Inhibition of sulfate-reducing and methanogenic activities of anaerobic sewer biofilms by ferric iron dosing

Ferric iron is commonly used for sulfide precipitation in sewers, thus achieving corrosion and odour control. Its impact on the activities of sulfate-reducing bacteria and methanogens in anaerobic sewer biofilms is investigated in this study. Two lab-scale rising main sewer systems fed with real sewage were operated for 8 months. One received Fe³⁺ dosage (experimental system) and the other was used as a control. In addition to precipitating sulfide from bulk water, Fe³⁺ dosage was found to significantly inhibit sulfate reduction and methane production by sewer biofilms. The experimental reactor discharged an effluent containing a higher concentration of sulfate and a lower concentration of methane in comparison with the reference reactor. Batch experiments showed that the addition of ferric ions reduced the sulfate reduction and methane production rates of the sewer biofilms by 60% and 80%, respectively. The batch experiments further showed that Fe³⁺ dosage changed the final products of sulfate reduction with sulfide accounting for only 54% of the sulfate reduced. The other products could not be confirmed, but were not dissolved inorganic sulfur species such as sulfite or thiosulfate. The results suggest the addition of Fe³⁺ at upstream locations would minimize the ferric salts required for achieving the same level of sulfide removal. Fe³⁺ dosing could also substantially reduce the formation of methane, a potent greenhouse gas, in sewers.     

Nitrite effectively inhibits sulfide and methane production in a laboratory scale sewer reactor

The production and emission of hydrogen sulfide and methane by anaerobic microoganisms in sewer systems is a well-documented problem. The effectiveness of nitrite in controlling sulfide and methane production was tested in a laboratory scale sewer reactor. Nitrite was continuously dosed in the reactor for 25 days at concentrations of 20-140mgN/L. No sulfide and methane accumulation was observed in the reactor in the presence of nitrite. A significant reduction was observed in the sulfate reduction and methane production capabilities of the biofilm. Nitrite also stimulated biological sulfide oxidation within the biofilm. The nitrite uptake rate of the reactor increased over the nitrite dosing period and nitrous oxide production was observed within the biofilm. When nitrite addition was stopped, sulfate reduction and methane production gradually resumed, and reached pre-nitrite addition levels after 2.5 months. The slow recovery suggests that nitrite can be applied intermittently for sulfide and methane control, which represents a key advantage over similar chemicals such as nitrate and oxygen. The study demonstrates nitrite addition as a promising and effective strategy for the management of sulfide and methane in sewers. Further investigation and optimization are still required before application in the field.     

Iron salts dosage for sulfide control in sewers induces chemical phosphorus removal during wastewater treatment

Chemical phosphorus (P) removal during aerobic wastewater treatment induced by iron salt addition in sewer systems for sulfide control is investigated. Aerobic batch tests with activated sludge fed with wastewater containing iron sulfide precipitates showed that iron sulfide was rapidly reoxidised in aerobic conditions, resulting in phosphate precipitation. The amount of P removed was proportional to the amount of iron salts added, and for the sludge used, ratios of 0.44 and 0.37 mgP/mgFe were obtained for ferric and ferrous dosages, respectively. The hydraulic retention time (HRT) of iron sulfide in sewers was found to have a crucial impact on the settling of iron sulfide precipitates during primary settling, with a shorter HRT resulting in a higher concentration of iron sulfide in the primary effluent and thus enabling higher P removal. A mathematical model was developed to describe iron sulfide oxidation in aerated activated sludge and the subsequent iron phosphate precipitation. The model was used to optimise FeCl₃ dosing in a real wastewater collection and treatment system. Simulation studies revealed that, by moving FeCl₃ dosing from the WWTP, which is the current practice, to a sewer location upstream of the plant, both sulfide control and phosphate removal could be achieved with the current ferric salt consumption. This work highlights the importance of integrated management of sewer networks and wastewater treatment plants.     

Nutrient addition to enhance biological treatment of greywater.

