Effect of chemical fertilizers on the fractionation of Cu,Cr and Ni in contaminated soil

Effect of chemical fertilizers (urea, NH₄Cl, Ca(NO₃)₂, KCl and KH₂PO₄) on the fractionation of Cu, Cr and Ni was studied by a 4-month incubation experiment. Using sequential extraction procedure, it was found that the application of fertilizers could change the distribution of Cu, Cr and Ni in the fractions of soil. Applying urea (CO(NH₂)₂) significantly decreased the concentrations of Cu, Cr and Ni in water soluble plus exchangeable (WE) fraction, but increased those in Fe–Mn oxides bound (FM) fraction (p < 0.01). However, application of NH₄Cl caused an increase in the WE fraction by 27.7% for Cu, 111.5% for Cr and 20.4% for Ni. The CO(NH₂)₂ raised the soil pH from 4.51 to 4.96, whereas NH₄Cl lowered the pH of soil by 0.44 units. The WE fraction of the three heavy metals was significantly increased, while the FM fraction was significantly decreased by adding KCl (p < 0.01). Moreover, the supply of KH₂PO₄ reduced the WE and carbonate bound (CB) fractions of Cu, Cr and Ni in the soil, however, it raised Cu and Ni in the residual (RS) fraction and Cr in the FM fraction. In addition, the mobility index indicated that KCl and NH₄Cl increased the mobility of Cu, Cr and Ni in the soil, whereas urea and KH₂PO₄ decreased the mobility of the three metals in the soil. These results suggest that applying chemical fertilizers does not only provide plant nutrients, but may also change the speciation and mobility of heavy metals in the soil.     

Synthesis of In‐House Produced Calibrated Silver Phosphate with a Large Range of Oxygen Isotope Compositions

The large range of stable oxygen isotope values of phosphate‐bearing minerals and dissolved phosphate of inorganic or organic origin requires the availability of in‐house produced calibrated silver phosphate of which isotopic ratios must closely bracket those of studied samples. We propose a simple protocol to synthesise Ag₃PO₄ in a wide range of oxygen isotope compositions based on the equilibrium isotopic fractionation factor and the kinetics and temperature of isotopic exchange in the phosphate–water system. Ag₃PO₄ crystals were obtained from KH₂PO₄ that was dissolved in water of known oxygen isotope composition. Isotopic exchange between dissolved phosphate and water took place at a desired and constant temperature into PYREX? tubes that were placed in a high precision oven for defined run‐times. Samples were withdrawn at desired times, quenched in cold water and precipitated as Ag₃PO₄. We provide a calculation sheet that computes the δ¹⁸O of precipitated Ag₃PO₄ as a function of time, temperature and δ¹⁸O of both reactants KH₂PO₄ and H₂O at t = 0. Predicted oxygen isotope compositions of synthesised silver phosphate range from ?7 to +31‰ VSMOW for a temperature range comprised between 110 and 130 °C and a range of water δ¹⁸O from ?20 to +15‰ VSMOW.     

Importance of submarine groundwater discharge as a source of nutrients for the Neuse River Estuary,North Carolina

Seepage rate and chemical composition of groundwater discharge entering the Neuse River Estuary (NRE) were quantified over an annual cycle from July 2005 through June 2006. Lee type seepage meters were deployed at eight locations within the NRE to quantify the amount of submerged groundwater discharge (SGD) entering the system. Sediment porewater nitrate (NO₃ ⁻), ammonium (NH₄ ⁺), and phosphate (PO₄ ⁻³) were also quantified at each of these locations to determine groundwater chemical composition. Seepage rates for the system ranged from 0.004 to 0.035 m³ m⁻² d⁻¹. Both the average and median value for the system-wide SGD were 0.01 m³ m⁻²d⁻¹. There were no significant differences between upstream and downstream seepage rates or between those at the north and south side of the estuary. Seepage rates varied greatly in time and space. Discharging groundwater was NO₃ ⁻ deplete but highly enriched in NH₄ ⁺. Porewater PO₄ ⁻³ levels varied but were usually present below Redfield values due to NH₄ ⁺ enrichment. SGD nutrient loading represented a small part of watershed nitrogen and phosphorus loading, 0.8% and 1.0%, respectively.     

