Geothermal power plants at Mt. Amiata (Tuscany-Italy): mercury and hydrogen sulphide deposition revealed by vegetation

At Mt. Amiata (Italy) geothermal energy is used, since 1969, to generate electricity in five plants with a nominal capacity of 88 MW. Anomalous levels of mercury characterise geothermal fluids of Mt. Amiata, an area renowned for its vast cinnabar deposits and for the mercury production carried out in the past. Mercury emission rates range from 300 to 400 g/h, or 3-4 g/h per MW electrical installed capacity. These emissions are coupled with a release of 7-8 kg/(h MW) of hydrogen sulphide (H2S). Mercury is discharged as Hg0 gaseous species and reaches the atmosphere with the non-condensable gas fraction. In this fraction, CO, is the major component (94-98%), H2S is around 1% and mercury concentration is as high as 1-10 mg/Nm3. Leaves of a spontaneous grass (Avena sterilis), at the end of the vegetative cycle, were used as mercury bioconcentrators to map deposition near geothermal power plants and to calculate the corresponding average levels of Hg0 in the air. Direct measurements of mercury and hydrogen sulphide vapours in the air reached by power plant emissions showed a ratio of about 1-2000. This ratio was applied to calculate average levels of hydrogen sulphide starting from mercury deposition mapping: typical concentrations of mercury and hydrogen sulphide were of the order of 10-20 ng/m3 and 20-40 microg/m3, respectively.     

Catalytic combustion of methane over commercial catalysts in presence of ammonia and hydrogen sulphide

The performance of different commercially available catalysts (supported Pd, Pt, Rh, bimetallic Pd-Pt, and Cr-Cu-Ti oxide catalyst) for the oxidation of methane, alone and in presence of ammonia and hydrogen sulphide is studied in this work. Catalysts performance was evaluated both in terms of activity and resistance to poisoning. The main conclusions are that supported Pd and Rh, present the highest activities for methane oxidation, both alone and in presence of ammonia, whereas they are severely poisoned in presence of H2S. Pt and Cr-Cu-Ti are less active but more sulphur resistant, but their activity is lower than the residual activity of sulphur-deactivated Pd and Rh catalysts. The Pd-Pt catalyst exhibits low activity and it is quickly deactivated in presence of hydrogen sulphide.     

Photolysis of low concentration H2S under UV/VUV irradiation emitted from microwave discharge electrodeless lamps

The photolysis of simulating low concentration of hydrogen sulfide malodorous gas was studied under UV irradiation emitted by self-made microwave discharge electrodeless lamps (i.e. microwave UV electrodeless mercury lamp (185/253.7 nm) and iodine lamp (178.3/180.1/183/184.4/187.6/206.2 nm)). Experiments results showed that the removal efficiency (eta H2S) of hydrogen sulfide was decreased with increasing initial H2S concentration and increased slightly with gas residence time; H2S removal efficiency was decreased dramatically with enlarged pipe diameter. Under the experimental conditions with pipe diameter of 36 mm, gas flow rate of 0.42 standard l s(-1), eta H2S was 52% with initial H2S concentration of 19.5 mg m(-3) by microwave mercury lamp, the absolute removal amount (ARA) was 4.30 microg s(-1), and energy yield (EY) was 77.3 mg kW h(-1); eta H2S was 56% with initial H2S concentration of 18.9 mg m(-3) by microwave iodine lamp, the ARA was 4.48 microg s(-1), and the EY was 80.5mg kW h(-1). The main photolysis product was confirmed to be SO4(2-) with IC.     

