Cationic surfactant as a sensitizer for the spectrophotometric determination of hydrogen sulphide in air and evaluation of a new absorbing medium containing triethanolamine-zinc acetate-sodium hydroxide

An extractive spectrophotometric method for the determination of trace amounts of hydrogen sulphide after fixing the gas in triethanolamine (TEA)-zinc acetate-sodium hydroxide solution is described. The method is based on the reaction of iodate with hydrogen sulphide in the presence of acid and excess chloride ion leading to the formation of ICl2- species which is used to iodinate 2',7'-dichlorofluorescein to form 2',7'-dichloro-4',5'-diiodofluorescein. The iodinated product formed is extracted into an organic solvent and sensitized by equilibrating with a cationic surfactant, cetrimide, in the presence of acetate buffer (pH 5.9 +/- 0.1). The colour system obeys Beer's law over the range 0-1 microg of hydrogen sulphide and the relative standard deviation is 2.4% for 10 determinations at 0.75 microg of hydrogen sulphide. The effect of interfering gases on the determination is discussed. The proposed absorbing solution has been evaluated using a hydrogen sulphide permeation device. This absorbing solution has an absorption efficiency of > 93% at a flow rate of 1.5 litre min(-1) for a sampling period of 2 h. The fixed H2S is stable for 40 days. The method has been applied to determine residual H2S levels in a laboratory fume hood and in the vicinity of sewage pumping station. The method can be used to determine as little as 0.05 microg of hydrogen sulphide.     

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.     

Comparison of sludge characteristics and PCR-DGGE based microbial diversity of nanofiltration and microfiltration membrane bioreactors

The objective of this study was to compare the sludge characteristics and microbial community diversity between the submerged nanofiltration membrane bioreactor (NF MBR) and microfiltration membrane bioreactor (MF MBR) treating the same municipal wastewater. The influence of a higher concentration of organic matter and salt was investigated. The results of water qualities showed that the dissolved organic carbon (DOC), total phosphorus (T-P) and salt concentrations of the supernatant in the NF MBR were three, four and two times as high as those in the MF MBR, respectively. The specific oxygen uptake rate of the NF MBR (2.9+/-0.4 mg O(2)g(-1)MLSSh(-1)) was lower than that of the MF MBR (4.3+/-1.1 mg O(2)g(-1)MLSS h(-1)). Result of extractable extracellular polymeric substances showed that the NF MBR sludge had more protein and less polysaccharide compared to the MF MBR sludge, whereas specific amount of total organic carbon were the same in both MBRs. The median floc diameters of the NF MBR and the MF MBR were 72+/-12 microm and 59+/-12 microm, respectively, which could be attributable to the different polysaccharide concentrations between both MBR mixed liquor. A higher concentration of materials (DOC, T-P and salt) in the bioreactor, determined by the high rejection rate of the NF membrane, did not significantly affect the microbial diversity under similar operation 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.     

两相分配式生物反应器处理高盐废水中的苯酚

采用新型两相分配式生物反应器(TPPB)和前期研究得到的高效苯酚降解菌对高盐废水中苯酚的降解进行研究,研究中确定煤油为反应系统的最佳有机溶剂,并考察了废水苯酚含量、废水盐度以及搅拌器搅拌速度对苯酚降解的影响。结果表明,反应系统能正常降解苯酚含量为1 000～2 500 mg/L的高盐苯酚废水;反应系统在含盐量为100 g NaCl/L、搅拌速度为50 r/min的运行工况条件下,降解时间缩短为52 h,总酚去除率为20.58 mg/(L.h)。     

Verification of the "first flush" phenomenon in mine water from coal mines in the Upper Silesian Coal Basin, Poland

Case studies of Grodziec and Siersza mines in the Upper Silesian Coal Basin confirm that mine water accumulating in and over-flowing from abandoned coal mines is subject to a "first flush" phenomenon. The accumulated products of sulphide oxidation are dissolved in the rising mine water and flushed out at concentrations several times those observed during mine operation. Following the first overflow, sulphate concentration and hydrogen ion activity decay exponentially. In the case of workings in Siersza, decay constants of -0.003 to -0.005 day(-1) are observed, corresponding to flushing times of 480 to 820 days, some 10-20 times the period required for the workings to flood. Quantities of leachable sulphur in the abandoned workings of 0.02-0.03% are adequate to explain the observed concentrations of sulphate in the first flush, and this figure is tentatively supported by laboratory analyses.     

