Photocatalytic degradation of organic wastes by electrochemically assisted TiO2 photocatalytic system

Photocatalytic degradation of organic wastes with nanosized titanium dioxide particles has been studied for a long time in order to offer an appropriate method for wastewater treatment, but its practical application is greatly limited by the slow process. In this work, an electrochemically assisted TiO2 photocatalytic system was set-up by combining a TiO2 photocatalytic cell with a three-electrode potentiostatic unit. The composite system revealed high photocatalytic activity towards organic wastes mineralization. After continuous treatment for 0.5 h, the maximum absorption of rhodamine 6G (R-6G) was reduced by more than 90%; chemical oxygen demand (COD) and biochemical oxygen demand (BOD5) of textile dye wastewater (TDW) were decreased by 93.9 and 88.7%, respectively. The biodegradability of TDW was also improved because the COD/BOD5 ratio decreased from 2.1 to 1.2. All these results indicated that the composite system could be used for effective organic wastes mineralization or as a feasible detoxification and color removal pretreatment stage for biological post treatment.     

Functional classification of swine manure management systems based on effluent and gas emission characteristics

Gaseous emissions from swine (Sus scrofa) manure storage systems represent a concern to air quality due to the potential effects of hydrogen sulfide, ammonia, methane, and volatile organic compounds on environmental quality and human health. The lack of knowledge concerning functional aspects of swine manure management systems has been a major obstacle in the development and optimization of emission abatement technologies for these point sources. In this study, a classification system based on gas emission characteristics and effluent concentrations of total phosphorus (P) and total sulfur (S) was devised and tested on 29 swine manure management systems in Iowa, Oklahoma, and North Carolina in an effort to elucidate functional characteristics of these systems. Four swine manure management system classes were identified that differed in effluent concentrations of P and S, methane (CH4) emission rate, odor intensity, and air concentration of volatile organic compounds (VOCs). Odor intensity and the concentration of VOCs in air emitted from swine manure management systems were strongly correlated (r2 = 0.88). The concentration of VOC in air samples was highest with outdoor swine manure management systems that received a high input of volatile solids (Type 2). These systems were also shown to have the highest odor intensity levels. The emission rate for VOCs and the odor intensity associated with swine manure management systems were inversely correlated with CH4 and ammonia (NH3) emission rates. The emission rates of CH4, NH3, and VOCs were found to be dependent upon manure loading rate and were indirectly influenced by animal numbers.     

Greenhouse gas emissions from two soils receiving nitrogen fertilizer and swine manure slurry

The interactive effects of soil texture and type of N fertility (i.e., manure vs. commercial N fertilizer) on N(2)O and CH(4) emissions have not been well established. This study was conducted to assess the impact of soil type and N fertility on greenhouse gas fluxes (N(2)O, CH(4), and CO(2)) from the soil surface. The soils used were a sandy loam (789 g kg(-1) sand and 138 g kg(-1) clay) and a clay soil (216 g kg(-1) sand, and 415 g kg(-1) clay). Chamber experiments were conducted using plastic buckets as the experimental units. The treatments applied to each soil type were: (i) control (no added N), (ii) urea-ammonium nitrate (UAN), and (iii) liquid swine manure slurry. Greenhouse gas fluxes were measured over 8 weeks. Within the UAN and swine manure treatments both N(2)O and CH(4) emissions were greater in the sandy loam than in the clay soil. In the sandy loam soil N(2)O emissions were significantly different among all N treatments, but in the clay soil only the manure treatment had significantly higher N(2)O emissions. It is thought that the major differences between the two soils controlling both N(2)O and CH(4) emissions were cation exchange capacity (CEC) and percent water-filled pore space (%WFPS). We speculate that the higher CEC in the clay soil reduced N availability through increased adsorption of NH(4)(+) compared to the sandy loam soil. In addition the higher average %WFPS in the sandy loam may have favored higher denitrification and CH(4) production than in the clay soil.     

