Relationship between release of nitric oxide and CO2 and their dependence on oxidation reduction potential in wastewater treatment

Nitric oxide (NO) is an intermediate of denitrification process and can be produced by denitrifiers, nitrifiers and other bacteria. In our experiments we measured the dynamic flow of NO depending on oxidation reduction potential (ORP). Different ORP-ranges were related to various carbon loading stages in the wastewater treatment pilot plant. Nitrification and denitrification were achieved by a sequence of aeration and non-aeration periods. Our measurements show that different carbon loading conditions (low feed, balanced and overloaded conditions) did not change the range of the mixing ratio of NO emissions when the aeration conditions like air-flow and temperature were kept constant. Minimum and maximum NO mixing ratios were 34.7 and 91.8 ppbv; 52.3 and 91.3 ppbv; 57.6 and 109 ppbv for low feed, balanced and overloaded conditions, respectively. The curve of the NO graph relied on nitrification/denitrification dynamics. The dependence of NO release on different ORP and CO2-release during the various conditions are shown. Longer aeration times resulted in an increased release of gaseous NO. The net-release of NO g(-1) nitrogen removed was between 0.014% and 0.028%. The NO fluxes to the air were observed between 8.3 and 14.9 mg m(-2) d(-1) NO. The major release occurred during high aeration periods whereas the concentration of dissolved [NOaq] in the wastewater was less than 0.05% of the gaseous release due to very low solubility of the NO.     

Fe~(3+)掺杂TiO_2/凹凸棒复合材料的光催化性能

采用酸催化的溶胶-凝胶法制备了一系列Fe3+掺杂TiO2/凹凸棒(Fe3+-TiO2/ATP)复合光催化剂材料。在可见光条件下,以亚甲基蓝(MB)溶液的光催化降解反应,评价了样品的光催化性能,研究了TiO2负载量、Fe3+掺杂量和焙烧温度对复合材料光催化性能的影响。在单因素实验的基础上,采用正交实验设计(L25(53))优化了催化剂的制备条件。光催化实验结果表明,MB在复合材料上的光催化降解反应遵循Langmuir-Hinshelwood(L-H)动力学模型。正交实验结果表明,当TiO2负载量为15%、Fe3+掺杂量为0.5%和焙烧温度为550℃时,得到的复合材料对MB的光催化降解效率最佳,测得表观反应速率常数kapp为6.09×10-3min-1,反应4 h后MB的降解率(Dt)可达75.88%,相同实验条件下与P25(1.51×10-3min-1)相比较,反应速率提高了4.03倍,降解率提高了45.05%。另外,复合材料的沉降性能优于P25,易于分离,是一类有应用前景的复合光催化剂。     

Field test of a cross-injection scheme for stimulating in situ denitrification near a municipal water supply well

A pilot-scale test of an in situ denitrification scheme was undertaken to assess an adaptation of the nutrient injection wall (NIW) technology for treating a deep (30-40 m) nitrate contamination problem (N-NO(-)(3) ~ 10-12 mg/L). The adaptation is called the Cross-Injection Scheme (CIS). It duplicates the NIW method without a wall; wells are installed and operated directly in the aquifer and high-flux zones of the aquifer are preferentially targeted for treatment. The test was conducted on the site of a municipal water supply well field, with the supply well pumping between 15-80 m(3)/h. Acetate was periodically injected into the aquifer between an injection-extraction well pair positioned across the normal direction of flow. The injected pulses were then permitted to move with the water toward the municipal wells, providing a carbon supply to drive the desired denitrification. The fate of nitrate, nitrite, acetate and sulphate were monitored at multilevel wells located between the injection location and the municipal wells. The acetate pulsing interval was approximately weekly (9 h injections), so that the system was operating passively 95% of the time. Previous work on the site has established that the highest solute fluxes were associated with a 1-3 m thick zone about 35 m below surface. This zone was found to respond to the acetate additions as a function of the municipal pumping rate and the carbon-to-nitrogen ratio (i.e., determined by the injected acetate concentration). Initially, acetate was injected just below the theoretical stoichiometric requirement for complete denitrification and nitrate disappearance was accompanied by nitrite production. Increasing the C:N ratio (doubling the acetate injection concentration) increased the removal of nitrate and diminished the occurrence of nitrite. Slowing the municipal pumping rate, with a C:N ratio of 1.2-1.6, resulted in complete nitrate attenuation with no nitrite production and no sulfate reduction. The experiment demonstrated that the CIS injection scheme is a viable option for the treatment of nitrate contamination in situ near high-capacity wells.     

