Liquid-gas partitioning of selected volatile organic sulfur compounds in anaerobically digested sludges

The gas phase partitioning of volatile organic sulfur compounds (VOSCs) in anaerobic sludge digesters contributes to odors and can impact upon the suitability of biogases for use in alternative energy recovery technologies. In the present study, effective Henry's law coefficients (H') were estimated for methyl mercaptan (MM), dimethyl sulfide (DMS), and dimethyl disulfide (DMDS) in both deionized water and deactivated digested sludge. It was found that the complex matrix of digested sludge did not significantly affect the partitioning of VOSCs. Therefore, partitioning of VOSCs in digesters could be represented by their partitioning in clean water. A regression model was developed for the linear relationship between ln H' and 1/T in the gas-water system. The H' values of MM, DMS, and DMDS were able to be calculated over a temperature range of 12-58 °C.     

Removal of odorous sulphur-containing gases by a new isolate from activated sludge.

Biological treatment of odorous sulphur-containing compounds is attracting attention due to its benign eco-friendliness, energy-savings and low operating costs. As the biological treatment efficiency of dimethylsulphide (DMS) reported was often low and variable, selection of useful DMS-degrading microorganisms is of importance for the enhancement of the biological deodorizing process. This paper reports the successful isolation of a DMS-degrading bacterium from activated sludge, using the enrichment isolation technique. The isolate was identified by 16S rRNA gene sequencing, and found to belong to the alpha group of Proteobacteria, with an identity of 99.4% and 99.1% to the 16S rRNA gene sequences of Afipia felis and Pseudomonas carboxydohydrogena, respectively. The isolate was able to metabolize DMS as well as hydrogen sulphide (H2S). A batch experiment was performed to assess the removal characteristics of DMS by the isolate. The results showed that over half of DMS could be removed by the isolate in 3 hours when the initial DMS amount was approximately 10 micromol and 25 micromol. Removal of H2S by the isolate was evaluated by a continuous test in a 2-L gas-bubbling bottle. Although part of the H2S removal by the mineral medium itself was observed in the control test, the majority of H2S removal was believed to be attributed to the metabolic activity of the isolate. In conclusion, the isolate might be potentially useful for the enhancement of the biological deodorizing processes.     

Biofiltration of hydrogen sulfide by Sulfolobus metallicus at high temperatures

Biofiltration of reduced sulfur compounds such as hydrogen sulfide has been mainly applied to emissions at mild temperatures (25 to 35 °C). However, an important number of industrial gaseous emission containing sulfur compounds, from diverse industrial sectors (petroleum refinery, cellulose production, smelting, rendering plants and food industries) are emitted at temperatures over 50 °C. Most of the studies on thermophilic systems report that a higher elimination capacity can be obtained at elevated temperature, allowing the design of smaller equipment for the same loading rate than that required for removing the same load under mesophilic conditions. A biotrickling filter inoculated with Sulfolobus metallicus, which operates at three different residence times, 60, 80 and 120 s, and two different temperatures (45 and 55 °C) for treating H(2)S is reported. The input loads of H(2)S were progressively increased from 0 to 100 gS/m(3). The aim of this study was to determine the capacity and ability of S. metallicus to oxidize H(2)S at high temperatures. The better removal capacity of H(2)S obtained was 37.1 ± 1.7 gS/m(3) h at 55 °C for a residence time of 120 s. The difference of the removal capacity of H(2)S between the two temperatures was 4 g/m(3) h on average of sulfur removal for the different residence times.     

Aeration tank odour by dimethyl sulphoxide (DMSO) waste in sewage.

Sewage plants can experience dimethyl sulphide (DMS) odour problems by at least one mg/L dimethylsulphoxide (DMSO) waste residue in plant influent, through a DMSO/DMS reduction mechanism. This bench-scale batch study simulates in bottles the role of poor aeration in wastewater treatment on the DMSO/DMS and sulphate/H2S reduction. The study compares headspace concentrations of sulphide odorants developed by activated sludge (closed bottles, half full) after six hours under anoxic versus anaerobic conditions, with 0 versus 2 mg/L DMSO addition. Anoxic sludge (0.1 - 2 mg/L dissolved oxygen, DO) with DMSO resulted in about 50 ppmv DMS and no other sulphide, while DMSO-free sludge was free of detectable sulphides. Anaerobic sludge (no measurable DO to the point of sulphate reduction) with DMSO resulted in 22/4/37 ppmv of H2S/methanethiol (MT)/DMS, while DMSO-free sludge resulted in 44/8/2 ppmv of H2S/MT/DMS. It is concluded that common "anoxic" aeration tank zones with measurable DO in bulk water but immeasurable DO inside sludge flocs (nitrate reducing) experience DMSO reduction to DMS that is oxidation resistant and becomes the most important odorant. Under anaerobic conditions, H2S from sulphate reduction becomes an additional important odorant. A strategy is developed that allows operators to determine from the quantity of different sulphides whether the DMSO/DMS mechanism is important at their wastewater plant.     

