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Strand et al. (2002) discovered small metal alloy grains rich in Cu, Co, and Sn (maximum size 150 µm) in vesicles of lava from Kilauea Volcano. These alloys are also found in basaltic rocks of several Italian volcanoes. To better understand the origin of these metal-rich grains, bombs from Stromboli Volcano were examined. Two bomb types were collected from Stromboli: pumiceous bombs and scoriaceous bombs. Bulk rock trace element geochemistry indicates that there are no significant differences in Cu, Co, or Sn (the three major components of the metal alloys) between the pumiceous and scoriaceous bombs. Comparison of olivine melt inclusion and matrix glass concentrations from these rocks shows that the pumiceous bombs are more primitive (melt inclusions: MgO 2.7-5.8 wt. %; matrix glass: MgO 5.1-6.50 wt. %) and are more S-rich (melt inclusions: maximum 0.13 wt. %; matrix glass: maximum 0.06 wt. % ) than the scoriaceous bombs. The melt inclusions and matrix glass in the scoriaceous bombs are more evolved (melt inclusions: MgO 3.0-4.3 wt. %; matrix glass: MgO 2.7-3.7 wt. %) and are S-poor (melt inclusions: maximum 0.06 wt. %; matrix glass: b.d.l. ). However, Cl concentrations in melt inclusions and matrix glass are more similar for both bomb types. Metal alloys were counted in thin section for each sample. The crystallized interiors of the bombs contain more metal grains than the glassy exteriors. Pumiceous bombs (from more primitive, S-rich magma) contain more metal grains of a larger size than the scoriaceous bombs (from more fractionated, S-poor magma). This indicates that S (and Cl) are probable transport ligands for the metals in the alloys. As S (and Cl) move through the glass of an erupted cooling bomb, they complex with volatile chalcophile metals (Cu, Co, and Sn). These vapor-phase metal sulfides and chlorides move to inflating vesicles. Here the sulfide and chloride complexes become reduced and metal alloys condense, as S and Cl escape as gas. Non-degassed primitive magma may provide more S (but not necessarily more metals) to create the higher abundance of alloys hosted by the vesicles of the pumiceous bombs.

Eleven gas species, including CO, CO2, H2, H2O, H2S, HCl, NOX, O2, SO2, COS and SO3, were measured in a 150 kWth, staged, pulverized coal, down-fired combustor using a Fourier transform infrared (FTIR) spectrometer, gas chromatograph (GC), and a Horiba PG-250 5-gas analyzer. Additional gases such as HCN, NH3, CH4, and other hydrocarbons were also measured. Seven coals of varying rank and composition were investigated. Measurements were obtained in reducing (S.R. = 0.85) and oxidizing (S.R. = 1.15) conditions. In particular, sulfur- and chlorine-containing species including H2S, SO2, COS, SO3, and HCl are discussed. In the reducing zone, all four measured sulfur species were present although SO3 was only 1-3% of the total coal sulfur. A trade-off between SO2, H2S, and COS was clearly identifiable according to S.R. H2S and COS increased and SO2 decreased in highly reducing or high-CO regions. The total amount of sulfur in the measured species in the reducing zone was estimated to be about 65-80% of the total coal sulfur. The total amount of sulfur measured in the four gases increased linearly with coal sulfur in both the oxidizing and reducing zones for the seven coals considered. In the oxidizing zone, SO3 remained low (1-3% of total sulfur) with the only other measurable sulfur bearing species being SO2. Chlorine was found to be released in the reducing zone and form primarily HCl. As the HCl was transported into the oxidizing region, the chlorine remained as HCl. Measurement of HCl was difficult, making some of the data incomplete. The HCl concentration was found to be affected by the flow rate of gases into the sampling line and gas analyzers suggesting HCl is highly reactive and needs to be quenched rapidly or it will react during sampling. Several trends in the data were matched by equilibrium calculations including trends for H2S, COS and SO2 in both reducing and oxidizing conditions. SO3 did not match equilibrium although the amount of SO3 was proportional to the amount of sulfur in the coal. HCl, though consistent with cited literature for several coals, did not agree with equilibrium trends or values.

