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This study investigated the practical application of combined advanced oxidation processes (AOPs), such as homogeneous TiO2 photocatalysis and heterogeneous photo-Fenton, for the treatment of tannery wastewaters. An optimization study was conducted on the photocatalytic degradation of tannery wastewaters, in order to understand the effects of different operating parameters on the degradation kinetics. The chemical oxygen demand of tannery wastewater decreased from an initial level of 3,400 mg/L in raw wastewater to 140 mg/L (96% removal) in wastewater treated by the combined advanced oxidation process at optimum pH 7, TiO2 dosage of 0.2 g/L, Fe2+ dosage of 0.5 g/L, H2O2 dosage of 1.8 g/L and a treatment time of 4 hours. The biodegradability of wastewater increased from an initial level of 0.4 to 0.7 after treatment under optimum experimental conditions at a treatment time of 60 min. An annual treatment cost of US$21.34/m3 of treated water was obtained. The combined advanced oxidation process proved to be an efficient and appropriate technique for the effective removal of complex organic compounds in industrial wastewater.
- biodegradability
- combined advanced oxidation process
- photocatalysis
- solar photo-Fenton
- synergetic effect
- tannery wastewaters
Tanneries are typically characterized as pollution-intensive industrial complexes that generate widely varying, high-strength wastewaters (Chowdhury et al. 2013). The variability of tannery wastewaters arises not only from the fill and draw-type operation associated with tanning processes, but also from the different procedures used for hide preparation, tanning and finishing. These procedures are dictated by the kind of raw hides employed and the required characteristics of the finished product. The tanning industry also has a very high toxic intensity per unit of output. During the tanning process at least about 0.3 kg of chemicals are added per kilogram of skin/hides (Durai & Rajasimman 2011). Tanneries generate wastewater in the range of 30–35 litre per kilogram of skin/hide processed with variable pH (6–10.5), total suspended solids (TSS) (526–2,865 mg/L), biochemical oxygen demand (BOD) (100–2,906 mg/L), chemical oxygen demand (COD) (2,102–11,153 mg/L) (Lofrano et al. 2013). One of the refractory groups of chemicals in tannery wastewater derives mainly from tannins. Tannins are characterized by complex chemical structures, because they are composed of an extended set of chemicals such as phenol, naphthalene, formaldehyde and melamine-based syntans, and acrylic resins. The BOD5/COD ratio of tannins is also lower than other compounds. However, it is worth noting that no one of these compounds showed a BOD5/COD ratio higher than 0.4, indicating a very low biodegradability for each of them (Lofrano et al. 2013).
The main treatment processes used at tannery plants are primary clarification (sedimentation), secondary treatment (activated sludge process) and/or tertiary processes (membrane processes as ultrafiltration). The activated sludge process has been the most common wastewater treatment process for the removal of organics in our country; however, it is inefficient for the removal of recalcitrant organics and micro-pollutants in tannery wastewater. The mixture of compounds used in the tannery process can be released into the environment because the compounds remain even after conventional treatment (activated sludge process, aerobic sequencing batch reactor, anaerobic filters, upflow anaerobic sludge blanket and membrane bioreactor) and negatively affect organisms and the environment. The wastewater of tanneries has also been associated with a huge foaming problem on surface waters (Durai & Rajasimman 2011). The high concentrations of pollutants with low biodegradability in tannery wastewater represent a serious and actual technological and environmental challenge. Therefore, many researchers have attempted to develop new technologies for complementing or even replacing some of these treatments (Khansorthong & Hunsom 2009).
Advanced oxidation processes (AOPs) can be considered an effective alternative and have become the most widely used treatment technologies for organic pollutants not treatable by conventional technologies due to their high chemical stability and/or low biodegradability. AOPs involve the generation of highly reactive radical species, mainly the hydroxyl radical (OH•) to oxidize the organic matter to the end products of water and carbon dioxide (Trabelsi-Souissi et al. 2013). The use of sunlight as the source of irradiation to perform AOPs reduces the processing costs and makes them more affordable for commercial use as a water treatment technology (Babuponnusami & Muthukumar 2012). These processes can be used before or after conventional treatment or even as the principal stage, depending on the characteristics of the wastewater and the quality requirements of the treated wastewater (Zgajnar et al. 2011).
Among various AOPs, Fenton reagent (Fe2+ + H2O2) and photocatalysis (TiO2 + UV) have been intensively investigated for environmental applications during the last decades. They have both been recognized as 'green technologies'. Above all, the Fenton reaction can be initiated in conditions of normal temperature and pressure with no external energy, thus it can hopefully be utilized in water in situ remediation areas (Eskelinen et al. 2010). In the photocatalytic research field, some catalysts, for example, TiO2, CdS and GaP have proved to possess high activity with solar light irradiation, thus endless clean solar energy is a powerful support for this technology (Sauer et al. 2006; Rauf et al. 2011). However, the classic Fe2+-based Fenton system requires operation at pH < 3.0 to prevent the precipitation of Fe2+ and Fe3+. Usually, a large excess of Fe salts in traditional Fenton systems cannot be recycled, producing large amounts of chemical sludge (Su et al. 2012; Hermosilla et al. 2012). The major drawback of TiO2/UV photocatalysis was that its high efficiency occurred only under UV irradiation, which can use only 3–4% of the solar energy reaching the earth (Portjanskaja et al. 2009). Thus, in order to extend the practical applications of industrial and environmental interest, some efforts have been made to develop a synergistic reaction to enhance the Fenton reaction and TiO2 photocatalysis. For instance, when Fenton is combined with the TiO2 photocatalysis reaction, the efficacies of both the systems for the production of radicals are enhanced (Chen et al. 2013). The conduction band (CB) electrons and photoenergy can accelerate the ferric and ferrous iron cycles (Fe2+/Fe3+); at the same time, Fenton reagent (Fe2+/H2O2) inhibits the electron–hole recombination by scavenging CB electrons of photo-excited TiO2 to increase the lifetime of the valence band hole and subsequently generate more radicals. Moreover, electrons from TiO2 decompose more oxidants to radicals, which can promote the Fenton reaction efficiency drastically (Kim et al. 2012).
The present study demonstrates that the synergistic combination of TiO2 photocatalysis (solar/TiO2) and Fenton reaction (Fe2+/H2O2) produces a marked kinetic enhancement of the degradation of tannery wastewaters at neutral pH conditions, which is detrimental to Fenton oxidation.
Wastewater source and characterization
Tannery wastewaters were obtained from a tannery near Erode, Tamil Nadu, India. The tests were performed with primary treated wastewater (collected at the outlet of the plain sedimentation tank). The sample was collected in plastic cans that were transported to a laboratory and stored at 4 °C. The physicochemical characteristics of the wastewater, determined using standard methods, are listed in Table 1. After the primary treatment, the BOD5 to COD ratio was 0.40, indicating the non-biodegradable character of the wastewater and the possible presence of minimally biodegradable chemical substances, which undermine biological treatment (Lofrano et al. 2013). Even after complete treatment, the treated wastewater did not satisfy the minimum national standards for discharge (MINAS 2007). Upgrade of the tannery's existing tannery wastewater treatment system is needed.
All reagents used in this experiment were of analytical grade and used as received without further purification. The chemicals used in this study are ferrous sulphate heptahydrate (FeSO4.7H2O), hydrogen peroxide (H2O2 30% w/w), sodium thiosulphate (Na2O3S2), sulphuric acid (H2SO4), potassium dichromate (Cr2K2O7), mercuric sulphate (HgSO4), ferrous ammonium sulphate (Fe(NH4)2(SO4)2·6H2O), sodium hydroxide (NaOH), and sodium sulphite (Na2SO3), and were purchased from Merck (India). The photocatalyst employed was commercial TiO2 (P25), and was supplied by Degussa (Germany). According to the manufacturer's specifications, P25 has an elementary particle size of 30 nm, a Brunauer–Emmett–Teller (BET) specific surface area of 50 m2/g and crystalline mode comprising 80% anatase and 20% rutile.
Experimental methods
All photocatalytic experiments were carried out at Anna University Campus, Tirunelveli, India (8°44′N 77°44′E). The experiments were conducted using a laboratory-scale reactor system made from borosilicate glass having a size of 0.3 m (length) × 0.2 m (width) × 0.04 m (depth) operated in the batch mode. The irradiation surface area was 0.06 m2. Irradiation was carried out in the open air with continuous aeration by a pump to provide oxygen and for the complete mixing of the reaction mixture. In all cases, 1 L of reaction mixture was irradiated. The reactor was exposed to strong solar irradiation from January to April between 11 a.m. and 3 p.m. The solar ultraviolet radiation was measured by a global UV radiometer which provided data in terms of incident energy per surface area (ultraviolet intensity 32 ± 2 W/m2). Initially, the pH of the wastewater was adjusted to a predetermined value (2–8) by adding sulphuric acid or sodium hydroxide. Then the required amount of ferrous sulphate (0–1 g/L) and TiO2 (0–0.25 g/L) was added to the wastewater and stirred well to enhance the homogeneity of wastewater during the reaction. H2O2 (0–2.2 g/L) was added (considered the beginning of the experiment) and the mixture was solar irradiated. The required amount of sample was withdrawn from the reactor at selected time intervals. Immediately after collecting each sample, sodium sulphite solution (approximately 0.5 mL per 10 mL wastewater sample) was added to quench the oxidation reaction for H2O2 decomposition, and the pH was raised by adding sodium hydroxide to precipitate iron salt and TiO2 particles. All experiments were performed in triplicate and averages were reported. The COD and BOD3 of the samples were carried out as per Standard Methods (APHA 2005).
