PO4 Concentration Research Articles

Absorption and Transport of Phosphorus in Nodulated Soybean Plants and Diagnosis of Phosphorus Status Using Xylem Sap Analysis

Phosphorus (P) is an essential major element for plants. The absorption and transport of P are important for soybean growth and yield, including nodule growth and N2 fixation. Through an analysis of xylem sap, we investigated how nodulated soybean plants absorb PO4 via the roots and transport it to the shoot. The nodulated soybean plants were treated with 0, 50, and 250 μM PO4 concentrations for 1, 3, 7, and 15 days. The PO4 concentration in the xylem sap significantly decreased after 1 day of P deprivation, and then it gradually decreased for 15 days. The high-concentration (250 μM PO4) treatment increased the PO4 concentrations in the xylem sap at 7- and 15-day timepoints but not at the 1- or 3-day timepoints. The soybean plants were treated with 0, 25, 50, 100, 150, 250, and 500 μM PO4 for 3 days. The PO4 absorption rate increased consistently in conjunction with the increase in the PO4 concentration; however, the PO4 concentrations in the xylem sap increased only from 0 to 50 μM PO4 but were constant under higher P concentrations. The soybean plants accumulated extra PO4 in the roots. The PO4 concentration in the xylem sap immediately reflected the P deficiency conditions; thus, this index may be used as an indicator for the diagnosis of P deficiency.

Screening redox stability of iron rich by-products for effective phosphate immobilisation in freshwater sediments

Iron (Fe) rich by-products can be added to lake or river sediments to immobilise phosphate (PO4) and lower eutrophication risks. These Fe materials differ in mineralogy and specific surface area, hence differing in PO4 sorption capacity and stability under reducing conditions. This study was set up to identify key properties of these amendments in their capacity to immobilise PO4 in sediments. Eleven Fe rich by-products, collected from drinking water treatment plants and acid mine drainage, were characterised. The PO4 adsorption to these by-products was first determined under aerobic conditions and the solid-liquid distribution coefficient KD for PO4 correlated strongly to oxalate extractable Fe content. A static sediment-water incubation test was subsequently used to evaluate the redox stability of these by-products. The reductive processes gradually released Fe to solution and more Fe was release from the amended than from the control sediments. The total Fe release to solution was positively related to ascorbate reducible Fe fractions in the by-products, suggesting that such fractions indicate potential loss of P retention capacity on the long term. The final PO4 concentration in the overlying water was 5.6 mg P L−1 in the control and was successfully lowered by factor 30–420 depending on the by-product. The factor by which solution PO4 was reduced in Fe treatments increased with increasing KD determined under aerobic conditions. This study suggests that efficient by-products to trap P in sediments are characterised by a high oxalate Fe content and a low reducible Fe fraction.

A new method for phosphate purification for oxygen isotope ratio analysis in freshwater and soil extracts using solid-phase extraction with zirconium-loaded resin.

Phosphate (PO4 ) oxygen isotope (δ18 OPO4 ) analysis is increasingly applied to elucidate phosphorus cycling. Due to its usefulness, analytical methods continue to be developed and improved to increase processing efficiency and applicability to various sample types. A new pretreatment procedure to obtain clean Ag3 PO4 using solid-phase extraction (SPE) with zirconium-loaded resin (ZrME), which can selectively adsorb PO4 , is presented and evaluated here. Our method comprises (1) PO4 concentration, (2) PO4 separation by SPE, (3) cation removal, (4) Cl- removal, and (5) formation of Ag3 PO4 . The method was tested by comparing the resulting δ18 OPO4 of KH2 PO4 reagent, soil extracts (NaHCO3 , NaOH, and HCl), freshwater, and seawater with data obtained using a conventional pretreatment method. PO4 recovery of our method ranged from 79.2% to 97.8% for KH2 PO4 , soil extracts, and freshwater. Although the recovery rate indicated incomplete desorption of PO4 from the ZrME columns, our method produced high-purity Ag3 PO4 and accurate δ18 OPO4 values (i.e., consistent with those obtained using conventional pretreatment methods). However, for seawater, the PO4 recovery was low (1.1%), probably due to the high concentrations of F- and SO4 2- which interfere with PO4 adsorption on the columns. Experiments indicate that the ZrME columns could be regenerated and used repeatedly at least three times. We demonstrated the utility of ZrME for purification of PO4 from freshwater and soil extracts for δ18 OPO4 analysis. Multiple samples could be processed in three days using this method, increasing sample throughput and potentially facilitating more widespread use of δ18 OPO4 analysis to deepen our understanding of phosphorus cycling in natural environments.