纳米TiO2/EP光催化降解罗丹明B废水的研究

通过溶胶-凝胶法制备出可漂浮于水面的膨胀珍珠岩(EP)负载型TiO2,研究其在水中对罗丹明B(RB)的去除效果、吸附降解动力学以及最佳工艺条件,并研究其多次回收再生后的降解效果。结果表明,浸渍3次的负载型TiO2光催化活性最高,回收5次后活性变化很小,降解率下降不到8%;光催化剂用量为0.2 g,20 mL初始浓度为10 mg/L和15mg/L RB溶液光照6 h后降解率分别达98%和74%。在实验浓度范围内,该光催化反应可用一级反应动力学方程描述。     

A/O膜生物反应器处理高浓度氨氮废水试验研究

对A/O膜生物反应器处理高浓度氨氮废水进行了研究,着重考察硝化液回流比和C/N对系统脱氮效能的影响.研究表明,当硝化液回流比为2、C/N为6时.系统对COD、氨氮、TN的平均去除率分别达96.17%、97.76%、76.29%;A/O膜生物反应器稳定运行期间,氨氮容积负荷去除量与进水氨氮容积负荷呈现良好的线性关系;当A/O膜生物反应器内MLSS稳定在9～13 g/L时,上清液COD较低,膜压差增长缓慢.     

纳米TiO_2/EP光催化降解罗丹明B废水的研究

通过溶胶-凝胶法制备出可漂浮于水面的膨胀珍珠岩（EP）负载型TiO2,研究其在水中对罗丹明B（RB）的去除效果、吸附降解动力学以及最佳工艺条件,并研究其多次回收再生后的降解效果。结果表明,浸渍3次的负载型TiO2光催化活性最高,回收5次后活性变化很小,降解率下降不到8%;光催化剂用量为0.2 g,20 mL初始浓度为10 mg/L和15mg/L RB溶液光照6 h后降解率分别达98%和74%。在实验浓度范围内,该光催化反应可用一级反应动力学方程描述。     

Photocatalytic bacterial inactivation by polyoxometalates

The photocatalytic inactivation (PCI) of Escherichia coli (Gram-negative) and Bacillus subtilis (Gram-positive) was performed using polyoxometalate (POM) as a homogeneous photocatalyst and compared with that of heterogeneous TiO₂ photocatalyst. Aqueous suspensions of the microorganisms (10⁷–10⁸ cfu ml⁻¹) and POM (or TiO₂) were irradiated with black light lamps. The POM-PCI was faster than (or comparable to) TiO₂-PCI under the experimental conditions employed in this study. The relative efficiency of POM-PCI was species-dependent. Among three POMs (H₃PW₁₂O₄₀, H₃PMo₁₂O₄₀, and H₄SiW₁₂O₄₀) tested in this study, the inactivation of E. coli was fastest with H₄SiW₁₂O₄₀ while that of B. subtilis was the most efficient with H₃PW₁₂O₄₀. Although the biocidal action of TiO₂ photocatalyst has been commonly ascribed to the role of photogenerated reactive oxygen species such as hydroxyl radicals and superoxides, the cell death mechanism with POM seems to be different from TiO₂-PCI. While TiO₂ caused the cell membrane disruption, POM did not induce the cell lysis. When methanol was added to the POM solution, not only the PCI of E. coli was enhanced (contrary to the case of TiO₂-PCI) but also the dark inactivation was observed. This was ascribed to the in situ production of formaldehyde from the oxidation of methanol. The interesting biocidal property of POM photocatalyst might be utilized as a potential disinfectant technology.     