This study compares the chemical oxygen demand (COD) removal and respiration rates of a microbial population treating real and synthetic greywaters dosed with nutrient supplements. The nutrient composition of the real and synthetic greywaters was analysed and the dosing regime for nitrogen, phosphorus and a range of trace metals planned accordingly. The doses consisted of eight single additives (macronutrients and trace metals) to the control greywater and six trace metal additions to C: N : P balanced greywater. The COD removal for the control real and synthetic greywater in lab-scale activated sludge systems (0.038 and 0.286 kg COD kg MLSS(-1) d(-1), respectively) confirmed nutrient limitation and the poor degree of greywater treatment. Nutrient dosing increased the COD removal rate and oxygen uptake rate in many cases. The greatest stimulation of microbial activity was observed with zinc additions to C: N: P balanced real greywater (1.291 kg COD kg MLSS(-1) d(-1) over 30 times the control). Inhibitory effects to various extents were rare and limited mainly to the additions of metals to synthetic greywater. The dominance of chemicals effects was observed on addition of some micronutrients; notably iron and aluminium, metals on which many coagulants for use in biotreatment of other wastewaters are based. The data indicate that the impact of understanding microbial processes and the nutrients required for wastewater treatment can only serve to optimise process efficiency for the proposed treatment of greywater.     

Evaluation of chemicals to control the generation of malodorous hydrogen sulfide in waste water

The effect of hydrogen peroxide, sodium/calcium hypochlorite and ferrous/ferric salts on hydrogen sulfide dissolved in waste water were investigated to establish an effective odour control system for Kuwait Sewage Networks. The waste water samples were collected from the inlet structure of main pumping station with pressure pipelines and analyzed for dissolved sulfide and pH before and after addition of chemicals individually and in combination under controlled laboratory conditions. The waste water contained dissolved sulfide in the range of 18 to 25 mg/l and pH ranged between 7.2 and 7.8. Various concentrations of above mentioned chemicals were tried to determine the accurate chemical requirement for oxidation or precipitation of dissolved sulfide in waste water. The reaction temperature was maintained at 35°C (±2°C), the normal temperature of waste water in Kuwait during summer. To oxidize 1 g of sulfide 1.25, 2.0 and 1.8 g hydrogen peroxide, sodium hypochlorite and calcium hypochlorite were required respectively. To remove 1 g of sulfide by precipitation with ferrous sulfate and ferric salt solution, 8 g and 4 g ferrous and ferric salt were required respectively under laboratory investigations. A combination of sodium hydroxide and sodium hypochlorite was also studied to control malodorous hydrogen sulfide in waste water. The addition of sodium hydroxide with sodium hypochlorite in waste water reduced the demand of hypochlorite 50%. This procedure was found to be cost effective and best suited for the warm climate of Kuwait and was implemented in the field at a screw conveyor type lifting station with gravity sewer pipelines. When sodium hypochlorite was injected without shock loadings of sodium hydroxide 46% reduction of dissolved sulfides was recorded and it was increased to 57% with shock loadings of sodium hydroxide, though the quantity of sodium hypochlorite was reduced to half than the former case. Similarly, 45 and 70% reduction in the emission of gaseous hydrogen sulfide was recorded with NaOCl injection without and with NaOH shock loading respectively. The cost comparison of all the chemicals when applied in field is also presented.     

Long-term field test of an electrochemical method for sulfide removal from sewage

Corrosion caused by hydrogen sulfide leads to significant costs for the rehabilitation or replacement of corroded sewer pipes. Conventional methods to prevent sewer corrosion normally involve the dosing of significant amounts of chemicals with the associated transport and storage costs as well as considerable maintenance and control requirement. Recently, a novel chemical free method for sulfide abatement based on electrochemical sulfide oxidation was shown to be highly effective for the removal of sulfide from synthetic and real sewage. Here, we report on the electrochemical removal of sulfide using Ta/Ir and Pt/Ir coated titanium electrodes under simulated sewer conditions during field trials. The results showed that sulfide can successfully be removed to levels below the normal target value at the end of a simulated rising main (i.e. <1 mg/L). A coulombic efficiency for dissolved oxygen generation of ∼60% was obtained and was independent of the current density. Scaling of the electrode and the membrane was observed in the cathode compartment and as a result the cell potentials increased over time. The cathode potentials returned to their original potential after switching the polarity every two days, but a more frequent switching would be needed to reduce the energy requirements of the system. Accelerated lifetime experiments indicated that a lifetime of 6.0 ± 1.9 years can be expected under polarity switching conditions at a pH of 14 and significantly longer at lower pH values. As operating the system without switching simplifies construction as well as operation, the choice whether to switch or not will in practice depend on operational cost (higher/lower energy) versus capital cost (reactor and peripherals). Irrespective of the approach, our study demonstrates that electrochemical sulfide control in sewer systems may be an attractive new option.     

