Fixed-bed study for lanthanide (La, Eu, Yb) ions removal from aqueous solutions by immobilized Pseudomonas aeruginosa: experimental data and modelization

A fixed-bed study was carried out by using cells of Pseudomonas aeruginosa immobilized in polyacrylamide gel as a biosorbent for the removal of lanthanide (La, Eu, Yb) ions from aqueous solutions. The effects of superficial liquid velocity based on empty column, particle size, influent concentration and bed depth on the lanthanum breakthrough curves were investigated. Immobilized biomass effectively removed lanthanum from a 6 mM solution with a maximum adsorption capacity of 342 micromolg(-1) (+/-10%) corresponding closely to that observed in earlier batch studies with free bacterial cells. The Bohart and Adams sorption model was employed to determine characteristic parameters useful for process design. Results indicated that the immobilized cells of P. aeruginosa enable removal of lanthanum, europium and ytterbium ions from aqueous effluents with significant and similar maximum adsorption capacities. Experiments with a mixed cation solution showed that the sequence of preferential biosorption was Eu3+ > or = Yb3+ > La3+. Around 96+/-4% of the bound lanthanum was desorbed from the column and concentrated by eluting with a 0.1 M EDTA solution. The feasibility of regenerating and reusing the biomass through three adsorption/desorption cycles was suggested. Neural networks were used to model breakthrough curves performed in the dynamic process. The ability of this statistical tool to predict the breakthrough times was discussed.     

Performance of an immobilized cell biofilter for ammonia removal from contaminated air stream

The performance of a lab scale biofilter packed with biomedia, encapsulated by sodium alginate and polyvinyl alcohol was used for treating ammonia (NH(3)) gas at different loading rates. The metabolic end products during NH(3) oxidation were NH(4)(+), NO(3)(-) and NO(2)(-). It is noteworthy to mention that the immobilized cell biofilter required no separate acclimatization period and showed high removal efficiencies during the start of continuous experiments. The removal efficiency was nearly 100% when ammonia loading was 4.5gm(-3)h(-1) and the maximum elimination capacity achieved in this study was 5.5gNH(3)m(-3)h(-1) at a loading rate of 7.5gm(-3)h(-1). Shock loading studies were carried out to ascertain the response of the immobilized cells to fluctuations in inlet concentration and flow rate. The inlet loading rates were varied between 0.05 and 6gNH(3)m(-3)h(-1) during this phase of operation. The biofilter responded effectively to these shock loading conditions and recovered rapidly within 4-8h. Pressure drop values were consistently less and insignificant. The results from this study indicated that this immobilized cell biofilter could be considered as a potential option to treat NH(3) under steady and transient state operation.     

Alginate immobilized enrichment culture for atrazine degradation in soil and water system

An atrazine degrading enrichment culture, a consortium of bacteria of genus Bacillus along with Pseudomonas and Burkholderia, was immobilized in sodium alginate and was used to study atrazine degradation in mineral salts medium (MSM), soil and wastewater effluent. Sodium alginate immobilized consortium, when stored at room temperature (24 ± 5°C), was effective in degrading atrazine in MSM up to 90 days of storage. The survival of bacteria in alginate beads, based on colony formation unit (CFU) counts, suggested survival up to 90 days and population counts decreased to 1/5^th on 120 days. Comparison of atrazine degrading ability of the freely suspended enrichment culture and immobilized culture suggested that the immobilized culture took longer time for complete degradation of atrazine as a lag phase of 2 days was observed in the MSM inoculated with alginate immobilized culture. The free cells resulted in complete degradation of atrazine within 6 days, while immobilized cells took 10 days for 100% atrazine degradation. Further, immobilized cultures were able to degrade atrazine in soil and wastewater effluent. Alginate beads were stable and effective in degrading atrazine till 3rd transfer and disintegrated thereafter. The study suggested that immobilized enrichment culture, due to its better storage and application, can be used to degrade atrazine in soil water system.     