Feasibility and cost of creating an iron-phosphate coating on pyrrhotite to prevent oxidation

 Acid mine drainage (AMD) occurs when sulfide minerals are exposed to an oxidizing environment. Most of the methods for preventing AMD are either short-term or high cost solutions. Coating with iron phosphate is a new technology for the abatement of AMD. It involves treating the sulfide with a coating solution composed of H₂O₂, KH₂PO₄, and sodium acetate as a buffer agent. The H₂O₂ oxidizes the sulfide surface and produces Fe³⁺ so that iron phosphate precipitates as a coating on the sulfide surface. Experiments performed under laboratory conditions prove that an iron phosphate coating can be established on pyrrhotite surfaces with optimal concentrations of the coating solution in the range of: 0.2M/0.01M H₂O₂, 0.2M KH₂PO₄, and 0.2M sodium acetate NaAc, depending on the experimental scale. Iron phosphate coating may be a long-term solution to the problem of AMD. The method would be easy to implement; the reagent cost, however, is not low enough, although it is lower than the conventional treatment with lime. Received: 30 March 1995 · Accepted: 6 September 1995     

Extraction and distribution of soil organic and inorganic selenium in coal mine environments of Wyoming, USA

 Selenium (Se), an animal toxicant and aquifer contaminant, occurs in coal mine environments of Wyoming. There is a paucity of information on solution-phase Se speciation in mine soils. The objectives of this study were to compare Se extraction efficiencies of various reagents and to characterize SeO^2– ₃ (selenite), SeO^2– ₄ (selenate) and organic Se components in these extracts. Forty coal mine soils were extracted using DI (deionized) water, hot water (0.1% CaCl₂), AB-DTPA, NaOH, and KH₂PO₄. Each solution was analyzed for total dissolved Se, and inorganic and organic Se fractions. Both inorganic and organic Se fractions were detected in the soil extracts. The order of Se (total, inorganic, and organic) extraction efficiency for different reagents was DI water < hot water < AB-DTPA < NaOH < KH₂PO₄. The inorganic–organic Se ratios in DI water, hot water, AB-DTPA, NaOH, and KH₂PO₄ extracts were 60 : 40, 26 : 74, 61 : 39, 87 : 13, and 52 : 48, respectively, indicating predominance of inorganic Se in all but the hot water extract. Selenite was the dominant inorganic species in AB-DTPA and KH₂PO₄ extracts, while SeO^2– ₄ was the major Se species in the DI water, hot water, and NaOH extracts. Significant correlations (P<0.01) were observed among extractable inorganic Se [NaOH and KH₂PO₄ (r=0.95); hot water and AB-DTPA (r=0.89)], total soluble Se [DI water with hot water (r=0.98) and AB-DTPA (r=0.95)], and Se species [SeO^2– ₃ in AB-DTPA with SeO^2– ₄ in NaOH (r=0.94) and SeO^2– ₃ in KH₂PO₄ (r=0.88)]. These correlations are indicative of Se extraction efficiency, thermodynamically predicted chemical transformations (such as oxidation of SeO^2– ₃ to SeO^2– ₄), and probable interconversions between the organic and inorganic Se fractions (r=0.70 in KH₂PO₄ extracts); as a whole the correlations can be used as statistical validations of possible geochemical processes. Received: 21 August 1995 · Accepted: 16 October 1995     