Box–Behnken experimental design
The Box–Behnken design (BBD) statistical experiment had been used on the advanced oxidation of pollutants. BBD is the optimization of analytical methods. Hence, BBD was used to investigate the effects of important operating parameters in the degradation of tannery wastewaters and to optimize the system. This is a type of response surface method (RSM) which is based on three level incomplete factorial designs. It requires fewer runs when compared to other RSM designs, making its application more economical (Masomboon et al. 2010). Basically, this optimization process involves three major steps: (1) performing the statistically designed experiments, (2) estimating the coefficients in a mathematical model and (3) predicting the response and checking the adequacy of the model. The Box–Behnken experimental design is used for evaluation of a dependent variable as functions of independent variables. The pH, TiO2, Fe2+ and H2O2 concentrations were considered as independent variables. The COD removal efficiency was considered as a dependent variable in the Box–Behnken statistical design method. The pH was varied between 6 and 8, the TiO2 concentration was varied between 0.10 g/L and 0.30 g/L, the Fe2+ concentration was varied between 0.25 g/L and 0.75 g/L and the H2O2 concentration was varied between 1.60 g/L and 2.00 g/L. A total of 29 experiments were employed in this analysis, using Design Expert Version 9.0.2 software (Stat-Ease, Inc., Minneapolis, USA). To simplify the recording of the conditions of each experiment and the processing of the experimental data, the factor levels were selected taking the high level as +1 and the lower level as −1.
Model fitting and statistical analysis
The experimental data for COD removal by combined advanced oxidation process are given in Table 2. From the results obtained in the trials performed with the BBD, the following quadratic model equation was established to correlate the dependent and independent variables: 1
The regression coefficients of the model describing the COD removal are summarized in Table 3. Analysis of variance (ANOVA) was applied in order to evaluate the significance of the fit of the developed model. P < 0.05 indicates that the model terms are significant at 95% confidence level or more. For the model predicted by Equation (1), P was less than 0.0001, indicating that it was significant for describing the COD removal efficiency. The lack of fit value 5.77 is not significant at the P value > 0.05. For a model to be successfully used for prediction, the lack of fit should be insignificant and the response surfaces sufficiently explained by the regression equation. A positive effect of a factor means that the response is improved when the factor level increases and a negative effect of the factor means that the response is not improved when the factor level increases. The factors that had relatively less effect on COD removal efficiency were the TiO2 concentration (P = 0.0131) and the interactions between Fe2+ concentration and TiO2 concentration (P = 0.1445) and between pH and TiO2 concentration (P = 0.0139). As can be seen in Equation (1), the positive effects were the individual factors of TiO2 concentration, pH and Fe2+ concentration, in this order. The negative effects were the double interaction between Fe2+ concentration and H2O2 concentration, the double interaction between pH and TiO2 concentration and the factor of H2O2 concentration, as well as the double interaction between TiO2 concentration and H2O2 concentration. The high correlation between actual experimental data and the model for COD removal (R2 = 0.9785) showed that 97.85% of the variability observed in data can be explained by the model built for COD removal efficiency, leaving only 2.15% of variability owing to random error. Consequently, the quadratic model given by Equation (1) can be used to predict the COD removal efficiency, create and explore the response surface and find the optimal conditions of the process.
Effect of pH
To determine the effect of pH, the degradation of tannery wastewater was investigated at pH values of 2 to 8. At an optimal pH of 7, the decrease in COD was greatest (75%) (Figure 1). In the solar/TiO2/Fe2+/H2O2 process, at an acidic pH, the surface of TiO2 is occupied with H+ ions, which retards the generation of OH•. When the pH increases, the active hydroxyl groups on the TiO2 surface also increase. Consequently, the faster generation of OH• radicals accelerates COD removal efficiency (Kashif & Ouyang 2009). The Fenton reaction, which occurred on the photo-excited TiO2 surface, appeared to produce a more reactive oxidant (e.g., OH•) than the Fe(IV) species, which was usually formed by the Fenton reaction at neutral pH. As a result, the integrated solar/TiO2/Fe2+/H2O2 system can enhance the rate of contaminant oxidation by increased production of reactive oxidants.
Three-dimensional (3D) response surface and contour plot are presented in Figure 2. Such a plot presents the function of two variables, maintaining all others at the fixed levels. According to the literature, 3D surface and corresponding contour plots provide a clear and straightforward evaluation of the effects of the investigated experimental variables. In Figure 2, the influence of initial pH and TiO2 concentration on the COD removal of tannery wastewater by solar/TiO2/Fe2+/H2O2 process is presented. According to the shape of the 3D surface, larger amplitudes of COD removal were obtained by varying the initial pH than by varying TiO2, so it can be concluded that initial pH is a more influential parameter than TiO2.
Effect of TiO2
To determine the effect of TiO2 dosage, the degradation of tannery wastewater was investigated by varying TiO2 dosage from 0 to 0.25 g/L. Maximum COD removal of 71% was obtained at 0.2 g/L TiO2 (Figure 3). As the TiO2 dosage increased from 0.1 to 0.2 g/L, the number of photons absorbed and the number of organic molecules adsorbed also increased because of the increased number of catalytic particles. The density of particles in the area of illumination also increased, enhancing degradation, likely due to an increased number of available adsorption and catalytic sites on the TiO2. A further increase beyond this optimum catalyst loading, however, may cause light scattering and a screening effect, reducing the specific activity of the catalyst (Ghaly et al. 2007; Adishkumar et al. 2014). In addition, at high TiO2 concentrations, aggregation of particles will reduce the interfacial area between the reaction solution and the photocatalyst, decreasing the number of active sites on the catalyst surface. Agglomeration and sedimentation of the TiO2 particles were observed when more than 0.2 g/L of TiO2 was added. In such a condition, part of the catalyst surface probably became unavailable for photon absorption and organic adsorption, providing little stimulation to the catalytic reaction. This may have been the reason for the decrease in the degradation rate (Oller et al. 2006). The addition of small amounts of Fe2+ can significantly increase the generation rate of hydroxyl radicals, thereby enhancing the oxidation efficiencies of organic pollutants mediated by TiO2 (Baycan Parilti & Atken 2011). The positive effect of coupling photo-Fenton-like reactions with semiconductor photocatalysis can be attributed to the increased production of active radicals through decomposition of oxidants by both heterogeneous and homogeneous catalysts (Zhang et al. 2011).
Effect of ferrous dosage
To determine the effect of Fe2+ dosage, the degradation of tannery wastewater was investigated by varying Fe2+ dosage from 0 to 1 g/L. Maximum COD removal of 70% was observed for 0.5 g/L Fe2+ (Figure 4). The relatively low treatment efficiency of tannery wastewater at a low dosage of Fe2+ likely reflected an insufficient number of Fe2+ ions, leading to the low production of hydroxyl radicals available for the Fenton reaction. Treatment efficiency increased with Fe2+ dosage, because as the amount of Fe2+ and Fe3+ ions increased, the catalytic effect on H2O2 also increased. As the dosage of Fe2+ exceeded 0.5 g/L, copious leaching of Fe2+ in the form of Fe (OH)2 would occur, restricting the decrease in COD. Fe2+ may also tend to scavenge OH•, decreasing treatment efficiency. Liou et al. (2003) reported that ·OH inhibition occurs in the photo-Fenton reaction with high ferrous concentrations. Moreover, high iron concentrations are not desirable since they are likely to increase iron precipitation (Deng 2007; Adishkumar et al. 2012). TiO2 is more effective due to the formation of electron–hole pairs under UV illumination. Nevertheless, recombination of electrons and holes inhibits the photocatalytic reaction process. Some oxidants improve the performance of UV/TiO2 treatment by capturing the electrons ejected from TiO2, reducing the probability of recombination of e− and h+VB, and yielding higher available numbers and the survival time of h+VB. Baycan Parilti & Atken (2011) reported that for the removal of organic contaminants in pulp mill effluents (COD concentrations = 1,500 mg/L), the addition of small amounts of Fe2+ can significantly increase the generation rate of OH•, thereby enhancing the oxidation efficiencies of organic pollutants mediated by TiO2. Consequently, higher concentrations of OH• radicals and Fe(III) can be attained with the solar UV/TiO2/Fe(III) treatment compared to the conventional TiO2 treatment process. Kitsiou et al. (2009) reported that separate coupling of TiO2 with Fe2+ or H2O2 has little effect on the degradation efficiency of imidacloprid, a systemic chloronicotinoid insecticide (20 mg/L initial concentration),while the simultaneous use of TiO2, Fe2+ and H2O2 leads to significantly increased rates, presumably due to the combined effect of homogenous and heterogeneous photocatalytic reactions.