Interactive effects of nitrogen and phosphorus loadings on nutrient removal from simulated wastewater using Schoenoplectus validus in wetland microcosms

The concentrations of nutrients (N and P) in the wastewater and loading rate to the constructed wetlands may influence the nutrient removal from the secondary-treated municipal wastewater using wetland plants. Three loading rates of N (low 5.7, medium 34.3 and high 103 mg N d(-1)) and two of P (low 3.4 and high 17.1 mg P d(-1)) were studied in simulated secondary-treated municipal wastewater using Schoenoplectus validus (Vahl) A. L?ve & D. L?ve in the vertical free surface-flow wetland microcosms. After 70-d growth, there were significant interactive effects of N and P on the total, above-ground and root biomass. The below-ground biomass (rhizome and root) was negatively affected by the high N treatment. The tissue concentrations of N increased with an increase in N additions and decreased with an increase in P applications, whereas the tissue concentrations of P increased with an increase in P additions and decreased with an increase in N applications at the low P treatment, but increased at the high P treatment. Significant interactive effects of N and P loadings were found for the removal efficiencies of NH(4) and P, but not that of NO(x). The plant uptake, substrate storage and other losses (e.g. denitrification and formation of organic film) had similar contribution to N removal when N loading was relatively low. The P storage by substrate was the main contribution to P removal when P loading was high, but plant uptake was the major factor responsible for P removal when P loading was low and N loading was high. The high nutrient availability and optimum ratio of N:P are required to stimulate growth of S. validus, resulting in preferential allocation of resources to the above-ground tissues and enhancing the nutrient removal efficiencies, but the high N concentration in wastewater may hamper the growth of S. validus in constructed wetlands.     

Ozone disintegration of excess biomass and application to nitrogen removal.

A pilot-scale facility integrated with an ozonation unit was built to investigate the feasibility of using ozone-disintegration byproducts of wasted biomass as a carbon source for denitrification. Ozonation of biomass resulted in mass reduction by mineralization as well as by ozone-disintegrated biosolids recycling. Approximately 50% of wasted solids were recovered as available organic matter (ozonolysate), which included nonsettleable microparticles and soluble fractions. Microparticles were observed in abundance at relatively low levels of ozone doses, while soluble fractions became dominant at higher levels of ozone doses in ozone-disintegrated organics. Batch denitrification experiments showed that the ozonolysate could be used as a carbon source with a maximum denitrification rate of 3.66 mg nitrogen (N)/g volatile suspended solids (VSS) x h. Ozonolysate was also proven to enhance total nitrogen removal efficiency in the pilot-scale treatment facility. An optimal chemical oxygen demand (COD)-to-nitrogen ratio for complete denitrification was estimated as 5.13 g COD/g N. The nitrogen-removal performance of the modified intermittently decanted extended aeration process dependent on an external carbon supply could be described as a function of solids retention time.     

Hydraulic constraints on the performance of a groundwater denitrification wall for nitrate removal from shallow groundwater

Denitrification walls are a practical approach for decreasing non-point source pollution of surface waters. They are constructed by digging a trench perpendicular to groundwater flow and mixing the aquifer material with organic matter, such as sawdust, which acts as a carbon source to stimulate denitrification. For efficient functioning, walls need to be permeable to groundwater flow. We examined the functioning of a denitrification wall constructed in an aquifer consisting of coarse sands. Wells were monitored for changes in nitrate concentration as groundwater passed through the wall and soil samples were taken to measure microbial parameters inside the wall. Nitrate concentrations upstream of the wall ranged from 21 to 39 g N m(-3), in the wall from 0 to 2 g N m(-3) and downstream from 19 to 44 g N m(-3). An initial groundwater flow investigation using a salt tracer dilution technique showed that the flow through the wall was less than 4% of the flow occurring in the aquifer. Natural gradient tracer tests using bromide and Rhodamine-WT confirmed groundwater bypass under the wall. Hydraulic conductivity of 0.48 m day(-1) was measured inside the wall, whereas the surrounding aquifer had a hydraulic conductivity of 65.4 m day(-1). This indicated that during construction of the wall, hydraulic conductivity of the aquifer had been greatly reduced, so that most of the groundwater flowed under rather than through the wall. Denitrification rates measured in the center of the wall ranged from 0.020 to 0.13 g N m(-3) day(-1), which did not account for the rates of nitrate removal (0.16-0.29 g N m(-3) day(-1)) calculated from monitoring of groundwater nitrate concentrations. This suggested that the rate of denitrification was greater at the upstream face of the wall than in its center where it was limited by low nitrate concentrations. While denitrification walls can be an inexpensive tool for removing nitrate from groundwater, they may not be suitable in aquifers with coarse textured subsoils where simple inexpensive construction techniques result in major decreases in hydraulic conductivity.     

