969 resultados para Partial cation exchange


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The optimum parameters for synthesis of zeolite NaA based on metakaolin were investigated according to results of cation exchange capacity and static water adsorption of all synthesis products and selected X-ray diffraction (XRD). Magnetic zeolite NaA was synthesized by adding Fe3O4 in the precursor of zeolite. Zeolite NaA and magnetic zeolite NaA were characterized with scanning electron microscopy (SEM) and XRD. Magnetic zeolite NaA with different Fe3O4 loadings was prepared and used for removal of heavy metals (Cu2+, Pb2+). The results show the optimum parameters for synthesis zeolite NaA are SiO2/Al2O3 = 2.3, Na2O/SiO2 = 1.4, H2O/Na2O = 50, crystallization time 8 h, crystallization temperature 95 �C. The addition of Fe3O4 makes the NaA zeolite with good magnetic susceptibility and good magnetic stability regardless of the Fe3O4 loading, confirming the considerable separation efficiency. Additionally, Fe3O4 loading had a little effect on removal of heavy metal by magnetic zeolite, however, the adsorption capacity still reaches 2.3 mmol g�1 for Cu2+, Pb2+ with a removal efficiency of over 95% in spite of 4.7% Fe3O4 loading. This indicates magnetic zeolite can be used to remove metal heavy at least Cu2+, Pb2+ from water with metallic contaminants and can be separated easily after a magnetic process.

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Water and ammonium retention by sandy soils may be low and result in leaching of applied fertiliser. To increase water and nutrient retention, zeolite is sometimes applied as a soil ameliorant for high value land uses including turf and horticulture. We have used a new modified kaolin material (MesoLite) as a soil amendment to test the efficiency of NH4+ retention and compared the results with natural zeolite. MesoLite is made by caustic reaction of kaolin at temperature between 80-95°C; although it has a moderate surface area, its cation exchange capacity is very high;(SA=13m2/g,CEC=500meq/100g). A 13cm tall sand column filled with ~450g of sandy soil homogeneously mixed with 1, 2, 4, and 8g of MesoLite or natural zeolite per 1kg of soil was prepared. After saturation with local bore water, concentrated ammonium sulfate solution was injected at the base. Then, bore water was passed from bottom to top through the column at amounts up to 6 pore volumes and at a constant flow rate of 10ml/min using a peristaltic pump. Concentrations of leached NH4+ were determined using an AutoAnalyser. The concentration of NH4+ leached from the column with 0.4% MesoLite was greatly (90%) reduced relative to unamended soil. Under these conditions NH4+ retention by the soil-MesoLite mixture was 11.5 times more efficient than the equivalent soil-natural zeolite mixture. Glasshouse experiments conducted in a separate study show that NH4+ adsorbed by MesoLite is available to plants.

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Sandy soils have low nutrient holding capacity and high water conductivity. Consequently, nutrients applied as highly soluble chemical fertilisers are prone to leaching, particularly in heavily irrigated environments such as horticultural soils and golf courses. Amorphous derivatives of kaolin with high cation exchange capacity may be loaded with desired nutrients and applied as controlledrelease fertilisers. Kaolin is an abundant mineral, which can be converted to a meso-porous amorphous derivative (KAD) using facile chemical processes. KAD is currently being used to sequester ammonium from digester effluent in sewage treatment plants in a commercial environment. This material is also known in Australia by the trade name MesoLite. The ammonium-saturated form of KAD may be applied to soils as a nitrogen fertiliser. Up to 7% N can be loaded onto KAD by contacting it with high-ammonia concentration wastewater from sewerage treatment plants. This poster paper demonstrates plant uptake of nitrogen from KAD and compares its efficiency as a fertiliser with NH4SO4. Rye grass was grown in 1kg pots in a glass-house. Nitrogen was applied at a range of rates using NH4SO4 and two KAD materials carrying 7% and 3% nitrogen, respectively. All other nutrients were applied in adequate amounts. All treatments were replicated three times. Plants were harvested after four weeks. Dry mass and N concentrations were determined by standard methods. At all N application rates, ammonium-loaded KAD produced significantly higher plant mass than for NH4SO4. The lower fertiliser effectiveness of NH4SO4 is attributed to possible loss of some N through volatilisation. Of the two KAD types, the material with lower CEC value supported slightly higher plant yields. The KAD materials did not show any adverse effect on availability of trace elements, as evidenced by lack of deficiency symptoms and plant analyses. Clearly, nitrogen loaded on to KAD in the form of ammonium is likely to be protected from leaching, but is still available to plants. These data suggest that KAD-based fertilisers may be suitable substitutes for water soluble N, K and other cation fertilisers for leaching soils.