In Figure 5, the influence of Fe2+ and TiO2 concentration on the COD removal of tannery wastewater by the solar/TiO2/Fe2+/H2O2 process is presented. According to the shape of the 3D surface, larger amplitudes of COD removal were obtained by varying the Fe2+ than by varying TiO2, and it can be concluded that Fe2+ is a more influential parameter than TiO2. Figure 6 presents the influence of H2O2 concentration and Fe2+ concentration. In Figure 6, a much higher influence of Fe2+ concentration can be observed than H2O2 concentration.
Effect of H2O2 dosage
To maintain efficiency, it is necessary to choose the optimum concentration of H2O2. The effect of the addition of 0–2.2 g/L H2O2 on the COD removal is shown in Figure 7. Increasing the concentration of H2O2 correspondingly increased COD removal up to an H2O2 concentration of 1.8 g/L. The enhancement of degradation by the addition of H2O2 is due to an increase in the hydroxyl radical concentration. H2O2 can compensate for the lack of O2 and can function as an external electron scavenger (Barakat et al. 2005), trapping the photo-generated CB electron, inhibiting the electron–hole recombination and producing hydroxyl radicals (Ginni et al. 2014). Figure 8 presents the influence of H2O2 concentration and TiO2 concentration. In Figure 8, a much higher influence of H2O2 concentration can be observed than TiO2 concentration. Mahmoudi et al. (2005) reported that an optimal concentration of H2O2 increases the formation rate of hydroxyl radicals due to reduction of H2O2 at the CB and because of self-decomposition occurring during solar illumination. Increased H2O2 concentration may promote an inhibitory effect, due to the hydroxyl radical scavenging and the formation of another radical , having an oxidation potential considerably smaller than HO•. The combination of Fe2+, H2O2, TiO2 and irradiation, i.e., photo-Fenton and photocatalysis, improves the destruction of some resistant pollutants (Vincenzo et al. 2006).
Kinetics of tannery wastewater degradation
In order to achieve the proper design of a solar photo reactor, it is very important to determine the kinetic coefficients involved in a reaction. Treatment efficiency of tannery wastewater by the solar, solar/Fe2+, solar/TiO2, solar/H2O2, solar/TiO2/H2O2, solar/Fe2+/H2O2 and solar/TiO2/Fe2+/H2O2 processes are shown in Figure 9. The kinetics of degradation of tannery wastewater for the solar/TiO2/H2O2, solar/Fe2+/H2O2 and solar/TiO2/Fe2+/H2O2 processes are discussed below. First-order kinetic model was utilized as follows: 2 where C0, C, t and k are the initial COD, final COD, degradation time (h) and the global reaction apparent rate constant (h−1), respectively. The order of rate constants was solar/TiO2/Fe2+/H2O2 − 0.80 h−1 (R2 = 0.93) > solar/Fe2+/H2O2 − 0.30 h−1 (R2 = 0.94) > solar/TiO2/H2O2 − 0.20 h−1 (R2 = 0.97).
Effect of hydraulic retention time
In this study, the efficiency of solar/TiO2/Fe2+/H2O2 process was carried out under optimum conditions. Nearly all (96%) COD was depleted at 4 hours (Figure 10). By increasing the contact time, the exposure of the reaction mixture to solar light allowed the utilization of more energy to produce more hydroxyl radicals from H2O2, TiO2 and Fe2+. Table 4 shows the treated characteristics of the tannery wastewater. The COD and BOD5 of tannery wastewater after treatment were reduced to 140 mg/L and 90 mg/L. Treatment of tannery wastewater by the solar/TiO2/Fe2+/H2O2 process increased biodegradability from 0.4 to 0.7 in 1 hour (Figure 10). The increase of BOD5/COD ratio to 0.70 upon treatment of the wastewater in the combined advanced oxidation process for 1 hour clearly indicates the breakdown of organic compounds into biodegradable forms, and the improvement in biodegradability of the wastewater. Therefore, wastewaters of combined AOPs can be efficiently post-treated in a biological process for the elimination of residual organic compounds of wastewaters.
Synergetic effect
The advantage of AOPs is enhanced by the fact that there are different OH• radical production possibilities, so they can be adapted to specific treatment requirements. On the other hand, the relatively high operating cost of these processes compared to biological treatment is the main disadvantage. To tackle this problem and to increase the efficiency of AOPs, a combined or integrated process can be used. Using a combined process as a pretreatment process reduces organic loading and the cost of post-treatment. The main parameter in the combined process used to evaluate the effectiveness of the system is the synergetic effect, a parameter of the enhancement of the degradation of organic compounds using the combined method relative to the linear combination method. The synergetic effect could be estimated as follows: 3
Factors such as design, construction, operation and maintenance of combined advanced oxidation processes are more difficult than those of the individual methods. However, by combining the various technologies, lower capital and operating costs are achievable. The purpose of combining AOPs is to enhance the degradation rate that is not achievable by a single process alone under the same condition (Mohejerani et al. 2009). Based on the reaction rate constant, the synergetic effect of solar/TiO2/Fe2+/H2O2 process was 1.6. The use of the combined system in the AOP part will enhance the oxidation and biodegradability in less time. Behaviour of the integration of combined AOPs and biological treatment processes is defined in Equation (4) by a new parameter to depict the biodegradability enhancement: 4
This equation shows the amount of additional BOD produced by the combined process. The synergetic biodegradability enhancement effect of this combined homogeneous and heterogeneous advanced oxidation process is based on the BOD5/COD ratio. At 1 hour treatment the BOD5/COD ratio was 0.50, 0.50 and 0.70 for solar/TiO2/H2O2 process, solar/Fe2+/H2O2 process and solar/TiO2/Fe2+/H2O2 process, respectively. Based on the BOD5/COD ratio, the synergetic biodegradability enhancement effect of the combined process was 0.70. When compared to rate of degradation, the combined homogeneous and heterogeneous process is more effective than the individual processes.
Design of the field-scale reactor
The field-scale reactor was designed to treat the tannery wastewater with a flow rate of 96 m3/d. The reactor was designed for 96% COD removal. The average yearly solar UV light intensity for the study location was calculated as 23 ± 2 W/m2, and the average daily useful solar hours were found to be 6 hours. Sagawe et al. (2003) suggested the equation for the kinetic model, which accounts for the effect of pollutant concentration, volumetric flow rate, light intensity and solar irradiation area; these were used to arrive at a lump parameter (K3) (Equation (5)): 5 where K3 = a lump kinetic parameter representing the efficiency of the photocatalyst (m3/W·min); C0 = inlet concentration of COD (mg/L); C = outlet concentration of COD (mg/L); Q = volumetric flow rate (m3/min); qUV = time averaged radiation density flux (W/m2); and A = effective area of solar irradiation (m2).
The scaling up of the field-scale reactor can be given by the following equations (Equations (6) and (7)): 6 7 The depth of the reactor, based on detention time, included free board = 0.1 m.
Cost analysis
Cost analysis was carried out by analysing the degradation process under optimal conditions. The operating cost for treating tannery wastewater by solar/TiO2/Fe2+/H2O2 process has been evaluated. Table 5 presents the solar/TiO2/Fe2+/H2O2 process operating and annual treatment costs per m3 of treated water necessary to remove 96% of COD. An annual treatment cost of US$21.34/m3 of treated water was obtained.
The degradation of tannery wastewater has been studied by means of the combined homogeneous and heterogeneous AOP. Box–Behnken design results confirmed that the TiO2 concentration, pH and Fe2+ concentration positively affected COD removal efficiency in the solar/TiO2/Fe2+/H2O2 process. Based on experimental results, an empirical relationship between the COD removal efficiency and independent variables was obtained and expressed by the quadratic model Equation (1). The effect of experimental parameters on the COD removal efficiency of tannery wastewater was established by the response surfaces of the developed model. The optimal operation parameters for the solar/TiO2/Fe2+/H2O2 process for degradation of tannery wastewater were pH = 7, TiO2 = 0.2 g/L, Fe2+ = 0.5 g/L and H2O2 = 1.8 g/L. Under this condition, 96% COD removal efficiency was achieved after 4 hours of treatment. The kinetic study indicated that the degradation kinetics of tannery wastewater followed the first-order kinetic. When compared to the rate of degradation, the combined homogeneous and heterogeneous process is more effective than the individual processes. The combined process is a useful tool for enhancing the biodegradability of tannery wastewater in biodegradation of wastewater which enters into a biological wastewater treatment process. The obtained results showed the feasibility of combined advanced oxidation processes to achieve suitable water qualities for internal reuse.
- First received 9 December 2014.
- Accepted in revised form 17 May 2015.
- © IWA Publishing 2016


