Gregory K. Druschel

Involvement of Intermediate Sulfur Species in Biological Reduction of Elemental Sulfur under Acidic, Hydrothermal Conditions

ABSTRACT The thermoacidophile and obligate elemental sulfur (S8 0)-reducing anaerobe Acidilobus sulfurireducens 18D70 does not associate with bulk solid-phase sulfur during S8 0-dependent batch culture growth. Cyclic voltammetry indicated the production of hydrogen sulfide (H2S) as well as polysulfides after 1 day of batch growth of the organism at pH 3.0 and 81�C. The production of polysulfide is likely due to the abiotic reaction between S8 0 and the biologically produced H2S, as evinced by a rapid cessation of polysulfide formation when the growth temperature was decreased, inhibiting the biological production of sulfide. After an additional 5 days of growth, nanoparticulate S8 0 was detected in the cultivation medium, a result of the hydrolysis of polysulfides in acidic medium. To examine whether soluble polysulfides and/or nanoparticulate S8 0 can serve as terminal electron acceptors (TEA) supporting the growth of A. sulfurireducens, total sulfide concentration and cell density were monitored in batch cultures with S8 0 provided as a solid phase in the medium or with S8 0 sequestered in dialysis tubing. The rates of sulfide production in 7-day-old cultures with S8 0 sequestered in dialysis tubing with pore sizes of 12 to 14 kDa and 6 to 8 kDa were 55% and 22%, respectively, of that of cultures with S8 0 provided as a solid phase in the medium. These results indicate that the TEA existed in a range of particle sizes that affected its ability to diffuse through dialysis tubing of different pore sizes. Dynamic light scattering revealed that S8 0 particles generated through polysulfide rapidly grew in size, a rate which was influenced by the pH of the medium and the presence of organic carbon. Thus, S8 0 particles formed through abiological hydrolysis of polysulfide under acidic conditions appeared to serve as a growth-promoting TEA for A. sulfurireducens.

Organic Anion–Driven Solubilization of Precipitated and Sorbed Phytate Improves Hydrolysis by Phytases and Bioavailability to Nicotiana tabacum

Abstract Improved plant access to native soil phosphorus (P) species such as phytate (metal ion derivatives of myo-inositol hexakisphosphate (IHP)) could minimize agricultural dependence on nonrenewable mineral phosphates and reduce surface water pollution. Nicotiana tabacum plant lines with unique organic anion (OA) and phytase production patterns were used to investigate the effect of OA-driven solubilization on the bioavailability of precipitated and sorbed IHP. Organic anions released IHP sorbed to goethite (Gt) by chelation or reductive dissolution mechanisms in the order: ascorbate > citrate > oxalate > pyruvate > acetate. Transgenic tobacco overexpressing Peniophora lycii phytase (PHY) and a MATE-type citrate transporter (CIT) exuded 2.2- to 2.6-fold higher OA compared with that of wild-type plants. The PHY plants had 33-fold higher exudate phytase activity (6.0 × 10−2 nkat plant−1 day−1) compared with those of wild-type and CIT plants, produced the largest zone of iron-IHP hydrolysis in agar media, and incorporated the most shoot P (2.3 &mgr;g) when grown on Gt-IHP. Plants grown on IHP at 2× Gt saturation (0.26 mmol/L) were 10-fold higher in shoot P compared with the 1× Gt condition (0.13 mmol/L IHP) with PHY plants approaching excess P status (1 % shoot P). The addition of Gt diminished shoot P in plants grown without P (−70 to −80 %) and with phosphate (−50 %) or IHP (−100 %); the exception was the high citrate–exuding plant line (21 nmol citrate plant−1 day−1), for which phosphate uptake was only 20 % reduced. Plant OA production mitigates P inhibition by Gt when weakly sorbing phosphate species are supplied or when high phytase production by plants can maximize the hydrolysis of IHP.