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Despite common knowledge that the metal content adsorbed by fine particles is relatively higher compared to coarser particles, the reasons for this phenomenon has gained little research attention. The research study discussed in the paper investigated the variations in metal content for different particle sizes of solids associated with pollutant build-up on urban road surfaces. Data analysis confirmed that parameters favourable for metal adsorption to solids such as specific surface area, organic carbon content, effective cation exchange capacity and clay forming minerals content decrease with the increase in particle size. Furthermore, the mineralogical composition of solids was found to be the governing factor influencing the specific surface area and effective cation exchange capacity. There is high quartz content in particles >150µm compared to particles <150µm. As particle size reduces below 150µm, the clay forming minerals content increases, providing favourable physical and chemical properties that influence adsorption.

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Fatty acid methyl ester (FAME) profiles, together with Biolog substrate utilization patterns, were used in conjunction with measurements of other soil chemical and microbiological properties to describe differences in soil microbial communities induced by increased salinity and alkalinity in grass/legume pastures at three sites in SE South Australia. Total ester-linked FAMEs (EL-FAMEs) and phospholipid-linked FAMEs (PL-FAMEs), were also compared for their ability to detect differences between the soil microbial communities. The level of salinity and alkalinity in affected areas of the pastures showed seasonal variation, being greater in summer than in winter. At the time of sampling for the chemical and microbiological measurements (winter) only the affected soil at site 1 was significantly saline. The affected soils at all three sites had lower organic C and total N concentrations than the corresponding non-affected soils. At site 1 microbial biomass, CO 2-C respiration and the rate of cellulose decomposition was also lower in the affected soil compared to the non-affected soil. Biomarker fatty acids present in both the EL- and PL-FAME profiles indicated a lower ratio of fungal to bacterial fatty acids in the saline affected soil at site 1. Analysis of Biolog substrate utilization patterns indicated that the bacterial community in the affected soil at site 1 utilized fewer carbon substrates and had lower functional diversity than the corresponding community in the non-affected soil. In contrast, increased alkalinity, of major importance at sites 2 and 3, had no effect on microbial biomass, the rate of cellulose decomposition or functional diversity but was associated with significant differences in the relative amounts of several fatty acids in the PL-FAME profiles indicative of a shift towards a bacterial dominated community. Despite differences in the number and relative amounts of fatty acids detected, principal component analysis of the EL- and PL-FAME profiles were equally capable of separating the affected and non-affected soils at all three sites. Redundancy analysis of the FAME data showed that organic C, microbial biomass, electrical conductivity and bicarbonate-extractable P were significantly correlated with variation in the EL-FAME profiles, whereas pH, electrical conductivity, NH 4-N, CO 2-C respiration and the microbial quotient were significantly correlated with variation in the PL-FAME profiles. Redundancy analysis of the Biolog data indicated that cation exchange capacity and bicarbonate-extractable K were significantly correlated with the variation in Biolog substrate utilization patterns.

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The study investigated the adsorption and bioavailability characteristics of traffic generated metals common to urban land uses, in road deposited solids particles. To validate the outcomes derived from the analysis of field samples, adsorption and desorption experiments were undertaken. The analysis of field samples revealed that metals are selectively adsorbed to different charge sites on solids. Zinc, copper, lead and nickel are adsorbed preferentially to oxides of manganese, iron and aluminium. Lead is adsorbed to organic matter through chemisorption. Cadmium and chromium form weak bonding through cation exchange with most of the particle sizes. Adsorption and desorption experiments revealed that at high metal concentrations, chromium, copper and lead form relatively strong bonds with solids particles while zinc is adsorbed through cation exchange with high likelihood of being released back into solution. Outcomes from this study provide specific guidance for the removal of metals from stormwater based on solids removal.