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As for "kookiest" religion, as someone raised semi-Mormon, I can tell you firsthand that Mormonism is way crazier than Islam. According to our holy book, skin color is due to the amount of sin someone is born with. Plus, the entire thing was founded by a renown con-artist as a way to scam people into paying him money.
And don't even get me started on the religion that believes negative emotions are the souls of aliens flown to earth in golden airplanes.
The more you know, the harder it is to take decisive action. Once you become informed, you start seeing complexities and shades of gray. You realize that nothing is as clear and simple as it first appears. Ultimately, knowledge is paralyzing. - Bill Watterson
Who Is Chicago Ted?
I've debunked your comparison, shown it invalid and a red herring, criticized your injection of race where it is also invalid. Ya got nothin'. Moving on.
I think if Thomas Jefferson were looking down, the author of the Bill of Rights, on whats being proposed here, hed agree with it. He would agree that the First Amendment cannot be absolute. - Chuck Schumer (D). Yet, Madison and Mason wrote the Bill of Rights, according to Sheila Jackson Lee, 400 years ago. Yup, it's a fact.
I dont about others. I saw a good portion of the hearing. I didnt just view parts that were convenient to my viewpoint. No one was attacking 'Muslims.' Muslims were complimented on numerous occasions. The problem is not Muslims...never has been. The problem is extremists. ALWAYS has been.
I wasn't kidding about people having little control over their beliefs, by the way. I googled a quick search but couldn't find anything. Just as many emotions are now being isolated, so it is with the part of the brain that determines how we will think and what are opinions might be, depending on one particular part of the brain and how large it is. I believe it was also part of a series on PBS.
That suggested to me that each black line represented the number of times an important event was revisited with our thoughts, and the level of importance was measured by the number of black lines.
The good thing about science is that it's true whether or not you believe in it. ― Neil deGrasse Tyson