A new sampling method with zirconium‐loaded resin for phosphate oxygen isotope analysis in oligotrophic freshwater systems

The phosphate oxygen isotope ratio ( ) is a useful technique to trace the sources and biogeochemical cycles of phosphorus (P) in aquatic ecosystems. However, has not been widely used in oligotrophic freshwater systems due to technical and methodological difficulties in collecting sufficient phosphate (PO4 ) for the analysis, which sometimes requires hundreds of liters of the water sample. In this study, a new approach (PaS-Zir) was developed for the analysis in oligotrophic freshwater systems using zirconium (Zr)-loaded (ZrIRC) resin, which has a high affinity for PO4 . ZrClO2 was added to Amberlite IRC748 to obtain the ZrIRC resin. The adsorption/desorption experiment using KH2 PO4 with a known value of was conducted to determine the adsorption/desorption properties of the resin and the likelihood of isotopic fractionation. By installing mesh bags filled with the resin, the PaS-Zir approach was used in two rivers with low PO4 concentrations (0.2 and 5.3μmol/L). A conventional sampling method was also performed in the study river with a higher PO4 concentration to validate the efficacy of the PaS-Zir method. The adsorption/desorption experiment demonstrated that the ZrIRC resin possessed a sufficient adsorption capacity (153 μmol/resin-mL) and exhibited little isotopic fractionation during the adsorption/desorption processes. Using the PaS-Zir method, we were able to collect sufficient PO4 samples for the analysis from the rivers within at least 4 days of mesh bag installation. The values (14.2‰ ±0.2‰) obtained using the PaS-Zir method were comparable to those obtained using the conventional method (14.0‰ ±0.03‰). We proved that the PaS-Zir method is applicable to oligotrophic freshwater systems and is generally more efficient than the conventional method. In addition, our method is useful for improving the understanding of the P dynamics of oligotrophic ecosystems because of the extremely low concentration of PO4 commonly found in them, which are often prone to P pollution.

Drinking water services in the primary schools: evidence from coastal areas in Bangladesh

Salinity intrusion both in surface and groundwater caused a crisis for safe drinking water in coastal Bangladesh. The situation is even worse for children especially at school. However, information on water services in coastal schools is limited. Here we assess the quality of drinking water and supply infrastructures in the primary schools of a severely saline affected coastal area of Bangladesh. To fulfill the objective, thirty-eight schools were purposively selected and investigated in Dacope Upazila of Khulna district in Bangladesh. Findings revealed that harvested rainwater (63%) and pond (21%) are the major drinking water sources where countries’ leading water supply technology, tube well (16%) were the least used option. Moreover, salinity in all the tube wells exceeded the national standard. DO, pH, NO3, SO4 and PO4 concentration of all options satisfied national standards. However, total coliform counts exceeded the national standard. More than half of the samples had a low to high risk of indicator bacteria which is a major public health concern. Although 29% schools have installed portable water filtration units, those are grossly inaccessible for the students. Hence, students are reportedly consuming unsafe drinking water, and thus are vulnerable to water-borne diseases. The lack of resources and poorly designed infrastructure are the principal challenges to the safe drinking water supply. Therefore, disinfection at the point of use along with proper maintenance of the water infrastructure is urgent needs to safeguard potable water services in the primary schools of coastal Bangladesh.

Estimation of the natural background of phosphate in a lowland river using tidal marsh sediment cores

