Crist S. Khachikian

Reduced inorganic phosphorus in the natural environment: significance, speciation and determination

It is commonly assumed that phosphorus occurs almost exclusively in the environment as fully oxidized phosphate (primarily H(2)PO(4)(-) and HPO(4)(2-), where the oxidation state of phosphorus is +V). Recent developments in the field of microbiology and research on the origin of life have suggested a possibly significant role for reduced, inorganic forms of phosphorus in bacterial metabolism and as evolutionary precursors of biological phosphate compounds. Reduced inorganic forms of phosphorus include phosphorus acid (H(3)PO(3), P(+III)), hypophosphorus acid (H(3)PO(2), P(+I)) and various forms of phosphides (P(-III)). Reduced phosphorus has been detected in anaerobic sediments, sewage treatment facilities and in industrial and agricultural processes. Microbiological evidence suggests a significant role for reduced phosphorus species in metabolic processes and raises interesting questions regarding the biogeochemistry of this nutrient in the environment. However, the paucity of data on the presence and cycling of reduced phosphorus compounds in the environment requires attention in order to elucidate the role of these compounds in natural systems. This paper discusses the significance of reduced phosphorus in the natural environment, its speciation and methods of detection.

Detection of Geothermal Phosphite Using High Performance Liquid Chromatography

Little is known about the prebiotic mechanisms that initiated the bioavailability of phosphorus, an element essential to life. A better understanding of phosphorus speciation in modern earth environments representative of early earth may help to elucidate the origins of bioavailable phosphorus. This paper presents the first quantitative measurements of phosphite in a pristine geothermal pool representative of early earth. Phosphite and phosphate were initially identified and quantified in geothermal pool and stream samples at Hot Creek Gorge near Mammoth Lakes, California, using suppressed conductivity ion chromatography. Results confirmed the presence of 0.06 +/- 0.02 microM of phosphite and 0.05 +/- 0.01 microM of phosphate in a geothermal pool. In the stream, phosphite concentrations were below detection limit (0.04 microM) and phosphate was measured at 1.06 +/- 0.36 microM. The presence of phosphite in the geothermal pool was confirmed using both chemical oxidation and ion chromatography/mass spectrometry.

The development of iodide-based methods for batch and on-line determinations of phosphite in aqueous samples

Recent developments in the field of microbiology and research on the origin of life have suggested a possible significant role for reduced, inorganic forms of phosphorus (P) such as phosphite [HPO(3)(2-), P(+III)] and hypophosphite [H(2)PO(2)(-), P(+I)] in the biogeochemical cycling of P. New, robust methods are required for the detection of reduced P compounds in order to confirm the importance of these species in the overall cycling of P in the environment. To this end, we have developed new batch and flow injection (FI) methods for the determination of P(+III) in aqueous solutions. The batch method is based on the reaction of P(+III) with a mixed-iodide solution containing tri-iodide (I(3)(-)) and penta-iodide (I(5)(-)). The oxidation of P(+III) consumes free I(3)(-) and I(5)(-) in solution. The remaining I(3)(-) and I(5)(-) subunits are then allowed to react with the amylose content in starch to form a blue complex, which has a lambda(max) of 580 nm. The measurement of this blue complex is directly correlated with the concentration of P(+III). The on-line FI method employs the same reaction between P(+III) and mixed-iodide producing phosphate [P(+V)] that is determined spectrophotometrically by the molybdenum blue method employing ascorbic acid at a lambda(max) of 710 nm. The linear range for both the batch and FI determination of P(+III) was 1.0-50 microM with detection limits of 0.70 and 0.36 microM, respectively. Interference studies for the batch method show that arsenite [As(+III)] and sulfite [S(+IV)] can also be determined by this technique; however, these interferences can be circumvented by oxidizing As(+III) and S(+IV) using KMnO(4) which is an ineffective oxidant for P(+III). Both methods were applied to P(+III) determinations in ultra-pure water and simulated creek water. Results and analytical figures of merit are reported and future work is considered.

Design and development of an automated flow injection instrument for the determination of arsenic species in natural waters

The design and development of an automated flow injection instrument for the determination of arsenite [As(III)] and arsenate [As(V)] in natural waters is described. The instrument incorporates solenoid activated self-priming micropumps and electronic switching valves for controlling the fluidics of the system and a miniature charge-coupled device spectrometer operating in a graphical programming environment. The limits of detection were found to be 0.79 and 0.98 microM for As(III) and As(V), respectively, with linear range of 1-50 microM. Spiked ultrapure water samples were analyzed and recoveries were found to be 97%-101% for As(III) and 95%-99% for As(V), respectively. Future directions in terms of automation, optimization, and field deployment are discussed.

Laboratory Investigations of Weathering of Soils from Mammoth Mountain, CA, a Naturally CO2-Impacted Field Site

The potential impacts of CO2 leakage from a natural subsurface reservoir on soil and water quality were studied. Field measurements of soil pore CO2 concentrations and visual inspection of plants at Mammoth Mountain, CA, allowed the demarcation of tree-kill and non-tree-kill zones, with CO2 concentrations >100,000 ppm and ∼ 1,000 ppm, respectively. Soils collected from six sites along a transect stretching from the center of the tree-kill zone to an equidistant point into the non-tree-kill zone were analyzed for surface area and organic carbon content. Batch and column leaching tests were conducted to determine the extent of weathering induced by the presence of CO2 in the aqueous solution. Soils deep into the tree-kill area exhibited significantly higher surface areas (10.67 m(2)/g vs 2.53 m(2)/g) and lower organic carbon content (9,550 mg/kg vs 35,550 mg/kg). Batch results indicated that lower pH values (∼ 2) released higher concentrations of Mg, Si, Fe, and As, while, for soils in the tree-kill zone, longer-term batch results indicated higher releases at the higher pH of 5.5. Column experiments were used to compare the effects of pH adjusted using HCl vs CO2. For pore volumes (PV) < 100, CO2 enhanced trace element release. For 100 < PV < 10,000 concentrations of elements in the two systems were equivalent and steady. At PV > 10,000, after a drop in pH in the CO2 system, larger amounts of Fe and As were released, suggesting a CO2-induced dissolution of Fe-silicates/clays and/or reductive dissolution of Fe(3+) that releases Fe-bound arsenic. The specific role of pore water-dissolved CO2 on the release of trace elements is hitherto unknown. However, interactions of pore-water CO2 and the minerals in the Mammoth Mountain soils can cause the release of environmental pollutants.