Microbial acceleration of aerobic pyrite oxidation at circumneutral pH.

Pyrite (FeS2 ) is the most abundant sulfide mineral on Earth and represents a significant reservoir of reduced iron and sulfur both today and in the geologic past. In modern environments, oxidative transformations of pyrite and other metal sulfides play a key role in terrestrial element partitioning with broad impacts to contaminant mobility and the formation of acid mine drainage systems. Although the role of aerobic micro-organisms in pyrite oxidation under acidic-pH conditions is well known, to date there is very little known about the capacity for aerobic micro-organisms to oxidize pyrite at circumneutral pH. Here, we describe two enrichment cultures, obtained from pyrite-bearing subsurface sediments, that were capable of sustained cell growth linked to pyrite oxidation and sulfate generation at neutral pH. The cultures were dominated by two Rhizobiales species (Bradyrhizobium sp. and Mesorhizobium sp.) and a Ralstonia species. Shotgun metagenomic sequencing and genome reconstruction indicated the presence of Fe and S oxidation pathways in these organisms, and the presence of a complete Calvin-Benson-Bassham CO2 fixation system in the Bradyrhizobium sp. Oxidation of pyrite resulted in thin (30-50 nm) coatings of amorphous Fe(III) oxide on the pyrite surface, with no other secondary Fe or S phases detected by electron microscopy or X-ray absorption spectroscopy. Rates of microbial pyrite oxidation were approximately one order of magnitude higher than abiotic rates. These results demonstrate the ability of aerobic microbial activity to accelerate pyrite oxidation and expand the potential contribution of micro-organisms to continental sulfide mineral weathering around the time of the Great Oxidation Event to include neutral-pH environments. In addition, our findings have direct implications for the geochemistry of modern sedimentary environments, including stimulation of the early stages of acid mine drainage formation and mobilization of pyrite-associated metals.

Microbial Fe(III) oxide reduction potential in Chocolate Pots hot spring, Yellowstone National Park.

Chocolate Pots hot springs (CP) is a unique, circumneutral pH, iron-rich, geothermal feature in Yellowstone National Park. Prior research at CP has focused on photosynthetically driven Fe(II) oxidation as a model for mineralization of microbial mats and deposition of Archean banded iron formations. However, geochemical and stable Fe isotopic data have suggested that dissimilatory microbial iron reduction (DIR) may be active within CP deposits. In this study, the potential for microbial reduction of native CP Fe(III) oxides was investigated, using a combination of cultivation dependent and independent approaches, to assess the potential involvement of DIR in Fe redox cycling and associated stable Fe isotope fractionation in the CP hot springs. Endogenous microbial communities were able to reduce native CP Fe(III) oxides, as documented by most probable number enumerations and enrichment culture studies. Enrichment cultures demonstrated sustained DIR driven by oxidation of acetate, lactate, and H2 . Inhibitor studies and molecular analyses indicate that sulfate reduction did not contribute to observed rates of DIR in the enrichment cultures through abiotic reaction pathways. Enrichment cultures produced isotopically light Fe(II) during DIR relative to the bulk solid-phase Fe(III) oxides. Pyrosequencing of 16S rRNA genes from enrichment cultures showed dominant sequences closely affiliated with Geobacter metallireducens, a mesophilic Fe(III) oxide reducer. Shotgun metagenomic analysis of enrichment cultures confirmed the presence of a dominant G. metallireducens-like population and other less dominant populations from the phylum Ignavibacteriae, which appear to be capable of DIR. Gene (protein) searches revealed the presence of heat-shock proteins that may be involved in increased thermotolerance in the organisms present in the enrichments as well as porin-cytochrome complexes previously shown to be involved in extracellular electron transport. This analysis offers the first detailed insight into how DIR may impact the Fe geochemistry and isotope composition of a Fe-rich, circumneutral pH geothermal environment.

Use of acupuncture in the management of chronic haemophilia pain.