Investigation of solid-phase buffers for sulfur-oxidizing autotrophic denitrification.

This paper investigates biological denitrification using autotrophic microorganisms that use elemental sulfur as an electron donor. In this process, for each gram of nitrate-nitrogen removed, approximately 4.5 g of alkalinity (as calcium carbonate) are consumed. Because denitrification is severely inhibited below pH 5.5, and alkalinity present in the influent wastewaters is less than the alkalinity consumed, an external buffer was needed to arrest any drop in pH from alkalinity consumption. A packed-bed bioreactor configuration is ideally suited to handle variations in flow and nitrate loading from decentralized wastewater treatment systems, as it is a passive system and thus requires minimal maintenance; therefore, a solid-phase buffer packed with the elemental sulfur in the bioreactor is most suitable. In this research, marble chips, limestone, and crushed oyster shells were tested as solid-phase buffers. Bench- and field-scale studies indicated that crushed oyster shell was the most suitable buffer based on (1) the rate of dissolution of buffer and the buffering agent released (carbonate, bicarbonate, or hydroxide), (2) the ability of the buffer surface to act as host for microbial attachment, (3) turbidity of the solution upon release of the buffering agent, and (4) economics.     

Nitrate-consuming processes in a petroleum-contaminated aquifer quantified using push-pull tests combined with 15N isotope and acetylene-inhibition methods

Nitrate consumption in aquifers may result from several biogenic and abiotic processes such as denitrification, assimilatory NO3- reduction, dissimilatory NO3- reduction to ammonium (DNRA), or abiotic NO3- (or NO2-) reduction. The objectives of this study were to investigate the fate of NO3- in a petroleum-contaminated aquifer, and to assess the feasibility of using single-well push-pull tests (PPTs) in combination with 15N isotope and C2H2 inhibition methods for the quantification of processes contributing to NO3- consumption. Three consecutive PPTs were performed in a monitoring well of a heating oil-contaminated aquifer in Erlen, Switzerland. For each test, we injected 500 l of test solution containing 0.5 mM Br- as conservative tracer and either 0.5 mM unlabeled NO3- or approximately 0.3 mM 15N-labeled NO3- as reactant. Test solutions were sparged during preparation and injection with either N2, Ar or 10% C2H2 in Ar. After an initial incubation period of 1.5-3.2 h, we extracted the test solution/groundwater mixtures from the same location and measured concentrations of relevant species including Br-, NO3-, NO2-, N2O, N2, and NH4+. In addition, we determined the 15N contents of N2, N2O, NH4+, and suspended biomass from 15N/14N isotope-ratio measurements. Average total test duration was 50.5 h. First-order rate coefficients (k) were computed from measured NO3- consumption, N2-15N production and N2O-15N production. From measured NO3- consumption we obtained nearly identical estimates of k for all PPTs with small 95% confidence intervals, indicating good reproducibility and accuracy for the tests. Estimates of k from N2-15N production and N2O-15N production indicated that denitrification accounted for only 46-49% of observed NO3- consumption. Production of N2-15N in the presence of C2H2 was observed during one of the tests, which may be an indicator for abiotic NO3- reduction. Moreover, 15N isotope analyses confirmed occurrence of assimilatory NO3- reduction (0.58 at.% 15N in suspended biomass) and to a smaller extent DNRA (up to 4 at.% 15N in NH4+). Our results indicated that the combination of PPTs, 15N-isotope and C2H2 inhibition methods provided improved information on denitrification as well as alternative fates of NO3- in this aquifer.     