Abstract. Elevated phosphate (PO4) concentrations can harm the ecological status in water by eutrophication. In the majority of surface waters in lowland regions such as Flanders (Belgium), the local PO4 levels exceed the limits defined by environmental policy and fail to decrease, despite decreasing total phosphorus (P) emissions. In order to underpin the definition of current limits, this study was set up to identify the pre-industrial background PO4 concentration in surface water of the Scheldt River, a tidal river in Flanders. We used the sedimentary records preserved in tidal marsh sediment cores as an archive for reconstructing historical changes in surface water PO4. For sediment samples at sequential depths below the sediment surface, we dated the time of sediment deposition and analysed the extractable sediment P. The resulting time series of sediment P was linked to the time series of measured surface water-PO4 concentrations (data 1967–present). By combining those datasets, the sorption characteristics of the sediment could be described using a Langmuir-type sorption model. The calibrated sorption model allowed us to estimate a pre-industrial background surface water PO4 levels, based on deeper sediment P that stabilized at concentrations smaller than the modern. In three out of the four cores, the sediment P peaked around 1980, coinciding with the surface water PO4. The estimated pre-industrial (∼1800) background PO4 concentration in the Scheldt River water was 62 [57; 66 (95 % CI)] µg PO4-P L−1. That concentration exceeds the previously estimated natural background values in Flanders (15–35 µg TP L−1) and is about half of the prevailing limit in the Scheldt River (120 µg PO4-P L−1). In the 1930s, river water concentrations were estimated at 140 [128; 148] µg PO4-P L−1, already exceeding the current limit. The method developed here proved useful for reconstructing historical background PO4 concentrations of a lowland tidal river. A similar approach can apply to other lowland tidal rivers to provide a scientific basis for local catchment-specific PO4 backgrounds.

Mine drainage precipitates attenuate and conceal wastewater-derived phosphate pollution in stream water

Hydrous ferric-oxide (HFO) coatings on streambed sediments may attenuate dissolved phosphate (PO4) concentrations at acidic to neutral pH conditions, limiting phosphorus (P) transport and availability in aquatic ecosystems. Mesh-covered tiles on which “natural” HFO from abandoned mine drainage (AMD) had precipitated were exposed to treated municipal wastewater (MWW) effluent or a mixture of stream water and effluent. Between 42 and 99% of the dissolved P in effluent was removed from the water to a thin coating (~2 μm) of HFO on the mesh. Geochemical equilibrium model results predicted the removal of 76 to 99% of PO4 from the water by adsorption to the HFO, depending on the HFO quantity, initial PO4 concentration, and pH. The measurements and model results indicated the capacity for P removal decreased as the concentration of P associated with the HFO increased. Continuing accumulation of HFO from upstream AMD sources replenish the in-stream capacity for P attenuation below the MWW discharge. This indicates AMD pollution may conceal P inputs and limit the amount of dissolved P transported to downstream ecosystems. However, HFO-rich sediments also represent a potential source of “legacy” P that could confound management practices intended to decrease nutrient and metal loadings.

Content of nutrients and limitation of phytoplankton primary production in the specially protected natural area “Cape Martyan” (Black Sea)

The results are presented of studying the content of nitrogen compounds and mineral phosphorus, as well as phytoplankton primary production (PPP). The research was carried out in 2017–2019 in the marine area of the specially protected natural area “Cape Martyan” located on the southern coast of Crimea (Black Sea). As found, during summer in the surface seawater layer, PPP can be limited by both nitrogen and phosphorus. The dependence of PPP variation on the concentration of total nitrogen in water is not significant, while the dependence on the concentration of phosphorus is significant. It is shown that during the entire annual cycle, concentrations of nitrites, nitrates, ammonium, and mineral phosphorus vary but remain within the limits that do not lead to water hypereutrophication. A high ecological significance of precipitation was revealed: the related increase in PO4 concentration caused a transition in PPP limitation mode from phosphorus to nitrogen one. Using theoretical concepts, it is substantiated that, under oligotrophic conditions, an increase in the concentration of the substrate limiting PPP in water results in an increase in the rate of its uptake from the environment in accordance with the negative feedback of natural regulation of ecosystem homeostasis. Under conditions of eutrophication, the effect of production processes on water conditioning by the factor of nutrients decreases.

Increasing Phosphorus Uptake Efficiency by Phosphorus-Starved Microalgae for Municipal Wastewater Post-Treatment.

Four microalgal species, Chlorella vulgaris, Botryococcus braunii, Ankistrodesmus falcatus, and Tetradesmus obliquus were studied for enhanced phosphorus removal from municipal wastewater after their exposure to phosphorus starvation. Microalgae were exposed to phosphorus starvation conditions for three and five days and then used in a batch experiment to purify an effluent from a small WWTP. After 3-day P-starvation, C. vulgaris biomass growth rate increased by 50% and its PO4 removal rate reached > 99% within 7 days. B. braunii maintained good biomass growth rate and nutrient removal regardless of the P-starvation. All species showed 2–5 times higher alkaline phosphatase activity increase for P-starved biomass than at the reference conditions, responding to the decline of PO4 concentration in wastewater and biomass poly-P content. The overall efficiency of biomass P-starvation on enhanced phosphorus uptake was found to be dependent on the species, N/P molar ratio in the wastewater, as well as the biomass P content.