Removal of the hazardous dye rhodamine B through photocatalytic and adsorption treatments

This paper reports on photocatalytic and adsorptive treatment of a hazardous xanthene dye, Rohdamine B, in wastewater. The photocatalytic degradation was carried out in the presence of the catalyst TiO(2) and the effects of pH, concentration of the dye, amount of TiO(2), temperature and electron acceptor H(2)O(2) on the degradation process were observed. It was found that photocatalytic degradation by TiO(2) is an effective, economical and faster mode of removing Rohdamine B from aqueous solutions. Attempts were also made to utilize activated carbon and rice husk as potential adsorbents to remove Rhodamine B from wastewater. The adsorption studies were carried out at 40, 50 and 60 degrees C, and the effects of pH, temperature, amount of adsorbents, concentration of adsorbate, etc., on the adsorption were measured. On the basis of adsorption data the Langmuir and Freundlich adsorption isotherm models were also confirmed. The adsorption isotherm constants thus obtained were employed to calculate thermodynamic parameters like Gibb's free energy, change in enthalpy and entropy. In order to observe the quality of wastewater COD measurements were also carried out before and after the treatments. A significant decrease in the COD values was observed, which clearly indicates that both photocatalytic and adsorption methods offer good potential to remove Rhodamine B from industrial effluents.     

Influence of parameters on the heterogeneous photocatalytic degradation of pesticides and phenolic contaminants in wastewater: a short review

In recent years, the application of heterogeneous photocatalytic water purification processes has gained wide attention due to its effectiveness in degrading and mineralizing the recalcitrant organic compounds as well as the possibility of utilizing the solar UV and visible-light spectrum. This paper aims to review and summarize the recent works on the titanium dioxide (TiO(2)) photocatalytic oxidation of pesticides and phenolic compounds, predominant in storm and wastewater effluents. The effects of various operating parameters on the photocatalytic degradation of pesticides and phenols are discussed. Results reported here suggest that the photocatalytic degradation of organic compounds depends on the type and composition of the photocatalyst and, light intensity, initial substrate concentration, amount of catalyst, pH of the reaction medium, ionic components in water, solvent types, oxidizing agents/electron acceptors, catalyst application mode, and calcination temperature in the water environment. A substantial amount of research has focused on the enhancement of TiO(2) photocatalysis by modification with metal, non-metal and ion doping. Recent developments in TiO(2) photocatalysis for the degradation of various pesticides and phenols are also highlighted in this review. It is evident from the literature survey that photocatalysis has good potential to remove a variety of organic pollutants. However, there is still a need to determine the practical utility of this technique on a commercial scale.     

光催化氧化处理低浓度含醇废水实验

室内实验了TiO2紫外光催化氧化处理废水中的低浓度甲醇。通过对TiO2催化剂活性及添加方式、溶液pH、紫外光强与催化剂加量等参数优化,在TiO2加入浓度为300mg/L和120 W紫外灯照射条件下,对6.8L甲醇浓度为2.77%的低浓度含醇废水持续处理70min后,废水中的甲醇去除率可达98.31%。该实验为进一步处理低浓度含醇废水提供了方法依据。     

TiO2光催化降解有机颜料艳红RGS母液研究

以TiO2为催化剂,对有机颜料艳红RGS母液进行了一系列光催化降解试验.考察了催化剂用量、溶液pH值、初始浓度、不同光源和照射时间对脱色率的影响.结果表明,溶液相对初始浓度为0.2、pH<8、催化剂用量为1g/L时,以紫外灯(254nm)为光源,反应120 min,脱色率可达93%以上.     

Effect of land use on methane flux from soil

The precise effects of natural and disturbed terrestrial systems on the atmospheric CH4 pool are uncertain. This study was conducted to quantify and compare CH4 fluxes from a variety of ecosystems in central Iowa. We investigated agricultural systems under different management practices, a hardwood forest site, native and restored prairies, and a municipal landfill. Flux measurements were obtained using a closed-chamber method, and measurements were compiled by sampling over the 1993 and 1994 growing seasons. In 1993, most of the agricultural sites were net CH4 producers with cumulative CH4 fluxes ranging from -0.02 to 3.19 g m(-2) over the 258-d sampling season, while the natural ecosystems were net CH4 consumers, with cumulative seasonal fluxes ranging from -0.27 to -0.07 g m-2 258 d(-1). In 1994, only the landfill and the agricultural site treated with broadcast liquid swine manure (LSM) were net CH4 producers, while the remainder of the natural and agricultural ecosystems were net CH4 consumers, with mean seasonal flux rates ranging from -0.43 to -0.008 g m(-2) 271 d(-1). We hypothesize that the differences in CH4 fluxes between the two years are due to differences in rainfall. To illustrate the integration between land use and CH4 flux, we computed an area-weighted soil CH4 flux for the state of Iowa. Our calculations yielded a net average soil CH4 flux of 139,000 Mg CH4 for 1993 and 1994.     