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The synthesis of organoclays (OC) by intercalation of quaternary ammonium cation (QAC) into expanding clay minerals, notably montmorillonite (Mt), has attracted a great deal of attention during the past two decades. The OC have also found applications in the manufacture of clay polymer nanocomposites (CPN) and environmental remediation. Despite the wealth of information that exists on the formation and properties of OC, some problems remain to be resolved. The present contribution is an attempt at clarifying two outstanding issues, based on the literature and experimental data obtained by the authors over the past years. The first issue concerns the relationship between the cation exchange capacity (CEC) of the Mt and the basal spacing of the OC which, in turn, is dependent on the concentration and the nature of the added QAC. At a concentration less than 1 CEC, organo-Mt (OMt) formed using the QAC with a short alkyl chain length with nc < 16 (e.g., dodecyl trimethylammonium) gives basal spacings of 1.4–1.6 nm that are essentially independent of the CEC. However, for long-chain QAC with nc ≥ 16 (e.g., hexadecyl trimethylammonium), the basal spacing varies with the QAC concentration. For Mt with a CEC of 80–90 meq/100 g, the basal spacing of the OC increases gradually with the CEC and shows a sudden (stepwise) increase to 3.2–3.8 nm at a QAC concentration of 1.5 CEC and to 3.5–4.0 nm at a concentration of 2.0 CEC. The second issue pertains to the “locking” effect in QAC- and silane-modified pillared interlayered clays (PILC) and Mt. For silylated Mt, the “locking” effect results from the covalent bonding of silane to two adjacent layers within a single clay mineral particle. The same mechanism can operate in silane-grafted PILC but in this case, the “locking” effect may primarily be ascribed to the pillaring of adjacent basal surfaces by metal hydr(oxides).

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Recently, studies have identified high zinc levels in various environmental resources, and excessive intake of zinc has long been considered to be harmful to human health. The aim of this research was to investigate the effectiveness of tricalcium aluminate (C3A) as a removal agent of zinc from aqueous solution. Inductively coupled plasma-atomic emission spectrometer (ICP-AES), X-ray diffraction (XRD) and scanning electron microscopy (SEM) have been used to characterize such removal behavior. The effects of various factors such as pH influence, temperature and contact time were investigated. The adsorption capacity of C3A for Zn2+ was computed to be up to 13.73 mmol g−1, and the highest zinc removal capacity was obtained when the initial pH of Zn(NO3)2 solution was between 6.0 and 7.0, with temperature around 308 K. The XRD analysis showed that the resultant products were ZnAl-LDHs. Combined with the analysis of solution component, it was proved the existence of both precipitation and cation exchange in the removal process. From the experimental results, it was clear that C3A could be potentially used as a cost-effective material for the removal of zinc in aqueous environment.

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Laboratory-based relationships that model the phytotoxicity of metals using soil properties have been developed. This paper presents the first field-based phytotoxicity relationships. Wheat(Triticum aestivum L) was grown at 11 Australian field sites at which soil was spiked with copper (Cu) and zinc (Zn) salts. Toxicity was measured as inhibition of plant growth at 8 weeks and grain yield at harvest. The added Cu and Zn EC10 values for both endpoints ranged from approximately 3 to 4760 mg/kg. There were no relationships between field-based 8-week biomass and grain yield toxicity values for either metal. Cu toxicity was best modelled using pH and organic carbon content while Zn toxicity was best modelled using pH and the cation exchange capacity. The best relationships estimated toxicity within a factor of two of measured values. Laboratory-based phytotoxicity relationships could not accurately predict field-based phytotoxicity responses.

