Q/I) relationships to compare the ammonium retention capacity of the Warra soil with other similar soils throughout the region that did not contain elevated subsoil ammonium concentrations. Analysis of Q/I curves revealed that in the concentration range studied, the amount of ammonium retained on high affinity adsorption sites in all 3 soils was low, and the Warra soil was not significantly different from the other 2 soils. The ability of the soils to retain ammonium in the soil solution against leaching [i.e. their potential buffer capacity (PBC)] did differ between soils and was greatest at Warra. This indicates that at any one time the Warra soil holds more ammonium on the exchange complex and less in solution than the other soils examined. It was concluded that ammonium is no more likely to leach through the surface horizons of the Warra soil than the other soils examined. Indeed, the data indicated that the Warra soil probably has greater capacity to retain ammonium against leaching due to its greater PBC. Consequently, it is considered unlikely that leaching of ammonium has been a major contributor to the subsoil ammonium concentrations at Warra.

High concentrations of ammonium (up to 270 kg N/ha) have been observed in a Vertisol soil below 1 m depth near Warra in south-east Queensland. This study examined the possibility that increased water movement into the subsoil after the removal of native vegetation, and a subsequent increase in periods of waterlogging, could have triggered nitrate ammonification and be responsible for the production of ammonium. Two incubation experiments were conducted to test this hypothesis. The first involved the incubation of repacked cores that had been amended with 30 mg N/kg of 5 atom% 15N nitrate under low oxygen conditions for a period of 360 days. Over this time period the 15N enrichment of the exchangeable ammonium fraction was monitored in order to detect any reduction of nitrate to ammonium. The second experiment involved the incubation of soil amended with 30 mg N/kg of 5 atom% 15N nitrate under waterlogged and low oxygen conditions for 75 days. During this period the redox potential of the soil was monitored using a field test to determine if reducing conditions would develop in this soil over a period of waterlogging, combined with the monitoring of any nitrate reduction to ammonium. The results of these experiments indicated that a small amount of nitrate ammonification (

Improvements to peroxide oxidation methods for analysing acid sulfate soils (ASS) are introduced. The soil solution ratio has been increased to 1 : 40, titrations are performed in suspension, and the duration of the peroxide digest stage is substantially shortened. For 9 acid sulfate soils, the peroxide oxidisable sulfur value obtained using the improved method was compared with the reduced inorganic sulfur result obtained using the chromium reducible sulfur method. Their regression was highly significant, the slope of the regression line was not significantly different (P = 0.05) from unity, and the intercept not significantly different from zero. A complete sulfur budget for the improved method showed there was no loss of sulfur as has been reported for earlier peroxide oxidation techniques. When soils were very finely ground, efficient oxidation of sulfides was achieved, despite the milder digestion conditions. Highly sulfidic and organic soils were shown to be the most difficult to analyse using either the improved method or the chromium method. No single analytical method can be universally applied to all ASS, rather a suite of methods is necessary for a thorough understanding of many ASS. The improved peroxide method, in combination with the chromium method and the 4 M HCl extraction, form a sound platform for informed decision making on the management of acid sulfate soils.

Improvements to the routine methods for the determination of actual acidity in suspension for acid sulfate soils (ASS) are introduced. The titratable sulfidic acidity (TSA) results using an improved peroxide-based method were compared with the theoretical acidity predicted by the chromium reducible sulfur method for 9 acid sulfate soils. The regression between these 2 measures of sulfidic acidity was highly significant, the slope of the regression line not significantly different from unity (P = 0.05) and the intercept not significantly different from zero. This contrasts with results of other workers using earlier peroxide oxidation methods, where TSA substantially underestimated the theoretical acidity predicted by reduced inorganic sulfur analysis. Comparison was made between the 2 principal measurements from the improved peroxide method (TSA and SPOS), with SPOS converted to theoretical sulfidic acidity to allow comparison. The relationship between these 2 measurements was highly significant. The effects of titration in suspension, as well as raising titration end points to pH 6.5, were investigated, principally with respect to the titratable actual acidity (TAA) result. TAA results obtained by KCl extraction were compared with those obtained using BaCl2, MgCl2, and water extraction. TAA in 1 M KCl suspensions titrated to pH 6.5 agreed well with titratable actual acidity measured using the 25-h extraction approach of the Lin et al. (2000a) BaCl2 method. Both BaCl2 and KCl solutions were ineffective at fully recovering acidity from synthetic jarosite without repeated extraction and titration. The application of correction factors for the estimation of total actual acidity in ASS is not supported by the results of this investigation. Acid sulfate soils that contain substantial quantities of jarosite or other acid-producing but relatively insoluble sulfate minerals continue to prove problematic to chemically analyse; however, an approach for estimating this component is discussed.