Numerical simulation of a fine-grained denitrification layer for removing septic system nitrate from shallow groundwater

One of the most common methods to dispose of domestic wastewater involves the release of septic effluent from drains located in the unsaturated zone. Nitrogen from such systems is currently of concern because of nitrate contamination of drinking water supplies and eutrophication of coastal waters. It has been proposed that adding labile carbon sources to septic distribution fields could enhance heterotrophic denitrification and thus reduce nitrate concentrations in shallow groundwater. In this study, a numerical model which solves for variably saturated flow and reactive transport of multiple species is employed to investigate the performance of a drain field design that incorporates a fine-grained denitrification layer. The hydrogeological scenario simulated is an unconfined sand aquifer. The model results suggest that the denitrification layer, supplemented with labile organic carbon, may be an effective means to eliminate nitrogen loading to shallow groundwater. It is also shown that in noncalcareous aquifers, the denitrification reaction may provide sufficient buffering capacity to maintain near neutral pH conditions beneath and down gradient of the drain field. Leaching of excess dissolved organic carbon (DOC) from the denitrification layer is problematic, and causes an anaerobic plume to develop in simulations where the water table is less than 5-6 m below ground surface; this anaerobic plume may lead to other down gradient changes in groundwater quality. A drain field and denitrification layer of smaller dimensions is shown to be just as effective for reducing nitrate, but has the benefit of reducing the excess DOC leached from the layer. This configuration will minimize the impact of wastewater disposal in areas where the water table is as shallow as 3.5 m.     

分段进水多级生物膜反应器脱氮效能影响因素研究

采用分段进水多级生物膜反应器处理高氮低碳小城镇污水,考察负荷、溶解氧和温度对反应器脱氮效能的影响。实验结果表明:负荷、溶解氧和温度对反应器脱氮效能有显著影响。在水温为20～25℃,DO为5 mg/L,负荷为1 kgCOD/(m3.d),挂膜密度为30%,第1、3、6级分段进水,流量分配比为2∶2∶1的条件下,在反应器中可成功构建出高效同时硝化反硝化系统,出水COD、NH4+-N和TN浓度分别为33 mg/L、2.6 mg/L和29.4 mg/L,去除率分别为90.1%、96.0%和63.9%。当水温≤15℃时,硝化速率受温度的影响显著。     

长江水絮凝污泥制备光催化剂及其催化活性

用聚硅硫酸钛絮凝处理长江水,所产生的絮凝污泥经干燥、煅烧处理后制备了具有较高催化活性的复合光催化剂,并用XRD对其进行了表征。考察了絮凝pH值、煅烧温度、絮凝剂投加量和光催化剂投加量等因素对复合光催化剂光催化降解活性艳红K-2BP溶液的影响。结果表明,当絮凝pH值为4,煅烧温度为500℃,絮凝剂投加量为0．2g／L时,制备的复合光催化剂催化活性最佳,光催化降解浓度为25mg／L的活性艳红K-2BP溶液15min后降解率达99．9％,与同等实验条件下P-25的降解效率相当。     

Denitrification in the river estuaries of the northern Baltic Sea

Estuaries have been suggested to have an important role in reducing the nitrogen load transported to the sea. We measured denitrification rates in six estuaries of the northern Baltic Sea. Four of them were river mouths in the Bothnian Bay (northern Gulf of Bothnia), and two were estuary bays, one in the Archipelago Sea (southern Gulf of Bothnia) and the other in the Gulf of Finland. Denitrification rates in the four river mouths varied between 330 and 905 micromol N m(-2) d(-1). The estuary bays at the Archipelago Sea and the Gulf of Bothnia had denitrification rates from 90 micromol N m(-2) d(-1) to 910 micromol N m(-2) d(-1) and from 230 micromol N m(-2) d(-1) to 320 micromol N m(-2) d(-1), respectively. Denitrification removed 3.6-9.0% of the total nitrogen loading in the river mouths and in the estuary bay in the Gulf of Finland, where the residence times were short. In the estuary bay with a long residence time, in the Archipelago Sea, up to 4.5% of nitrate loading and 19% of nitrogen loading were removed before entering the sea. According to our results, the sediments of the fast-flowing rivers and the estuary areas with short residence times have a limited capacity to reduce the nitrogen load to the Baltic Sea.     