subset: commoncrawl


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Here, the best carry-on luggage for the road, from duffels to roller and collapsible options.Samsonite Freeform 21 Inch Carry on Spinner. This eye-catching spinner offers a winning balance of features, durability, and price. Best Carry-On Luggage Under 50. 10. American Tourister iLite Xtreme Spinner 21.The smallest piece is appropriate as a carry-on with all airlines. This set has four multi-directional spinner wheels with a squared design for maximum capacity and expandable capacity. Бесплатная доставка. This sturdy Kenneth Cole Reaction spinner is your best mate on your travels. Available in a solid shade, this Out of Bounds ABS carry on is both stylish and functional.Samsonite Winfield 2 Fashion Hardside 20 Inch Spinner Luggage Carry On Suitcase. Don Nelson. Ive used the Costco Kirkland Hybrid Spinner for several business trips since I bought it a year ago and it is the best carry-on Ive every used.Scudder35. The smaller regional aircraft simply are not sized to fit full-sized carry-on luggage. To expect that one will is simply unrealistic. Up to 70 off the best brands. Learn More. Get an American Express Premier Rewards Gold Card earn a 50 statementSamsonite Luggage. 19" Omni Hardside Carry-On Spinner. руб. 7,840.46 Gilt.23" Superlative Small Hardside Carry-On Spinner Upright Suitcase. руб. 11,227.54 Gilt. Best Small Carry-on Luggage Reviews. 1: Travelon Wheeled Underseat Carry -On. 2: Samsonite Silhouette Sphere 2 Softside Spinner Boarding Bag.There are many products to choose from when it comes to getting a good small carry-on luggage. The Kids Travel Zone Kids Small Spinner Carry-on is perfect for: Cross country road trips Traveling to Aunts and Uncles Cruising with mom and dad Visiting grandparents Make your childs luggage special. The Best Spinner Carry-On Luggage - Carry On Guy.Kipling Darcey Small Special Spinner Wheeled Carry On Luggage Suitcase - Black. Made of a soft polyester, you can squeeze this carry on spinner into some pretty small spaces. The SwissGear 21 Sion also has a number of features that make it one of the best carry on luggage options. List of the best carry on luggage currently available on the market, as ranked by consumers.Travelpro Luggage Maxlite 2 20" Expandable Spinner Travelpro - The Travelpro maxlite 2 20-inches expandable spinner upright luggage is ultra-lightweight, and features a 4-wheel spinner system that Both the smallest spinner and satchel can be used as carry-on.Multiple pockets and the duffel bag take care of your smaller items. This is a well though-out set that deserves its place on the best luggage sets list. Weve covered the best spinner carry on luggage, full size suitcase and spinner luggage sets.Our top pick for best luggage spinner for easy storage! If you live in a small space, then this spinning luggage is perfect for you. Sort by: Best Match. Orders. Newest. Seller rating. Price.small spinner luggage carry on. This is Amazons 1 selling carry-on luggage for business travel good reason! Samsonite Luggage Review: Its lightweight with re-engineered spinner wheels forIts light, strong and holds a lot making it good for both business and personal travel. On the lid, theres a mesh pocket for smaller items like Best Carry-On Spinner Luggage.International carry-on bags are actually smaller than domestic carry-on bags, as they need to be between 18-20. Since some airlines enforce smaller dimensions for acceptable carry-on luggage, this Commuter option is smaller than others in the Briggs Riley line ofOn top of the style component, the best element of the Delsey Chatelet Hard Carry On are the Japanese HInomoto double spinner wheels. Best Garment Bag Carry On Rolling Tote. If youre looking for something fashionable, you cant go wrong with the Delsey Quilted Tote.The small front compartment is specially designed to hold compact laptops or tablets, so you dont have toLooking for the best lightweight spinner luggage? The Best Carry-on Luggage. Courtesy of Amazon and Zappos.Biaggi Contempo Four-Wheel Spinner Collapsible. This carry-ons many airport-friendly features include four spinning wheels, front compartments and a side handle for easier hoisting into the overhead bin. There are multiple zippered pockets so you can store shoes, toiletries, jewelry, and other small accesories. What we love the most about this product is it comes with an integrated luggage scale in the handle.Best carry-on luggage spinner. The Hedgrens best feature is its effortless wheels. Theyre typical plastic spinner wheels, but compared with Delsey and Genius Pack luggage, this suitcase was much easier to roll across anBecause its small and hard-sided, the Hedgren carries less than the expandable Ogio Layover. Shop the best carry-on luggage at the Samsonite store online. Choose from carry-on travel bags and baggage including suitcases, garment bags, and duffel bags.Samsonite Eco-Nu 20" Expandable Spinner. Why Spinner Luggage? If you look at any airline boarding queue youll see people flying with smaller hand-held bags like backpacks or duffel bags to get around the size limits.The Best Carry On Luggage For Kids All The Airline Rules (2016). I am looking to buy new carry on luggage (21") that is lightweight and is roomyIf you do still want a small spinner the Rimowa polycarbonate ones are highlyAlso, not sure how well the wheels would hold up on a checked luggage bag thatbest luggage, luggage sale, best luggage brands, luggage bags, luggage reviews, cheap carry on luggage, best suitcase, cheap luggage, small luggage, lightest luggageCostco Kirkland Signature 2017 4 Wheel Spinner Carry On Luggage - First Look - Duration: 4:36. Mike Mu 4,929 views. There is also a small size pocket, zipped close to keep other smaller valuables. The Bon Air Spinner is a good looking case which is also a very highBest Carry On Luggage With USB Chargers Reviews 2017 2018. Luggage Buying Tips. Hanging Leather Toiletry Bag For Men Best Of 2017 2018. It has lots of good pockets, and this version is small enough to be carry -on for many airlines.Carry on suitcases used to come with just 2 wheels, but now youll find lots of 4 wheel carry on luggage. Spinner luggage allow for more mobility since the 4 wheels will spin and turn in any direction. No smaller compartments, which we perhaps would have wished for. Thats easily solved though by using packing cubes or just zippered plastic bags.Samsonite Carry On Luggage Inova Spinner 20 Review. Why Cycling is the Best Way to Explore the World.
Delsey Luggage Helium Aero Expandable Spinner Trolley (29) If you are looking stylish and easy carry Delsey luggage set luggage for your journey here is withOur team of experts has selected the best luggage sets out A bag small enough to carry on — rather than Steve Madden Luggage. Small (1). Sneaker (3). Solana (3).Cheap Samsonite Luggage Silhouette 11 22" Carry-on Expandable Upright Spinner - Black Best Deal! These are the best carry-on luggage from Samsonite, TravelPro, Tom Bihn, and others.If you make a purchase by clicking one of our links, we may earn a small share of the revenue.Samsonite MightLight 2 21" Spinner. Best Wheeled Carry-On. 6. Ever Moda Chevron 360 Spinner Luggage Carry On (Royal Blue).This 21 inch spinner has fit easily in overhead bins on two different domestic airlines, but not on the smaller commuter jets. It holds enough for multiple day trips or even a week if you are a light packer. There are also many distinct types of luggage from which you can choose as well.Spinner luggage These are rolling luggage pieces with multidirectional wheels that rotate 360 degrees for increased mobility.Youll have to check larger duffel bags, but smaller ones are ideal as carry-on luggage. Based on overall rating, quality of materials, size, and reputation of the maker, the Samsonite Hyperspace Spinner is one of the best carry onitem (a purse, laptop bag, backpack or other small bag) and a larger carry on bag, you will never have to worry about an airline losing your luggage or Reviews Best Soft-Sided Carry-On Luggage On Wheels. Travelpro Maxlite4 International Carry-On Spinner Suitcase.A few people who bought this bag found it a bit small inside. Overall, the Travelpro is a stylish and durable carry-on bag with a fantastic lifetime warranty. Luggage, Suitcase and Carry-On Spinner Reviews. Hey there!Best Softside Rollaboard Carry-On If youre prone to sticker shock Id advise MaxLites spinner carry-on, but as farIts small enough to keep under your seat, big enough to pack for the weekend, and its got wheels your shoulders will love! Shop Carry On, Spinner Luggage Best of the Best at eBags - experts in bags and accessories since 1999.Carry-on Luggage Guide. Underseat Travel Guide. 10 Must-Have Bags for Business Travel. Womens classic luggage rack. Carry on bag size china airlines. Small carry on luggage reviews travelpro. Cheap luggage philadelphia 2014.21 4 wheel spinner quarterly Best suitcase for international travel 2015 holidays Buy roof rack perth zoo Luggage scale for sale philippines vios. Best Budget Carry On Luggage: When traveling, many fliers like to avoid the trouble of checking in their baggage with the airlines.The 22" Silhouette Spinner is small enough to pass as a carry-on yet roomy enough to hold your essentials for a business trip or weekend getaway.
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Essential is what our early literacy programs need to be—especially if we want children's librarian jobs to be considered necessary community services. Make it your mission this year to increase early literacy services at your site by offering at least one nursery-rhyme-based program a month for ages birth to two years old.
Chew That Book: Why Babies Belong in Libraries | First Steps
This article was published in School Library Journal's November 2013 issue. Subscribe today and save up to 35% off the regular subscription rate.
The Pleasure Principle: Children (and grown-ups) tend to do what's most fun | First Steps
First Steps began almost nine years ago, in February of 2004. Our first column was about the importance of having fun, because we believed that fun was a key element in any discussion of early literacy. We still do. Learning to read isn't easy. It's hard work, and children need to be motivated to put forth the effort. Like adults, they're inclined to do what's most enjoyable for them.
As 2013 approaches, Nell is celebrating 40 […]
Why Offer Black Storytime? | First Steps
Imagine that while interviewing for a library job you're asked, "What would storytime specifically for African-American families look like to you?" That's what happened to Kirby McCurtis. "I thought it was an especially interesting and challenging question," says Kirby, who aced the interview and is now Multnomah County Library's (MCL) newest African-American librarian. "It stayed with me even after the second interview. Now that I am working here, I have the opportunity to answer it every Saturday. It's very exciting!"
The Neglected Ones: Children of undocumented immigrants seldom receive the services they need | First Steps
These days the news is full of polarizing stories about undocumented immigrants. Rarely do we hear about the 4.5 million children born each year in the United States to undocumented immigrant parents.
Mind Readers: Thinking Out Loud Can Raise Children's Comprehension Skills | First Steps
It's toddler storytime: let the rumpus begin! Toddlers bound quickly into the room. One hurdles mom's legs while waiting for the opening song. Some hop, others roam, and a few practically climb our unflappable colleague Janie. Even after getting most of their wiggles out, many toddlers continue to float around the room—until Janie begins to read one of her favorite books, Owl Babies (Candlewick, 1996) by Martin Waddell.
Give Them a Big Hand: Puppets are great motivators for children who are learning to read
One of the most surprising early literacy questions we've encountered is about puppets. It came from a youth librarian whose director insisted that he couldn't see how using puppets "has any value whatsoever, as far as early literacy is concerned." "What can I tell him?" she asked us.
Oh, my. Where to start?
Print motivation, most likely. What motivates children more than having fun? Puppets are nothing if not fun. A puppet sharing a story enchants a preschool […]
A Running Start: We're excited about the latest programs for very young learners | First Steps
It's good to begin the New Year with enthusiasm. Here at Multnomah County Library we're excited about several things. First, and perhaps most importantly, we're looking forward to being successful at the ballot box in May, when primary voters will be asked to renew the bulk of our funding. Fortunately, the library is well-regarded in the Portland, OR, community, and we're likely to secure the support we need.
We're also excited about rolling out the new "Every Child […]
When Trauma Hits Home: Did you know that infants are the largest single group of victims? | First Steps
One of the most startling things we learned this year is that 48.6 percent of trauma victims in our state of Oregon are younger than six years old. And infants make up the largest single group of victims. These children may experience violence at home or within their neighborhoods; they may face separation from a parent or caregiver because of divorce, death, incarceration, or even military deployment.
We were attending a training session […]
Get Ready, Get Set… | First Steps
In a perfect world, every child would enter kindergarten happy, healthy, and eager to learn. They'd run into their classrooms anxious to see friends and already in love with their teachers. But it's not quite a perfect world here in Portland, OR. A large percentage of our children of color and those from low-income families aren't ready to learn when they enter the Portland Public Schools (PPS). A recent study found that […]
The Power of Words | First Steps
How librarians can help close the vocabulary gap
We've never forgotten a story that Micki Freeny, coordinator of youth services at the District of Columbia Public Library, told us about her daughter. Kyle was four years old when she asked a cashier if the mints on the restaurant counter were "complimentary." "No dear," replied the woman, "they're free." Kyle is now a Harvard-educated attorney who still enjoys meals out with her mom, and […]
A Happy Ending | First Steps
Outcomes-based evaluations help us define what we're trying to accomplish
Spring is the time of year when we ask our early childhood community partners to help us measure the effectiveness of our outreach services or—said another way—evaluate the outcomes of our programs. Outcomes are what the participants will know or be able to do after participating in our programs. For example, one parent wrote, "I will be more patient when I read with my daughter. […]
Have You Heard the Word?: National Poetry Month is a great time to share the joy of poetry with children | First Steps
Our evening walks around Portland are even more delightful these days as more and more neighbors have added poetry posts to their yards. Poetry posts, you ask? They are simple wooden poles, kind of like a "For Sale" signpost, but with a see-through, covered box attached. Inside the box is a poem, often in multiple copies so that passersby may help themselves. We don't know if poetry posts exist outside Portland, […]
It's Never Too Early: Parents should talk to their young ones long before they can speak | First Steps
The young woman sitting alone near the front of the MAX train car was speaking passionately, presumably to a friend on a cellphone. Nothing new—we overhear all sorts of conversations these days. But then, unexpectedly, she lifted a blue bundle to her face, and it became clear that she was talking to her infant son. Some assumptions, thankfully, are so wrong.
Somewhere, she had learned how important it is to talk to […]
The Amazing Brain: Babies start learning to read the day they're born | First Steps
How exactly does early brain development relate to reading? That's what our clients want to know. Many of them aren't interested in hearing about neurons and synapses, but they find the basic concepts of brain development fascinating. Here's what we've come up with for our elevator speech.
Children start learning to read the day they're born. That's because reading is part of language development, and children begin learning language when they're infants. Decades ago, when we started […]
Natural-Born Scientists: Children's curiosity about the world begins at birth | First Steps
After seven months of inescapable rain here in Oregon, the warm sun has emerged and blossoms have burst forth. Nature's reawakening leaves us wondering how the dogwoods and magnolias can triumph over the soggy soil. The physical world is a source of curiosity for many, and making sense of it is a lifelong challenge.
Children are born curious. Some more than others, but all are inclined to poke, prod, inspect, and inquire. Most ask tons of questions, beginning with the universal […]
Ready, Set, Go! Storytime Can Help Children (and Parents) Become Kindergarten-ready. | First Steps
On these early autumn days, in communities big and small, kindergarteners are stuffing backpacks with colored markers, glue sticks, tissues, and sometimes a favorite book or stuffed animal. Getting ready to start school requires so much preparation that it often eats up the last few weeks of summer. But as we know, preparing for kindergarten entails a lot more than one month of gathering supplies and buying new shoes.
What should young children know going into kindergarten? How to share and […]
Model Behavior: Children (and Adults) Often Learn Best by Seeing and Doing | First Steps
Children (and adults) often learn best by seeing and doing
Watching our Commander-in-Chief read Where the Wild Things Are (HarperCollins, 1964) at the White House Easter Egg Roll gave us chills, even though we had to experience it vicariously on YouTube. We had often heard the new president suggest to parents that they "turn off the TV and read to your child." Now he was modeling just how to do that. And he did a pretty darn good job of it.
Modeling […]
Something to Smile About: A Statewide Early Literacy Program Is Making a Big Difference | First Steps
As our communities face serious economic challenges, it's easy to focus solely on the dire news of the day: dwindling budgets, programs at risk. So, now more than ever, it's important to appreciate the work that energizes us and gives us hope. Here in Oregon one such program is our new statewide training project to increase early childhood literacy skills.
In 2008, after many years of planning and securing funds, Reading for Healthy Families: Building Communities of Learning was launched in […]
Make a Joyful Noise: A Simple Song Has the Power to Bring People Together | First Steps
The mothers and children enter the neighborhood meeting room. A raw, icy blast of wind follows the families through the door. Mothers unlayer little ones. Off come the boots and hats and mittens and coats. Babies are unswaddled from the brilliantly colored cloths that are artfully and securely knotted around their mothers. The toddlers and older preschoolers are pulled toward the bright toys and art supplies, and the babies remain tucked in close to their mothers. We gather around a […]
The (Really) Big Six: Early Literacy Skills | First Steps
Without these preliteracy skills, children can't become skilled readers
Phonological awareness. Print motivation. Remember how strange some of the six early literacy skills sounded when librarians first heard about them? These days, the six skills (which also include vocabulary, print awareness, narrative skill, and letter knowledge) seem to be household words in libraries that serve young children. But back in 2000, when the National Reading Panel first brought these skills to our attention through the Association for Library Service to Children […]