Characterization of Organic Phosphorus Form and Bioavailability in Lake Sediments using P Nuclear Magnetic Resonance and Enzymatic Hydrolysis.

Lake sediments are known to be a significant source of phosphorus (P) to plankton populations under certain biogeochemical conditions; however, the contribution of sediment organic P (P) to internal P loads remains poorly understood. We investigated P speciation and bioavailability in sediments collected over multiple months from a shallow, eutrophic bay in Lake Champlain (Missisquoi Bay, VT) using solution P nuclear magnetic resonance (NMR) spectroscopy and enzymatic hydrolysis (EH) analysis of sediments collected during years with (2008) and without (2007) algal blooms. Sediments collected during bloom onset (July) and peak bloom (August) months contained the largest proportion of enzyme-labile P, whereas pre- and postbloom sediments were primarily composed of nonlabile P. Monoester P to diester P ratios changed with respect to depth, particularly during bloom periods. Monoester P and DNA accumulation, likely from settling particulate matter, began at the onset of the bloom and continued into October 2008 during the postbloom period. The disappearance of inositol hexakisphosphate stereoisomers and the generation of orthophosphate at lower sediment depths was also evident in August 2008. Principal components analysis of EH and NMR species proportions confirmed differences between sediment cores collected during bloom onset and peak bloom, compared with pre- and postbloom sediments. Large enzyme-labile and P species proportions corresponded to increased sediment P flux and reduced manganese and iron species in porewater. These findings suggest that interseasonal changes in P speciation may influence P mobility in sediments and contribute to important feedback dynamics between biological productivity and sediment water interface geochemistry.

The mobility of phosphorus, iron, and manganese through the sediment–water continuum of a shallow eutrophic freshwater lake under stratified and mixed water-column conditions

The management of external nutrient inputs to eutrophic systems can be confounded due to a persistent pool of phosphorus (P) in lake sediments. The behaviors of P and trace metals depend largely on the reductive dissolution of amorphous iron (Fe) and manganese (Mn) (oxy)hydroxides in sediments; however, a holistic understanding of these dynamics in relation to the broader ecological and hydrodynamic conditions of the system remains elusive. We used a high-frequency monitoring approach to develop a comprehensive conceptual model of P, Mn, and Fe dynamics across the sediment water continuum of a shallow bay in Lake Champlain (Missisquoi Bay, USA). The greatest release of sediment P, Mn, and Fe occurred under stable hydrodynamic conditions, particularly during the onset of the cyanobacterial bloom and was associated with low available P and the accumulation of soluble Mn and Fe above the sediment–water interface (SWI). During the warmest part of the season, bloom severity and sediment P release was partially regulated by hydrodynamic drivers, which changed on hourly time scales to affect redox conditions at the SWI and bottom water concentrations of soluble P, Mn, and Fe. A geochemically distinct increase in soluble P and Fe concentrations, but not Mn, marked the influence of riverine inputs during a late season storm disturbance. Despite continued depletion of the reactive sediment P and metals pool into the bloom period, declining temperatures and a well-mixed water column resulted in bloom senescence and the return of P, Mn, and Fe to surface sediments. The closed cycling of P and metals in Missisquoi Bay poses a significant challenge for the long-term removal of P from this system. Multiple time-scale measures of physical and biogeochemical changes provide a basis for understanding P and trace metals behavior across sediments and the water column, which shape seasonally variable cyanobacterial blooms in shallow eutrophic systems.