Phosphate pollution in the groundwater of lower Vamsadhara river basin, India

 The lower Vamsadhara river basin, spreading over an area of 817 sq.km in northern Andhra Pradesh, represents a typical rural setting. The occurrence of phosphorus-bearing minerals reported in literature, and the increasing application of phosphatic fertilizers in the area have prompted these studies. Water samples from 113 wells were analysed for Ca, Mg, Na, K, Cl, SO₄, HCO₃, F, NO₃ and PO₄. The results indicate the presence of phosphate in the groundwater ranged from 0.72 to 7.07 mg/l, which is beyond the limits recommended for domestic and water treatment purposes. Samples of soils and weathered rocks were analyzed for their water-soluble phosphate and other chemical parameters. The water-soluble phosphate in the widely used fertilizers of the area was determined. The spatial variation of phosphate in the aquifer and the soil leachate characteristics supplemented by the chemical equilibrium calculations clearly indicate the dominance of geological sources over the fertilizer sources in contributing PO₄ to the groundwaters. Received: 4 March 1996 / Accepted: 29 July 1996     

Phosphorus dynamics and corn growth under applications of corn stalks biochar in a clay soil

Biochar prepared from corn stalks is used as a source of phosphorus in this study. The hypotheses were to investigate effects of biochar applications in clay soil on availability, changes of phosphorus pools and maximum adsorption of phosphorus as well as corn growth. The soil was placed in plastic pots with each contains 3 kg of this soil. Biochar was added at levels of 0 (control), 6.5 (B₁), 19 (B₂), and 38 (B₃) g pot^?1. In this experiment, the pot was planted with corn (Zea mays). The results of this study revealed that the biochar application enhanced available phosphorus (Olsen-P) from 11.51 to 17.10 mg kg^?1. Adding biochar significantly increased the amount of NH₄Cl-P, NaHCO₃-P_o, and NaOH I-P_o fractions (p?≤?0.05), but it significantly decreased HCl-P_i fraction (p?≤?0.05). Addition of biochar at the highest level increased the fresh and dry matter productions by up to about 75 and 48.7%, respectively, compared to the control. The phosphorus uptake by corn plants significantly increased with increasing levels of biochar. The removal efficiency (% sorption) and maximum adsorption (b) of phosphorus increased with increasing level of biochar addition compared to control. Consequently, it is recommended to add biochar produced from corn stalks to the soil in order to substitute phosphate fertilizers.     

Specific affinity for phosphate uptake and specific alkaline phosphatase activity as diagnostic tools for detecting phosphorus-limited phytoplankton and bacteria

We analyzed responses of soluble reactive phosphorus (SRP), bioavailable phosphate (PO₄), particulate phosphorus, turnover time of orthophosphate (T_t), and alkaline phosphatase activity (APA) to varying degrees of nutrient stress. The nutrient stress was evoked by different treatments in concentration and combination of inorganic nitrogen (N) and phosphorus (P), and labile organic carbon (glucose) to mesocosms in experiments carried out in eutrophic southern (Odense Fjord, Denmark) and northern (Tvärminne Archipelago, Finland) coastal zones of the Baltic Sea. Despite seasonal and geographical differences, similar responses were observed in both experiments. Low SRP (<100 nmol l^?1), shortT _t (<10 h), and increased levels of APA were observed in both N+P balanced and P deficient treatments, while the opposite trend was observed in P replete treatments. The shortestT _t and the highest APA were found when glucose was combined with N treatment. Bioavailable PO₄ was estimated usingT _t and P uptake rates as derived from stoichiometric conversion of carbon based primary and bacterial production. With shorterT _t, the PO₄ pool declined to <1 nmol-P l^?1, whereas the SRP background pool (difference between SRP and PO₄) remained relatively constant (c. 50 nmol l^?1). APA was inversely related to PO₄ but not to SRP. Responses of specific APA and specific affinity for PO₄ uptake, which are APA and PO₄ uptake rates (inverse ofT _t), respectively, normalized to the summed P biomass of phytoplankton and bacteria, responded consistently to the pattern and magnitude of nutrient limitation evoked in our experiments. Our results, together with a literature survey, suggest that both parameters can be useful in examining PO₄ availability for the natural phytoplankton and bacteria community in P starved aquatic systems.     