Effect of liquid manure on the mole fraction of nitrous oxide evolved from soil containing nitrate

The same emission factor is applied to fertiliser N and manure N when calculating national N2O inventories. Manures and fertilisers are often applied together to meet the N needs of the crop, but little is known about potential interactions leading to an increase in denitrification rate or a change in the composition of the end-products of denitrification. We used the 15N gas-flux method in a laboratory experiment to quantify the effect of liquid manure (LM) application on the fluxes of N2 and N2O when the soil contained fertiliser 15NO3-. LM increased the mole fraction of N2O from 0.5 to 0.85 in the first 12 h after application. More than 94% of the N2O was from the reduction of NO3-, probably due to aerobic nitrate respiration as well as respiratory denitrification.     

Decomposition of low-concentration gas-phase toluene using plasma-driven photocatalyst reactor

Plasma-driven photocatalysis system was prepared and performed. To overcome the treatment difficulty of volatile organic compounds, non-thermal plasma was used as a light source of photocatalysis. The removal of low-concentration toluene was investigated and secondary products were analyzed by gas chromatograph–mass spectroscopy. The plasma-driven photocatalyst reactor using direct current as a light source and titanium dioxide catalyst loaded on activated carbon fiber (TiO₂/ACF) as photocatalyst was studied. It was found that plasma-driven photocatalysis system could significantly increase the removal effect of toluene. The number of secondary products was largely decreased. It means that plasma-driven photocatalysis hybrid system was an effective method for the removal of volatile organic compounds.     

银钛共负载型光催化材料降解甲基橙废水

以膨胀珍珠岩为载体,采用溶胶凝胶法对其进行负载,制备出不同类型的光催化材料（TiO2．EP、Ag＋-TiO2-EP）,并在模拟日光条件下,研究其对甲基橙溶液的降解效果。结果表明,浸渍3次且担载0．04％Ag＋的负载型TiO2光催化活性最高,在光催化剂用量为0．3g,20mL初始浓度为10mg／L甲基橙溶液光照4h后降解率可达81．6％,且甲基橙的光催化降解服从一级动力学方程。回收3次后仍有较强的活性,其2h降解率为24．8％。     

Fe^3＋掺杂TiO2/凹凸棒复合材料的光催化性能

采用酸催化的溶胶-凝胶法制备了一系列Fe^3＋掺杂TiO2/凹凸棒（Fe^3＋-TiO2/ATP）复合光催化剂材料。在可见光条件下,以亚甲基蓝（MB）溶液的光催化降解反应,评价了样品的光催化性能,研究了TiO2负载量、Fe^3＋掺杂量和焙烧温度对复合材料光催化性能的影响。在单因素实验的基础上,采用正交实验设计（L25（53））优化了催化剂的制备条件。光催化实验结果表明,MB在复合材料上的光催化降解反应遵循Langmuir-Hinshelwood（L-H）动力学模型。正交实验结果表明,当TiO2负载量为15%、Fe^3＋掺杂量为0.5%和焙烧温度为550℃时,得到的复合材料对MB的光催化降解效率最佳,测得表观反应速率常数kapp为6.09×10^-3min^-1,反应4 h后MB的降解率（Dt）可达75.88%,相同实验条件下与P25（1.51×10^-3min^-1）相比较,反应速率提高了4.03倍,降解率提高了45.05%。另外,复合材料的沉降性能优于P25,易于分离,是一类有应用前景的复合光催化剂。敏世雄王芳魏立强王永生冯雷佟永纯韩玉琦