Effect of lead, mercury and cadmium on a sulphate-reducing bacterium

A sulphate-reducing bacterial strain isolated from the south-west coast of India resembling Desulfosarcina in its physiology was tested for its behaviour towards HgCl(2), CdSO(4) and Pb(NO(3))(2). The order of toxicity to growth of these metal salts in a lactate-based medium at 50 microg ml(-1) concentrations was Cd>Pb>Hg and to respiration Pb>Cd>Hg. Inhibitory concentrations (viz. 100 microg ml(-1) of HgCl(2) and 200 microg ml(-1) of Pb(NO(3)(2)) had a stimulatory effect when the substrate was changed to acetate. With sodium acetate at 0.1% concentration, Hg and Pb had maximum stimulatory effect for growth and sulphide production. Experiments conducted directly with sediment slurries amended with lactate showed that all three metals (at levels below their inhibitory concentrations, i.e. 50 microg ml(-1) of metal salt for Cd and Hg and 100 microg ml(-1) for Pb) inhibited sulphate-reducing activity (SRA) with Pb decreasing the peak production by 68%. The order of toxicity in both lactate and acetate-amended slurry was Pb>Cd>Hg and Pb>Hg>Cd, respectively. With acetate, SRA in the presence of Cd and Hg was stimulated 110% and 27%, respectively. Pb inhibited SRA by 11%. There is a general reduction in the inhibition of sulphide production in slurries as compared with pure culture of the isolate.     

Analysis of anaerobic BTX biodegradation in a subarctic aquifer using isotopes and benzylsuccinates

In situ biodegradation of benzene, toluene, and xylenes in a petroleum hydrocarbon contaminated aquifer near Fairbanks, Alaska was assessed using carbon and hydrogen compound specific isotope analysis (CSIA) of benzene and toluene and analysis of signature metabolites for toluene (benzylsuccinate) and xylenes (methylbenzylsuccinates). Carbon and hydrogen isotope ratios of benzene were between -25.9 per thousand and -26.8 per thousand for delta13C and -119 per thousand and -136 per thousand for delta2H, suggesting that biodegradation of benzene is unlikely at this site. However, biodegradation of both xylenes and toluene were documented in this subarctic aquifer. Biodegradation of xylenes was indicated by the presence of methylbenzylsuccinates with concentrations of 17-50 microg/L in three wells. Anaerobic toluene biodegradation was also indicated by benzylsuccinate concentrations of 10-49 microg/L in the three wells with the highest toluene concentrations (1500-5000 microg/L toluene). Since benzylsuccinate typically accounts for a very small fraction of the toluene present in groundwater (generally <1 mol%), the signature metabolite approach works best at higher toluene concentrations when it is not constrained by detection limits. In wells with lower toluene concentrations (410-640 microg/L), carbon and hydrogen isotopic values were enriched by up to approximately 2 per thousand for delta13C and approximately 70 per thousand for delta2H. This evidence of isotopic fractionation verifies the effects of biodegradation in these low concentration wells where metabolites may already be below detection limits. The combined use of signature metabolite and CSIA data is particularly valuable given the challenge of verifying biodegradation in subarctic environments where degradation rates are typically much slower than in temperate environments.     

Biological treatment process of air loaded with an ammonia and hydrogen sulfide mixture

The physico-chemical characteristics of granulated sludge lead us to develop its use as a packing material in air biofiltration. Then, the aim of this study is to investigate the potential of unit systems packed with this support in terms of ammonia and hydrogen sulfide emissions treatment. Two laboratory scale pilot biofilters were used. A volumetric load of 680 g H2S m(-3) empty bed day(-1) and 85 g NH3 m(-3) empty bed day(-1) was applied for eight weeks to a unit called BGSn (column packed with granulated sludge and mainly supplied with hydrogen sulfide); a volumetric load of 170 g H2S m(-3) empty bed day(-1) and 340 g NH3 m(-3) empty bed day(-1) was applied for eight weeks to the other called BGNs (column packed with granulated sludge and mainly supplied with ammonia). Ammonia and hydrogen sulfide elimination occur in the biofilters simultaneously. The hydrogen sulphide and ammonia removal efficiencies reached are very high: 100% and 80% for BGSn; 100% and 80% for BGNs respectively. Hydrogen sulfide is oxidized into sulphate and sulfur. The ammonia oxidation products are nitrite and nitrate. The nitrogen error mass balance is high for BGSn (60%) and BGNs (36%). This result could be explained by the denitrification process which would have occurred in anaerobic zones. High percentages of ammonia or hydrogen sulfide are oxidized on the first half of the column. The oxidation of high amounts of hydrogen sulfide would involve some environmental stress on nitrifying bacterial growth and activity.     