Acidification processes and soil leaching influenced by agricultural practices revealed by strontium isotopic ratios

In natural river systems, the chemical and isotopic composition of stream- and ground waters are mainly controlled by the geology and water-rock interactions. The leaching of major cations from soils has been recognized as a possible consequence of acidic deposition from atmosphere for over 30 years. Moreover, in agricultural areas, the application of physiological acid fertilizers and nitrogen fertilizers in the ammonia form may enhance the cation leaching through the soil profile into ground- and surface waters. This origin of leached cations has been studied on two small and adjacent agricultural catchments in Brittany, western France. The study catchments are drained by two first-order streams, and mainly covered with cambisoils, issued from the alteration and weathering of a granodiorite basement. Precipitations, soil water- and NH₄ acetate-leachates, separated minerals, and stream waters have been investigated. Chemical element ratios, such as Ba/Sr, Na/Sr and Ca/Sr ratios, as well as Sr isotopic ratios are used to constrain the relative contribution from potential sources of stream water elements.Based on Sr isotopic ratio and element concentration, soil water- and NH₄ acetate leaching indicates (1) a dominant manure/slurry contribution in the top soil, representing a cation concentrated pool, with low ⁸⁷Sr/⁸⁶Sr ratios; (2) in subsoils, mineral dissolution is enhanced by fertilizer application, becoming the unique source of cations in the saprolite. The relatively high weathering rates encountered implies significant sources of cations which are not accessory minerals, but rather plagioclase and biotite dissolution.Stream water has a very different isotopic and chemical composition compared to soil water leaching suggesting that stream water chemistry is dominated by elements issued from mineral and rock weathering. Agriculture, by applications of chemical and organic fertilizers, can influence the export of major base cations, such as Na⁺. Plagioclase dissolution, rather than anthropogenically controlled soil water, seems to be the dominant source of Na⁺ in streams. However, Ca²⁺ in streams is mostly derived from slurries and manures deposited on top soils, and transferred into the soil ion-exchange pool and stream waters. Less than 10% of Na⁺, 5-40% of Sr²⁺ and 20-100% of Ca²⁺ found in streams can be directly derived from the application of organic fertilizers.     

Phosphorous concentration,solubility and species in the groundwater in a semi-arid basin,southern Malayer,western Iran

In areas of intensive crop production, continual phosphorous (P) applications as P fertilizer and farmyard manure have been made at levels exceeding crop requirement. As a result, surface soil accumulations of P have occurred to such an extent that loss of P in surface runoff and a high risk for P transfer into groundwater in concentrations exceeding the groundwater quality standard has become a priority management concern. Phosphorous content of groundwater was determined in order to examine dissolved P concentration and species in the groundwater and mineral solubilitiy in a semi-arid region of southern Malayer, western Iran. The speciation for P in groundwater was calculated using geochemical speciation model PHREEQC. The concentration of total P in the groundwater (0.01–2.56 mg P l⁻¹) and estimated concentrations of HPO₄ ²⁻ (49.5–89%), H₂PO₄ ⁻ (1.5–17.3%), CaHPO₄ ⁺ (5.7–36.1%), and CaPO₄ ⁻ (1.4–12.2%) varied considerably amongst the groundwater. Results suggest that the concentration of P in the groundwater could be primarily controlled by the solubility of octacalcium phosphate and β-tricalcium phosphate. Large amounts of P fertilizer, inadequate management of P fertilization, and low irrigation efficiency, coupled with sandy soils in some parts of the study area could be mainly responsible for the greater P in the groundwater. In general, the greater the dissolved P concentration in the groundwater, the closer the solution was to equilibrium with respect to the more soluble Ca-phosphate minerals. The groundwater P content could be potentially used to identify areas where management approaches, such as P applied and crop type planted, could be adjusted to different types of soils, geology and topography.     

