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Compositional analysis of formation water geochemistry and microbiology of commercial and carbon dioxide-rich wells in the southwestern United States

Studies of naturally occurring subsurface carbon dioxide (CO 2 ) accumulations can provide useful information for potential CO 2 injection projects; however, the microbial communities and formation water geochemistry of most reservoirs are understudied. Formation water and microbial biomass were sampled at four CO 2 -rich reservoir sites: two within Bravo Dome, a commercial CO 2 field in New Mexico; one northwest of Bravo Dome in Colorado (Oakdale Field); and one southwest of Bravo Dome in New Mexico (Rafter “K” Ranch). Aside from the Rafter “K” Ranch site, minor differences were observed in the geochemistry of formation water collected from these sites compared to historical data. No organisms were significantly associated with Oakdale Field compared to the other three sites, nor were any hydrogeochemical or gas geochemical parameters (for example, CO 2 concentration) found to have significant associations with the microbial ecology of these four sites. Microorganisms from these sites were metabolically diverse and had the potential to (1) generate methane, (2) produce corrosive hydrogen sulfide (H 2 S), and (3) rapidly biofoul and (or) clog pore spaces by shifting microbial communities with changes in salinity or nutrient supply. This study demonstrates that high concentrations of CO 2 in subsurface reservoirs apparently have not imparted a distinct geochemical or microbiological signature on the associated formation waters and that the microorganisms in these reservoirs are metabolically diverse and could adapt to geochemical changes in the subsurface.

Colorado, New Mexico, Texas, Oklahoma↗

Formation of methane and carbon dioxide from dimethylselenide in anoxic sediments and by a methanogenic bacterium

Anaerobic San Francisco Bay salt marsh sediments rapidly metabolized [ 14 C]dimethylselenide (DMSe) to 14 CH 4 and 14 CO 2 . Addition of selective inhibitors (2-bromoethanesulfonic acid or molybdate) to these sediments indicated that both methanogenic and sulfate-respiring bacteria could degrade DMSe to gaseous products. However, sediments taken from the selenium-contaminated Kesterson Wildlife Refuge produced only 14 CO 2 from [ 14 C]DMSe, implying that methanogens were not important in the Kesterson samples. A pure culture of a dimethylsulfide (DMS)-grown methylotrophic methanogen converted [ 14 C]DMSe to 14 CH 4 and 14 CO 2 . However, the organism could not grow on DMSe. Addition of DMS to either sediments or the pure culture retarded the metabolism of DMSe. This effect appeared to be caused by competitive inhibition, thereby indicating a common enzyme system for DMS and DMSe metabolism. DMSe appears to be degraded as part of the DMS pool present in anoxic environments. These results suggest that methylotrophic methanogens may demethylate methylated forms of other metals and metalloids found in nature.

California↗

Microbiological reduction of Sb(V) in anoxic freshwater sediments

Microbiological reduction of millimolar concentrations of Sb(V) to Sb(III) was observed in anoxic sediments from two freshwater settings: (1) a Sb- and As-contaminated mine site (Stibnite Mine) in central Idaho and 2) an uncontaminated suburban lake (Searsville Lake) in the San Francisco Bay Area. Rates of Sb(V) reduction in anoxic sediment microcosms and enrichment cultures were enhanced by amendment with lactate or acetate as electron donors but not by H2, and no reduction occurred in sterilized controls. Addition of 2- 14 C-acetate to Stibnite Mine microcosms resulted in the production of 14 CO 2 coupled to Sb(V) reduction, suggesting that this process proceeds by a dissimilatory respiratory pathway in those sediments. Antimony(V) reduction in Searsville Lake sediments was not coupled to acetate mineralization and may be associated with Sb-resistance. The microcosms and enrichment cultures also reduced sulfate, and the precipitation of insoluble Sb(III)-sulfide complexes was a major sink for reduced Sb. The reduction of Sb(V) by Stibnite Mine sediments was inhibited by As(V), suggesting that As(V) is a preferred electron acceptor for the indigenous community. These findings indicate a novel pathway for anaerobic microbiological respiration and suggest that communities capable of reducing high concentrations of Sb(V) commonly occur naturally in the environment.