Dynamics and dynamic modelling of H2S production in sewer systems

Accurate and reliable predictions of sulfide production in a sewer system greatly benefit formulation of appropriate strategies for optimal sewer management. Sewer systems, rising main systems in particular, are highly dynamic in terms of both flow and wastewater composition. In order to get an insight in sulfide production as a response to the dynamic changes in sewer conditions, several measurement campaigns were conducted in two rising mains in Gold Coast, Australia. The levels of various sulfur species and volatile fatty acids (VFAs) were monitored through hourly sampling for periods ranging from 8 to 29 h. The results of these field studies showed large temporal as well as spatial variations in sulfide generation. A dynamic sewer model taking into account the hydraulics and the biochemical transformation processes was formulated and calibrated and validated using the data collected during the four measurement campaigns at the two sites. The model was demonstrated to reasonably well describe the temporal and spatial variations in sulfide, sulfate and VFA concentrations. Application of the model was illustrated with a case study aimed to optimize oxygen injection to one of the two mains studied, which is being used as a means to control sulfide production on this site. The model predicted that, moving the current oxygen injection point to a location close to the end of the sewer line could achieve the same degree of sulfide control with only 50% of the current oxygen use. This study highlighted that the location at which oxygen is injected plays a major role in sulfide control and a dynamic model could be used to make a proper choice of the location.     

Electrochemical sulfide removal from synthetic and real domestic wastewater at high current densities

Hydrogen sulfide generation is the key cause of sewer pipe corrosion, one of the major issues in water infrastructure. Current abatement strategies typically involve addition of various types of chemicals to the wastewater, which incurs large operational costs. The transport, storage and application of these chemicals also constitute occupational and safety hazards. In this study, we investigated high rate electrochemical oxidation of sulfide at Ir/Ta mixed metal oxide (MMO) coated titanium electrodes as a means to remove sulfide from wastewater. Both synthetic and real wastewaters were used in the experiments. Electrochemical sulfide oxidation by means of indirect oxidation with in-situ produced oxygen appeared to be the main reaction mechanism at Ir/Ta MMO coated titanium electrodes. The maximum obtained sulfide removal rate was 11.8 ± 1.7 g S m⁻² projected anode surface h⁻¹ using domestic wastewater at sulfide concentrations of ≥30 mg L⁻¹ or higher. The final products of the oxidation were sulfate, thiosulfate and elemental sulfur. Chloride and acetate concentrations did not entail differences in sulfide removal, nor were the latter two components affected by the electrochemical oxidation. Hence, the use of electrodes to generate oxygen in sewer systems may constitute a promising method for reagent-free removal of sulfide from wastewater.     

Evaluation of oxygen injection as a means of controlling sulfide production in a sewer system

Oxygen injection is often used to control biogenic production of hydrogen sulfide in sewers. Experiments were carried out on a laboratory system mimicking a rising main to investigate the impact of oxygen injection on anaerobic sewer biofilm activities. Oxygen injection (15-25 mg O₂/L per pump event) to the inlet of the system decreased the overall sulfide discharge levels by 65%. Oxygen was an effective chemical and biological oxidant of sulfide but did not cause a cessation in sulfide production, which continued in the deeper layers of the biofilm irrespective of the oxygen concentration in the bulk. Sulfide accumulation resumed instantaneously on depletion of the oxygen. Oxygen did not exhibit any toxic effect on sulfate reducing bacteria (SRB) in the biofilm. It further stimulated SRB growth and increased SRB activity in downstream biofilms due to increased availability of sulfate at these locations as the result of oxic conditions upstream. The oxygen uptake rate of the system increased with repeated exposure to oxygen, with concomitant consumption of organic carbon in the wastewater. These results suggest that optimization of oxygen injection is necessary for maximum effectiveness in controlling sulfide concentrations in sewers.     