提高二氧化钛光催化活性的研究进展

综合国内外资料，介绍了TiO2的特殊性及其光催化作用的机理，就提高TiO2光催化活性的方法，包括TiO2的表面修饰、改变体系的各种条件及TiO2在体系中的状态等几方面进行了较为全面的概述。并提出了今后的研究方向与趋势。     

Photocatalytic activity of tungsten-doped TiO2 with hydrothermal treatment under blue light irradiation

Tungsten doping and hydrothermal treatment were found to significantly improve the visible-light photoactivity of TiO(2) synthesized by the sol-gel method. It was observed that TiO(2) doped with a 0.5% W:Ti mole ratio and treated with 4 h of hydrothermal curing showed photoactivity under blue light irradiation equal to 74% of the commercial Degussa P-25 under UV irradiation, i.e., 0.01 mM 2-chlorophenol was completely removed in 120 and 90 min, respectively. Light absorptivity and photocatalytic activity under blue light irradiation were not dependent on the crystallite structure of the TiO(2). The oxidation kinetics under blue light irradiation can be effectively explained by the Langmuir-Hinshelwood model with an apparent reaction rate constant and a Langmuir constant of 3.60 × 10(-4) mM min(-1) and 206.53 mM(-1), respectively.     

Lagoon-biogas emissions and carbon balance estimates of a swine production facility

Gaseous emissions from animal manure storage facilities can contribute to global greenhouse gas inventories. Biogas fluxes were measured for one year from a 2-ha anaerobic lagoon that received waste from a 10500-head swine (Sus scrofa) finishing operation in southwestern Kansas. During 2001, ebullition of biogas was measured continuously by using floating platforms equipped with gas-collection domes. Periodically, the composition of the biogas was determined by using gas chromatography. Detailed records of feed quality and quantity and animal weights and gains also were obtained to determine the carbon budget of the facility (barns and lagoon). Flux of biogas was very seasonal, with peak emission (18.7 mol m(-2) d(-1)) occurring in early June. Nearly 50% of the annual biogas losses occurred during a 30-d period beginning on day of year (DOY) 146. Flux patterns suggest that the start of the high biogas production period was governed by temperature, while the decline in production in mid-June was caused by substrate limitations. Average biogas composition was 0.71 L CH4 L(-1). The quantity of CH4 released from the lagoon was 86.3 Mg yr(-1), which represents about 38 g of CH4 per kg of animal weight gain. The average flux density of biogas from the lagoon was 382 mol m(-2) yr(-1) or 728 mol yr(-1) per resident animal where the resident animal population was 10500. Flux rates of CH4 were 1.7 to 3.4 times less than predictions made with Intergovernmental Panel on Climate Change (IPCC) models. Additional research is needed on the carbon budgets of other animal feeding operations so that better estimates of greenhouse gas emissions can be determined.     

Development of a dynamic model to predict PM10 emissions from swine houses

Influences on dust emissions from livestock operations are number, weight, and kind of animals and characteristics of the housing system. Differences between facilities cannot be explained solely by mechanistic input variables. The objective of this study was to characterize the main input variables for modeling emissions of particulate matter with a mass median diameter < or = 10 microm (PM10) from swine facilities using a data-based model. Investigations were performed in mechanically ventilated facilities for weaning, growing-finishing, and sows in Italy and Germany. The measurements included inside and outside concentration of airborne PM10 particles (scatter light photometry), ventilation rate (calibrated measuring fans), indoor air climate at a measuring frequency of 60 s, feeding times, and animal-related data such as weight and animal activity. Dust concentration and emission were simulated using a dynamic transfer function. The results indicated that the average PM10 emission rate was influenced considerably by housing system. The simulation of the PM10 emission rate resulted in a mean percentage error per data set of 21 to 39%, whereas the average simulated and measured emission rate per data set differed by about 4 to 19%. High prediction errors occurred especially during situations in which the absolute level and spatial location of the measured activity peaks did not correspond with the measured dust peaks. Further recommendations of the study were to improve continuous and accurate measurements of input variables, such as the activity level in animal houses, and to optimize the amount of measuring days in relation to the model accuracy.     