The effect of sulfide on alpha-glucosidases: implications for starch degradation in anaerobic bioreactors

Membrane associated alpha-glucosidase activity was investigated in a methanogenic bioreactor (MR) and a biosulfidogenic bioreactor (SR). Temperature and pH optima studies showed temperature optima of 50 degrees C and pH optima of 8.0 for the alpha-glucosidases from both the MR and SR. Sulfide (at a concentration of 150 mg l(-1)) resulted in the complete loss of all alpha-glucosidase activity in both the MR and SR. beta-Glucosidase activities in our bioreactors were previously shown to be stimulated in the presence of sulfide. alpha-Glucosidases, in contrast, are inhibited by sulfide. This differential effect of sulfide on alpha-glucosidase and beta-glucosidase activities is highlighted and is of crucial consequence to the respective degradation and utilization of starch and cellulose substrates in natural anaerobic environments and anaerobic bioreactors specifically designed for the accelerated digestion of wastewater sludge under biosulfidogenic conditions.     

A theory on the mechanisms regulating the bioavailability of mercury in natural waters

A number of quantifiable properties of natural waters have been used by various scientists to 'explain' the Hg content in fish (e.g. pH, level of bioproduction, humosity, conductivity, calcium content, oxygen conditions, zinc and selenium content). This work presents a theory aimed at providing an explanation of the chemical mechanisms behind many established statistical relationships. The theory focuses on some equilibrium reactions and the causal relationships behind these reactions. The basic concept of the theory is that the activity of Hg(2+) in natural waters is essentially regulated by the activity of S(2-), which, in turn, is strongly affected by pH and redox conditions. Due to protonisation reactions, the S(2-) activity is very low at natural pH levels. The equilibrium between Hg(2+) and HgS(s) is given by the solubility constant Ks = 10(-52). This is an extremely low constant, which indicates that, in the presence of sulphide, essentially all Hg will appear as HgS(s). The Hg(2+) activity, and the Hg content in fish, can be increased if the S(2-) activity is decreased by lowering the pH and/or increasing the redox potential. Besides sulphide there are two other elements with a similar relationship towards Hg; namely, Se and Te (Ks = 10(-58) and Ks = 10(-70), respectively). The Hg(2+) concentration in natural waters varies quite widely, but is often about 5 ng litre(-1). This is a high concentration in these contexts. Such as high concentration can prevail only if the S(2-) (and/or the Se(2-)) activity is very small. In waters where the S(2-) and/or the Se(2-)) activity is high, e.g. from sulphide rocks in the drainage area, or if S(2-) and/or Se(2-) are added to the water, the Hg(2+) activity, and the Hg content in fish, will be effectively reduced.     

亚铁离子生物氧化-还原法连续脱除硫化氢

为了降低工业废气中的硫化氢去除工艺成本和运行费用,对三价铁盐吸收与氧化亚铁硫杆菌对Fe²⁺的生物氧化联合作用脱除H₂S进行了研究。通过生物氧化塔中的固定化氧化亚铁硫杆菌细胞再生的Fe³⁺溶液,在H₂S还原吸收塔中脱除H₂S。通过单因素实验分别优化了生物氧化塔和H₂S吸收塔的运行参数,在生物氧化塔曝气量为150 L/h,停留时间为11 h,吸收液中Fe³⁺浓度为0.121~0.143 mol/L,吸收液流量为0.3 L/h,进气量为100 L/h条件下,进气中H₂S浓度分别为2.28和9.11 mg/L,系统连续运行至200 min时趋于相对稳定,当系统连续运行稳定时,H₂S的脱除率可分别达到95%和91%,脱除效果显著。     

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.     

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.     