Removal of volatile organic compounds by heterogeneous ozonation on microporous synthetic alumina silicate

A hybrid process combining adsorption and ozonation was examined as an alternative treatment for odorous volatile organic compounds (VOCs). Methyl ethyl ketone (MEK) was chosen to study the influence of operating parameters. Two synthetic aluminosilicates (faujasite-Y and ZSM-5) were tested for adsorption and reactivity with ozone. The adsorption equilibrium measurement on both adsorbents showed that adsorption performance depends on temperature but is not sensitive to relative humidity, due to the hydrophobic properties of the materials. Adsorbed VOCs were oxidized at low temperature when ozonated flow was sent to the reactor. Regeneration of the fixed bed was achieved at the same time, releasing mainly CO(2) and H(2)O. Intermediates of oxidation, such as 2,3-butanedione and acetic acid, were identified, leading to incomplete mineralization. The influence of concentration and humidity are discussed. Four successive cycles were tested: after the first adsorption/ozonation cycle, the adsorption efficiency was not affected during subsequent cycles. These results show that the same sample of adsorbent can be used in the treatment process for a long time. Ozonation regeneration is a promising process for VOC removal.     

Removal of target odorous molecules on to activated carbon cloths.

Activated carbon materials are adsorbents whose physico-chemical properties are interesting for the treatment of odorous compounds like hydrogen sulfide. Indeed, their structural parameters (pore structure) and surface chemistry (presence of heteroatoms such as oxygen, hydrogen, nitrogen, sulfur, phosphorus) play an important role in H2S removal. The cloth texture of these adsorbents (activated carbon cloths) is particularly adapted for dealing with high flows, often found in the treatment of odor emissions. Thus, this paper first presents the influence of these parameters through adsorption isothermal curves performed on several materials. Secondly, tests in a dynamic system are described. They highlight the low critical thickness of the fabric compared to granular activated carbon.     

Removal of hydrogen sulfide using palygorskite in a fixed bed adsorber

This work describes the use of a novel palygorskite, a type of magnesium aluminium silicate clay possessing a high specific surface area and pore surface activity, as a low cost and highly efficient adsorbent for hydrogen sulfide (H(2)S) removal. Adsorption of H(2)S on palygorskite pretreated with acid or base was investigated in a fixed bed adsorber. The samples after base pretreatment had better dynamic adsorption performances than raw material and samples pretreated with acid. The H(2)S adsorption capacity decreased with an increase in inlet H(2)S concentration. This can be interpreted by the fact that H(2)S adsorption on the surface of palygorskite is chemisorption. The adsorption capacity increased from 25 to 50 °C, then decreased from 50 to 100 °C, which indicates that chemisorption took place and its better reaction temperature was around 50 °C.     

Development of passive samplers for the detection of chlorinated hydrocarbons in sewers

In this work a system of passive samplers was developed to examine volatile chlorinated hydrocarbons in the gas phase of sewer systems. The adsorption kinetics of chloroform, trichloroethylene and perchloro-ethylene on the adsorption materials Tenax TA, Amberlite XAD-2, Activated Charcoal, Carbosieve S-III and Carboxen-563 were surveyed in laboratory experiments. The highest values of recovery were found for Tenax TA. Further experiments were conducted, regarding the influence of different temperatures. The only significant deviation from the reference kinetics was observed at a temperature as low as 4°C. In order to examine sewer gases a stainless steel sampling system was designed which contained six glass cartridges filled with Tenax TA, and which could be fixed to the steps in the manholes. Using this system, samples were taken at seven locations within the sewer network of Bayreuth, a medium-sized town with little industry, in order to optimise the period of sampling. At least one of the three compounds could be detected at six locations within one week of sampling. An amount of perchloroethylene which exceeded all other results by two orders of magnitude indicated the large adsorption capacity of the chosen material Tenax TA. A linear decrease with increasing height above the waste water table was found; furthermore the sampling device was proved suitable for the localisation of sources of discharge.     

Study of the effect of DMSO on VOS odour production in a wastewater plant.