Unusually high concentrations of ammonium have been observed in a Vertisol below 1 m depth in south-east Queensland. This study investigated the possibility that an absence of nitrification is allowing this ammonium to accumulate and persist over time, and examined the soil environmental characteristics that may be responsible for limiting nitrifying organisms. The possibility that anaerobiosis, soil acidity, soil salinity, low organic carbon concentrations, and/or an absence of active nitrifying microorganisms were responsible for limiting nitrification was examined in laboratory and field studies. The presence/absence of anaerobic conditions was determined qualitatively using a field test to give an indication of electron lability. In addition, an incubation study was conducted and soil environmental conditions were improved for nitrifying organisms by adjusting the pH from 4.4 to 7, adjusting the electrical conductivity from 1.6 to 0.5 dS/m, amending with a soluble carbon substrate at a rate of 500 mg/kg, and using microorganisms from the surface horizon to inoculate to the subsoil. Over a 180-day period no nitrification was detected in the control samples from the incubation study, indicating that an extremely low rate of nitrification is likely to be responsible for allowing ammonium to accumulate in this soil. Analysis of the effect of soil environmental conditions on nitrification revealed that anaerobic conditions did not exist at depth and that pH, EC, organic carbon, and inoculation treatments added in isolation had no effect on nitrification. However, when inoculum was added to the soil in combination with pH, a significant increase in nitrification was observed, and the greatest amount of nitrification was observed when inoculum, pH, and EC treatments were added in combination. It was concluded that the reason for the low rate of nitrification in this soil is primarily the absence of a significant population of active nitrifying microorganisms, which may have been unable to colonise the subsoil environment due to its acidic, and to a lesser extent, its saline environment.

The brown kandosol soils at Weipa, North Queensland, contain little soil phosphorus (P). Plant-available fractions (considered in this study to include resin, hydroxide, and dilute acid extractable P) approximate 85 ˜g P/g, or 70% of total soil P, the majority of which is in labile organic forms, highlighting the importance of P cycling within the native eucalypt forest. A field experiment was undertaken to evaluate the effect of soil handling during bauxite mining on the distribution of P between the various soil fractions. This study showed that soil stripping and replacement disrupts the P cycle and affects the proportional distribution of P between soil fractions. Horizon mixing during soil handling severely reduces the size of plant-available soil P fractions in surface soils ( 0–5 cm depth) and this can only be partially compensated by the addition of fertiliser. A survey of rehabilitated sites of differing ages showed that restoration of soil organic P fractions is extremely slow, with the overall distribution of P within replaced soils remaining different from that within undisturbed soils 15 years after rehabilitation to native forest or exotic pasture species.

Exchange and solution phase characteristics were evaluated on surface and subsoil horizons of 60 acid, highly weathered soils in the unamended state, and on 39 of the surface horizons following addition of CaCO3 or CaSO4.2H2O. Soil solutions from unamended surface samples were dominated by Na (median concentration 0.65 mM), while the other major cations were present at lower levels (median concentrations: Ca, 0.09; Mg, 0.14; K, 0.28 mM). This pattern was more pronounced in the subsoil samples where the median concentrations of the nutrient cations were < 0.05 mM, whereas the median concentration of Na was 0.28 mM. The cation exchange capacity of surface samples was dominated by Ca, Mg and Al, while Al was the major exchangeable cation in the subsoil. Addition Of CaSO4.2H2O decreased soil solution pH and increased electrical conductivity and the concentration of Ca, Mg, Na, K and Al in the soil solution. The soil solution pH change resulting from CaSO4.2H2O addition could not be predicted on the basis of the characteristics of the soil in the unamended state.

Short term root growth bioassays using mungbean (Vigna radiata (L.) Wilczek) were conducted on 39 surface soils in the unamended state and following the addition of CaCO3 or CaSO4.2H2O. Root length after 48 h growth was related to solid phase and soil solution Ca and Al attributes. Suitable diagnostic indices for the prediction of Ca limitations to root growth were either Ca saturation of the cation exchange capacity or Ca activity ratio (CAR) defined as the ratio of the activity of ca2+ in the soil solution to the summed activities of Ca2+, Mg2+, Na+, K+ and Al3+. Values corresponding to 90% relative root length were 34% for Ca saturation and 0.10 for CAR. The activities of Al3+ and AlOH2+ were the Al attributes most strongly correlated with root growth; an Al3+ activity of 1.9 �m~ and an AlOH2+ activity of 0.46 �m corresponded to 90% relative root length. The results suggest that organically complexed Al and the ion pairs Al(OH)+2, Al(OH)04 and AlSO+4 are not plant-toxic. The most effective diagnostic criterion for A1 toxicity in this study was the calcium-aluminium balance (CAB), defined as 2 log(Ca2+) - 6 log(Al3+). The CAB value corresponding to 90% relative root length was 31. The correlation between root growth and CAB was further improved by inclusion of a pH term; this may indicate toxic effects of H+ per se.