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Premio Dardos means "Prize Darts" in Spanish. The Award recognizes those who transmit cultural, ethical, literary, and personal values through writing.
Thank you to Prynka@MyDiary for nominating me for this award.
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My Nominations:


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San Pedro, Belize
Immerse yourself in Caribbean culture during a stay in Belize's San Pedro. Located on the southern section of Ambergris Caye, San Pedro is reminiscent of a postcard with its coconut palm trees dotting the shores, quaint guesthouses, boutique resorts and turquoise waters. San Pedro Town is the only urbanised section on the island and is typically explored by renting a golf cart, a bicycle or by venturing out on foot.
Fishing was once the town's biggest industry; however, due to increased interest in its gorgeous landmarks and scenery, tourism has become number one. There are a few dive operators peppered throughout the island who take visitors to some of the most famous dive sites in the world. Diving around San Pedro is even fantastic for those who are only beginners.
Cruise Deals
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Port Location
Cruise ships anchor in Belize City's harbour, where passengers can take a ferry to San Pedro's terminal. This is approximately an 80 minute journey.
Port Facilities
There are quite a few facilities located near the San Pedro Belize Express terminal, including restaurants, cafés, hotels, a shopping centre, transport rental shops and banks. On top of this, there are many local attractions nearby as well.
How to Get Around
One of the most prominent modes of transport in San Pedro is the golf cart. Many rent these, as well as bicycles, to get around the town. Others take to comfortable sandals or go barefoot before exploring the streets and seaside.
Travel times from San Pedro Belize Express terminal:
On foot:
It is a 16 minute journey to Caribbean Villas
It is a 10 minute journey to Chuck & Robbie's Scuba Diving and Instruction
It is a 6 minute journey to The Office Bar and Grill located in San Pedro's Lagoon.
By taxi:
It is a 3 minute journey to Caribbean Villas
It is a 13 minute journey to Chuck & Robbie's Scuba Diving and Instruction
It is a 2 minute journey to The Office Bar and Grill located in San Pedro's Lagoon.
General Information
Currency – San Pedro's official currency is the Belize dollar (BZ$). Coins come in the denominations of 1, 2, 10, 25 and 50 cents and BZ$1. Banknotes come in BZ$2, BZ$5, BZ$10, BZ$20, BZ$50 and BZ$100.
Time Zone – Belize falls under Central Standard Time (CST), which puts it 6 hours behind Coordinated Universal Time (UTC). Daylight Savings Time is not currently observed.
Weather – San Pedro is characterised by Belize's tropical climate. Its hottest month is August, with temperatures averaging 29 degrees Celsius, and the coldest is January, with average temperatures of 24 degrees Celsius. June to December is Belize's wet season, when Caribbean storms have been known to make landfall.
Bird Watching at Lalas Bird Sanctuary – Bird-lovers rejoice! San Pedro is home to a private bird sanctuary found south of the town at the Caribbean Villas. In this seaside forest, visitors are treated to an abundance of tropical trees and shrubs, including the gumbo limbo, the wild sapodilla, the coco plum and the bearded fig. Visitors can achieve a great vantage point on the 'people perch', where bird watching is at its prime. On the perch, tourists can take in 360-degree views of the Caribbean, Hol Chan Marine Reserve, San Pedro, San Pedro Lagoon and Chetumal Bay. Some bird species to look out for include white-eyed vireos, black catbirds, white-collared seedeaters, golden-fronted woodpeckers and the hooded oriole to name a few. Be sure to bring along your camera to take some stunning shots.
Diving and Snorkelling – Explore San Pedro's magical underwater worlds by diving and snorkelling in some of its incredible surrounding sites. The waters are calm thanks to the protection from the barrier reef, and visibility in the ocean is second to none. The Hol Chan Marine Reserve is a world-famous diving spot home to tropical clouds of fish and multi-coloured coral formations. Marine life here includes docile nurse sharks, turtles and stingrays. Local dive shops like Chuck & Robbie's Scuba Diving and Instruction rent out snorkelling and diving gear, and also take visitors on twice-daily diving trips to Hol Chan Marine Reserve and other unspoiled reefs. Stop by their beachfront shop in San Pedro Town for advice and more information on dive excursions.
San Pedro Lagoon – If you're staying in San Pedro until late, pay a visit to San Pedro Lagoon for a beautiful sunset. Have a meal at one of the popular surrounding restaurants, including The Office and Barrel Bar; each have fantastic views of the surrounding reef and waters and visitors can enjoy delicious seafood and scene-setting music.


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This month I have been spending a lot of time behind the camera between weddings, shooting some family photos for my sister-in-law, and attempting to take Christmas pictures of the girls. I am really enjoying it and I even bought some editing software to begin learning basic photo editing skills. And I must say, that part I am loving!
I know that I have a LOT to learn when it comes to photography in general, especially editing, but I'm having a great time playing around and exploring. I watch Lightroom tutorials all the time and its fascinating to me to watch an average photo transform into something so eye-catching and sharp with a few simple edits. It makes me want to keep learning more!
So, photography has been what I've been up to this month and it has been great putting my mind to something other than "Mommy mode". Next step: buying a decent camera of my own so that I can stop bugging Tina to borrow hers ;)
When we went out the other day for those pictures of the girls, Mike snapped a few of me when we were done. And by done, I mean, the girls were OVER it. And anyone taking pictures of me is a big no-no in Addy's book. For some reason, she hates when I am photographed. Addy wouldn't stand for me being in a picture without her, so note her little head in the bottom. Mike took about 10 pictures of me and no matter how I stood or where I went, that little head followed me everywhere. I thought about trying to edit it out, but number one, I probably wouldn't do a very good job, and number two, it's become part of the story :)
Happy October!