Co-treatment of hydrogen sulfide and methanol in a single-stage biotrickling filter under acidic conditions

Biofiltration of waste gases is cost-effective and environment-friendly compared to the conventional techniques for treating large flow rates of gas streams with low concentrations of pollutants. Pulp and paper industry off-gases usually contain reduced sulfur compounds, such as hydrogen sulfide and a wide range of volatile organic compounds (VOCs), e.g., methanol. It is desirable to eliminate both of these groups of compounds. Since the co-treatment of inorganic sulfur compounds and VOCs in biotrickling filters is a relatively unexplored area, the simultaneous biotreatment of H2S and methanol as the model VOC was investigated. The results showed that, after adaptation, the elimination capacity of methanol could reach around 236 g m(-3) h(-1) with the simultaneous complete removal (100%) of 12 ppm H2S when the empty bed residence time is 24 s. The pH of the system was around 2. Methanol removal was hardly affected by the presence of hydrogen sulfide, despite the low pH. Conversely, the presence of the VOC in the waste gas reduced the efficiency of H2S biodegradation. The maximal methanol removal decreased somewhat when increasing the gas flow rate. This is the first report on the degradation of methanol at such low pH in a biotrickling filter and on the co-treatment of H2S and VOCs under such conditions.     

Is the OECD acute worm toxicity test environmentally relevant? The effect of mineral form on calculated lead toxicity

In a series of experiments the toxicity of lead to worms in soil was determined following the draft OECD earthworm reproduction toxicity protocol except that lead was added as solid lead nitrate, carbonate and sulphide rather than as lead nitrate solution as would normally be the case. The compounds were added to the test soil to give lead concentrations of 625-12 500 microg Pb g(-1) of soil. Calculated toxicities of the lead decreased in the order nitrate> carbonate> sulphide, the same order as the decrease in the solubility of the metal compounds used. The 7-day LC50 (lethal concentration when 50% of the population is killed) for the nitrate was 5321+/-275 microg Pb g(-1) of soil and this did not change with time. The LC50 values for carbonate and sulphide could not be determined at the concentration ranges used. The only parameter sensitive enough to distinguish the toxicities of the three compounds was cocoon (egg) production. The EC50s for cocoon production (the concentration to produce a 50% reduction in cocoon production) were 993, 8604 and 10246 pg Pb g(-1) of soil for lead nitrate, carbonate and sulphide, respectively. Standard toxicity tests need to take into account the form in which the contaminant is present in the soil to be of environmental relevance.     

A high performance liquid chromatography method for determination of gas-phase hydrogen peroxide in ambient air using Fenton's chemistry

A new method for determination of hydrogen peroxide in atmospheric samples is described. Cryogenically collected H2O2 is reacted with sodium salicylate in the presence of Fe(2+) to produce dihydroxybenzoate, which is separated from the reaction mixture by high performance liquid chromatography and detected by UV absorption. Measurements of atmospheric H2O2 were conducted in Las Vegas, NV from June 1999 to December 1999 to evaluate and characterize the method. Measured mixing ratios of H2O2 (there were also non-detects) ranged from 0.012 to 2.74 ppbv, with expected correlations to primary gaseous pollutants and strong seasonal variation consistent with a photochemically derived species. It was concluded that the method is easy to use and has sufficient sensitivity and selectivity to be useful in atmospheric monitoring.     

生物法降解养殖场臭气中H_2S的反应器启动

畜禽养殖场臭气成分复杂,完全去除较为困难。生物法是目前应用较广泛的脱臭方法,其中能否将生物膜附着在填料上是影响生物法去除恶臭气体效率的重要因素。本实验采用定时定量投加Na2S的方式驯化活性污泥,并选用MLSS浓度和SO42-浓度增量变化2个指标作为污泥驯化成熟的指标,比传统的以MLSS作为污泥驯化成熟的指标更准确。采用循环污泥的挂膜方式,运行2 d后,通入新鲜的空气和H2S气体,2周后反应器启动成功。     

生物法降解养殖场臭气中H2S的反应器启动

畜禽养殖场臭气成分复杂,完全去除较为困难。生物法是目前应用较广泛的脱臭方法,其中能否将生物膜附着在填料上是影响生物法去除恶臭气体效率的重要因素。本实验采用定时定量投加Na2S的方式驯化活性污泥,并选用MLSS浓度和SO42-浓度增量变化2个指标作为污泥驯化成熟的指标,比传统的以MLSS作为污泥驯化成熟的指标更准确。采用循环污泥的挂膜方式,运行2 d后,通入新鲜的空气和H2S气体,2周后反应器启动成功。     