掺杂型二氧化钛纳米管光催化降解甲基橙研究

利用本实验室制备的N-F原子掺杂二氧化钛纳米管作催化剂,在可见光区对甲基橙(MO)进行光催化降解实验。在催化剂用量固定为3cm2时考察了不同初始浓度、pH值、溶解氧(DO)等对降解率的影响。结果表明,在可见光区该催化剂具有较高的光催化活性;当溶液DO为19.2mg/L、pH值为3、初始浓度为10mg/L、反应时间300min时,降解率可达82.3%。     

Photocatalytic degradation of disperse blue 1 using UV/TiO2/H2O2 process

The photocatalytic degradation of a dye derivative, C.I. disperse blue 1 (1), has been investigated under UV light irradiation in the presence of TiO2 and H2O2 under a variety of conditions. The degradation was studied by monitoring the change in substrate concentration employing UV spectroscopic technique as a function of irradiation time. The degradation was studied under different conditions such as different types of TiO2, reaction pH, catalyst and substrate concentration containing hydrogen peroxide (H2O2), besides molecular oxygen in the presence of TiO2. The degradation of dye was also investigated under sunlight and the efficiency of degradation was compared with that of the artificial light source. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 was found to be more efficient for the degradation of the dye.     

Degradation of a commercial textile biocide with advanced oxidation processes and ozone

The occurrence of significant amounts of biocidal finishing agents in the environment as a consequence of intensive textile finishing activities has become a subject of major public health concern and scientific interest only recently. In the present study, the treatment efficiency of selected, well-known advanced oxidation processes (Fenton, Photo-Fenton, TiO(2)/UV-A, TiO(2)/UV-A/H(2)O(2)) and ozone was compared for the degradation and detoxification of a commercial textile biocide formulation containing a 2,4,4'-trichloro-2'-hydroxydiphenyl ether as the active ingredient. The aqueous biocide solution was prepared to mimic typical effluent originating from the antimicrobial finishing operation (BOD(5,o) < or =5 mg/L; COD(o)=200 mg/L; DOC(o) (dissolved organic carbon)=58 mg/L; AOX(o) (adsorbable organic halogens)=48 mg/L; LC(50,o) (lethal concentration causing 50% death or immobilization in Daphnia magna)=8% v/v). Ozonation experiments were conducted at different ozone doses (500-900 mg/h) and initial pH (7-12) to assess the effect of ozonation on degradation (COD, DOC removal), dearomatization (UV(280) and UV(254) abatement), dechlorination (AOX removal) and detoxification (changes in LC(50)). For the Fenton experiments, the effect of varying ferrous iron catalyst concentrations and UV-A light irradiation (the Photo-Fenton process) was examined. In the heterogenous photocatalytic experiments, Degussa P25-type TiO(2) was used as the catalyst and the effect of reaction pH (3, 7 and 12) and H(2)O(2) addition on the photocatalytic treatment efficiency was examined. Although in the photochemical (i.e. Photo-Fenton, TiO(2)/UV-A and TiO(2)/UV-A/H(2)O(2)) experiments appreciably higher COD and DOC removal efficiencies were obtained, ozonation appeared to be equally effective to achieve dearomatization (UV(280) abatement) at all studied reaction pH. During ozonation of the textile biocide effluent, AOX abatement proceeded significantly faster than dearomatization and was complete after 20 min ozonation (267 mg O(3)). On the other hand, for complete detoxification, ozonation had to be continued for at least 30 min (corresponding to 400mg O(3)). Effective AOX and acute toxicity removal was also obtained after heterogeneous photocatalytic treatment (TiO(2)/UV-A and TiO(2)/UV-A/H(2)O(2)). The Fenton-based treatment experiments and particularly the dark Fenton reaction resulted in relatively poor degradation, dearomatization, AOX and acute toxicity removals.     

La掺杂TiO2/有机改性膨润土对TNT弹药废水的光催化降解性能研究

利用超声强化溶胶-凝胶法制备了La掺杂TiO2/有机改性膨润土复合光催化材料并进行了结构表征;以弹药废水中主要污染物质TNT作为目标物,考察了影响光催化降解性能的因素.结果表明：有机改性后复合材料的吸附性能和光催化性能均有所增加,对TNT的60min的吸附去除率和光催化降解率分别达到9.68％和94.53％;影响TNT光催化降解率的因素有光照时间、催化剂用量、TNT初始浓度、溶液pH值和光照强度.     

