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PubMed1983

Radioactive-induced tumors by phosphorus-32 as colloidal compound.

Chromic colloidal phosphate labeled with 32P, which has been proposed for the treatment of several articular diseases, was injected intra-articularly in the knee joint of adult Wistar rats. After a 270 days minimum latent period, tumors began to appear in the injected zone, to a 70% frequency. Ten lung metastases were detected. In five cases, squamous cell carcinomas were induced in the injected area. The relevance of a sound evaluation of the risk involved in treatments with radioactive isotopes, is discussed.

Animals↗
PubMed2005

An experimental and theoretical evaluation of the reactions of silver hyponitrite with phosphorus halides. In search of the elusive phosphorus-containing hyponitrites.

In the reaction of F2PBr, F2P(O)Br, (C6F5)2PBr, (CH3)2P(S)Br, and (CH3)2P(O)Cl with silver hyponitrite (AgON=NOAg), nitrous oxide (N2O) and mu-oxo phosphorus species were obtained in all cases rather than the plausible hyponitrite alternative. Theoretical calculations of the geometries and expected decomposition pathways of the phosphorus-containing hypothetical hyponitrites were carried out at the B3LYP/6-311+G(2df)//B3LYP/6-31+G(d) level. The cis-hyponitrite, XON=NOX (X=PF2, OPF2), is predicted to concertedly decompose to N2 plus phosphorus-containing radicals (OPF2, O2PF2) or to N2O plus the mu-oxo phosphorus species, X-O-X, (X=PF2, OPF2) with the former pathway having a smaller activation barrier (4.6 kcal/mol, X=PF2; 10.5 kcal/mol, X=OPF2). On the other hand, trans-hyponitrite can only decompose to N2 plus the phosphorus-containing radicals, because there is a very high barrier for rearrangement to cis-hyponitrite. These results are in disagreement with experiment, because only the mu-oxo phosphorus species are observed. Reconciliation between experiment and theory is made for X=OPF2 when a silver cation is included in the calculations. In THF (as a model for neat F2P(O)Br), the silver cation is predicted to reverse the order of the two transition states through stronger interactions with the oxygen atoms in the transition state of the N2O-producing pathway. Thus, Ag(I) is predicted to be not only catalytic for X=OPF2 but also product-specific toward the mu-oxo products.

Catalysis↗
PubMed2006

Nitrogen and phosphorus dynamics of a re-wetted shallow-flooded peatland.

Minerotrophic peatlands play an important role in the regulation of water quality and quantity but due to drainage and agricultural land use most of these systems have lost this function. In Central Europe, many re-wetting projects have been implemented to restore wetlands for multifunctional purposes during the last years. The Pohnsdorfer Stauung (Northern Germany) is a eutrophic fen which was used for intensive agriculture for 40 years. The peatland is divided in two subareas by a small stream. In the scope of re-wetting measures, one subarea (westpolder) was flooded by blockading the main drainage ditch in 1996/97, a second subarea (eastpolder) was re-connected to the stream by an inlet and outlet in 2001. Nitrogen and phosphorus dynamics were investigated in the surface water of these systems over a 5-year (westpolder) and 3-year (eastpolder) period, and balances were calculated. In both polders high dynamics of nitrogen and phosphate concentrations were observed in the surface water. Nitrate peaked in the winter months, whereas ammonium, phosphate and organically bound nitrogen (N(org)) revealed highest values during summer. Daily balances for the eastpolder and annual balances for both polders were calculated. In both polders nitrate was retained but phosphate and N(org) were exported. Differences of the nutrient dynamics and the absolute and relative balances between the polders were due to the different hydrology: the eastpolder received a high nitrate load by the stream, in the westpolder nutrient loads are low and internal nutrient cycles are dominating. During the summer months, high ammonium concentrations, oxygen depletion, and phosphate release occur in the warm, stagnant water of both polders. Normally, high phosphate and ammonium concentrations did not coincided with discharge phases from the polders. However, in August 2002 after heavy rainfall high phosphorus and ammonium discharge was observed. One important factor influencing the detected nutrient dynamics and balances is the change from a drained and fertilized peatland to a flooded wetland in only a few years. We conclude that continuous water flow and stable water levels are desired for flooded peatlands to prevent high concentrations of ammonium and phosphate and to utilize the potential for nitrate retention. In degenerated peatlands, flooding should only be regarded as an easy technological solution in order to conserve the peat mineralization, and to form the foundation for the further development of the peatland to a more efficient nutrient retaining system.