Drinking Water Quality and Options for the Primary Schools of a Salinity Affected Coastal Area of Bangladesh

Salinity intrusion caused a serious crisis for safe drinking water in the coastal areas of Bangladesh. The situation is even worse for children especially at school. However, information on water services in coastal schools are limited. Here we assess the quality of drinking water and supply infrastructures in the primary schools of a severely saline affected coastal area of Bangladesh. To fulfill the objective, thirty-eight schools were purposively selected and investigated in Dacope Upazila of Khulna district in Bangladesh. Findings revealed that, harvested rainwater (63%), pond (21%) and tube wells (16%) are the only drinking water sources. DO, pH, NO3, SO4 and PO4 concentration of the drinking water satisfied the quality standard. In contrast, total coliform counts exceeded the national standard. Harvested rainwater and pond showed more susceptibility to microbial contaminations as compared that of tube wells which have high salt content. Although 29% schools have installed portable water filtration unit, those are grossly inaccessible for the students. Therefore, students are reportedly consuming unsafe drinking water, and thus are vulnerable to water-borne diseases. The lack of resources and poorly designed infrastructure are the principal challenges of safe drinking water supply at primary schools of coastal Bangladesh.

Does differential phosphorus processing by plankton influence the ecological state of shallow lakes?

Shallow lakes have a tendency to settle into turbid or clear-water states, the latter having lower concentrations of total phosphorus (TP). However, how P-cycling is affected by and perhaps contributes to maintaining the different states is not well understood, in part because quantifying the processes involved by traditional methods is difficult. To elucidate these processes, we conducted experiments using 32P-PO4 as a tracer on samples collected from the unrestored, unvegetated sections of Huizhou West Lake where turbid water prevails as well as the restored, clear-water, macrophyte-rich waters of the lake. We measured PO4 uptake rates, 32P-PO4 accumulation by various plankton size-fractions (picoplankton (0.2–2 μm), nanoplankton (2–20 μm) and microplankton (>20 μm)) as well as release rates of 32P-PO4 by labelled plankton. Our results revealed slow PO4 uptake in the turbid state due to low PO4 concentration, slow recycling of the high particulate P, and high levels of particulate 32P which may allow for continuous high growth and biomass of phytoplankton. In contrast, in the clear water state, the uptake of PO4 was rapid due to a higher PO4 concentration, the recycling rates of particulate 32P were high and the levels of particulate 32P were low, potentially constraining the phytoplankton growth. A greater proportion of particulate 32P was in the microplankton fraction in clear waters, suggesting that grazing by microplankton may play an important role in the rapid P recycling in clear-waters. Our results provide some evidence for a reinforcement of the turbid conditions (low recycling rate) when the lake is in a turbid state and vice versa when in the clear water state. The results add new knowledge to the understanding of P cycling in shallow lakes and illustrate the utility of using P-kinetics in contrasting states in plankton communities.

Coupling between sediment biogeochemistry and phytoplankton development in a temperate freshwater marsh (Charente-Maritime, France): Evidence of temporal pattern

In freshwater systems, sediment can be an important source for the internal loading of PO4. The limiting character of this element in such system leads to consider this phenomenon in terms of eutrophication risks and water quality stakes. A four-months follow-up (January, March, April and May 2019) was carried out in a strong phosphate (PO4) limited secondary channel from an artificial irrigation system of Charente Maritime (France) to link the mobilization of remineralization products in the upper 6 cm layer of sediment (conventional core slicing/centrifugation and DET probes) and the phytoplankton biomass dynamics in the water column. Results showed congruent patterns between the temporal succession of the organic matter mineralization processes in the sediment and the primary biomass dynamics in the water column. In January and March (considered in winter), PO4 proved to be retained by adsorption onto iron oxides in anoxic sediment since pore water nitrate inhibited for about a month the respiration of metal oxides in the first cm of sediment, thus limiting PO4 availability and the phytoplankton growth. In April and May (early spring), after exhaustion of pore water nitrate, the dissolutive reduction of iron oxides released PO4 into pore water generated a significant diffusive outgoing flux from the sediment to the water column with a maximum in April (-1.10E-04±2.81E-05 nmol cm−2 s−1). This release coincided with the nanophytoplankton bloom (5.50 µg Chla L−1) and a potential increase of PO4 concentration in the water column. This work provides some insight on the importance of benthic-pelagic coupling in anthropogenic systems. This conceptual model has to be deployed on other sites of interest where internal loading of P takes precedence over external inputs and nitrate mitigation drives its benthic recycling and ultimately its bioavailability. This is to be essential to characterize the aquatic environment quality in order to limit eutrophication risks.