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President Barack Obama and his wife, Michelle, have not been shy about expressing their views on higher education. Whether they are discussing the importance of financial aid, considering ways to make a bachelor's degree more attainable for low-income students or expanding job-training programs, they frequently articulate the importance of college - as well as the hurdles many families face as students pursue a degree. Recently, the president released his 2015 budget. This preliminary financial plan includes billions of dollars set aside for educational purposes, and some of the appropriations could have a direct impact on students who are struggling to pay for college.
Would you like to see more education news like this in your inbox on a regular basis? Subscribe to our email newsletter!


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Revision history of "Category:Bragg gratings"
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I really liked 'Her'. Phoenix really played a good character. When you really got to see him open up, you found he was highly articulate and aware of his own feelings. #SpikeJonze really wrote a badass script. I was totally lost in the movie, the acting was so blessed good. Powerful message at the end about Love--that the Heart isn't just a container that gets filled; it is something that expands proportionately to how much Love it receives. When Love expands our hearts, even if we cannot share life with each other in the physical, even if we move on, we do not Love each other less, only more--for the truth is--my addition--we are all connected, and we never really apart.
I am learning to see relationship as serving to expand my heart only, not to possess physical bodies. That is why Love does not and cannot possess. No matter how your relationships are, if you can really look and see how they have expanded your heart, they have done their job.
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Or you can sit down with me, go over your criteria and I will set up a search for you.


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text:
Latest news in other media
Police foil Hindu right wing's bid to evoke communal violence following desecration of temple in Malappuram
Rozina Sheikh, whose mother works as a tailor, scores 97 percentile rank in Class 12; aspires to become a doctor
Amarnath Yatra a case of 'militarised pilgrimage', says Jammu Kashmir Coalition of Civil Society in report
Triple talaq against Sharia, Muslims should refrain from eating cow meat: Dewan Ajmer Syed Zainul Abedin Ali Khan
RSS men found guilty of killing two CPM workers
A court here has found five RSS-BJP workers guilty of murdering two CPM workers at Kadukkamkunnu in Malampuzha.
Justice Suresh Kumar Paul of Palakkad additional district court (2) on Monday convicted Manikandan, Rajesh, Murukadas, Suresh and Gireesh — all hailing from Kadukkamkunnu — for murdering Gopalakrishnan and his relative Raveendran. The victims were hacked to death on October 29, 2007.
The fourth and sixth accused were acquitted by the court for want of evidence. The quantum of sentence will be pronounced on Wednesday.
The prosecution case is that the convicts committed the murder due to personal grudge and political enmity.
Categories: Other News ، From India ، Opinion ،
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Last update:
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cancelTag what you see on the picture : clothes, celebrities, bloggers, series, movies and brands.
Originally posted 39 months ago bykennedypurdyy_
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Be the first to post a tip. You will help 1 person.Do you have fashionista friends? Ask them if they know where to get this hat!
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George W. Goes Against The Conventional Wisdom
ABC News and FoxNews Channel are both reporting that the President will nominate Judge John Roberts to fill the vacancy on the Supreme Court. This goes against the conventional wisdom because most were expecting a Hispanic or a woman. Here are his qualifications:
Nominated to: Court of Appeals, District of Columbia Circuit
Status of nomination: Confirmed 5/8/2003 May 8, 2003: The Committee voted out Roberts 16-3.
- Born 1955, Buffalo, NY
- B.A., 1976, summa cum laude & J.D., 1979, magna cum laude, Harvard University
- 1979-80, Clerk for Judge Friendly, Second Circuit
- 1980-81, Clerk, Associate Justice Rehnquist, Supreme Court
- U.S. Department of Justice
- 1981-81, Special Assistant to U.S. Attorney General William French Smith
- 1989-93, Principal Deputy Solicitor General
- 1982-86, White House Counsel's Office, Associate Counsel to the President
- Hogan & Hartson, LLP, Washington, DC
- 1986-89, Associate
- 1993-present, Partner
General Background. Mr. Roberts, a partner at the D.C. law firm Hogan & Hartson, has long-standing and deep connections to the Republican Party. He is a member of the Republican National Lawyers Association and worked as a political appointee in both the Reagan and Bush I administrations. President George H.W. Bush nominated Mr. Roberts to the D.C. Circuit, but he was considered by some on the Senate Judiciary Committee to be too extreme in his views, and his nomination lapsed. He was nominated by President George W. Bush to the same seat in May 2001.
Reproductive Rights. s a Deputy Solicitor General, Mr. Roberts co-wrote a Supreme Court brief in Rust v. Sullivan, for the first Bush administration, which argued that the government could prohibit doctors in federally-funded family planning programs from discussing abortions with their patients. The brief not only argued that the regulations were constitutional, notwithstanding the Supreme Court's decision in Roe v. Wade, but it also made the broader argument that Roe v. Wade was wrongly decided - an argument unnecessary to defend the regulation. The Supreme Court sided with the government on the narrower grounds that the regulation was constitutional.
Environmental Issues. As a student, Mr. Roberts wrote two law review articles arguing for an expansive reading of the Contracts and Takings clauses of the Constitution, taking positions that would restrict Congress' ability to protect the environment. As a member of the Solicitor General's office, Mr. Roberts was the lead counsel for the United States in the Supreme Court case Lujan v. National Wildlife Federation, in which the government argued that private citizens could not sue the federal government for violations of environmental regulations.
As a lawyer in private practice, Mr. Roberts has also represented large corporate interests opposing environmental controls. He submitted an amicus brief on behalf of the National Mining Association in the recent case Bragg v. West Virginia Coal Association. In this case, a three-judge panel of the Fourth Circuit reversed a district court ruling that had stopped the practice of "mountaintop removal" in the state of West Virginia. Citizens of West Virginia who were adversely affected by the practice had sued the state, claiming damage to both their homes and the surrounding area generally. Three Republican appointees - Judges Niemeyer, Luttig, and Williams - held that West Virginia's issuance of permits to mining companies to extract coal by blasting the tops off of mountains and depositing the debris in nearby valleys and streams did not violate the 1977 Federal Surface Mining Control and Reclamation Act. This decision was greeted with great dismay by environmental groups. In another case, Roberts represented one of several intervenors in a case challenging the EPAÃÂs promulgation of rules to reduce nitrogen oxide emissions.
Civil Rights. After a Supreme Court decision effectively nullified certain sections of the Voting Rights Act, Roberts was involved in the Reagan administration's effort to prevent Congress from overturning the Supreme Court's action. The Supreme Court had recently decided that certain sections of the Voting Rights Act could only be violated by intentional discrimination and not by laws that had a discriminatory effect, despite a lack of textual basis for this interpretation in the statute. Roberts was part of the effort to legitimize that decision and to stop Congress from overturning it.
Religion in Schools. While working with the Solicitor General's office, Mr. Roberts co-wrote an amicus brief on behalf of the Bush administration, in which he argued that public high schools can include religious ceremonies in their graduation programs, a view the Supreme Court rejected.
Pro Bono. Mr. Roberts has engaged in significant pro bono work while at Hogan and Hartson, including representation of indigent clients and criminal defendants.
Other Information. Mr. Roberts is a member of two prominent, right-wing legal groups that promote a pro-corporate, anti-regulatory agenda: the Federalist Society and the National Legal Center For The Public Interest, serving on the latter group's Legal Advisory Council.source The President picked someone that I believe that I could support Blogger's 1st Amendment Pledge If the FEC makes rules that limit my First Amendment right to express my opinion on core political issues, I will not obey those rules.


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WOW! That is two heck of a nice Thule cufftitles you´v got there! Congrats!
WOW! That is two heck of a nice Thule cufftitles you´v got there! Congrats!
As others have said the one looks good but not sure on the other. I only have an RZM.
Very nice indeed Sayle
"In all my years as a soldier, I have never seen men fight so hard." - SS Obergruppenfuhrer Wilhelm Bittrich - Arnhem
A hand embroidered, uniform remvoved example from the estate of Sturmbannfuhrer Alfred Arnold. The lettering on this example is thinner than the letters on the example that started this thread(especially evident in the horizontal top of the "T"). The reinforcing on the reverse is also different. I have never seen another original example so I cannot judge whether the one at the start of this thread is a copy or a variation due to another manufacturer. Due to the limited time this unit was in existance, I doubt there was more than one supplier.
Thanks for posting those pics, Bob. Yours does have a passing resemblance to mine, although due to wear and loosening of threads mine looks quite a bit more "schmucked". Mine also has some white aluminum oxide, which has stained the surrounding band and backing ribbon. Underneath that ribbon can be seen a thin black reinforcement cloth and the cream threads that run through the bullion on the front...
Similar Threads