Multiple sulfur isotopes fractionations associated with abiotic sulfur transformations in Yellowstone National Park geothermal springs

BackgroundThe paper presents a quantification of main (hydrogen sulfide and sulfate), as well as of intermediate sulfur species (zero-valent sulfur (ZVS), thiosulfate, sulfite, thiocyanate) in the Yellowstone National Park (YNP) hydrothermal springs and pools. We combined these measurements with the measurements of quadruple sulfur isotope composition of sulfate, hydrogen sulfide and zero-valent sulfur. The main goal of this research is to understand multiple sulfur isotope fractionation in the system, which is dominated by complex, mostly abiotic, sulfur cycling.ResultsWater samples from six springs and pools in the Yellowstone National Park were characterized by pH, chloride to sulfate ratios, sulfide and intermediate sulfur species concentrations. Concentrations of sulfate in pools indicate either oxidation of sulfide by mixing of deep parent water with shallow oxic water, or surface oxidation of sulfide with atmospheric oxygen. Thiosulfate concentrations are low (<6xa0μmolxa0L-1) in the pools with low pH due to fast disproportionation of thiosulfate. In the pools with higher pH, the concentration of thiosulfate varies, depending on different geochemical pathways of thiosulfate formation. The δ34S values of sulfate in four systems were close to those calculated using a mixing line of the model based on dilution and boiling of a deep hot parent water body. In two pools δ34S values of sulfate varied significantly from the values calculated from this model. Sulfur isotope fractionation between ZVS and hydrogen sulfide was close to zero at pHu2009<u20094. At higher pH zero-valent sulfur is slightly heavier than hydrogen sulfide due to equilibration in the rhombic sulfur–polysulfide – hydrogen sulfide system. Triple sulfur isotope (32S, 33S, 34S) fractionation patterns in waters of hydrothermal pools are more consistent with redox processes involving intermediate sulfur species than with bacterial sulfate reduction. Small but resolved differences in ∆33S among species and between pools are observed.ConclusionsThe variation of sulfate isotopic composition, the origin of differences in isotopic composition of sulfide and zero–valent sulfur, as well as differences in ∆33S of sulfide and sulfate are likely due to a complex network of abiotic redox reactions, including disproportionation pathways.

Determination of Fe(II), Fe(III) and Fetotal in thermal water by ion chromatography spectrophotometry (IC-Vis)

ABSTRACT Determination of iron speciation in water is one of the major challenges in environmental analytical chemistry. Here, we present and discuss a method for sampling and analysis of dissolved Fe(II), Fe(III), and Fetotal concentrations in natural thermal water covering a wide range of temperature, pH, chemical composition, and redox conditions. Various methods were tried in the collection, preservation, and storage of natural thermal water samples for the Fe(II) and Fe(III) determinations, yet the resultant Fe speciation determined was often found to be significantly affected by the methodology applied. Due to difficulties in preserving accurate Fe speciation in natural samples for later laboratory analysis, a field-deployed on-site method using ion-chromatography and spectrophotometry was developed and tested. The IC-Vis method takes advantage of ion chromatographic separation of Fe(II) and Fe(III), followed by post-column colour reaction and spectrophotometric detection, thus allowing analysis of Fe(II) and Fe(III) in a single 15-minute run. Additionally, Fetotal can be determined after sample oxidation. The analytical detection limits are ~2 µg L−1 (LOD) using 200–1000 µL injection volumes and depend on the blank and reagent quality. The power of this method relies on the capability to directly determine a wide range of absolute and relative concentrations of Fe(II) and Fe(III) in the field. The field-deployed IC-Vis method was applied for the determination of Fe(II) and Fe(III) concentrations in natural thermal water with discharge temperatures ranging from 12°C to 95°C, pH between 2.46 and 9.75, and Fetotal concentrations ranging from a few μg L−c up to 8.3 mg L−1.

Potential use of sulfite as a supplemental electron donor for wastewater denitrification

Biological denitrification typically requires the addition of a supplemental electron donor, which can add a significant operating expense to wastewater treatment facilities. Most common electron donors are organic, but reduced inorganic sulfur compounds (RISCs), such as sulfide (HS−) and elemental sulfur (S0), may be more cost-effective. S0 is an inexpensive and well characterized electron donor, but it provides slow denitrification rates due to its low solubility. A lesser-known RISC is sulfite (

Advancing Geomicrobiology and Microbial Geochemistry

{text{SO}}_{3}^{2 - }