Environmental Science & Technology↗

The organic geochemistry of black sedimentary barite: Significance and implications of trapped fatty acids

Fatty acids isolated in sedimentary black barite (BaSO 4 ) from Arkansas and Nevada were identified by gas chromatography-mass spectroscopy. The dominant or major fatty acids found in these beds of barite are C 16:0 , C 18:0 , and C 18:1 . The occurrence and distribution of these acids in this type of rock may serve as “molecular fingerprints” of microbial biogeochemical processes. The organic matter and associated microorganisms are shown to be trapped within the finely crystalline barite, thus forming a closed system for microbial diagenesis. Important differences that occur in the distribution of the lesser or minor fatty acids probably result from: (1) the nature of the progenitor organic detritus in the environment of barite deposition: and (2) the subsequent degree of microbiological alteration of the parent organic debris swept into and trapped in the depositional environment. Three general models of sedimentary environments are proposed in which anoxic conditions may prevail and where barium sulfate (BaSO 4 ) may precipitate: (1) in a silled basin with semi-restricted circulation; (2) on an outer continental shelf where the slope is encroached upon by water of the oxygen minimum layer; (3) on a low-energy, inner shelf or semi-restricted embayment impinged by a wedge of anoxic water. The major geochemical and geological parameters which are believed to be the significant factors controlling the formation and high grade of these organic-rich, black bedded barites are: (1) a unique source of barium-rich fluid that only contains trace amounts of other elements; (2) the presence of an anoxic bottom environment within the depositional basin; (3) a reflux source of sulfate ion; (4) an adequate source of organic matter. The results of this study may serve as guidelines for future exploration in similar, untested sedimentary basins, especially those with rocks of middle Paleozoic age.

Arkansas, Nevada↗

Growth and survival of Escherichia coli and enterococci populations in the macro-alga Cladophora (Chlorophyta)

The macro-alga Cladophora glomerata is found in streams and lakes worldwide. High concentrations of Escherichia coli and enterococci have been reported in Cladophora along the Lake Michigan shore. The objective of this study was to determine if Cladophora supported growth of these indicator bacteria. Algal leachate readily supported in vitro multiplication of E. coli and enterococci, suggesting that leachates contain necessary growth-promoting substances. Growth was directly related to the concentration of algal leachate. E. coli survived for over 6 months in dried Cladophora stored at 4°C; residual E. coli grew after mat rehydration, reaching a carrying capacity of 8 log CFU g -1 in 48 h. Results of this study also show that the E. coli strains associated with Cladophora are highly related; in most instances they are genetically different from each other, suggesting that the relationship between E. coli and Cladophora may be casual. These findings indicate that Cladophora provides a suitable environment for indicator bacteria to persist for extended periods and to grow under natural conditions.

FEMS Microbiology Ecology↗

Microbiological and chemical quality of ground water used as a source of public supply in southern Missouri — Phase II, April–July, 1998