Conservation of Natural Resources↗
PubMed2000

Phosphoacetylcholinesterase: toxicity of phosphorus oxychloride to mammals and insects that can be attributed to selective phosphorylation of acetylcholinesterase by phosphorodichloridic acid.

Phosphorus oxychloride (POCl(3)) is an intermediate in the synthesis of many organophosphorus insecticides and chemical warfare nerve gases that are toxic to insects and mammals by inhibition of acetylcholinesterase (AChE) activity. It was therefore surprising to observe that POCl(3), which is hydrolytically unstable, also itself gives poisoning signs in ip-treated mice and fumigant-exposed houseflies similar to those produced by the organophosphorus ester insecticides and chemical warfare agents. In mice, POCl(3) inhibits serum butyrylcholinesterase (BuChE) at a sublethal dose and muscle but not brain AChE at a lethal dose. In houseflies, POCl(3)-induced brain AChE inhibition is correlated with poisoning and the probable cause thereof. POCl(3) in vitro is selective for AChE (IC(50) = 12-36 microM) compared with several other serine hydrolases (BuChE, carboxylesterase, elastase, alpha-chymotrypsin, and thrombin) (IC(50) = 88-2000 microM). With electric eel AChE, methylcarbamoylation of the active site with eserine reversibly protects against subsequent irreversible inhibition by POCl(3). Most importantly, POCl(3)-induced electric eel AChE inhibition prevents postlabeling with [(3)H]diisopropyl phosphorofluoridate; i.e., both compounds phosphorylate at Ser-200 in the catalytic triad. Pyridine-2-aldoxime methiodide does not reactivate POCl(3)-inhibited AChE, consistent with an anionic phosphoserine residue at the esteratic site. The actual phosphorylating agent is formed within seconds from POCl(3) in water, has a half-life of approximately 2 min, and is identified as phosphorodichloridic acid [HOP(O)Cl(2)] by (31)P NMR and derivatization with dimethylamine to HOP(O)(NMe(2))(2). POCl(3) on reaction with water and HOP(O)Cl(2) have the same potency for inhibition of AChE from either electric eel or housefly head as well as the same toxicity for mice. In summary, the acute toxicity of POCl(3) is attributable to hydrolytic activation to HOP(O)Cl(2) that phosphorylates AChE at the active site to form enzymatically inactive [O-phosphoserine]AChE.

Acetylcholine↗
PubMed2001

Treatment of greenhouse wastewater using constructed wetlands.

Five wetland designs, based on conventional surface flow (SF) and subsurface flow (SSF) approaches, were assessed for nitrogen and phosphorus removal from greenhouse wastewater. Results indicated none of the individual designs assessed was capable of providing the highest treatment effect for all nutrients of concern; however, the SF wetland emerged as the most appropriate design for the treatment of greenhouse wastewater. The highest mean phosphorus reduction of 65% was observed in the unplanted SF wetlands. Peak nitrate reductions of 54% were observed in the 15-cm deep SF wetlands and ammonia removal of 74% was achieved in the unplanted SF wetlands. Nitrate concentration in the greenhouse effluent can be reduced to acceptable levels for the protection of freshwater aquatic life (i.e., less then 40 ppm) using a loading rate of 1.65 g NO3-N/m2/day and a design water depth of 30 cm or greater. Based on available literature and the results of this research project, a multistage design, consisting of an unplanted pre-treatment basin followed by a 25 to 35 cm deep surface flow marsh with open water components, is recommended.

Agriculture↗
PubMed2003

Phycoremediation: key issues for cost-effective nutrient removal processes.