Phosphate amendment of metalliferous waste rocks, Century Pb-Zn mine, Australia: Laboratory and field trials

The aim of the study was to determine whether the application of phosphate compounds (phosphorite rock, phosphate fertilizer) to polyminerallic waste rocks can inhibit sulfide oxidation and metal mobility (Cu, Pb, Zn, Cd, Ni, Mn, Mg). Waste rocks comprised sulfidic carbonaceous shales and were sourced from the Century Pb-Zn mine, NW Queensland, Australia. The acid producing, Pb-Zn rich rocks consisted of major quartz, muscovite/illite, dolomite, siderite and kaolinite as well as smaller amounts of sulfide minerals (e.g. galena, sphalerite, pyrite). Laboratory leach experiments were conducted on finely granulated phosphate-treated waste rocks (>2 to <30 mm) over 13 weeks, whereas phosphate amendment of coarsely granulated waste rocks (sand to boulder size) was investigated using heap leach piles at the mine site over an 11 months period. Results of the laboratory experiments demonstrate that the treatment of finely granulated waste rocks with phosphorite rock produced leachates with near-neutral pH values due to calcite dissolution. This in turn did not allow the leaching of apatite, formation of secondary phosphate phases and phosphate stabilization to occur. Metal mobility in these amended wastes was restricted by the dissolution of calcite and the resultant near-neutral pH conditions. By contrast, the application of the water-soluble phosphate fertilizer MKP (KH₂PO₄) to polyminerallic sulfidic waste rocks during the short-term laboratory experiments led to the formation of phosphate coatings and precipitates and inhibited acid and metal release (Cd, Mn, Ni, Pb, Zn). At least in the short term, the application of phosphate fertilizers proved to be an effective method. However, results of the long-term field trials demonstrate that coarsely granulated waste rocks were not coated by secondary phosphate phases and that amendment by phosphorite rock or superphosphate fertilizer did not improve leachate quality compared to the unamended waste. Thus, phosphate stabilization appears ineffective in suppressing oxidation of sulfides in coarsely granulated mine wastes.     

The influence of topography and land use on water quality of Xiangxi River in Three Gorges Reservoir region

A self-organizing map (SOM) was used to cluster the water quality data of Xiangxi River in the Three Gorges Reservoir region. The results showed that 81 sampling sites could be divided into several groups representing different land use types. The forest dominated region had low concentrations of most nutrient variables except COD, whereas the agricultural region had high concentrations of NO₃N, TN, Alkalinity, and Hardness. The sites downstream of an urban area were high in NH₃N, NO₂N, PO₄P and TP. Redundancy analysis was used to identify the individual effects of topography and land use on river water quality. The results revealed that the watershed factors accounted for 61.7% variations of water quality in the Xiangxi River. Specifically, topographical characteristics explained 26.0% variations of water quality, land use explained 10.2%, and topography and land use together explained 25.5%. More than 50% of the variation in most water quality variables was explained by watershed characteristics. However, water quality variables which are strongly influenced by urban and industrial point source pollution (NH₃N, NO₂N, PO₄P and TP) were not as well correlated with watershed characteristics.     

Effects of stormwater nutrient discharges on eutrophication processes in nearshore waters of the Florida keys