Evaluation of the trophic state predicted from lab and Landsat data of western coastal water of Suez Bay, Egypt

This study aimed to compare the trophic status assessments of the western coastal waters of Suez Bay, Gulf of Suez, Egypt. The Trophic Index (TRIX) that depends on the lab-based water quality measurements of nutrients, chlorophyll-a (Chl-a) and dissolved oxygen, was compared with the Carlson trophic state index that integrates lab-based data such as NH4 or PO4 concentration with Landsat data and geographic information system (GIS) techniques. The physicochemical properties were determined, which indicated that Suez Bay was in an eutrophication state limited by both N and Si. It was suggested that the most influential activities be the industrial and domestic drains that raised the TRIX value to 5.59 with a mesotrophic state on average. Likewise, phosphorus trophic status mapping applying Carlson trophic state index showed high activity nearby drain outlets, especially at the Cabanon drain. The regression statistical model indicated a relationship between lab data of nutrients and band values extracted from Landsat images. Accordingly, the integration of remote sensing and GIS techniques with laboratory data is useful for predicting the state of water quality in the coastal areas with a single lab-based water quality parameter.

Experiment-based geochemical modeling of Arsenic(V) and Arsenic(III) adsorption onto aquifer sediments from an inland basin

Natural occurrence of groundwater arsenic (As) exists in many aquifers and threatens the health of hundreds of millions of people. Adsorption of As is critical to its distribution in aquifer groundwater, as it can lower dissolved As concentrations and provide a source for As mobilization. However, little is known about As adsorption onto aquifer sediments in inland basins. To fill this gap, we investigated As(V) and As(III) adsorption onto a brown sediment hosting low-As groundwater and two gray sediments hosting high-As groundwater sampled from an approximate flow path of the Hetao Basin, China. Those three sediments had total Fe contents of around 1.3% and As contents of around 9.0 μg/g. Arsenic(III) adsorption were kinetically faster than As(V) adsorption on the sediments. The characteristics of As(V) and As(III) adsorption both exhibited nonlinear isotherms, with adsorption decreasing with increases in pH from around 7 to 9 (typical ambient groundwater pH of inland basins). Generally, As(V) adsorption was greater than As(III) adsorption at pH < 7.5, whereas the opposite was true at pH > 7.5. Phosphate competed more strongly with As(V) adsorption than As(III) adsorption, while HCO3 competed more strongly with As(III) adsorption. Aqueous As(III) was oxidized to As(V) by interaction with the brown sediment, mainly due to its high content of extractable Mn(IV) oxides. Arsenic adsorption onto the sediments was primarily controlled by the content and crystallinity of their Fe(III) oxides. The brown sediment showed weaker affinity for As(V) and As(III) than the gray sediments, possibly due to the better crystallinity of the Fe(III) oxides in the brown sediment. In the two gray sediments containing Fe(III) oxides with similar crystallinities, the As adsorption capacity was related to the content of Fe(III) oxides. Geochemical models were developed to quantitatively simulate As(V) and As(III) adsorption onto aquifer sediments. Experimental data were approximated well by these models, indicating that As(V) adsorption decreases at elevated pH and PO4 concentration, while As(III) desorption is favored at high pH and concentrations of HCO3 and PO4. According to the models, the extent and kinetics of As(III) oxidation are controlled by the number of free oxidation sites in Mn(IV) oxides, pH, and As(III) concentration. This study suggests that the characteristics of As adsorption are highly dependent on the mineral phases existing in the sediments, which must be fully understood to quantify the reactive transport of groundwater As in aquifer systems.

Aquatic Plants, Landoltia punctata, and Azolla filiculoides as Bio-Converters of Wastewater to Biofuel.