Phycoremediation applied to the removal of nutrients from animal wastewater and other high organic content wastewater is a field with a great potential and demand considering that surface and underground water bodies in several regions of the world are suffering of eutrophication. However, the development of more efficient nutrient removal algal systems requires further research in key areas. Algae growth rate controls directly and indirectly the nitrogen and phosphorus removal efficiency. Thus, maximum algae productivity is required for effective nutrient removal and must be considered as a key area of research. Likewise, low harvesting costs are also required for a cost-effective nutrient removal system. The use of filamentous microalgae with a high autoflocculation capacity and the use of immobilized cells have been investigated in this respect. Another key area of research is the use of algae strains with special attributes such as tolerance to extreme temperature, chemical composition with predominance of high added value products, a quick sedimentation behavior, or a capacity for growing mixotrophically. Finally, to combine most of the achievements from key areas and to design integrated recycling systems (IRS) should be an ultimate and rewarding goal.

Biodegradation, Environmental↗
PubMed2004

Influence of the carbon/nitrogen/phosphorus ratio on polycyclic aromatic hydrocarbon degradation by Mycobacterium and Sphingomonas in soil.

Biodegradation of polycyclic aromatic hydrocarbons (PAHs) in the environment is often limited due to unfavorable nutrient conditions for the bacteria that use these PAHs as sole source of carbon and energy. Mycobacterium and Sphingomonas are 2 PAH-degrading specialists commonly present in PAH-polluted soil, but not much is known about their specific nutrient requirements. By adding different inorganic supplements of nitrogen (N) and phosphorus (P), affecting the overall carbon/nitrogen/phosphorus ratio of soil in soil slurry degradation tests, we investigated the impact of soil inorganic N and P nutrient conditions on PAH degradation by PAH-degrading Sphingomonas and Mycobacterium strains. The general theoretically calculated C/N/P ratio of 100/10/1 (expressed in moles) allowed rapid PAH metabolization by Sphingomonas and Mycobacterium strains without limitation. In addition, PAH-degradation rate and extent was not affected when ca. ten times lower concentrations of N and P were provided, indicating that Sphingomonas and Mycobacterium strains are capable of metabolizing PAHs under low nutrient conditions. Nor does PAH-degradation seem to be affected by excesses of N and P creating an imbalanced C/N/P ratio. However, supplements of N and P salts increased the salinity of soil slurry solutions and seriously limited or even completely blocked biodegradation.

Biodegradation, Environmental↗
PubMed2005

A comparison between the theory and reality of full-scale step-feed nutrient removal systems.

Capacity enhancement and volume reduction benefits of step-feeding fully aerobic bioreactors has been well documented. Application of step-feed technology to biological nutrient removal (BNR) systems, particularly those removing nitrogen alone or both nitrogen and phosphorus, is relatively new to the industry. In recent years, a number of full-scale step-feed facilities have been brought into service. This paper reviews nine full-scale step-feed biological nutrient removal systems--both nitrogen removal alone, and nitrogen and phosphorus removal. The objective is to compare the theoretical benefits of such systems with their actual operation. The predicted benefits of reduced bioreactor volume or increased process capacity, reduced energy usage, more robust nitrification performance, and the flexibility to tune (or de-tune) nitrification efficiency were verified in full-scale systems. Equations are also presented that may be used in the prediction of step-feed benefits. There are two primary drivers for considering a step-feed biological reactor system: 1. Reduced bioreactor volume for a defined capacity or performance or increased process capacity given a fixed bioreactor volume. 2. More robust nitrification performance. Full-scale operation of these step-feed nutrient removal systems provides a real world basis for the claimed benefits of step-feed operation. These systems have uniformly shown additional capacity. A number of them have also exhibited more robust performance, especially during storms. Where possible, side-by-side comparisons of full-scale step-feed systems with non-step-feed systems have exhibited greater process reliability and flexibility.

Bioreactors↗
PubMed2006

Dynamics of phosphorus, nitrogen and carbon removal in a horizontal subsurface flow constructed wetland.

The dynamics of nitrogen (N), phosphorus (P) and carbon (C) accumulation in the filter material of a horizontal subsurface constructed wetland (HSSF CW; established in 1997) and in a specially designed oil-shale ash filter (2002) for P retention have been studied. Concentrations of N, P and C in filter media (coarse sand) in the HSSF beds show an increasing trend. Both the annual accumulation of P and increasing outflow concentrations of P in the HSSF CW reflect the possible saturation of filter media with P after 8 years working. Tested ash material derived from oil-shale combustion demonstrated very high P removal efficiency in laboratory batch experiments. However, during the first 4 months of the in situ ash filter experiment, the efficiency of P removal was about 71% (an average outflow concentration of 1.9 mg L(-1) was achieved). Subsequently, the efficiency decreased to 10-20%, which might be a sign of saturation or clogging due to quick biofilm development on the ash particles. The increasing of hydraulic retention time and the improvement of design for maximal contact between material and wastewater are considered to be key factors that can provide optimal pH for the removal processes.