Odours caused by volatile organic sulphides (VOS) have a history spanning over 20 years for Philadelphia's Northeast Water Pollution Control Plant (NEWPCP). A "canned corn" type of odour has caused residential complaints. Traditional odour control approaches based on hydrogen sulphide failed. This study confirmed that dimethyl sulphoxide (DMSO) from a chemical facility was the dominant cause of the "canned corn" nuisance odour in the form of dimethyl sulphide (DMS). During a discharge, DMSO concentrations up to 12 mg/L were found in the influent of the NEWPCP. Each DMSO concentration peak induced a DMS peak. DMS concentrations increased from less than 50 microg/L to 6 mg/L with a corresponding decrease in DMSO. Approximately 79% of DMSO from the primary sedimentation influent was passed to the effluent, and to downstream processes, such as the aeration tanks where the DMS was volatilised by the aeration. The DMS partial pressure in ambient air of NEWPCP can be between 0.03 and 0.18 x 10(-3) atm during a DMSO discharge. From the above information, the potential of VOS production is estimated and a practical plan for remediation can be designed.     

Applications and limitations of ADM 1 in municipal wastewater solids treatment.

The ADM 1 model has been implemented in a steady-state whole wastewater plant simulator. The ADM 1 model has been in use with good success for approximately 2 years on a wide range of wastewater treatment facilities. However, a number of modifications were necessary to allow it to be used in the context of municipal wastewater treatment. It was found that the model's use was greatly simplified if used in conjunction with a larger plant simulator to assist in the feed fractionation. It was also found that a better fit to actual operating data was achieved if some of the slowly biodegradable particulate fraction was partitioned into ADM particulate fractions other than the composite fraction. Another significant limitation of the model is in the absence of phosphorus modeling. The ADM model needs to have phosphorus handling for all the relevant fractions, and needs to include the handling of inorganic reactions such as struvite precipitation and metal phosphate/metal hydroxide precipitation. Activity effects on chemical equilibria are significant when considering phosphorus. Also of importance in wastewater treatment is the fate of sulfur compounds. This includes the generation of H2S in the digester gas and the fate of the sulfur species in the digested sludge (as a predictor of odour-generating potential).     

Modifying ADM1 to include formation and emission of odourants.

A mathematical model that is based upon the ADM1 structure has been developed to describe the formation and emission of odourous compounds in anaerobic sludge digestion. Special emphasis is given to the general mechanisms for the formation of common odorous sulfur compounds that are found in anaerobic digesters: methyl mercaptan, dimethyl sulfide and hydrogen sulfide, as well as volatile fatty acids and ammonia. The model includes multiple-reaction stoichiometry, microbial growth kinetics and conventional material balances for an ideally mixed reactor. Simulations that were performed with the model revealed that changes in common operational parameters such as temperature, HRT and sludge metal content can dramatically impact upon the gas phase concentrations of odourants. Additional research is required to reduce uncertainty in the model formulation.     

Understanding odorants associated with compost, biomass facilities, and the land application of biosolids.

Odorous water and air can result from compost, biomass facilities and land application of biosolids. Common odorous compounds from these biodegradation systems include alcohols, aldehydes, fatty acids, solvents and various sulfur and nitrogen compounds. Each odorant possesses a unique individual odor signature i.e. odor character or quality, odor threshold concentration and chemical concentration. This paper develops an initial understanding of how the volatile odorous chemicals and their relative concentrations produced are related to the total odor quality from the process by their odor threshold concentrations. The compost process is used as an example. It was estimated, that on day 1 and 7, the primary fatty acids controlling the fermented and rotten odors were butyric acid and valeric acids, individually, unpleasant and rancid odors, respectively, although acetic acid had the highest fatty acid concentration on both days. In the same way, aldehydes and ketones controlled the disappearance of the sweet odor from day 1 to 7.     

Equilibrium, kinetic and thermodynamic studies of mercury adsorption on almond shell

The application of almond shell as a low cost natural adsorbent to remove Hg(2+) from aqueous solution was investigated. Batch experiments were carried out to evaluate the adsorption capacity of the material. The chemical and physical parameters such as pH, sorbent amount, initial ion concentration, and contact time were optimized for the maximum uptake of mercury onto the solid surface. Adsorption isotherms were expressed by Langmuir and Freundlich adsorption models, and the experimental data were found to fit the Langmuir model rather than the Freundlich. The maximum adsorption capacity obtained from the Langmuir isotherm was 135.13 mg/g. A kinetic study was carried out with pseudo-first-order and pseudo-second-order reaction equations and it was found that the Hg(2+) uptake process followed the pseudo-second-order rate expression. The thermodynamic values, ΔG(0), ΔH(0) and ΔS(0), indicated that adsorption was an endothermic and spontaneous process. The potential of this material for mercury elimination was demonstrated by efficient Hg(2+) removal from a synthetic effluent.     