Model description of an alternately operated wastewater treatment plant--evaluation of the applicability of SimpleTreat

Alternately operated wastewater treatment plants (WWTPs) are fundamentally different compared to conventional activated sludge WWTPs with respect to flow patterns and aeration in the biological reactors. Several model applications exist for conventional WWTPs, e.g. SimpleTreat, and in this study the effect of substituting a complex discontinuous operation, involving alternating degradation and flow conditions between two reactors, with one single bioreactor with continuos flow (SimpleTreat) has been investigated by setting up two models representing the respective operation schemes. The discontinuous operation induces fluctuations in the outlet concentrations that are not modelled with the single bioreactor model, however, the fluctuations and the associated uncertainties were found to be insignificant compared to the influence of the input parameter uncertainties on the model results. An empirical relationship between an aggregate pseudo-1st order degradation rate for the single bioreactor model and realistic aerobic and anoxic 1st order degradation rates, respectively, has been established. When using this aggregate degradation rate in the single bioreactor model an outlet concentration can be calculated that deviates no more than 2% from the mean outlet concentration from the alternating operation model. For substances with aerobic half-lives longer than approximately 2 h, which is valid for many chemical substances, the aggregate 1st order degradation rate can be set equal to the aerobic 1st order degradation rate.     

1-Butanol removal from a contaminated airstream under continuous and diurnal loading conditions

A polysulfone microporous membrane module was investigated for control of 1-butanol-contaminated gas streams. A diurnal loading condition, using two different butanol concentrations, was used to simulate start-up and stop conditions associated with shift work. The membrane module was also used to remove 1-butanol from air under continuous loading conditions in a bioreactor. The reactors were seeded with a mixed bacterial consortium capable of butanol biodegradation. Biokinetic parameters for butanol utilization were determined for the culture to be a maximum specific utilization rate (k) equal to 4.3 d(-1) and a half saturation constant (Ks) equal to 8.9 mg L(-1). A biofilter running only with diurnal loading conditions giving a "40-hr work-week" had an average 1-butanol removal rate of 29% (111 ppm, 74 gm(-3) hr(-1)) from a 350-ppm influent at the end of an 8-hr operational day. End-of-day removal varied between 4 and 67% during the operational period. With continuous steady-state operation followed by placement on a diurnal loading schedule and influent butanol concentrations increased to 700 ppm, butanol removal averaged 38% (269 ppm, 145 gm-3 hr(-1)). Under continuous loading, steady-state conditions, 1-butanol removal from the airstream was greater than 99% (200 ppm, 73 gm-3 hr(-1)). These results suggest that the bioreactor can be operated on a diurnal schedule or 40-hr week operational schedule without any decline in performance.     

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.     

模拟车用工况下5 kW燃料电池尾气净化系统

模拟了车用工况下燃料电池发动机脉冲式排氢的特点,设计开发了一套质子交换膜燃料电池的尾气净化系统,并以5 kW燃料电池的尾气排放为例,研究其净化效果。研究了电池阳极排放氢气缓冲前后尾气中氢气浓度的变化,以及不同空速条件下氢气的去除效果。结果表明：电堆阳极排放氢气经过缓冲处理后,尾气中氢气浓度趋于平稳,大部分工况下处在2%以下,达到了安全处理的要求;尾气中氢气的去除效果与空速密切相关。对自制的整体式催化剂而言,当空速低于20 000 h^-1时,氢气的去除率能达到约95%,而当空速达到39 270 h^-1时,氢气的去除率仅为10.9%。鉴于这一问题,提出通过采用尾排空气的分流手段调整催化燃烧反应器对空速的要求,以提高尾气中氢气的去除率。     

Hydrogen production by anaerobic microbial communities exposed to repeated heat treatments.

Biological hydrogen production by anaerobic mixed communities was studied in laboratory-scale bioreactors using sucrose as the substrate. A bioreactor in which a fraction of the return sludge was exposed to repeated heat treatments performed better than a control bioreactor without repeated heat treatment of return sludge and produced a yield of 2.15 moles of hydrogen per mole of sucrose, with 50% hydrogen in the biogas. Terminal restriction fragment length polymorphism analysis showed that two different Clostridium groups (comprised of one or more species) were dominant during hydrogen production. The relative abundance of two other non-Clostridium groups increased during periods of decreased hydrogen production. The first group consisted of Bifidobacterium thermophilum, and the second group included one or more of Bacillus, Melissococcus, Spirochaeta, and Spiroplasma spp.     