Solubility of volatile organic compounds in aqueous ammonia solution

The Ostwald solubility coefficient, L of 17 volatile organic compounds (VOCs) from the gas phase into water and dilute aqueous ammonia solutions was determined by the equilibrium partitioning in closed system-solid phase micro extraction (EPICS-SPME) method at 303 K and at 0-2.5 mol dm(-3) ammonia concentrations. Ammonia increased the solubility of all VOCs nearly linearly, but to a different extent. The difference in the solubility values in aqueous ammonia solutions (Lmix) compared to pure water (L) is explained on the basis of a Linear Solvation Energy Relationship (LSER) equation made applicable for solvent mixtures, logLmix - logL = x((sNH3 - sH2O)pi2H + (aNH3 - aH2O)Sigma2H + (bNH3 - bH2O)Sigmabeta2H + (vNH3 - VH2O)Vx). sNH3 - sH2O, aNH3 - aH2O, bNH3 - bH2O, vNH3 - vH2O are the differences of solvent parameters, x is the mole fraction, pi2H is the solute dipolarity-polarizability, Sigmaalpha2H is the effective hydrogen bond acidity of the solute, Sigmabeta2H is the effective hydrogen bond basicity of the solute and Vx, the McGowan characteristic volume. The most significant term was v, the phase hydrophobicity. The solubility behavior was explained by the change in structure of the aqueous solution: the presence of ammonia reduces the cavity effect. These findings show that the presence of compounds such as ammonia, frequently observed in environmental waters, especially wastewaters, affect the fugacity of VOCs, having consequences for the environmental partitioning of VOCs and having technical consequences towards wastewater treatment technologies.     

采用杂多酸化合物溶液同时脱硫脱氮的实验研究

本文对液相催化氧化脱硫脱氮的新方法进行了研究 ,在鼓泡反应发生器内进行了液相催化氧化脱硫脱氮的实验。采用钼硅酸溶液及其还原产物脱除烟气中的SO2 和NOX,分别就吸收液的浓度、pH值、温度、停留时间等因素对SO2 和NOX 去除效率的影响及其变化规律进行了研究。实验结果表明 ,钼硅酸能十分有效地吸收SO2 ,将SO2 氧化成H2 SO4,并使杂多酸还原为杂多蓝。随后又被用于去除NOX,把NOX 还原成N2 ,蓝色溶液再次被氧化成为黄色溶液     

Removal of carbonyl sulfide using activated carbon adsorption

Wastewater treatment plant odors are caused by compounds such as hydrogen sulfide (H2S), methyl mercaptans, and carbonyl sulfide (COS). One of the most efficient odor control processes is activated carbon adsorption; however, very few studies have been conducted on COS adsorption. COS is not only an odor causing compound but is also listed in the Clean Air Act as a hazardous air pollutant. Objectives of this study were to determine the following: (1) the adsorption capacity of 3 different carbons for COS removal; (2) the impact of relative humidity (RH) on COS adsorption; (3) the extent of competitive adsorption of COS in the presence of H2S; and (4) whether ammonia injection would increase COS adsorption capacity. Vapor phase react (VPR; reactivated), BPL (bituminous coal-based), and Centaur (physically modified to enhance H2S adsorption) carbons manufactured by Calgon Carbon Corp. were tested in three laboratory-scale columns, 6 in. in depth and 1 in. in diameter. Inlet COS concentrations varied from 35 to 49 ppmv (86-120 mg/m3). RHs of 17%, 30%, 50%, and 90% were tested. For competitive adsorption studies, H2S was tested at 60 ppmv, with COS at 30 ppmv. COS, RH, H2S, and ammonia concentrations were measured using an International Sensor Technology Model IQ-350 solid state sensor, Cole-Parmer humidity stick, Interscan Corp. 1000 series portable analyzer, and Drager Accuro ammonia sensor, respectively. It was found that the adsorption capacity of Centaur carbon for COS was higher than the other two carbons, regardless of RH. As humidity increased, the percentage of decrease in adsorption capacity of Centaur carbon, however, was greater than the other two carbons. The carbon adsorption capacity for COS decreased in proportion to the percentage of H2S in the gas stream. More adsorption sites appear to be available to H2S, a smaller molecule. Ammonia, which has been found to increase H2S adsorption capacity, did not increase the capacity for COS.     