Rainfall events cause episodic discharges of groundwaters contaminated with septic tank effluent into nearshore waters of the Florida keys, enhancing eutrophication in sensitive coral reef communities. Our study characterized the effects of stormwater discharges by continuously (30-min intervals) measuring salinity, temperature, tidal stage, and dissolved oxygen (DO) along an offshore eutrophication gradient prior to and following heavy rainfall at the beginning of the 1992 rainy season. The gradient included stations at a developed canal system (PP) on Big Pine Key, a seagrass meadow in a tidal channel (PC), a nearshore patch reef (PR), a bank reef at Looe Key National Marine Sanctuary (LK), and a blue water station (BW) approximately 9 km off of Big PIne Key. Water samples were collected at weekly intervals during this period to determine concentrations of total nitrogen (TN), ammonium (NH₄ ⁺), nitrate plus nitrite NO₃ ^? plus NO₂ ^?), total phosphorus (TP), total dissolved phosphorus (TDP), soluble reactive phosphorus (SRP), and chlorophyll a (chl a). Decreased salinity immediately followed the first major rainfall at Big Pine Key, which was followed by anoxia (DO <0.1 mg I^?1), high concentrations of NH₄ ⁺ (≈24 μM), TDP (≈1.5 μM), and chl a (≈20 μg I^?1). Maximum concentration of TDP (≈0.30 μM) also followed the initial rainfall at the PC, PR, and LK stations. In contrast, NH₄ ⁺ (≈4.0 μM) and chl a (0.45 μg I^?1) lagged the rain event by 1–3 wk, depending on distance from shore. The highest and most variable concentrations of NH₄ ⁺, TDP, and chl a occurred at PP, and all nutrient parameters correlated positively with rainfall. DO at all stations was positively correlated with tide and salinity and the lowest values occurred during low tide and low salinity (high rainfall) periods. Hypoxia (DO <2.5 mg I^?1) was observed at all stations follwing the stormwater discharges, including the offshore bank reef station LK. Our study demonstrated that high frequency (daily) sampling is necessary to track the effects of episodic rainfall events on water quality and that such effects can be detected at considerable distances (12 km) from shore. The low levels of DO and high levels of nutrients and chl a in coastal waters of the Florida Keys demand that special precautions be exercised in the treatment and discharge of wastewaters and land-based runoff in order to preserve sensitive coral reef communities.     

Urban land-use effects on groundwater phosphate distribution in a shallow aquifer, Nanfei River basin, China

Groundwater, surface water, soil and river sediment samples, and information on land use in the Nanfei River basin (NRB) of China have been analyzed to study the geochemistry, distribution, and mobilization of phosphorus. The distribution of phosphate (PO ₄ ^3??/sup> ) and the relationships between PO ₄ ^3??/sup> and several constituents in groundwater were studied. Partial correlation analysis relating PO ₄ ^3??/sup> to types of land use was conducted using the data analyzing tool SPSS 15.0. The processes controlling the transport of PO ₄ ^3??/sup> are discussed. The conclusions from this study are: (1) urban land use has obvious impact on PO ₄ ^3??/sup> in groundwater, the average concentration of PO ₄ ^3??/sup> being 4.37?mg/L, greater than that resulting from farmland and mixed land use, which have average PO ₄ ^3??/sup> concentrations of 0.10 and 0.18?mg/L, respectively; (2) the partial correlation between PO ₄ ^3??/sup> and types of land use is significant with a coefficient of 0.760; (3) the PO ₄ ^3??/sup> concentrations in surface water are generally higher than those in groundwater, and the total phosphorus (TP) concentrations in river sediments are generally higher than those in soil samples; (4) groundwater is a carrier of PO ₄ ^3??/sup> and is likely responsible for the redistribution of PO ₄ ^3??/sup> in different regions of NRB.     

Impact of Oyster Farming on Diagenetic Processes and the Phosphorus Cycle in Two Estuaries (Brittany,France)

This study aims to compare the impact of oyster cultures on diagenetic processes and the phosphorus cycle in the sediments of the Aber Benoît and the Rivière d’Auray, estuary of Brittany, France. Our results showed clear evidence of the seasonal impact of oyster cultures on sediment characteristics (grain size and organic matter parameters) and the phosphorus cycle, especially in the Aber Benoît. At this site, seasonal variations in sulfide and Fe concentrations in pore waters, as well as Fe–P concentrations in the solid phase, highlighted a shift from a system governed by iron reduction (Reference) to a system governed by sulfate reduction (beneath oyster). This could be partly explained by the increase in labile organic matter (i.e., biodeposits) beneath oysters, whose mineralization by sulfate led to high sulfide concentrations in pore waters (up to 4,475 µmol l^?1). In turn, sulfide caused an enhanced release of phosphate in the summer, as adsorption sites for phosphate decreased through the formation of iron–sulfide compounds (FeS and FeS₂). In the Aber Benoît, dissolved Fe/PO₄ ratios could be used as an indicator of phosphate release into oxic water. Low Fe/PO₄ ratios in the summer indicated higher effluxes of phosphate toward the water column (up to 47 µmol m^?2 h^?1). At other periods, Fe/PO₄ ratios higher than 2 mol/mol indicated very low phosphate fluxes. In contrast, in the Rivière d’Auray, the occurrence of macroalgae, stranding regularly all over the site, clearly masked the impact of oyster cultures on sediment properties and the phosphorus cycle and made the use of Fe/PO₄ ratios more difficult in terms of indicators of phosphate release.     