The protection of public health through quality public ground-water systems is the responsibility of the U. S. Environmental Protection Agency and the State of Missouri, through the Missouri Department of Natural Resources, Public Drinking Water Program. Approximately 95 percent of the public-water supplies in Missouri use ground water as their source of drinking water through more than 3,700 public wells. Karst terrain, intensive agricultural operations, extensive numbers of on-site sewage systems, and poor well construction can lead to chemical and microbiological contamination of the contributing aquifers. Sitespecific studies and routine regulatory monitoring have produced information on the overall quality and potability of the State's public-drinking-water supplies, but little is known about the presence of viruses. The U.S. Geological Survey, in cooperation with the Missouri Department of Natural Resources, sampled 109 public-water supplies to characterize the physical, chemical, bacterial, and viral conditions in southern Missouri. During April to July 1998, these wells were sampled for nutrients, total organic carbon, optical brighteners, indicator bacteria, enteric viruses, and ribonucleic acid and somatic coli phages. These constituents indicate possible surface contamination of the sampled aquifer. Selection of the wells to be sampled depended on the age of the well (pre-1970), land use, geohydrology, and well construction. None of the physical or chemical constituents measured or analyzed exceeded Missouri's Drinking Water Standards set by the Public Drinking Water Program of the Missouri Department of Natural Resources. The majority of ammonia plus organic nitrogen, nitrite, and phosphorus concentrations were below the laboratory's minimum reporting levels. There were a greater number of detects above the minimum reporting level with respect to the nitrite plus nitrate, ammonia, orthophosphate, and total organic carbon concentrations. Analyses included comparing and contrasting the data by grouping according to well age and construction, karst type, geohydrology, soil type, and land use. There was little variation in well construction between selected wells. The results indicated several groupings of similar and dissimilar concentrations, most expected because of hydrological, physical, or land use differences. Dissolved oxygen values indicated distinct variation in the different groupings. There were significant differences in dissolved oxygen values between the secondary and non-karst areas, the Ozark confined and Ozark unconfined geohydrologic groups, and between agricultural and other land uses. In groupings by soil and geohydrology, the Missouri bootheel region differed with respect to ammonia, total organic carbon, and phosphorus when compared with the other groups. Less than 10 percent of the wells sampled tested positive for bacterial contamination. E. coli was the most frequently detected bacterium. The public wells at Monett and West Plains, Missouri, had plates with colonies too numerous to count for all three indicator bacteria. Further analyses by rRNA (ribosomal RiboNucleic Acid) hybridization techniques detennined that much of the bacteria present were from ruminant and human sources. No enteric viruses were detected in the 109 samples. Both ribonucleic acid and somatic coliphage were detected at two wells. One additional well had ribonucleic acid coliphage and another had somatic coliphage for a total of four wells with coliphage selects.

Missouri↗

Hydrogeochemical processes governing the origin, transport and fate of major and trace elements from mine wastes and mineralized rock to surface waters

The formation of acid mine drainage from metals extraction or natural acid rock drainage and its mixing with surface waters is a complex process that depends on petrology and mineralogy, structural geology, geomorphology, surface-water hydrology, hydrogeology, climatology, microbiology, chemistry, and mining and mineral processing history. The concentrations of metals, metalloids, acidity, alkalinity, Cl - , F - and SO 4 2- found in receiving streams, rivers, and lakes are affected by all of these factors and their interactions. Remediation of mine sites is an engineering concern but to design a remediation plan without understanding the hydrogeochemical processes of contaminant mobilization can lead to ineffective and excessively costly remediation. Furthermore, remediation needs a goal commensurate with natural background conditions rather than water-quality standards that might bear little relation to conditions of a highly mineralized terrain. This paper reviews hydrogeochemical generalizations, primarily from US Geological Survey research, that enhance our understanding of the origin, transport, and fate of contaminants released from mined and mineralized areas. Mobility of potential or actual contaminants from mining and mineral processing activities depends on (1) occurrence : is the mineral source of the contaminant actually present? (2) abundance : is the mineral present in sufficient quantity to make a difference? (3) reactivity : what are the energetics, rates, and mechanisms of sorption and mineral dissolution and precipitation relative to the flow rate of the water? and (4) hydrology : what are the main flow paths for contaminated water? Estimates of relative proportions of minerals dissolved and precipitated can be made with mass-balance calculations if minerals and water compositions along a flow path are known. Combined with discharge, these mass-balance estimates quantify the actual weathering rate of pyrite mineralization in the environment and compare reasonably well with laboratory rates of pyrite oxidation except when large quantities of soluble salts and evaporated mine waters have accumulated underground. Quantitative mineralogy with trace-element compositions can substantially improve the identification of source minerals for specific trace elements through mass balances. Post-dissolution sorption and precipitation (attenuation) reactions depend on the chemical behavior of each element, solution composition and pH, aqueous speciation, temperature, and contact-time with mineral surfaces. For example, little metal attenuation occurs in waters of low pH (<3.5) and metals tend to maintain element ratios indicative of the main mineral or group of minerals from which they dissolved, except Fe, SiO 2 , and redox-sensitive oxyanions (As, Sb, Se, Mo, Cr, V). Once dissolved, metal and metalloid concentrations are strongly affected by redox conditions and pH. Iron is the most reactive because it is rapidly oxidized by bacteria and archaea and Fe(III) hydrolyzes and precipitates at low pH (1&ndash;3) which is related directly to its first hydrolysis constant, pK 1 = 2.2. Several insoluble sulfate minerals precipitate at low pH including anglesite, barite, jarosite, alunite and basaluminite. Aluminum hydrolyzes near pH 5 (pK 1 = 5.0) and provides buffering and removal of Al by mineral precipitation from pH 4&ndash;5.5. Dissolved sulfate behaves conservatively because the amount removed from solution by precipitation is usually too small relative to the high concentrations in the water column and relative to the flow rate of the water.