Adsorption↗
PubMed2002

Phosphine and methane generation by the addition of organic compounds containing carbon-phosphorus bonds into incubated soil.

Formation of phosphine and methane in anaerobic incubation systems was investigated under stirred and unstirred conditions. The PH3 and CH4 levels in the headspace, as well as the matrix-bound PH3 content in the stirred soil, significantly increased upon the addition of phosphonoacetic acid (P(O)(OH)2CH2COOH). Both the levels of matrix-bound PH3 and CH4 are positively correlated to the buffered dithionite fraction of reactive phosphorus in the soil samples, while a negative correlation was observed between matrix-bound PH3/CH4 levels and the reactive phosphorus fraction.

Bacteria, Anaerobic↗
PubMed2001

Effect of chemical composition on hydrophobicity and zeta potential of plasma sprayed HA/CaO-P2O5 glass coatings.

Multilayered plasma sprayed coatings on the surface of Ti-6Al-4V alloys have been prepared, which were composed of an underlayer of HA and a surface layer of a CaO-P2O5 glass-HA composite, with 2 or 4wt% of glass. Contact angle and surface tension variation with time, for both water and a protein solution, were determined by the sessile and pendent drop methods respectively using the ADSA-P software. Wettability studies showed that hydrophobicity of the coatings increase with the glass addition. The work of adhesion of albumin was also altered in a controlled manner by the addition of the CaO-P2O5 glass, being lower on the composite coatings than on HA. Zeta potential (ZP) results showed that composite coatings presented a higher net negative charge than HA coatings and that ZP values were also influenced by the content of the glass. This study demonstrated that the surface properties of those coatings may be modified by the addition of CaO-P2O5 glass.

Calcium Compounds↗
PubMed2004

Carbonate formation on bioactive glasses.

The system termed 58S is a sol-gel-synthesized bioactive glass composed of SiO2, CaO, and P2O5, used in medicine as bone prosthetic because, when immersed in a physiological fluid, a layer of hydroxycarbonate apatite is formed on its surface. The mechanism of bioactive glass 58S carbonation was studied in the vacuum by means of in-situ FTIR spectroscopy with the use of CO2, H2O, and CD3CN as probe molecules. The study in the vacuum was necessary to identify both the molecules specifically involved in the carbonation process and the type of carbonates formed. Bioactive glass 58S was compared to a Ca-doped silica and to CaO. On CaO, ionic carbonates could form by contact with CO2 alone, whereas on 58S and on Ca-doped silica carbonation occurred only if both CO2 and an excess of H2O were present on the sample. The function of H2O was not only to block surface cationic sites, so that CO2 could not manifest its Lewis base behavior, but also to form a liquid-like (mono)layer that allowed the formation of carbonate ions. The presence of H2O is also supposed to promote Ca2+ migration from the bulk to the surface. Carbonates formed at the surface of CaO and of Ca-bearing silicas (thus including bioactive glasses) are of the same type, but are produced through two different mechanisms. The finding that a water excess is necessary to start heavy carbonation on bioactive glasses seemed to imply that the mechanism leading to in-situ carbonation simulates, in a simplified and easy-to-reproduce system, what happens both in solution, when carbonates are incorporated in the apatite layer, and during sample shelf-aging.

Apatites↗
PubMed2004

Open, cyclic, and bicyclic compounds of double silylated phosphorus and boron.

Salt elimination reactions of tris(trimethylsilyl)silyl potassium (1), and two 1,4-dipotassiooligosilanes (3, 5) with 2,2,6,6-tetramethylpiperidinodichloroborane and diethylaminodichlorophosphane have generated open (2), cyclic (4) and bicyclic (6) bora- and phosphaoligosilanes. A monosilylated phosphane and the two five-membered cyclosilanes have been subjected to single crystal X-ray diffraction analysis.

Journal Article↗