Hydrogen peroxide mediated photodegradation of phenol as studied by a flash photolysis/HPLC technique

The technique of flash photolysis followed by high-performance liquid chromatography has been applied to the study of the photodegradation of phenol (I) in the presence of hydrogen peroxide. Progress of the reaction of I (0.1 mM) in undegassed aqueous solution ([H2O2]/[I] = 200/l) was observed by using multiple flashes (16 J). Analysis after a single flash indicated that catechol and hydroquinone were the primary products of the reaction. The reaction was found to be independent of pH in the range 7.0-9.0, but the yield of degradation decreased at pH > 9.0 and at pH < 7.0. The effects of the hydrogen peroxide concentration and flash energy on the chemical yield of the pollutant degradation, and product formation, were investigated as well. The mechanism of the reaction is discussed. A possibility of the application of flashlamps as powerful sources of the UV irradiation in industrial reactors for wastewater treatment is suggested.     

Determination of toxic cyclic heptapeptides by liquid chromatography with detection using ultra-violet, protein phosphatase assay and tandem mass spectrometry

Microcystins, toxic cyclic heptapeptides and nodularin-R, a toxic cyclic pentapeptide, were determined using liquid chromatography (LC) with detection using photo-diode array ultra-violet (PDA-UV) and protein phosphatase (PP) assay. Positive fractions were analysed for toxins using collision-induced dissociation (CID) and tandem MS/MS experiments which were carried out simultaneously using electrospray ion-trap instrumentation. Reversed-phase liquid chromatography (LC) using an acetonitrile/water gradient was used for the LC-MS(2) determination of six microcystins standards and nodularin. The molecular related ion species, [M+H](+)([M+2H](2+) in the case of MC-RR), were used as the precursor ions for MS(2) experiments. Optimum calibration and reproducibility data were obtained for MC-LR using LC-MS(2); 0.1-5.0 microg/ml, r2 = 0.992 (n = 3); % RSD < or =7.3 at 0.25 microg MC-LR/ml (n = 3). The detection limit (S/N = 3) was better than 0.1 ng. Water samples for microcystin analysis were first screened using protein phosphatase (PP) assays and positives were concentrated using C-18 solid-phase extraction. The developed method was applied to examine a lake in Ireland contaminated by Microcystis sp. and MC-LR and MC-LA were identified.     

Isotopic modelling of the significance of bacterial sulphate reduction for phenol attenuation in a contaminated aquifer

A Triassic sandstone aquifer polluted with a mixture of phenolic hydrocarbons has been investigated by means of high-resolution groundwater sampling. Samples taken at depth intervals of 1 m have revealed the presence of a diving pollutant plume with a sharply defined upper margin. Concentrations of pollutant phenols exceed 4 g/l in the plume core, rendering it sterile but towards the diluted upper margin evidence for bacterial sulphate reduction (BSR) has been obtained. Groundwaters have been analysed for both delta34S-SO4 and delta18O-SO4. Two reservoirs have been identified with distinct sulphate oxygen isotope ratios. Groundwater sulphate (delta18O-SO4 = 3-5/1000) outside the plume shows a simple linear mixing trend with an isotopically uniform pollutant sulphate reservoir (delta18O-SO4 = 10-12/1000) across the plume margin. The sulphur isotope ratios do not always obey a simple mixing relation, however, at one multilevel borehole, enrichment in 34SO4 at the plume margin is inversely correlated with sulphate concentration. This and the presence of 34S-depleted dissolved sulphide indicate that enrichment in 34SO4 is the result of bacterial sulphate reduction. Delta34S analysis of trace hydrogen sulphide within the plume yielded an isotope enrichment factor (epsilon) of -9.4/1000 for present-day bacterial sulphate reduction. This value agrees with a long-term estimate (-9.9/1000) obtained from a Rayleigh model of the sulphate reduction process. The model was also used to obtain an estimate of the pre-reduction sulphate concentration profile with depth. The difference between this and the present-day profiles then gave a mass balance for sulphate consumption. The organic carbon mineralisation that would account for this sulphate loss is shown to represent only 0.1/1000 of the phenol concentration in this region of the plume. Hence, the contribution of bacterial sulphate reduction to biodegradation has thus far been small. The highest total phenolic concentration (TPC) at which there is sulphur isotope evidence of bacterial sulphate reduction is 2000 mg/l. We suggest that above this concentration, the bactericidal properties of phenol render sulphate-reducing bacteria inactive. Dissolved sulphate trapped in the concentrated plume core will only be utilised by sulphate reducers when toxic phenols in the plume are diluted by dispersion during migration.     