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Negative potassium (K) balances in all broadacre grain cropping systems in northern Australia are resulting in a decline in the plant-available reserves of K and necessitating a closer examination of strategies to detect and respond to developing K deficiency in clay soils. Grain growers on the Red Ferrosol soils have increasingly encountered K deficiency over the last 10 years due to lower available K reserves in these soils in their native condition. However, the problem is now increasingly evident on the medium-heavy clay soils (Black and Grey Vertosols) and is made more complicated by the widespread adoption of direct drill cropping systems and the resulting strong strati. cation of available K reserves in the top 0.05-0.1 m of the soil pro. le. This paper reports glasshouse studies examining the fate of applied K fertiliser in key cropping soils of the inland Burnett region of south-east Queensland, and uses the resultant understanding of K dynamics to interpret results of field trials assessing the effectiveness of K application strategies in terms of K availability to crop plants. At similar concentrations of exchangeable K (K-exch), soil solution K concentrations and activity of K in the soil solution (AR(K)) varied by 6-7-fold between soil types. When K-exch arising from different rates of fertiliser application was expressed as a percentage of the effective cation exchange capacity (i.e. K saturation), there was evidence of greater selective adsorption of K on the exchange complex of Red Ferrosols than Black and Grey Vertosols or Brown Dermosols. Both soil solution K and AR(K) were much less responsive to increasing K-exch in the Black Vertosols; this is indicative of these soils having a high K buffer capacity (KBC). These contrasting properties have implications for the rate of diffusive supply of K to plant roots and the likely impact of K application strategies (banding v. broadcast and incorporation) on plant K uptake. Field studies investigating K application strategies (banding v. broadcasting) and the interaction with the degree of soil disturbance/mixing of different soil types are discussed in relation to K dynamics derived from glasshouse studies. Greater propensity to accumulate luxury K in crop biomass was observed in a Brown Ferrosol with a KBC lower than that of a Black Vertosol, consistent with more efficient diffusive supply to plant roots in the Ferrosol. This luxury K uptake, when combined with crops exhibiting low proportional removal of K in the harvested product (i.e. low K harvest index coarse grains and winter cereals) and residue retention, can lead to rapid re-development of stratified K profiles. There was clear evidence that some incorporation of K fertiliser into soil was required to facilitate root access and crop uptake, although there was no evidence of a need to incorporate K fertiliser any deeper than achieved by conventional disc tillage (i.e. 0.1-0.15 m). Recovery of fertiliser K applied in deep (0.25-0.3 m) bands in combination with N and P to facilitate root proliferation was quite poor in Red Ferrosols and Grey or Black Vertosols with moderate effective cation exchange capacity (ECEC, 25-35 cmol(+)/kg), was reasonable but not enough to overcome K deficiency in a Brown Dermosol (ECEC 11 cmol(+)/kg), but was quite good on a Black Vertosol (ECEC 50-60 cmol(+)/kg). Collectively, results suggest that frequent small applications of K fertiliser, preferably with some soil mixing, is an effective fertiliser application strategy on lighter clay soils with low KBC and an effective diffusive supply mechanism. Alternately, concentrated K bands and enhanced root proliferation around them may be a more effective strategy in Vertosol soils with high KBC and limited diffusive supply. Further studies to assess this hypothesis are needed.

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Radioactive particles from three locations were investigated for elemental composition, oxidation states of matrix elements, and origin. Instrumental techniques applied to the task were scanning electron microscopy, X-ray and gamma-ray spectrometry, secondary ion mass spectrometry, and synchrotron radiation based microanalytical techniques comprising X-ray fluorescence spectrometry, X-ray fluorescence tomography, and X-ray absorption near-edge structure spectroscopy. Uranium-containing low activity particles collected from Irish Sea sediments were characterized in terms of composition and distribution of matrix elements and the oxidation states of uranium. Indications of the origin were obtained from the intensity ratios and the presence of thorium, uranium, and plutonium. Uranium in the particles was found to exist mostly as U(IV). Studies on plutonium particles from Runit Island (Marshall Islands) soil indicated that the samples were weapon fuel fragments originating from two separate detonations: a safety test and a low-yield test. The plutonium in the particles was found to be of similar age. The distribution and oxidation states of uranium and plutonium in the matrix of weapon fuel particles from Thule (Greenland) sediments were investigated. The variations in intensity ratios observed with different techniques indicated more than one origin. Uranium in particle matrixes was mostly U(IV), but plutonium existed in some particles mainly as Pu(IV), and in others mainly as oxidized Pu(VI). The results demonstrated that the various techniques were effectively applied in the characterization of environmental radioactive particles. An on-line method was developed for separating americium from environmental samples. The procedure utilizes extraction chromatography to separate americium from light lanthanides, and cation exchange to concentrate americium before the final separation in an ion chromatography column. The separated radiochemically pure americium fraction is measured by alpha spectrometry. The method was tested with certified sediment and soil samples and found to be applicable for the analysis of environmental samples containing a wide range of Am-241 activity. Proceeding from the on-line method developed for americium, a method was also developed for separating plutonium and americium. Plutonium is reduced to Pu(III), and separated together with Am(III) throughout the procedure. Pu(III) and Am(III) are eluted from the ion chromatography column as anionic dipicolinate and oxalate complexes, respectively, and measured by alpha spectrometry.