Modeling bioaccumulation in humans using poly-parameter linear free energy relationships (PPLFERS)

Chemical partition coefficients between environmental media and biological tissues are a key component of bioaccumulation models. The single-parameter linear free energy relationships (spLFERs) commonly used for predicting partitioning are often derived using apolar chemicals and may not accurately capture polar chemicals. In this study, a poly-parameter LFER (ppLFER) based model of organic chemical bioaccumulation in humans is presented. Chemical partitioning was described by an air-body partition coefficient that was a volume weighted average of ppLFER based partition coefficients for the major organs and tissues constituting the human body. This model was compared to a spLFER model treating the body as a mixture of lipid (≈ octanol) and water. Although model agreement was good for hydrophobic chemicals (average difference 15% for log K_OW > 4 and log K_OA > 8), the ppLFER model predicted ~ 90% lower body burdens for hydrophilic chemicals (log K_OW < 0). This was mainly due to lower predictions of muscle and adipose tissue sorption capacity for these chemicals. A comparison of the predicted muscle and adipose tissue sorption capacities of hydrophilic chemicals with measurements indicated that the ppLFER and spLFER models' uncertainties were similar. Consequently, little benefit from the implementation of ppLFERs in this model was identified.     

Control of sulfide in sewer systems by dosage of iron salts: comparison between theoretical and experimental results, and practical implications

Removal of sulfide species from municipal sewage conveyance systems by dosage of iron salts is a relatively common practice. However, the reactions that occur between dissolved iron and sulfide species in municipal sewage media have not yet been fully quantified, and practical application relies heavily on empirical experience, which is often site specific. The aim of this work was to combine theoretical considerations and empirical observations to enable a more reliable prediction of the sulfide removal efficiency for a given dosing strategy. Two main questions were addressed, regarding the dominant sulfur species that results from the oxidation of sulfide by Fe(III) and the dominant precipitation reaction between Fe(II) and sulfide species. Comparison of thermodynamic prediction obtained by an equilibrium chemistry-based computer program (MINEQL+) with experimental results obtained by dosing ferrous salts showed that the product of precipitation is FeS under all operational conditions tested. Regarding the reaction between ferric salts and sulfide species, analysis of thermodynamic data suggested that the dominant product of sulfide oxidation under typical pe/pH conditions prevailing in municipal raw wastewater is SO(4)(2-). However, comparison between sulfide removal in laboratory experiments conducted with multiple samples of raw municipal sewage with a varying composition, and the prediction of MINEQL+ showed the main sulfide oxidation product to be S(0). In order to reduce sulfide in sewage to <0.1 mgS/l a minimal molar ratio of around 1.3 Fe to 1 S should be applied when ferrous salts are used, as compared with a minimal ratio of 0.9 Fe to 1 S required when ferric salts or a mixture of ferrous and ferric salts (at a 2 Fe(III) to 1 Fe(II) ratio) are used. It appears that the high Fe to S(-II) ratios often recommended in practice can be reduced considerably by applying tight in-line control.     

Chemical and biological technologies for hydrogen sulfide emission control in sewer systems: a review

Biogenic corrosion of sewers represents a cost of about 10% of total sewage treatment cost in Flanders (Belgium) and is further increasing. In the past, research has resulted in a number of prevention methods, such as injection of air, oxygen, H(2)O(2), NaClO, FeCl(3) and FeSO(4). The possibility of biological oxidation of sulfide using nitrate as the electron acceptor has also been explored in sewer systems. However, all of these methods have a problem with the high cost (euro 1.9-7.2 kg(-1)S removal). In this review, new approaches for hydrogen sulfide emission control in sewer systems are discussed. The control of hydrogen sulfide emission by using a microbial fuel cell (MFC) can be cost-effective while the BOD is removed partially. The use of phages that target sulfate-reducing bacteria (SRB) can possibly inhibit sulfide formation. Novel inhibitors, such as slow release solid-phase oxygen (MgO(2)/CaO(2)) and formaldehyde, warrant further study to control hydrogen sulfide emission in sewer systems.     