Gas Dilution Apparatus for Preparing Reproducible Dynamic Gas Mixtures in any Desired Concentration and Complexity

A portable gas dilution apparatus has been constructed by which reproducible known mixtures of the common air pollutants added to carbon filtered air can be prepared in any desired quantity, complexity, and concentration. Sulfur dioxide mixtures with and without the addition of nitrogen dioxide and/or ozone have been analyzed by the conductimetric, titrimetric, turbidimetric, and colorimetric methods. Excellent analytical agreement with the concentrations obtained from the volumes of sulfur dioxide, nitrogen dioxide, hydrogen sulflde, and air that are mixed has been shown by all these methods when an efficient absorber is used though the titrimetric method tended to give slightly low results. Some common absorbers show reduced efficiency in absorbing some of the gases. Nitrogen dioxide determinations by the Saltzman method are not significantly affected by the addition of sulfur dioxide to the nitrogen dioxide-air mixtures. A modification of the Saltzman reagent, due to Lyshkow, was tested. It accelerates the rate of color development and should be useful in the automatic nitrogen dioxide analyzer. The determination of hydrogen sulfide is not affected by the presence of nitrogen dioxide in the gas mixture but sulfur dioxide increases the sulfide reading by about 5-15% while ozone decreases the reading.     

Kinetic evaluation of H2S and NH3 biofiltration for two media used for wastewater lift station emissions

In this study, biofiltration using a natural wood chip medium and a commercial biofiltration medium was evaluated for the removal of moderate concentrations of hydrogen sulfide (H2S) (up to 100 parts per million by volume [ppmv]) in the presence of significant concentrations of ammonia (NH3). These levels were chosen as representative of wastewater lift station emissions in the Brownsville, TX, area. NH3-removing portions of the biofilms may compete with H2S-removing portions and inhibit H2S removal. H2S process removal efficiencies for the commercial and natural media ranged from 90 to 96% depending on inlet loading and media type and bed height. Kinetic analysis of the H2S removal process followed apparent first-order reaction behavior. The average first-order reaction rates were 0.03 sec(-1) for the commercial medium and 0.09 sec(-1) for the natural medium. Pressure drops across the columns ranged from 0.41 in. H2O/ft for the commercial medium to 1.41 in. H2O/ft for the natural medium. NH3 gas levels of up to 80 ppmv did not affect the H2S removal process efficiency, and calculated kinetic rate constants for H2S removal remained almost the same. The NH3 gas also was removed simultaneously with the H2S up to 98% removal efficiency by the commercial medium.     

Determination of Sulfur Oxides in the Flue Gases of the Pulping Processes

The body of information presented in this paper is directed to the operating personnel and process engineers employed in the power and recovery departments of a chemical pulping operation. The proper evaluation of the total analytical and sampling system (TASS), to be used in the determination of sulfur oxides is as important as a proper analytical and recording system (ARS). The presence of other sulfur gaseous compounds and particulates could greatly influence the results of the determination.

The analytical method employed determines sulfur dioxide and trioxide from an aliquot of the trapping solution, 3% hydrogen peroxide and 8 0% isopropyl alcohol respectively. The aliquot is titrated with barium perchlorate in the presence of Thorin indicator. The results of evaluating the method indicated negligible interference from the presence of hydrogen sulfide, mercaptans and nitrogen oxides. A blank correction of 15 parts per million (ppm) is recommended whenever 100 ppm of hydrogen sulfide or more are simultaneously present in the gas stream. Particulaies are shown to interfere either by addition or subtraction. Sulfate particulates that will add to the determination must be removed, but in doing so, care must be exerted to avoid surface-contacting conditions that promote reaction between carbonates and the sulfur oxides. The integrated method of sampling and analysis will permit determinations from a flue gas with sulfur oxides concentrations of 30 ppm and above. The relative standard deviation improves from 10% at 100 ppm SO₂ to 2.6% at 1000 ppm SO₂. In both cases, sulfides were present.