Soil solid phase and soil solution characteristics were evaluated on surface and subsoil horizons of 60 acid, highly weathered soils in the unamended state, and on a subset of 39 surface horizons following the addition of CaSO4.2H2O. The activity of Al3+ Was found to be strongly correlated with the soil solution pH, with Al3+ activity increasing as pH decreased. For surface soils in the unamended state, and for the majority of subsoils, the Al3+ activity calculated was comparable to the theoretical activity supported by the dissolution of gibbsite (Al2O3.3H2O). The Al3+ activity in CaSO4.2H2O-amended samples tended to fall below that maintained by gibbsite dissolution and was more closely correlated with the Al3+ activity supported by the dissolution of jurbanite (AlSO4 (OH).5H2O).

Soil solutions were extracted from surface and subsoil samples of highly weathered soils in the field moist state and from air-dry samples which had been re-wet and incubated at 28�C for 1 to 64 days. Soil solutions were analysed following filtration through 0.22 pm and 0-025 �m pore-diameter hembranes. Selected samples were also incubated following sterilization by gamma irradiation (50 kGy) to investigate the effects of microorganisims on soil solution C dynamics. Ultra-filtration did not affect the concentration of the major cations or anions but significantly reduced Al, Fe, Mn, Si and organic C concentration in some surface soil solutions extracted from field-moist samples and from re-wet air-dry samples after short incubation periods. The organically-complexed Al concentration in soil solution was significantly increased by air-drying and re-wetting soil; the organic Al concentration decreased with increased time of incubation to levels comparable with that present in field-moist samples. Inorganic monomeric Al reached a stable concentration, comparable with that in field moist samples, when air-dry soils were re-wet and incubated for 1 day. While gamma irradiation effectively sterilized the soil and stabilized the concentration of Al and organic C in solution, the magnitude of the changes in soil solution composition observed as a result of irradiation diminish the value of this finding.

Land disposal of secondary treated sewage effluent is being widely adopted in Australia as an alternative to tertiary treatment. At the Cleveland Waste Water Pollution Control Works, effluent has been applied to a Hapludalf at high rates (3000 mm yr) for more than 20 yr, adding an estimated 4.5 t P ha to the soil. Thus, this site provides an opportunity to assess the retention of P under conditions typical of southeast Queensland. Laboratory chemical fractionation and P sorption studies of effluent irrigated and control sites were undertaken to determine the amount and forms of P retained within this soil and its capacity to retain further P. Organic material (peat) which had accumulated on the surface of effluent irrigated plots, was also sampled and its P content determined. Accumulation of P was limited to the sandy surface soil, increasing total soil P content by ≈ 700 kg ha, with this increase being approximately evenly distributed between inorganic and organic pools. The excessive irrigation rate used on this site, and the management adopted, has resulted in a marked podzolization of the surface horizon, apparent in reduced extractable Fe and Al concentrations. The removal of these P adsorbing materials would contribute, along with P saturation and organic ligand competition, to the much lower P sorption capacity of irrigated sites relative to the control. The largest P pool was found to be the peat layer, containing approximately 1500 kg P ha. On this site P has accumulated principally in organic forms, both within the soil and as peat on its surface. This finding throws into question the common practice of predicting disposal scheme life on the basis of P adsorption curves.

Soil solutions were extracted by immiscible liquid displacement with trichlorotrifluoroethane and by centrifuge drainage from surface and subsoil samples having a wide range of chemical and physical properties. Extractions were performed on field-moist samples and on air-dry samples which were re-wetted to different matric suctions and for different lengths of time. The composition of the soil solution obtained was the same with both methods of extraction when samples had been pre-wet to a matric suction of 0-1 bar. Immiscible liquid displacement extracted solution from a krasnozem surface soil at suctions as great as 15 bar; in contrast, centrifuge drainage failed to extract solution from this soil at >3 bar. The concentration of ions in solutions extracted by displacement from soils with increasing matric suction rose to a far greater extent than that anticipated if concentration was the only mechanism operating. In re-wet air-dry samples, major cations and anions were at equilibrium levels in solution after incubation for 1 day; longer incubation times resulted in an artificial elevation of ionic strength through mineralization of organic matter in some surface samples. The levels achieved after 1 day were similar to those present in solutions extracted from field-moist samples.