Atrazine distribution measured in soil and leachate following infiltration conditions

Atrazine transport through packed 10 cm soil columns representative of the 0-10 cm soil horizon was observed by measuring the atrazine recovery in the total leachate volume, and upper and lower soil layers following infiltration of 7.5 cm water using a mechanical vacuum extractor (MVE). Measured recoveries were analyzed to understand the influence of infiltration rate and delay time on atrazine transport and distribution in the column. Four time periods (0.28, 0.8, 1.8, and 5.5 h) representing very high to moderate infiltration rates (26.8, 9.4, 4.2, and 1.4 cm/h) were used. Replicate soil columns were tested immediately and following a 2-d delay after atrazine application. Results indicate atrazine recovery in leachate was independent of infiltration rate, but significantly lower for infiltration following a 2-d delay. Atrazine distribution in the 0-1 and 9-10 cm soil layers was affected by both infiltration rate and delay. These results are in contrast with previous field and laboratory studies that suggest that atrazine recovery in the leachate increases with increasing infiltration rate. It appears that the difference in atrazine recovery measured using the MVE and other leaching experiments using intact soil cores from this field site and the rain simulation equipment probably illustrates the effect of infiltrating water interacting with the atrazine present on the soil surface. This work suggests that atrazine mobilization from the soil surface is also dependent on interactions of the infiltrating water with the soil surface, in addition to the rate of infiltration through the surface soil.     

Performance evaluation of waste activated carbon on atrazine removal from contaminated water

In this study, the potential of spent activated carbon from water purifier (Aqua Guard, India) for the removal of atrazine (2 chloro-4 ethylamino-6-isopropylamino-1, 3, 5 triazine) from wastewaters was evaluated. Different grades of spent activated carbon were prepared by various pretreatments. Based on kinetic and equilibrium study results, spent activated carbon with a grain size of 0.3-0.5 mm and washed with distilled water (designated as WAC) was selected for fixed column studies. Batch adsorption equilibrium data followed both Freundlich and Langmuir isotherm. Fixed bed adsorption column with spent activated carbon as adsorbent was used as a polishing unit for the removal of atrazine from the effluent of an upflow anaerobic sludge blanket (UASB) reactor treating atrazine bearing domestic wastewater. Growth of bacteria on the surface of WAC was observed during column study and bacterial activity enhanced the effectiveness of adsorbent on atrazine removal from wastewater.     

Loofa sponge immobilized fungal biosorbent: a robust system for cadmium and other dissolved metal removal from aqueous solution

The potential of loofa sponge discs to immobilize fungal biomass of Phanerochaete chrysosporium (a known biosorbent) was investigated as a low cost biosorbent for the removal of Cd(II) ions from aqueous solution. A comparison of the biosorption of Cd(II) by immobilized and free fungal biomass from 10 to 500 mg l(-1) aqueous solutions showed an increase in uptake of over 19% when the biomass is immobilized (maximum biosorption capacity of 89 and 74 mg Cd(II) g(-1) biomass for immobilized and free biomass respectively at a solution pH of 6). Equilibrium was established within 1h and biosorption was well defined by the Langmuir isotherm model. The immobilized biomass could be regenerated using 50 mM HCl, with up to 99% metal recovery and reused in ten biosorption-desorption cycles without significant loss of capacity. This study suggests that such an immobilized biosorbent system has the potential to be used in the industrial removal/recovery of cadmium and other pollutant metal ions from aqueous solution.     

Application of Klebsiella oxytoca immobilized cells on the treatment of cyanide wastewater

Klebsiella oxytoca, isolated from cyanide-containing industrial wastewater, has been shown to be able to biodegrade cyanide to non-toxic end products. The technology of immobilized cells can be applied in biological treatment to enhance the efficiency and effectiveness of biodegradation. In this study, potassium cyanide was used as the target compound and both alginate and cellulose triacetate techniques were applied for the preparation of immobilized cells. Results from this study show that KCN can be utilized as the sole nitrogen source by K. oxytoca. The free suspension systems reveal that the cell viability was highly affected by initial KCN concentration and pH. Results show that immobilized cell systems could tolerate a higher level of KCN concentration and wider ranges of pH. In the batch experiments, the maximum KCN removal efficiencies using alginate and cellulose triacetate immobilized beads were 0.108 and 0.101mM h(-1) at pH 7, respectively. Results also indicate that immobilized system can support a higher biomass concentration. Complete KCN degradation was observed after the operation of four consecutive degradation experiments with the same batch of immobilized cells. This suggests that the activity of immobilized cells can be maintained and KCN can be used as the nitrogen source throughout KCN degradation experiments. The maximum KCN removal rates using alginate and cellulose triacetate immobilized beads in continuous-column system were 0.224 and 0.192mMh(-1) with initial KCN concentration of 3mM, respectively. Results indicate that the immobilized cells of K. oxytoca would be applicable to the treatment of cyanide-containing wastewaters.     