Applied Geochemistry↗

Hydrogeology, water quality, and water-resources development potential of the upper Floridan Aquifer in the Valdosta area, south-central Georgia

Water quality in the Upper Floridan aquifer in the Valdosta, Georgia area is adversely affected by direct recharge from the Withlacoochee River. Water enters the aquifer along a short reach of the river where sinkholes have formed in the stream bed. The water receives little filtration as it recharges the Upper Floridan aquifer through these sinkholes. Naturally occurring organic material in the river provides a readily available source of energy for the growth of microbiota in the aquifer. Microbiological processes and chemical reactions in the aquifer produce methane and hydrogen sulfide as the water from the river mixes with ground water and moves downgradient in the aquifer. Humic substances associated with the organic material in the ground water in this area can form trihalomethanes when the water is chlorinated for public supply. To assess areas most suitable for ground-water supply development, areal distributions of total organic carbon, total sulfide, and methane in the Upper Floridan aquifer were mapped and used to evaluate areas affected by recharge from the Withlacoochee River. Areas where concentrations of total organic carbon, total sulfide, and methane were less than or equal to 2.0 milligrams per liter, 0.5 milligrams per liter, and 100 micrograms per liter, respectively, were considered to be relatively unaffected by recharge from the river and to have the greatest potential for water- resources development.

Georgia↗

Microbiology and oxidation-reduction geochemistry of the water-table and Memphis aquifers in the Allen well field, Shelby County, Tennessee

The shallow and Memphis aquifers in Shelby County, Tennessee, are valuable natural resources that are used for domestic, public-supply, and agricultural water use. The Memphis aquifer is the primary source for public supply in West Tennessee and provides 170 to 175 million gallons of water per day for more than 900,000 people (Robinson, 2018). The shallow aquifer includes the unconfined water table, provides domestic water supplies in Shelby County, and is susceptible to contamination from urban and industrial activities, underground storage tanks, old dumps, and other sources. Both aquifers are likely to be stressed in the future by factors such as population increase, contaminant migration from historical contamination sites, industrial and agricultural activities, climate change, and other competing demands on the water resources.

Tennessee↗

Microbial degradation of hydrochlorofluorocarbons (CHCl2F and CHCl2CF3) in soils and sediments

The ability of microorganisms to degrade trace levels of the hydrochlorofluorocarbons HCFC-21 and HCFC-123 was investigated. Methanotroph- linked oxidation of HCFC-21 was observed in aerobic soils, and anaerobic degradation of HCFC-21 occurred in freshwater and salt marsh sediments. Microbial degradation of HCFC-123 was observed in anoxic freshwater and salt marsh sediments, and the recovery of 1,1,1-trifluoro-2-chloroethane indicated the involvement of reductive dechlorination. No degradation of HCFC-123 was observed in aerobic soils. In same experiments, HCFCs were degraded at low (parts per billion) concentrations, raising the possibility that bacteria in nature remove HCFCs from the atmosphere.