M. S.

Three oxidants have been evaluated for use as alternative chemical pretreatments for Fena Lake, a surface water that supplies the U.S. Navy's Public Water System (PWS) on the volcanic island of Guam. The study consisted of two investigative components. The first and primary component included a bench-scale evaluation to study the effects of different pre-oxidant chemicals on the formation of chlorinated disinfection by-products (DBPs). The second and ancillary component included a series of water treatment and distribution system management studies that analyzed DBP formation within the treatment plant and water distribution system. The goal of this research was to reduce total trihalomethane (TTHM) and the five haloacetic acid (HAA5) formations in the PWS. In the primary component of the research, raw surface water from Fena Lake was collected by U.S. Navy personnel and shipped to University of Central Florida (UCF) laboratories for experimentation. Bench-scale tests that simulated the coagulation, flocculation, sedimentation and filtration (CSF) that comprises the Navy Water Treatment Plant (NWTP) were used to evaluate the use of two alternative pre-oxidants, potassium permanganate (KMnO4) and chlorine dioxide (ClO2) in lieu of gaseous chlorine (Cl2). The research assessed DBP formation by comparing several pretreatment scenarios, namely: (1) no pretreatment, (2) chlorine pretreatment, and (3) alternative oxidant pretreatment. KMnO4 pretreatment resulted in the lowest percent reduction of TTHMs and HAA5 relative to chlorine pretreatment, at 5.7% and 22.7%, respectively; however, this amount was still a reduction from the results demonstrated for the chlorine pretreatment condition. Without using a pre-oxidant, TTHM and HAA5 formation were reduced by 22.8% and 37.3%, respectively, relative to chlorine pretreatment. Chlorine dioxide demonstrated the greatest TTHM and HAA5 reduction relative to chlorine pretreatment at 34.4% and 53.3%, respectively. The second component of research consisted of a series of studies that evaluated distribution system operations and management alternatives to identify opportunities that could achieve DBP reduction within the PWS. Three concerns that were addressed were the NWTP's compliance with the U.S. Environmental Protection Agency's (USEPA's) Stage 2 Disinfectants/Disinfection By-Products (D/DBP) Rule, variable hydraulic detention times within a small subdivision in the distribution system, and severe weather. It was determined that: (1) A decision based on in-plant studies to cease prechlorination at the NWTP resulted in a decrease in TTHMs and HAA5s throughout the distribution system by 62% and 75%, respectively; (2) A fluoride tracer study led to the discovery of a valved pipeline responsible for elevated DBPs because of excessive water age that when exercised and managed resolved intermittent DBP spikes in the PWS; and (3) when the NWTP's ballasted floc clarifier (BFC) was operated in-series prior to the conventional CSF process during severe weather conditions the TTHM and HAA5 were below 39 ug/L and 29 ug/L, respectively, proving BFC in-series is a practical option for the plant during severe weather.

Total lead release in drinking water in the presence of free chlorine and chloramine residuals was investigated in field, laboratory and fundamental investigations for finished waters produced from ground (GW), surface (SW), saline (RO) and blended (B) sources. Field investigations found more total lead was released in the presence of chloramines than in the presence of free chlorine for RO and blended finished waters; however, there were no statistical differences in total lead release to finished GW and SW. Laboratory measurements of finished waters oxidation-reduction potential (ORP) were equivalent by source and were not affected by the addition of more than 100 mg/L of sulfates or chlorides, but were significantly higher in the presence of free chlorine relative to chloramines. Development of Pourbaix diagrams revealed the PbO2 was the controlling solid phase at the higher ORP in the presence of free chlorine and Pb3(CO3)2(OH)2(s) (hydrocerussite) was the controlling solid phase in the presence of chloramines at the lower ORP, which mechanistically accounted for the observed release of total lead as PbO2 is much less soluble than hydrocerussite. The lack of differences in total lead release to finished GW and SW was attributed to differences in water quality and intermittent behavior of particulate release from controlling solid films.

Hydrogen peroxide and chlorine detection is critical for many biological and environmental applications. Hydrogen peroxide plays important roles in a variety of fields including plant physiology, medical, environmental and biochemical applications. Its role in plant defense and signal transduction, diseases such as Parkinson's and Alzhemier's, industrial processes such as disinfection and wastewater treatment and biochemical enzymatic reactions is critical. Given the gamut of areas that hydrogen peroxide is a key component of; its detection assumes great importance. Similarly chlorine has long been used as a disinfectant for making drinking water safe, but excessive chlorination is an environmental and health hazard in itself. In this work, micromachining techniques have been used to design, fabricate and test electrochemical sensors and microneedle structure that can be integrated for detection of hydrogen peroxide and free chlorine. A novel nanomaterial has been integrated with the hydrogen peroxide microsensor, which greatly increases the sensor lifetime and robustness. Miniaturization, low detection limits, high sensitivity and selectivity, as well as ease of fabrication are some of the other advantages of this work.

The objective of the study was to compare the trihalomethanes (THMs) produced from ferrate with hypochlorite and to determine how different the THM production would be for a given degree of disinfection (3 log reduction in Heterotrophic Plate Count (HPC)). Different water samples were collected from Lake Claire, Atlantic Ocean, and secondary effluent from an advanced wastewater treatment plant. THM formation was determined using a standard assay over 7 days at room temperature. In addition samples were tested for Total Coliform Escherichia coli (TC/E.coli), and heterotrophic bacteria using HPC by spreadplating on R2A agar. Dissolved organic carbon (DOC) was measured as well. Dosages of 2, 5, and 10 ppm of hypochlorite and ferrate were used for Lake Claire and Atlantic Ocean water, while 1, 2, and 5 ppm dosages were used for wastewater treatment effluent. Ferrate resulted in 48.3% ± 11.2% less THM produced for the same level of disinfection (i.e. approximately 3 logs reduction in HPC). Oxidation of DOC was relatively small with a 6.1 to 11.6 % decrease in DOC being observed for ferrate doses from 2 to 10 mg/L. Free chlorine oxidation of DOC was negligible.