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If the synonym for egg on are wrong, please inform the site editors by writing a comment.
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Do you think it is a different synonym for the following except for egg on synonyms? Comment to add other egg on synonym.
Egg On synonym for verb push to do something
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text: Heroin is considered potent and addictive and users are often stigmatised as the other. On the internet, however, hegemonicideas about drugs can be resisted. This study elucidates how efforts to normalise and demonise heroin meet at a Swedish online message board (Flashback Forum). The study aims at analysing how heroin use is given meaning by discussants in athread called "I will start with heroin". The data were perceived and structured as a collaborative, overarching narrative about when, why, and for whom heroin use can make sense. Discussants used stories about pleasure‐seekers, miserable junkies, and self‐medicating addicts to depict the activity as unproblematic and rational, problematic and irrational, or as problematic and rational. No stories about heroin use departed from the plot‐lines of pleasure maximisation and pain minimisation. Results elucidate a discursive battle in which: (1) heroin use as minimisation of pain "wins" over heroin use as maximisation of pleasure; and (2) there is a general agreement that heroin use cannot be irrational and unproblematic at the same time. It is suggested that these features are central to contemporary drug discourse, and that they probably hinder public understanding of why people use heroin and therefore contribute to keep users stigmatised.


text: Home > Nation DAP did not fund lawlessness - OPAPP ABS-CBN News Posted at Jul 23 2014 01:33 PM | Updated as of Jul 23 2014 09:33 PM Share Save Facebook Twitter GPlus LinkedIn MANILA - The Office of the Presidential Adviser on the Peace Process (OPAPP) insisted the Disbursement Acceleration Program (DAP) it received was not used for lawlessness. In a statement, OPAPP Undersecretary Maria Cleofe Gettie Sandoval admitted the agency received DAP funds but "it is malicious to say that it was used to fund lawlessness in the Cordilleras in the form of human rights abuses." Of the P1.819 billion DAP allotted to the OPAPP, P208 million was used to support the implementation of the provisions of the Memorandum of Agreement signed between the government and the Cordillera Bodong Administration (CBA)-Cordillera People's Liberation Army (CPLA) in 2011. These include the the groups' transformation into an unarmed, socio-economic organization; final disposition of arms and forces; economic reintegration of profiled CPLA members; community development; and inter-municipal and inter-barangay development projects. The CPLA is now a legal and socio-economic entity called Cordillera Forum for Peace and Development. As part of the socio-economic integration component of the agreement, OPAPP said the DAP covered livelihood projects, employment as forest guards or as integree into AFP, farm-to-market roads, water systems, communal irrigation systems, and community infrastructures among others through the Payapa at Masaganang Pamayanan (PAMANA) program. Share Save Facebook Share on Twitter GPlus LinkedIn Read More: SC OPAPP dap CPLA Disbursement Acceleration Program /news/05/21/18/the-anc-brief-may-21-2018/sports/05/21/18/boxing-for-world-champ-ancajas-duty-to-help-struggling-fighters-beckons/entertainment/05/21/18/deadpool-2-propels-to-125-m-opening/overseas/05/21/18/filipino-nurse-stabbed-while-on-duty-in-saudi-hospital/overseas/05/21/18/palestinian-president-abbas-hospitalized-officials


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I'm pretty proud of my first foray into cross-stitch in what must be about 15 years, apart from the hair cross-stitches I did a couple of years ago, man those were cool, I need to get back into them.. My head malts like a cat and dog combined so I should have no trouble sourcing the material, I'll just give my hair a good, and definitely overdue brush.
I am dreaming really vividly at the moment, I know that has nothing to do with cross-stitch but it's starting to freak me out.
Happy Birthday Luci!!


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Samsung Pakistan had recently collaborated with the 'Pakistan Fashion Design Council' to orchestrate the 'Bridal Couture Week 2015' (BCW) in Lahore. This brilliant show featured the latest trends in classy bridal fashions. A unique highlight of the event was an enchanting 'Samsung Galaxy Lounge', where Pakistan's biggest creative icons, showbiz stars and accomplished designers could get a hands-on experience of the revolutionary new Galaxy Note5 and the S6 Edge+ devices, designed to nurture … [Read more...]
PakMobilePrice.com / Archives for Pakistan Fashion Design Council


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Bluboo Xtouch Flagship Available For $99 For First 3,000 Customers Until Nov. 10
The Bluboo Xtouch is a feature-rich flagship smartphone from the Chinese manufacturer. It has been launched with a preorder price tag of $179. However, Gear Best is running a promotional offer on Bluboo Xtouch that allows users to avail it for $149. Moreover, the retailer will further slash $50 on the $149 pricing for reviewers with excellent reviews to avail the handset for $99 only.
The Bluboo Xtouch is fitted with a 5-inch display that supports full HD resolution of 1920 x 1080 pixels. It delivers a pixel density of 441 ppi. The home button present below the display doubles up as a fingerprint recognition sensor.
It is powered by 64-bit MediaTek MT6753 chipset that features an octa-processor that is supported by 3 GB of RAM. The internal storage available on the Bluboo Xtouch is 32 GB. It carries support for 64 GB microSD card on its external storage slot. The 13-megapixel Sony IMX214 camera sensor is present on its rear panel and it is equipped with a front-facing snapper of 8-megapixel.
The 4G LTE chip on the device supports 4G download speeds of 150 Mbps and upload speeds of 50 Mbps. Other connectivity features of the device include Wi-Fi, Bluetooth, aGPS, and GLONASS. It is packed with a massive battery of 3,050 mAh capacity that delivers a standby time of 775 hours and talktime of 38 hours.
According to Gear Best's promotion page for Bluboo Xtouch, by applying the XTOUCHGB coupon code, the price of the device can be slashed to $149. However, this offer is only applicable on every Wednesday until Nov. 11. The preorder sale will expire on Nov. 18.
Among the customers of the Xtouch, Gear Best will award a discount $50 to first 3,000 buyers who place excellent reviews. This discount will further reduce the price of the handset to $99.
Source: YouTube / Bluboo Mobile


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The Beggar's Opera
Open Air
- Booking until: Saturday, 23 July 2011
The Beggar's Opera description
Discover the innocent but feisty heroine Polly Peachum, her wronged rival Lucy Lockit and Macheath, their irrepressible highwayman lover, as a tangled web of lies and deceit blissfully unravels. Deep in LondonÂ?s underworld, this comedy of highwaymen, hangmen and harlots is an uncompromising exposure of moral and financial corruption.Â
Director Lucy Bailey injects her trademark visual dynamism into John GayÂ?s original text and The City Waites, led by Roddy and Lucy Skeaping, use authentic instruments to recreate the popular ballads and folk tunes of the time
Theatre policy relating to cancelled performances to inclement weather:
The auditorium and stage are completely uncovered. Every effort to complete the performance will be made and the theatre reserves the right to stop and start the action as necessary. Performances are never cancelled or abandoned before the advertised starting time and then only in the event of very bad weather. If cancellation or abandonment is unavoidable, ticket holders will be entitled to equivalent seats for any other performance in the main season (excludes comedy and music events), subject to availability. Original tickets for a performance that has been cancelled can be exchanged directly with the box office at the Open Air Theatre for another performance.
Refunds are not given for cancellation or abandonment as a result of the weather.
Playing at Open Air
Regent's Park, London, NW1 4NU (venue info)Directions


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updated first post of this thread...
updated first post of this thread...
Why is there so much difference in size between the 2005-06-14 release and the 2005-06-22 release? It's almost a difference of about 60 MB. Are there fewer appz in the latest version of the add-on cd?
Just curious.
i don't know either... din removed anythingOriginally Posted by maspro
2005-07-07 is ready, going to upload on mon (currently no broadband)
Latest Download: UbuntuGuide 4.14 Add-On-CD
How does this fix sound problems?
for most of the PCs that i've tried... this solution will fix the soundOriginally Posted by filemanager
the ug-install.sh script will automatically install this section if answer is "Y" to it
I downloaded the file in my friend's place and copied it to a CD. Back home I copied the tgz file and l untar the file in my home directory. Opened a terminal and type in 'sudo sh /media/cdrom0/install.sh' but cannot. Wat should I be doing to do it right? Very newbie here. Pse help with step by step guide.
when you untar the file, there's an iso.Originally Posted by webbie180
burn the iso into cd. (if you are in ubuntu. right click the file -> burn),
once done burning, then issue the command
How to untar in Windows? As I dont have a cdwriter at home. My friend is using windows. I need to do everything under windows first. Thanks.
Last edited by webbie180; July 23rd, 2005 at 08:24 AM.
There is a free program called zipgenius, http://www.zipgenius.it/index2.html , that handles .tar. It replaced winzip on my win-comp a long time ago.
(\ /)
(> <)
This is Bunny. Bunny had a nasty disagreement with a chainsaw. He needs help. Money is good.