Treatment of wastewater from a cotton dyeing process with UV/H2O2 using a photoreactor covered with reflective material

Wastewater containing several dyes, including sulfur black from the dyeing process in a textile mill, was treated using a UV/H2O2 process. The wastewater was characterized by a low BOD/COD ratio, intense color and high acute toxicity to the algae species Pseudokirchneriella subcaptata. The influence of the pH and H2O2 concentration on the treatment process was evaluated by a full factorial design 22 with three replicates of the central experiment. The removal of aromatic compounds and color was improved by an increase in the H2O2 concentration and a decrease in pH. The best results were obtained at pH 5.0 and 6 g L(-1). With these conditions and 120 min of UV irradiation, the removal of the color, aromatic compounds and COD were 74.1, 55.1 and 44.8%, respectively. Under the same conditions, but using a photoreactor covered with aluminum foil, the removal of the color, aromatic compounds and COD were 92.0, 77.6 and 59.4%, respectively. Moreover, the use of aluminum foil reduced the cost of the treatment by 40.8%. These results suggest the potential application of reflective materials as a photoreactor accessory to reduce electric energy consumption during the UV/H2O2 process.     

Removal of C.I. Reactive Red 2 from aqueous solutions by chitin: an insight into kinetics, equilibrium, and thermodynamics

In this study, C.I. Reactive Red 2 (RR2) was removed from aqueous solutions by chitin. Exactly how the RR2 concentration, chitin dosage, pH, and temperature affected adsorption of RR2 by chitin was then determined. After reaction for 120 min, the amount of 10 and 20 mg/L RR2 absorbed onto chitin was 5.7 and 7.5 mg/g, respectively. The adsorption percentage increased from 56 to 94% when the chitin dosage was increased from 1.5 to 2.5 g/L. Experimental results indicated that the pseudo-second-order model best represents adsorption kinetics. Adsorption of RR2 increased as the temperature increased; however, it decreased with an increased pH. Experimental results further demonstrated that the Freundlich model is superior to the Langmuir model in fitting experimental isotherms. The ΔH° and ΔS° were 16.34 kJ/mol and 152.10 J/mol K, respectively. ΔH° suggested that adsorption of RR2 onto chitin was via physisorption.     

Evaluation of sludge reduction and phosphorus recovery efficiencies in a new advanced wastewater treatment system using denitrifying polyphosphate accumulating organisms.

A new biological nutrient removal process, anaerobic-oxic-anoxic (A/O/A) system using denitrifying polyphosphate-accumulating organisms (DNPAOs), was proposed. To attain excess sludge reduction and phosphorus recovery, the A/O/A system equipped with ozonation tank and phosphorus adsorption column was operated for 92 days, and water quality of the effluent, sludge reduction efficiency, and phosphorus recovery efficiency were evaluated. As a result, TOC, T-N and T-P removal efficiency were 85%, 70% and 85%, respectively, throughout the operating period. These slightly lower removal efficiencies than conventional anaerobic-anoxic-oxic (A/A/O) processes were due to the unexpected microbial population in this system where DNPAOs were not the dominant group but normal polyphosphate-accumulating organisms (PAOs) that could not utilize nitrate and nitrite as electron acceptor became dominant. However, it was successfully demonstrated that 34-127% of sludge reduction and around 80% of phosphorus recovery were attained. In conclusion, the A/O/A system equipped with ozonation and phosphorus adsorption systems is useful as a new advanced wastewater treatment plant (WWTP) to resolve the problems of increasing excess sludge and depleted phosphorus.     

阴离子有机改性膨润土吸附废水中甲基紫的热力学规律研究

采用十二烷基磺酸钠对膨润土进行改性,制得阴离子有机改性膨润土。通过静态吸附法探讨了改性膨润土对染料废水中甲基紫的吸附等温式和吸附热力学规律。结果表明,随着温度的升高,平衡吸附量增加;随着平衡浓度的增加,平衡吸附量不断增大,并趋于饱和。不同温度下吸附等温式与Langmuir方程拟合较好,热力学分析表明,吸附过程吸热,吸附焓变和熵变均为正值,吸附自由能变为负值。     

吹扫捕集/气相色谱-质谱法监测黄河干流水源地挥发性有机物

为了全面了解黄河干流重点城市水源地挥发性有机物的污染情况,采用吹扫捕集/气相色谱-质谱法对水源地38种挥发性有机物进行定性定量分析.该方法的加标回收率为94.4%～105.6%,精密度为1.7%～24.0%,检测限为0.02～0.04 μg/L,满足痕量有机物的分析要求.对3个城市水源地丰、平、枯水期进行监测分析.结果...