The objective of this research was to demonstrate the application of ultrasound to field sites having problems with precipitation build up and corrosion. PTW s are passive reactive walls containing zero-valent iron metal for in-situ remediation of contaminated groundwater. However, loss of reactivity over time due to build up of corrosion and other precipitates on the iron surface is a major concern. Ultrasound energy has been established as an effective tool for revitalizing iron surface. This research applied ultrasound energy to a zero-valent iron wall constructed below the ground surface to remove precipitates and iron corrosion, increasing iron reactivity. Two field sites were selected for the ultrasound application research project. These sites have PTWs installed for the remediation of chlorinated compounds such as TCE and its daughter products. The first site is located at Launch Complex 34 (LC 34), Cape Canaveral Air Station, Florida. The second site is located at Denver Federal Center, Lakewood, Colorado. The ultrasound was applied to these sites by introducing an ultrasonic transducer in wells installed within the wall or just upstream of the wall and then applying ultrasonic energy to the entire depth of the wall. The apparatus used for ultrasound application was an omni-directional tubular resonator. Two such ultrasound units with frequencies of 25 kHz and 40 kHz were used for ultrasound treatment. Kinetic batch studies were performed on iron samples taken before and after ultrasound treatment. The degradation rate constants and half-life values for TCE were then calculated and con1pared for pre-ultrasound and post-ultrasound iron san1p les. Sin1ultaneously grounchvater \vas analyzed for di ffercnt VOCs. Soni cation period as brief as 30 n1inutes sho\vcd signi fie ant in1pact on the firstorder rate constants for TCE degradation. An increase in sonication period proved to be even n1ore effective. A sonication period of 90 n1inutes decreased TCE half-life by 30-40% for the 40-kHz resonator and 60-75~o for the 25-kHz resonator, for both the field sites. The 25-kHz resonator proved to be more effective than the 40-kHz resonator. For both field sites, ultrasound treatn1ent significantly increased TCE degradation rates, indicating a ren1oval of corrosion products and precipitates from the iron surface due to ultrasound. This technology has shown a great potential in revitalizing iron reactivity, effectively increasing the PTW life expectancy.

Waste-fired boilers suffer severely from corrosion of critical components such as superheater tubes. In this work the high temperature corrosion of candidate superheater alloys have been investigated by detailed laboratory studies and controlled field exposures in full-scale boilers. In a laboratory study the detrimental effect of gaseous hydrochloric acid (HCl) on three  different ground surface and preoxidised austenitic stainless steels was investigated. Exposures were conducted in an environment comprising N2-10O2-5H2O-0.05HCl at both 400 °C and 700 °C. A positive effect of preoxidation is evident when the alloys are exposed at 400 °C. Oxide layers formed during preoxidation effectively suppress chlorine ingress and lower the corrosion rate for all three materials while accelerated corrosion and chlorine accumulation at the metal/oxide interface is detected for ground surface specimens. The positive effect of preoxidation is lost at 700 °C and corrosion resistance is dependent on alloying level. At 700 °C metal chloride evaporation contributes significantly to the material degradation. Based on the results, high temperature corrosion in the presence of gaseous HCl is discussed in general terms.  In two different waste-fired boilers measures for counteracting superheater corrosion were investigated. In a grate-boiler the deposit formation and high temperature corrosion of some candidate superheater materials were studied. Metal loss measurements showed unacceptably high corrosion rates for the lower alloyed ferritic steels 13CrMo44 (Fe-1Cr-0.5Mo) and HCM12A (Fe-11Cr-2W), as well as for the austenitic Super 304 (Fe-18Cr-9Ni-3Cu). The corrosion attack for these alloys was manifested by the formation of mixed metal chloride/metal oxide scales. A different type of behaviour was seen for the higher alloyed austenitic steels and nickel-base alloys, which were able to form a chromium-enriched oxide next to the metal. However, the alloys suffered from localised pitting attack. Since analyses of the deposit revealed appreciable amounts of low melting salt mixtures such as ZnCl2-KCl, PbCl2-KCl, FeCl2-KCl and NaCl-NiCl2, oxide dissolution in these molten salts is the probable reason for pitting attack. In a waste-fired boiler ammonium sulphate solution was added to the flue gas and the effect on flue gas and deposit composition was evaluated. It was evident that the sulphur-rich additive reduced the amount of alkali chlorides in both the flue gas and the deposit. Results also indicated that the initial corrosion rates were lowered with the use of ammonium sulphate. It was concluded that using the additive could be a possible strategy for changing the flue gas chemistry so that superheater corrosion is mitigated. / <p>QC 20110414</p>