A geochemical model for evaluating theories on the genesis of Florida''s sedimentary phosphate deposits

Present ionic concentrations of Ca ⁺⁺,HCO ₃ ^- ,and HPO ₄ ⁼ in surface and groundwater runoff in Florida indicate that phosphorus is being concentrated in rock through dissolution and reprecipitation, with calcium phosphate increasing at the expense of calcium carbonate. Analog computer simulation of a systems model of this process suggests that significant enrichment can occur in 20 million years. The degree of enrichment depends on the supply of new phosphorus to Florida through rain and oceanic exchange processes. If the calcium phosphate content of original rock is 0.5 to 1.0 percent (0.52 to 1.05 percent P ₂ O ₅),a formation with 10 to 20 percent calcium phosphate (CaPO ₄ or 10.5 to 21.0 percent P ₂ O ₅)as in the Hawthorn Formation (Miocene)may result. Nutrient upwelling along the continental slope coupled with transport to the estuaries by lateral eddy diffusion can supply an additional 400 mg P|m ² |yr which, if deposited, would result in a sediment with a 4.3 percent CaPO ₄ (4.5 percent P ₂ O ₅)content. If this is enriched later by resolution, 40 percent CaPO ₄ (42 percent P ₂ O ₅)results. Through geologic time, the ocean may be considered as a source of phosphorus to the land through rain or estuarine sediment.     

Renewable, controlled and environmentally safe phosphorus release in soils from mixtures of NH4 +-phillipsite tuff and phosphate rocks

 The renewable and controlled-release fertilization system investigated here uses NH₄ ⁺-exchanged phillipsite tuff, from Jordan, to help in the dissolution of phosphate rock. Accordingly, controlled and renewable soluble nitrogen, phosphate and Ca are released as nutrients for plants. NH₄ ⁺ phillipsite can sequester Ca ions released by the dissolution of phosphate rock, therefore, leading to further phosphate rock dissolution. In this study the results show that the amount of phosphate released is more than that released by phosphate rock alone. This method offers an alternative to the use of highly soluble fertilizers and may avoid environmental problems associated with their extensive use in agriculture. Received: 22 May 1997 · Accepted: 12 August 1997     

A geochemical model for evaluating theories on the genesis of Florida's sedimentary phosphate deposits

Present ionic concentrations of Ca ⁺⁺,HCO ₃ ^- ,and HPO ₄ ⁼ in surface and groundwater runoff in Florida indicate that phosphorus is being concentrated in rock through dissolution and reprecipitation, with calcium phosphate increasing at the expense of calcium carbonate. Analog computer simulation of a systems model of this process suggests that significant enrichment can occur in 20 million years. The degree of enrichment depends on the supply of new phosphorus to Florida through rain and oceanic exchange processes. If the calcium phosphate content of original rock is 0.5 to 1.0 percent (0.52 to 1.05 percent P ₂ O ₅),a formation with 10 to 20 percent calcium phosphate (CaPO ₄ or 10.5 to 21.0 percent P ₂ O ₅)as in the Hawthorn Formation (Miocene)may result. Nutrient upwelling along the continental slope coupled with transport to the estuaries by lateral eddy diffusion can supply an additional 400 mg P|m ² |yr which, if deposited, would result in a sediment with a 4.3 percent CaPO ₄ (4.5 percent P ₂ O ₅)content. If this is enriched later by resolution, 40 percent CaPO ₄ (42 percent P ₂ O ₅)results. Through geologic time, the ocean may be considered as a source of phosphorus to the land through rain or estuarine sediment.     