The aquatic plants, Azolla filiculoides, and Landoltia punctate, were used as complementing phytoremediators of wastewater containing high levels of phosphate, which simulates the effluents from textile, dyeing, and laundry detergent industries. Their complementarities are based on differences in capacities to uptake nitrogen and phosphate components from wastewater. Sequential treatment by L. punctata followed by A. filiculoides led to complete removal of NH4, NO3, and up to 93% reduction of PO4. In experiments where L. punctata treatment was followed by fresh L. punctata, PO4 concentration was reduced by 65%. The toxicity of wastewater assessed by shrimps, Paratya australiensis, showed a four-fold reduction of their mortality (LC50 value) after treatment. Collected dry biomass was used as an alternative carbon source for heterotrophic marine protists, thraustochytrids, which produced up to 35% dry weight of lipids rich in palmitic acid (50% of total fatty acids), the key fatty acid for biodiesel production. The fermentation of treated L. punctata biomass by Enterobacter cloacae yielded up to 2.14 mol H2/mole of reduced sugar, which is comparable with leading terrestrial feedstocks. A. filiculoides and L. punctata can be used as a new generation of feedstock, which can treat different types of wastewater and represent renewable and sustainable feedstock for bioenergy production.

Response‐surface methodology for the production and the purification of a new H2O2‐tolerant alkaline protease from Bacillus invictae AH1 strain

This work deals with the optimization of the culture conditions of Bacillus invictae AH1 in order to increase the production level of the proteolytic activity. Response-surface methodology (RSM) was applied for the most significant fermentation parameters (concentration of wheat bran and K2 HPO4 /KH2 PO4 ) that were earlier identified by Plackett-Burman Design from seven possible factors. A central composite design was used and the quadratic regression model of producing active protease was built. A maximum protease activity was reached and validated experimentally, using a maximum wheat bran concentration (50 g/L) with increased K2 HPO4 /KH2 PO4 concentration (2.275 g/L). Protease production obtained experimentally coincident with the predicted value and the model was proven to be adequate. Interestingly, the use of RSM increased the protease production by four times (7,000 U/mL) using a low-cost substrate and a culture time of 40 hr, as compared to the standard culture conditions. In the second part of this study, a H2 O2 -tolerant alkaline protease produced from B. invictae AH1 with a molecular mass of about 41 kDa, noted P3, was purified by successive steps of ultrafiltration, gel filtration and ion exchange chromatography. The K m and Vmax values of the purified protease using casein, as substrate, were about 4 mg/mL and 27 μM/min, respectively. The highest enzyme activity was found at pH 9.0 and a temperature of 60°C. In addition, the enzyme showed a quasi-total stability against H2 O2 (5% for 1 hr) and against most of the tested solid and liquid detergents, suggesting its eventual use in bio-detergent formulations.

A novel Mg(OH)2 binding layer-based DGT technique for measuring phosphorus in water and sediment.

Diffusive gradients in thin films (DGT) have gained wide attention for in situ measurement of reactive phosphorus species (PO4) in natural water, sediments and potentially soils. In this study, a novel Mg(OH)2 binding gel was formed using magnesium hydroxide obtained by in situ hydration of calcined magnesium oxide. Laboratory scale experiments showed that the novel Mg(OH)2 gel had a homogeneous dispersion of fine particles of Mg(OH)2 with a particle size of 2-5 μm. With 10 mL of 2.0 mol L-1 NaOH as the eluting agent, the optimal elution efficiency of PO4 on the Mg(OH)2 gel was 72 ± 5%. There were linear relationships between the accumulated PO4 mass and the applied PO4 concentration (0.1 to 20 mg P per L), time (0 to 24 h) and temperature (22 to 40 °C). The capacity of the Mg(OH)2 binding layer was determined to be 99.5 μg P per disc. Tests in synthetic seawater, Chaohu Lake and Yihai Pond confirmed that Mg(OH)2-DGT was able to accurately measure phosphorus up to 10 days. This was indicated by the good agreements between the concentrations measured by DGT (CDGT) technology and by an ex situ chemical method in solution (Csoln), with a CDGT/Csoln ratio between 0.91 and 1.09.