Experimental study on thermo-chemical phenomena during interaction of limestone concrete with liquid sodium under inert atmosphere

Sodium leak in fast breeder reactor, either from pipe in inert equipment cells or inside the reactor cavity may come in contact with the limestone sacrificial layer on structural concrete. Experimental studies are carried out to investigate thermal and chemical impact of sodium on the limestone concrete under different test conditions. Sodium pool is maintained at different temperature on the test blocks placed in leak tight test chamber. The temperatures at different locations, pressure, release of hydrogen and oxygen gas are monitored online during the experiments. On-set time and residence period for energetic thermal transients (ETT) along with peak and average heat generation rates are evaluated. Chemical parameters such as rate and extent of water release from concrete, sodium consumption, sodium hydroxide production and sodium emission into argon atmosphere are also elucidated. Preliminary analysis of test results revealed that when hot sodium at 500 °C reacts on cold concrete block, it monotonically cools down with low degree of interaction. However, supply of external heat to sodium pool triggers considerable reaction with or without occurrence of ETT phase.     

Dosing free nitrous acid for sulfide control in sewers: Results of field trials in Australia

Intermittent dosing of free nitrous acid (FNA), with or without the simultaneous dosing of hydrogen peroxide, is a new strategy developed recently for the control of sulfide production in sewers. Six-month field trials have been carried out in a rising main sewer in Australia (150 mm in diameter and 1080 m in length) to evaluate the performance of the strategy that was previously demonstrated in laboratory studies. In each trial, FNA was dosed at a pumping station for a period of 8 or 24 h, some with simultaneous hydrogen peroxide dosing. The sulfide control effectiveness was monitored by measuring, on-line, the dissolved sulfide concentration at a downstream location of the pipeline (828 m from the pumping station) and the gaseous H₂S concentration at the discharge manhole. Effective sulfide control was achieved in all nine consecutive trials, with sulfide production reduced by more than 80% in 10 days following each dose. Later trials achieved better control efficiency than the first few trials possibly due to the disrupting effects of FNA on sewer biofilms. This suggests that an initial strong dose (more chemical consumption) followed by maintenance dosing (less chemical consumption) could be a very cost-effective way to achieve consistent control efficiency. It was also found that heavy rainfall slowed the recovery of sulfide production after dosing, likely due to the dilution effects and reduced retention time. Overall, intermittent dose of FNA or FNA in combination with H₂O₂ was successfully demonstrated to be a cost-effective method for sulfide control in rising main sewers.     

Optimization of intermittent, simultaneous dosage of nitrite and hydrochloric acid to control sulfide and methane productions in sewers

Free nitrous acid (FNA) was previously demonstrated to be biocidal to anaerobic sewer biofilms. The intermittent dosing of FNA as a measure for controlling sulfide and methane productions in sewers is investigated. The impact of three key operational parameters namely the dosing concentration, dosing duration and dosing interval on the suppression and subsequent recovery of sulfide and methane production was examined experimentally using lab-scale sewer reactors. FNA as low as 0.26 mg-N/L was able to suppress sulfide production after an exposure of 12 h. In comparison, 0.09 mg-N/L of FNA with 6-h exposure was adequate to restrain methanogenesis effectively. The recovery of sulfide production was well described by an exponential recovery equation. Model-based analysis revealed that 12-h dosage at an FNA concentration of 0.26 mg-N/L every 5 days can reduce the average sulfide production by >80%. Economic analysis showed that intermittent FNA dosage is potentially a cost-effective strategy for sulfide and methane control in sewers.     

Pollution from Fish Farms

Fish farms are continuing to grow in numbers and in size. They cause concern because of their location in areas of high-quality water, frequently in the headwaters where there is little dilution for large volumes of effluent. This jeopardizes the water quality, and may affect the ecology of the river - migratory fish in particular.
The use of chemicals for the treatment of disease is causing concern, particularly if the river is used for potable abstraction. Little information is available on the low-level effects and the detection of chemicals such as antibiotics and hormones. The chemicals are not controlled nationally, the only control being through consents.
With the continued growth of the fish-farm industry, problems are likely to increase in the future unless a responsible attitude to their development is adopted.     

Environmental management in the steel industry —a survey

This survey deals with many environmental management problems in the iron and steel industry and it is mainly based on Japanese data. First, the characteristic features of pollution problems in the iron and steel industry are clarified by comparing with them those of other industries.

Second, a detailed classification is made of environmental pollution phenomena in the iron and steel industry, and a model plant adopting modern pollution control devices is introduced. Finally, taking a recycling system as an example, the necessity to establish total environmental management systems is emphasized.     