Persons with haemophilia experience persistent pain resulting in chronic arthritic symptoms. The older person with haemophilia who did not benefit from primary prophylaxis are particularly at risk for persistent pain in multiple target joints as a result of repeated joint bleeding with delayed treatment received. The National Pain Study, Ref. [11] identified over 700 persons with haemophilia who rated daily persistent pain as 4.22/10 (SD ± 2.05) using a visual analogue scale. The study suggests that persons are continually seeking additional resources to relieve pain. This study seeks to identify: (i) effects of acupuncture use for persons with haemophilia who experience persistent joint pain as a result of repeated haemarthrosis and (ii) document no reported increased bleeding risk as a result of acupuncture use. End points include the subjects reported perception of reduction in pain via the 10-point visual analogue pain scale and bleeding. Nine subjects participated in the study, some who received a factor replacement to 15% correction and others who did not receive factor prior to any acupuncture sessions totaling 14 acupuncture treatments. No one of the subjects experienced bleeding or bruising. Six of the nine subjects reported an improvement in pain scores by at least 50%. Seven of the nine quality of life (QOL) domains within the QOL SF-36 questionnaire improved, suggesting a perception by subjects of improvement. This study suggests that acupuncture therapy can be a safe additional modality for pain management therapies in persons with haemophilia, although larger randomized studies are needed for further validation.

Odor and volatile organic compound removal from wastewater treatment plant headworks ventilation air using a biofilter.

Laboratory-scale experiments and field studies were performed to evaluate the feasibility of biofilters for sequential removal of hydrogen sulfide and volatile organic compounds (VOCs) from wastewater treatment plant waste air. The biofilter was designed for spatially separated removal of pollutants to mitigate the effects of acid production resulting from hydrogen sulfide oxidation. The inlet section of the upflow units was designated for hydrogen sulfide removal and the second section was designated for VOC removal. Complete removal of hydrogen sulfide (H2S) and methyl tert-butyl ether (MTBE) was accomplished at loading rates of 8.3 g H2S/(m3 x h) (15-second empty bed retention time [EBRT]) and 33 g MTBE/(m3 x h) (60-second EBRT), respectively. In field studies performed at the Hyperion Treatment Plant in Los Angeles, California, excellent removal of hydrogen sulfide, moderate removal of nonchlorinated VOCs such as toluene and benzene, and poor removal of chlorinated VOCs were observed in treating the headworks waste air. During spiking experiments on the headworks waste air, the percentage removals were similar to the unspiked removals when nonchlorinated VOCs were spiked; however, feeding high concentrations of chlorinated VOCs reduced the removal percentages for all VOCs. Thus, biofilters offer a distinct advantage over chemical scrubbers currently used at publicly owned treatment works in that they not only remove odor and hydrogen sulfide efficiently at low cost, but also reduce overall toxicity by partially removing VOCs and avoiding the use of hazardous chemicals.

Odor and volatile organic compound treatment by biotrickling filters: pilot-scale studies at hyperion treatment plant.

A pilot-scale biotrickling filter was installed at the Hyperion Treatment Plant in Los Angeles, California, to study hydrogen sulfide (odor) and volatile organic compound (VOC) removal from headworks waste air. The performance of the reactor was continuously monitored during a 10-month period. At an average empty bed gas residence time of 24 seconds, 10 to 50 ppm of hydrogen sulfide was consistently removed at greater than 98% efficiency, corresponding to an average volumetric elimination capacity of 5.2 g/m3 x h. Concentration profiles over the height of the reactor indicated nearly complete removal in the first section of the reactor, suggesting that elimination capacities up to 30 g/m3 x h could be obtained. The odor reduction (as dilution to threshold) was 98%, which correlated with the efficiency of removal of hydrogen sulfide as the primary pollutant. Volatile organic compounds were present at concentrations up to 225 ppb. Moderate but significant removal of toluene and benzene was observed when the biotrickling filter was operated with pH control to neutralize sulfuric acid production from hydrogen sulfide oxidation. Xylenes and chlorinated VOCs were not removed regardless of experimental conditions in the reactor. The results led to the conclusion that VOC removal is the limiting process in biotrickling filters for the simultaneous removal of hydrogen sulfide and VOCs at publicly owned treatment works.