PO4 adsorption on the calcite surface modulates calcite formation and crystal size

Abstract Calcium carbonate (CaCO3) and particularly its stable phase, calcite, is of great geological significance in the deep carbon cycle since CaCO3 from biomineralized shells and corals form sedimentary rocks. Calcite also attracts attention in medical science and pharmacy as a primary or intermediate component in biomaterials because it possesses excellent biocompatibility along with suitable physicochemical properties. Calcite blocks have already been used during surgical procedures as a bone substitute for reconstructing bone defects formed by diseases and injury. When producing CaCO3 biomaterials and bioceramics, in particular, in vivo control of the size and polymorphic nature of CaCO3 is required. In this study, we investigated the effects of PO4 on calcite formation during the phase conversion of calcium sulfate anhydrate (CaSO4, CSA), which is sometimes used as a starting material for bone substitutes because of its suitable setting ability. CSA powder was immersed in 2 mol/L Na2CO3 solution containing a range of PO4 concentrations (0–60 mmol/L) at 40 °C for 3 days. The treated samples were investigated by X-ray diffraction, Fourier-transform infrared spectroscopy, X-ray fluorescence spectroscopy, and thermal analysis. In addition, the fine structures of the treated samples were observed by field-emission scanning electron microscopy, and the specific surface area was measured. We found that PO4, which is universally present in vivo, can modulate the calcite crystal size during calcite formation. A fluorescence study and calcite crystal growth experiments indicated that PO4 adsorbs tightly onto the surface of calcite, inhibiting crystal growth. In the presence of high PO4 concentrations, vaterite is formed along with calcite, and the appearance and stability of the CaCO3 polymorphs can be controlled by adjusting the PO4 concentration. These findings have implications for medical science and pharmacology, along with mineralogy and geochemistry.

Using Ca[sbnd]Fe layered double hydroxide transformation to optimise phosphate removal from waste waters

Single phase CaFe layered double hydroxide (LDH) minerals containing Cl− species in the interlayer was synthesized by coprecipitation with a CaII: FeIII ratio of 2: 1. In both phosphate (PO4) free water and at low aqueous PO4 concentration, the LDH was fully transformed into a mixture of a “ferrihydrite-like” material, calcite and soluble calcium species. Mössbauer spectroscopy and transmission electron microscopy showed that phosphate was removed by the “ferrihydrite like” phase that contained a significant quantity of Ca. At high phosphate concentration the Ca species released from the LDH precipitated to form hydroxyapatite leading to a maximal removal capacity of ~ 130 mg P-PO4 g−1. The CaFe LDH was deposited onto a pozzolana volcanic rock in order to perform a column experiment under hydrodynamic conditions for 70 days. A high removal capacity was observed, a qB of ~ 4 mg P-PO4 g−1 was measured at the breakthrough of the column, however the pH in the outflow was measured to be higher than 11. Such an increase was due to the very high solubility of the CaFe LDH.

Optimization of phosphate recovery from monkfish, Lophius vomerinus, processing by-products and characterization of the phosphate phases.

Fish-processing by-products represent an increasing proportion of wastes globally. Valorizing offers a sustainable alternative by harnessing high-value products through process development. This study aimed to develop and optimize a demineralization process to recover minerals from fish bones with subsequent recovery of phosphates from the resulting solution. The demineralization process was optimized under the following conditions: 5% H3 PO4 concentration (v/v), four extractions and solvent to feed ratio (v/w) of 5:1 at ambient temperature of 17 °C. This resulted in an ossein containing 2.0 ± 1.2 g kg-1 DM ash and 71.5 ± 3 g kg-1 DM hydroxyproline and mineral liquor. The phosphate precipitation from the mineral liquor was further optimized resulting in > 99% total P recovery at 75 °C reaction temperature and 1 mol L-1 Ca(OH)2 to mineral liquor ratio(v/v) of 0.95:1 for a reaction time of 17 min, per 150 mL starting mineral liquor. The precipitate contained 215.2 ± 3.0 g kg-1 DM dicalcium phosphate dihydrate (DCPD) with a net contribution of 17.2% P from the fishbones, and 25 ± 0.2 g DM of octacalcium phosphate (OCP) was precipitated from 150 mL starting mineral liquor at 25 °C reaction temperature, (1.2:1) 1 mol L-1 Ca(OH)2 to mineral liquor ratio (v/v) and reaction time of 17 min. The X-ray spectra confirmed the DCPD structure and Fourier transform infrared spectroscopy (FTIR) spectra indicated OCP precipitation. This work successfully illustrated the recovery of minerals from fish bones and the subsequent production of different high-quality phosphates from fish-processing by-products, thus indicating a potential source for high-value products. © 2018 Society of Chemical Industry.