负载型TiO2薄膜光催化剂降解亚甲基蓝

采用溶胶-凝胶法制备了玻璃负载的TiO2薄膜光催化剂，研究了该催化剂对亚甲基蓝溶液的光催化降解，考察了反应时间、水样的初始浓度、溶液的pH等对光催化降解效果的影响。     

Phosphorus fractionation in manure from swine fed traditional and low-phytate corn diets

Traditional corn (Zea mays L.) (TC), the primary grain used in swine (Sus scrofa) diets, stores a majority of its P as phytate, which is largely unavailable for digestion by nonruminant animals. Low-phytate corn (LPC) contains similar amounts of total P but a smaller percentage of P as phytate. When fed to swine, LPC increases P utilization and reduces P content of manure. While differences in P content between manure from animals fed TC and LPC diets have been documented, solubility and lability of manure P have not been compared. Manure P was characterized in manure from swine fed either LPC or TC diets in 2000 and 2001. Total P was lower (20 vs. 34 g kg(-1)) and N to P ratio was higher (4.5 vs. 3.3) in LPC manure than in TC manure. Manures were sequentially extracted with deionized water, 0.5 M NaHCO3, 0.1 M NaOH, and 1.0 M HCl. Extracts were analyzed for inorganic and total P. Most P (approximately 80%) in the extracts was in the inorganic form. Concentration of P in the water-extractable fraction was lower for LPC manure (10.2 g kg(-1) in 2000 and 9.7 g kg(-1) in 2001) than for TC manure (13.6 g kg(-1) in 2000 and 17.0 g kg(-1) in 2001). Percentage of total P in each extract was in the order of: H2O (60%), HCl (22%), NaHCO3 (12%), NaOH (8%), and residue (<1%). Total P and distribution of P in extracts indicates swine are able to utilize more P contained in LPC feed but the composition of P excreted in LPC manure is similar to TC manure. Solubility, crop availability, and lability of P in LPC manure should be similar to that of TC manure.     

Co-digestion of pig manure and glycerine: experimental and modelling study

It is a fact that the rapid increase of biodiesel production over the last years has resulted in the generation of large and constant amounts of glycerine, which is causing an oversupply problem. Since glycerine is a biodegradable organic compound exempt of nitrogen, it can be applied as a co-substrate in the anaerobic digestion process of pig manure (PM). In order to analyze the feasibility of a mixture of pig manure and glycerine in anaerobic processes and to define the effect originated by the nitrogen limitation when large amounts of glycerine are added, several biodegradability batch tests were performed with different mixtures. These were named as: 100% PM, 80% PM, 60% PM, 40% PM and 20% PM, in pig manure wet weight-basis. Furthermore, a modified model based on anaerobic digestion model no.1 (ADM1) was used to simulate the methane production profiles for the mixtures tested. Specifically, both experimental and model results show the power of the co-digestion technology. In particular, the mixture of 80% PM produced the highest methane production with 215 mL CH(4) g(-1) COD, almost 125% more methane than when pig manure was mono-digested. In contrast, the one with 20% PM was clearly inhibited by the volatile fatty acid due to the low nitrogen concentration of the mixture. In addition, the specific methane production predicted by the model was in good agreement with the experimental results, although in some samples the shape of the profiles did not match perfectly. Moreover, the modified ADM1 appears to be a useful tool to predict the methane production and the limitations related to the lack/excess of nitrogen during the co-digestion process of pig manure and glycerine.     

Gas emissions from dairy cows fed typical diets of Midwest, South, and West regions of the United States

Gas emissions were determined for dairy cows fed three diets formulated to represent feed ingredients typical of the Midwest, South, or West regions of the United States. Dairy cows were housed and monitored in 12 environmentally controlled rooms (4 cows diet). Two experiments were performed, representing two lactation stages (initial days in milk were 115 ± 39 d in Stage 1 and 216 ± 48 d in Stage 2). The results demonstrated that the combination of different dietary ingredients resulted in different gas emissions while maintaining similar dry matter intake (DMI) and milk yield (MY). Diet effect on ammonia (NH) emissions was more prominent in Stage 1. During Stage 1, cows fed the Midwest diet had the highest daily NH emission, corresponding to the highest crude protein (CP) concentration among the three regions. The differences in NH emissions (39.0%) were much larger than the percent difference in CP concentrations between diets (6.8%). Differences in N intake, N excretion, or milk urea N alone may not serve as a strong indicator of the potential to reduce NH emissions. Lower emissions of methane (CH) per unit DMI or per unit MY were observed for cows offered the South diet during Stage 1 as compared with that from cows offered the Midwest or West diets. No diet effect was observed for hydrogen sulfide (HS) emission per unit S intake, nor for nitrous oxide (NO) emission. The measured NH and CH emissions were comparable, but the NO emissions were much higher than those reported for tie-stall dairy barns in the literature.