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Nitrous oxide is the foremost greenhouse gas (GHG)generated by land-applied manures and chemical fertilisers (Australian Government 2013). This research project was part of the National Agricultural Manure Management Program and investigated the potential for sorbers (i.e. specific naturally-occurring minerals) to decrease GHG emissions from spent piggery litter (as well as other manures)applied to soils. The sorbers investigated in this research were vermiculite and bentonite. Both are clays with high cation exchange capacities, of approximately 100–150 cmol/kg Faure 1998). The hypothesis tested in this study was that the sorbers bind ammonium in soil solution thereby suppressing ammonia (NH3)volatilisation and in doing so, slowing the kinetics of nitrate formation and associated nitrous oxide (N2O) emissions. A series of laboratory, glasshouse and field experiments were conducted to assess the sorbers’ effectiveness. The laboratory experiments comprised 64 vessels containing manure and sorber/manure ratios ranging from 1 : 10 to 1 : 1 incorporated into a sandy Sodosol via mixing. The glasshouse trial involved 240 pots comprising manure/sorber incubations placed 5 cm below the soil surface, two soil types (sandy Sodosol and Ferrosol) and two different nitrogen (N) application rates (50 kg N/ha and 150 kg N/ha) with a model plant (kikuyu grass). The field trial consisted of 96, 2 m · 2 m plots on a Ferrosol site with digit grass used as a model plant. Manure/ sorber mixtures were applied in trenches (5 cm below surface) to these plots at increasing sorber levels at anNloading rate of 200 kg/ha. Gas produced in all experiments was plumbed into a purpose-built automated gas analysis (N2O, NH3, CH4, CO2) system. In the laboratory experiments, the sorbers showed strong capacity to decreaseNH3 emissions (up to 80% decrease). Ammonia emissions were close to the detection limit in all treatments in the glasshouse and field trial. In all experiments, considerable N2O decreases (>40%) were achieved by the sorbers. As an example, mean N2O emission decreases from the field trial phase of the project are shown in Fig. 1a. The decrease inGHGemissions brought about by the clays did not negatively impact agronomic performance. Both vermiculite and bentonite resulted in a significant increase in dry matter yields in the field trial (Fig. 1b). Continuing work will optimise the sorber technology for improved environmental and agronomic performance across a range of soils (Vertosol, Dermosol in addition to Ferrosol and Sodosols) and environmental parameters (moisture, temperature, porosity, pH).

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Land-applied manures produce nitrous oxide (N2O), a greenhouse gas (GHG). Land application can also result in ammonia (NH3) volatilisation, leading to indirect N2O emissions. Here, we summarise a glasshouse investigation into the potential for vermiculite, a clay with a high cation exchange capacity, to decrease N2O emissions from livestock manures (beef, pig, broiler, layer), as well as urea, applied to soils. Our hypothesis is that clays adsorb ammonium, thereby suppressing NH3 volatilisation and slowing N2O emission processes. We previously demonstrated the ability of clays to decrease emissions at the laboratory scale. In this glasshouse work, manure and urea application rates varied between 50 and 150 kg nitrogen (N)/ha. Clay : manure ratios ranged from 1 : 10 to 1 : 1 (dry weight basis). In the 1-year trial, the above-mentioned N sources were incorporated with vermiculite in 1 L pots containing Sodosol and Ferrosol growing a model pasture (Pennisetum clandestinum or kikuyu grass). Gas emissions were measured periodically by placing the pots in gas-tight bags connected to real-time continuous gas analysers. The vermiculite achieved significant (P ≤ 0.05) and substantial decreases in N2O emissions across all N sources (70% on average). We are currently testing the technology at the field scale; which is showing promising emission decreases (~50%) as well as increases (~20%) in dry matter yields. This technology clearly has merit as an effective GHG mitigation strategy, with potential associated agronomic benefits, although it needs to be verified by a cost–benefit analysis.