Polycrystalline apatite synthesized by hydrothermal replacement of calcium carbonates

Aragonite and calcite single crystals can be readily transformed into polycrystalline hydroxyapatite pseudomorphs by hydrothermal treatment in a (NH₄)₂HPO₄ solution. Scanning electron microscopy of the reaction products showed that the transformation of aragonite to apatite is characterised by the formation of a sharp interface between the two phases and by the development of intracrystalline porosity in the hydroxyapatite phase. In addition, electron backscattered diffraction (EBSD) imaging showed that the c-axis of apatite is predominantly oriented perpendicular to the reaction front with no crystallographic relationship to the aragonite lattice. However, the Ca isotopic composition of the parent aragonite, measured by thermal ionization mass spectrometry was inherited by the apatite product.Hydrothermal experiments conducted with use of phosphate solutions prepared with water enriched in ¹⁸O (97%) further revealed that the ¹⁸O from the solution is incorporated in the product apatite, as measured by micro-Raman spectroscopy. Monitoring the distribution of ¹⁸O with Raman spectroscopy was possible because the incorporation of ¹⁸O in the PO₄ group of apatite generates four new Raman bands at 945.8, 932, 919.7 and 908.8 cm⁻¹, in addition to the ν₁(PO₄) symmetric stretching band of apatite located at 962 cm⁻¹, which can be assigned to four ¹⁸O-bearing PO₄ species. The relative intensities of these bands reflect the ¹⁸O content in the PO₄ group of the apatite product. By using equilibrated and non-equilibrated solutions, with respect to the ¹⁸O distribution between aqueous phosphate and water, we could show that the concentration of ¹⁸O in the apatite product is linked to the degree of ¹⁸O equilibration in the solution. The textural and chemical observations are indicative of a coupled mechanism of aragonite dissolution and apatite precipitation taking place at a moving reaction interface.     

Surface alteration of arsenopyrite (FeAsS) by Thiobacillus ferrooxidans

The surface of arsenopyrite was characterized after acidic, oxidative leaching in the presence of the bacterial species Thiobacillus ferrooxidans. Polished single-crystal grains of arsenopyrite were reacted for 1, 2, and 3 weeks with T. ferrooxidans suspended in a solution (pH 2.3) of essential salts (MgSO₄·7H₂O, [NH₄]₂SO₄, KH₂PO₄, and KCl). Abiotic control experiments were conducted in identical solutions. Reaction between arsenopyrite and T. ferrooxidans in the essential salts solution produced a uniform solid FePO₄ overlayer (∼0.2 μm thick) on the arsenopyrite surface within 1 week. The overlayer was detected visually by scanning electron microscopy (SEM) and chemically by X-ray photoelectron spectroscopy (XPS). It could not be distinguished by energy-dispersive X-ray analyses. No overlayer formed in the abiotic control. The uniform thickness and lateral continuity of the overlayer suggest an inorganic origin promoted by bacterial production of Fe³⁺. Iron released from arsenopyrite was oxidized by bacteria and subsequently precipitated with PO₄³⁻ (from the essential salts), forming ferric phosphate. After 2 and 3 weeks, SEM images revealed a roughened arsenopyrite surface, and XPS depth profiles indicated a progressively thicker phosphate overlayer and continued oxidation, diffusion, and dissolution of arsenopyrite beneath the overlayer. After only 1 week, the cells were isolated from the arsenopyrite surface by the uniform overlayer. Therefore, bacteria need not be attached to arsenopyrite to promote rapid reaction, and the mechanism of alteration at the arsenopyrite surface must have been inorganic. Because the delicate overlayer did not prevent continued alteration of arsenopyrite, FePO₄ may not be an effective barrier to oxidation in the tailings environment. The FePO₄ coating has likely formed in other experiments using these bacteria but was not detected because analytical techniques were not sufficiently surface sensitive to identify a separate, compositionally distinct overlayer. Some previous experimental results thus may be misleading or inapplicable to the tailings environment.