Fresnel lens to concentrate solar energy for the photocatalytic decoloration and mineralization of orange II in aqueous solution

The decoloration and mineralization of the azo dye orange II under conditions of artificial ultraviolet light and solar energy concentrated by a Fresnel lens in the presence of hydrogen peroxide and TiO(2)-P25 was studied. A comparative study to demonstrate the viability of this solar installation was done to establish if the concentration reached in the focus of the Fresnel lens was enough to improve the photocatalytic degradation reaction. The degradation efficiency was higher when the photolysis was carried out under concentrated solar energy irradiation as compared to UV light source in the presence of an electron acceptor such us H(2)O(2) and the catalyst TiO(2). The effect of hydrogen peroxide, pH and catalyst concentration was also determined. The increase of H(2)O(2) concentration until a critical value (14.7 mM) increased both the solar and artificial UV oxidation reaction rate by generating hydroxyl radicals and inhibiting the (e(-)/h(+)) pair recombination, but the excess of hydrogen peroxide decreases the oxidation rate acting as a radical or hole scavenger and reacting with TiO(2) to form peroxo-compounds, contributing to the inhibition of the reaction. The use of the response surface methodology allowed to fit the optimal values of the parameters pH and catalyst concentration leading to the total solar degradation of orange II. The optimal pH range was 4.5-5.5 close to the zero point charge of TiO(2) depending on surface charge of catalyst and dye ionization state. Dosage of catalyst higher than 1.1 gl(-1) decreases the degradation efficiency due to a decrease of light penetration.     

膜-生物反应器中溶解性微生物产物的研究进展

本文就膜 -生物反应器中溶解性微生物产物的生成特性及其影响的研究进展进行了总结。在膜 -生物反应器中 ,膜的高效固液分离作用在提高系统容积负荷和出水水质的同时 ,也使生物反应器成为一个相对封闭的系统。以腐殖质、多糖、蛋白质等物质为主要成分的溶解性微生物产物是生物处理出水中溶解性TOC或COD的主要组成部分 ,主要产生于微生物的基质分解过程和内源呼吸过程 ,其高分子物质的含量较多且可生物降解性较差 ,因此 ,在膜 -生物反应器中会出现积累。溶解性微生物产物的过高积累不仅有可能降低膜过滤出水的水质稳定性 ,而且有可能影响污泥活性 ,并引起膜污染。进水浓度和污泥浓度是影响溶解性微生物产物产生量的重要因素。目前有关膜 -生物反应器中溶解性微生物产物的研究还很不完善 ,有很多问题需进一步研究     

Experimental in situ chemical peroxidation of atrazine in contaminated soil

Lab-scale experiments of in situ chemical oxidation (ISCO), were performed on soil contaminated with 100 mg kg(-1) of atrazine (CIET). The oxidant used was hydrogen peroxide catalysed by naturally occurring minerals or by soluble Fe(II) sulphate, added in aqueous solution. The oxidation conditions were: CIET:H2O2=1:1100, 2 PV or 3 PV reaction volume, Fe(II):H2O2=0, 1:22, 1:11. Stabilized (with KH2PO4 at a concentration of 16 g l(-1)) or non-stabilized hydrogen peroxide was used. The pH of the reagents was adjusted to pH=1 with sulphuric acid, or was not altered. Results showed that the addition of soluble Fe(II) increased the temperature of the soil slurry and the use of stabilized hydrogen peroxide resulted in a lower heat generation. The treatment reduced the COD of the soil of about 40%, pH was lowered and natural organic matter became less hydrophobic. The highest atrazine conversion (89%) was obtained in the conditions: 3 PV, Fe(II):H2O2=1:11 with stabilized hydrogen peroxide added in two steps. The stabilizer only increased H2O2 life-time significantly when soluble Fe(II) was added. Results indicate as preferential degradation pathway of atrazine in soil dechlorination instead of dealkylation.     

Effects of flow regime and flooding on heavy metal availability in sediment and soil of a dynamic river system

The acid volatile sulphide (AVS) and simultaneously extracted metals (SigmaSEM) method is increasingly used for risk assessment of toxic metals. In this study, we assessed spatial and temporal variations of AVS and SigmaSEM in river sediments and floodplain soils, addressing influence of flow regime and flooding. Slow-flowing sites contained high organic matter and clay content, leading to anoxic conditions, and subsequent AVS formation and binding of metals. Seasonality affected these processes through temperature and oxygen concentration, leading to increased levels of AVS in summer at slow-flowing sites (max. 37micromolg(-1)). In contrast, fast-flowing sites hardly contained AVS, so that seasonality had no influence on these sites. Floodplain soils showed an opposite AVS seasonality because of preferential inundation and concomitant AVS formation in winter (max. 3-30micromolg(-1)). We conclude that in dynamic river systems, flow velocity is the key to understanding variability of AVS and SigmaSEM.