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This thesis deals with the response of biodegradation of selected anthropogenic organic contaminants and natural autochthonous organic matter to low temperature in boreal surface soils. Furthermore, the thesis describes activity, diversity and population size of autotrophic ammonia-oxidizing bacteria (AOB) in a boreal soil used for landfarming of oil-refinery wastes, and presents a new approach, in which the particular AOB were enriched and cultivated in situ from the landfarming soil onto cation exchange membranes. This thesis demonstrates that rhizosphere fraction of natural forest humus soil and agricultural clay loam soil from Helsinki Metropolitan area were capable of degrading of low to moderate concentrations (0.2 50 µg cm-3) of PCP, phenanthrene and 2,4,5-TCP at temperatures realistic to boreal climate (-2.5 to +15 °C). At the low temperatures, the biodegradation of PCP, phenanthrene and 2,4,5-TCP was more effective (Q10-values from 1.6 to 7.6) in the rhizosphere fraction of the forest soil than in the agricultural soil. Q10-values of endogenous soil respiration (carbon dioxide evolution) and selected hydrolytic enzyme activities (acetate-esterase, butyrate-esterase and β-glucosidase) in acid coniferous forest soil were 1.6 to 2.8 at temperatures from -3 to +30 °C. The results indicated that the temperature dependence of decomposition of natural autochthonous soil organic matter in the studied coniferous forest was only moderate. The numbers of AOB in the landfarming (sandy clay loam) soil were determined with quantitative polymerase chain reaction (real-time PCR) and with Most Probable Number (MPN) methods, and potential ammonium oxidation activity was measured with the chlorate inhibition technique. The results indicated presence of large and active AOB populations in the heavily oil-contaminated and urea-fertilised landfarming soil. Assessment of the populations of AOB with denaturing gradient gel electrophoresis (DGGE) profiling and sequence analysis of PCR-amplified 16S rRNA genes showed that Nitrosospira-like AOB in clusters 2 and 3 were predominant in the oily landfarming soil. This observation was supported by fluorescence in situ hybridization (FISH) analysis of the AOB grown on the soil-incubated cation-exchange membranes. The results of this thesis expand the suggested importance of Nitrosospira-like AOB in terrestrial environments to include chronically oil-contaminated soils.

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The presence of a gonadotropin receptor binding inhibitor in pooled porcine follicular fluid has been demonstrated. Porcine follicular fluid fractionation on DE-32 at near neutral pH, followed by a cation exchange chromatography on SPC-50 and Cibacron blue affinity chromatography, yielded a partially purified gonadotropin receptor binding inhibitor (GI-4). The partially purified GI binding inhibitor inhibited the binding of both 125I labelled hFSH and hCG to rat ovarian receptor preparation. SDS electrophoresis of radioiodinated partially purified GI followed by autoradiography made it possible to identify the binding component as a protein of molecular weight of 80000. Subjecting 125I labelled GI-4 to chromatography on Sephadex G-100 helped obtain a homogeneous material, Gl-5. The 125I labelled GI-5 exhibited in its binding to ovarian membrane preparations characteristics typical of a ligand-receptor interaction such as saturability, sensitivity to reaction conditions as time, ligand and receptor concentrations and finally displaceability by unlabelled inhibitor as well as FSH and hCG in a dose dependent manner. This material could bind ovarian receptors for both FSH and LH, its binding being inhibited by added FSH or hCG in a dose dependent manner.