Applied and Environmental Microbiology↗

Natural inactivation of MS2, poliovirus type 1 and Cryptosporidium parvum in an anaerobic and reduced aquifer

Aims The study of microbial inactivation rates in aquifer systems has most often been determined in aerobic and oxidized systems. This study examined the inactivation (i.e. loss of infectivity) of MS2, poliovirus type 1 (PV1) and Cryptosporidium parvum in an anaerobic and reduced groundwater system that has been identified as storage zones for aquifer storage and recovery (ASR) facilities. Methods and Results Anaerobic and reduced (ORP < − 250 mV) groundwater from an artesian well was diverted to an above-ground, flow-through mesocosm that contained diffusion chambers filled with MS2, PV1 or Cryptosporidium parvum . The respective infectivity assays were performed on microorganisms recovered from the diffusion chambers during 30- to 58-day experiments. The net reduction in infectivity was 5.73 log 10 over 30 days for MS2, 5.00 log 10 over 58 days for PV1 and 4.07 log 10 over 37 days for C . parvum . The best fit inactivation model for PV1 was the log-linear model and the Weibull model for MS2 and C . parvum , with respective inactivation rates (95% confidence interval) of 0.19 (0.17–0.21) log 10 day −1 , 0.31 (0.19–0.89) log 10 day −1 and 0.20 (0.14–0.37) log 10 day −1 . Conclusions The groundwater geochemical conditions in this aquifer enhanced the inactivation of MS2, PV1, and C . parvum at rates approximately 2.0–5.3-fold, 1.2–17.0-fold, and 4.5–5.6-fold greater, respectively, than those from published studies that used diffusion chambers in aerobic-to-anoxic groundwater systems, with positive redox potentials. Significance and Impact of the Study Geochemical conditions like those in the aquifer zone in this study can naturally and significantly reduce concentrations of microbial indicators and pathogens of human health concern in injected surface water. Appropriate storage times for injected surface water could complement above-ground engineered processes for microorganism removal and inactivation (e.g. filtration, disinfection) by naturally increasing overall microorganism log-inactivation rates of ASR facilities.

Journal of Applied Microbiology↗

Spatial and temporal changes in microbial community structure associated with recharge-influenced chemical gradients in a contaminated aquifer

In a contaminated water‐table aquifer, we related microbial community structure on aquifer sediments to gradients in 24 geochemical and contaminant variables at five depths, under three recharge conditions. Community amplified ribsosomal DNA restriction analysis (ARDRA) using universal 16S rDNA primers and denaturing gradient gel electrophoresis (DGGE) using bacterial 16S rDNA primers indicated: (i) communities in the anoxic, contaminated central zone were similar regardless of recharge; (ii) after recharge, communities at greatest depth were similar to those in uncontaminated zones; and (iii) after extended lack of recharge, communities at upper and lower aquifer margins differed from communities at the same depths on other dates. General aquifer geochemistry was as important as contaminant or terminal electron accepting process (TEAP) chemistry in discriminant analysis of community groups. The Shannon index of diversity ( H ) and the evenness index ( E ), based on DGGE operational taxonomic units (OTUs), were statistically different across community groups and aquifer depths. Archaea or sulphate‐reducing bacteria 16S rRNA abundance was not clearly correlated with TEAP chemistry indicative of methanogenesis or sulphate reduction. Eukarya rRNA abundance varied by depth and date from 0 to 13% of the microbial community. This contaminated aquifer is a dynamic ecosystem, with complex interactions between physical, chemical and biotic components, which should be considered in the interpretation of aquifer geochemistry and in the development of conceptual or predictive models for natural attenuation or remediation.