Kinetics and stoichiometry of sulfide oxidation by sewer biofilms

Oxidation of sulfide under aerobic conditions by biofilms grown on municipal wastewater in 6 identical pipe reactors was investigated. The biofilms were grown at pH 7.6 and temperatures of 20 and 25 degrees C under aerobic-anaerobic transient conditions with pulse dosing of sulfide in the bulk water. The pulse dosing of sulfide served to simulate conditions in a gravity sewer located downstream of a pressure main. During growth of the biofilms, sulfide was pulse dosed in concentrations of 0, 0.5, 2.0 and 5.0 g Sm(-3) with a frequency of 1h(-1). Based on a series of batch experiments, kinetics and stoichiometry of sulfide oxidation by the sewer biofilms was investigated and a rate equation and a stoichiometric constant proposed. Sulfide oxidation kinetics was significantly faster for biofilms grown at sulfide loadings of 0.5, 2.0 and 5.0 g Sm(-3)h(-1) than for biofilms grown in the absence of sulfide. However, the kinetics of sulfide oxidation was relatively constant for biofilms grown at sulfide loadings above 0.5 g Sm(-3)h(-1). Mass balance calculations of dissolved oxygen and sulfur compounds suggested the oxidation product to be elemental sulfur. Further oxidation of elemental sulfur could not be documented.     

ORP-based oxygenation for sulfide control in anaerobic treatment of high-sulfate wastewater

A series of chemostat studies were conducted at a constant influent total organic carbon of 3750 mg/L (equivalent chemical oxygen demand (COD) of 10,000 mg/L) but at different influent sulfates of 1000, 3000 and 5000 mg/L in order to investigate the feasibility of online sulfide toxicity control through periodic oxygenation to the recycled biogas stream. The oxygen dosing for sulfide oxidation was regulated by using oxidation-reduction potential (ORP) as a controlling parameter. During oxygenation at elevated ORPs of -230 and -180 mV (50 and 100 mV above natural ORP of -280 mV, respectively), the dissolved and gaseous sulfides were completely eliminated which resulted in a concomitant improvement in methane yield by 56.3% at 5000 mg/L influent sulfate. However, at influent sulfates of 1000 and 3000 mg/L, both methane generation rate and sulfate removal efficiency were dropped appreciably at elevated ORPs. Facultative heterotrophs were found to consume as high as 66.3% of the influent COD during oxygenation. For effective sulfide oxidation at lower sulfate levels, it was no longer required to raise the ORP by as much as 50 or 100 mV. The actual needed ORP increase depended on the influent sulfate. This study had proven that the ORP-controlled oxygenation was reliable for achieving consistent online sulfide control during anaerobic treatment of high-sulfate wastewater.     

进水N/S值对同步脱硫反硝化特性的影响

研究了不同进水N/S值条件下,不同接种物的厌氧体系的同步脱硫反硝化特性。结果表明:在N/S为0.6或0.4的条件下,3个体系对硫化物的去除率均达到90%以上,其中以进水N/S为0.4时产生的悬浮态硫最多;硝态氮的去除特性与硫化物不同,3个体系对硝态氮的去除率均在进水N/S为1.0时达到100%,且此时N2的产量也最大。可见,尽管同步脱硫反硝化工艺具备同时脱氮及除硫的能力,但其进水N/S的控制值却不相同。对于脱硫而言,最佳的进水N/S为0.4;对于脱氮而言,最佳的进水N/S为1.0。此外,研究发现3个不同接种物的厌氧体系对硫化物及硝态氮的去除途径不同,进水N/S值的影响也有差异。对于接种了厌氧污泥的体系,存在自养反硝化和异养反硝化的竞争,改变进水N/S值可调节二者的竞争,高N/S值会抑制硫化物自养反硝化过程,降低对硫化物的去除率;对于接种脱氮硫杆菌的纯菌体系,多硫自催化反应会与硫化物自养反硝化反应竞争硫化物,降低对硝态氮的去除率,高N/S值会导致出水硝态氮浓度较高;对于添加脱氮硫杆菌的强化厌氧污泥体系,以硫化物自养反硝化过程为主,最佳的N/S为0.4。