Environmental Microbiology↗

The green alga, Cladophora, promotes Escherichia coli growth and contamination of recreational waters in Lake Michigan

A linkage between Cladophora mats and exceedances of recreational water quality criteria has been suggested, but not directly studied. Th is study investigates the spatial and temporal association between Escherichia coli concentrations within and near Cladophora mats at two northwestern Lake Michigan beaches in Door County, Wisconsin. Escherichia coli concentrations in water underlying mats were significantly greater than surrounding water (p < 0.001). Below mat E. coli increased as the stranded mats persisted at the beach swash zone. Water adjacent to Cladophora mats had lower E. coli concentrations, but surpassed EPA swimming criteria the majority of sampling days. A signifi cant positive association was found between E. coli concentrations attached to Cladophora and in underlying water (p < 0.001). The attached E. coli likely acted as a reservoir for populating water underlying the mat. Fecal bacterial pathogens, however, could not be detected by microbiological culture methods either attached to mat biomass or in underlying water. Removal of Cladophora mats from beach areas may improve aesthetic and microbial water quality at affected beaches. These associations and potential natural growth of E. coli in bathing waters call into question the efficacy of using E. coli as a recreational water quality indicator of fecal contaminations. Copyright ?? 2010 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

Journal of Environmental Quality↗

Bacterial Cycling of Methyl Halides

This chapter focuses on the monohalogenated methanes methyl chloride (MeCl) and methyl bromide (MeBr), their natural and anthropogenic sources, and their degradation by microorganisms, specifically by aerobic bacteria that can use MeBr and MeCl as sole source of carbon and energy. The biogeochemical cycle of methyl halides and the microbiology, biochemistry, genetics, and biotechnological potential of methyl halide-degrading microorganisms are discussed in the chapter. Methyl halides are the dominant halocarbons in the atmosphere. They play an important role in regulating stratospheric ozone concentrations and global warming as well, two factors governing planetary habitability. The monohalomethanes—methyl chloride (MeCl), methyl bromide (MeBr), and methyl iodide (MeI)—are trace gases in the atmosphere with average tropospheric-mixing ratios of 600, 10, and 2 parts per trillion (ppt), respectively. However, methyl halides are radiatively active and hence contribute to global warming by absorbing radiation in the infrared region. This is evident in their elevated global warming potential (GWP), a value calculated to quantify each compound's warming effect (on a mass basis) relative to the same mass of CO 2 . Compounds with high GWP including those like methyl halides with low concentrations may have considerable impact on atmospheric warming when compared with other “greenhouse” gases with low GWP.

Advances in Applied Microbiology↗

Epifluorescent direct counts of bacteria and viruses from topsoil of various desert dust storm regions

Topsoil from arid regions is the main source of dust clouds that move through the earth's atmosphere, and microbial communities within these soils can survive long-range dispersion. Microbial abundance and chemical composition were analyzed in topsoil from various desert regions. Statistical analyses showed that microbial direct counts were strongly positively correlated with calcium concentrations and negatively correlated with silicon concentrations. While variance between deserts was expected, it was interesting to note differences between sample sites within a given desert region, illustrating the 'patchy' nature of microbial communities in desert environments.

Research in Microbiology↗

Assessment of microbiological contamination of the Jacks Fork within the Ozark National Scenic Riverways, Missouri—phase I

The Ozark National Scenic Riverways (ONSR), the Nation's first scenic riverway, was created by an Act of Congress (Public Law 88-492) on August 24, 1964, for "the purpose of conserving and interpreting unique scenic and other natural values and objects of historic interest, including preservation of parts of the Current River and the Jacks Fork River in Missouri as free-flowing streams, preservation of springs and caves, management of wildlife, and provisions for use and enjoyment of the outdoor recreation resources thereof by the people of the United States" (National Park Service, 1981). The primary natural resources protected by the park are 134 miles of the Current and Jacks Fork Rivers. About 1.5 million people visit the ONSR annually to take advantage of excellent recreational opportunities, including canoeing, johnboating, swimming, fishing, tubing, camping, hiking, caving, horseback riding, and hunting.

Fact Sheet↗