Laboratory assessment of atrazine and fluometuron degradation in soils from a constructed wetland

Constructed wetlands offer promise for removal of nonpoint source contaminants such as herbicides from agricultural runoff. Laboratory studies assessed the potential of soils to degrade and sorb atrazine and fluometuron within a recently constructed wetland. The surface 3 cm of soil was sampled from two cells of a Mississippi Delta constructed wetland; one shallow area disturbed only hydrologically, and the second excavated to provide greater water-holding capacity. The excavated area was more acidic on average (pH 4.85 versus 5.21), but otherwise the physical properties and general microbial enzyme activities in the two areas were similar. Soils were treated with 84 and 68 microg kg(-1) soil (14)C-ring labeled atrazine and fluometuron, respectively, and incubated under either saturated (88% moisture, w:w) or flooded (1cm standing water) conditions. Soils were sampled over 32 days and extracted for herbicide and metabolite analysis. Under saturated conditions, fluometuron metabolized to desmethylfluometuron (DMF) with a half-life equal 25-27 days. However, under flooded conditions, the half-life of fluometuron was more than 175 days. Atrazine dissipated rapidly in saturated and flooded soil with a half-life of approximately 23 days, but only 10% of atrazine was mineralized to CO(2). The overall atrazine and fluometuron dissipation rates were similar between the two cells, but each area had a different pattern of metabolite accumulation. The major route of atrazine dissipation was incorporation of atrazine residues into methanol-nonextractable (soil-bound) components, with minimal extractable metabolite accumulation. A mixed-mode extractant (potassium phosphate:acetonitrile) recovered greater amounts of (14)C-residues from atrazine-treated soils, suggesting that hydrolysis of atrazine to hydroxylated metabolites was a major component of the bound residues. These studies indicate the potential for herbicide dissipation in wetland soils and a differential effect of flooding on the fate of these herbicides.     

Performance Evaluation of Waste Activated Carbon on Atrazine Removal from Contaminated Water

Abstract

In this study, the potential of spent activated carbon from water purifier (Aqua Guard, India) for the removal of atrazine (2 chloro-4 ethylamino-6-isopropylamino-1, 3, 5 triazine) from wastewaters was evaluated. Different grades of spent activated carbon were prepared by various pretreatments. Based on kinetic and equilibrium study results, spent activated carbon with a grain size of 0.3–0.5 mm and washed with distilled water (designated as WAC) was selected for fixed column studies. Batch adsorption equilibrium data followed both Freundlich and Langmuir isotherm. Fixed bed adsorption column with spent activated carbon as adsorbent was used as a polishing unit for the removal of atrazine from the effluent of an upflow anaerobic sludge blanket (UASB) reactor treating atrazine bearing domestic wastewater. Growth of bacteria on the surface of WAC was observed during column study and bacterial activity enhanced the effectiveness of adsorbent on atrazine removal from wastewater.     

Melamine-based organoclay to sequester atrazine

Sequestration of aqueous atrazine by organoclays prepared from the surfactant 6-piperazin-1-yl-N,N'-bis-(1,1,3,3-tetramethyl-butyl)-(1,3,5)triazine-2,4-diamine and Gonzales bentonite was assessed using 14C-labeled atrazine. Organoclays with varying ratios of surfactant to clay were evaluated with respect to their ability to sequester atrazine from an aqueous solution. Organoclays containing 100-200 g kg-1 surfactant on a total weight basis provided the most efficient adsorption of atrazine, with apparent KOC values exceeding 5000 l kg-1 at these loading fractions. Less than 12% of sequestered atrazine was released during four sequential day long washings, supporting our expectation that the majority of the reaction of atrazine with the surfactant lead to irreversible chemical bond formation through nucleophilic aromatic substitution.     

Macro-porosity and leaching of atrazine in tilled and orchard loamy soils

Atrazine is the most commonly detected herbicide in the groundwater. Leaching of atrazine largely depends on soil management practices. The aim of this study was to examine leaching of atrazine in tilled and orchard silty loam soils. The experimental objects included: conventionally tilled field (CT) with main tillage operations including pre-plow (10 cm) + harrowing, mouldboard ploughing (20 cm), and a 35 year-old apple orchard (OR) with a permanent sward. To determine leaching of atrazine soil columns of undisturbed structure were taken with steel cylinders of 21.5 cm diameter and 20 cm high from the depth of 0–20 cm. All columns were equilibrated at water content corresponding to field capacity (0.21 kg kg⁻¹). Atrazine suspended in distilled water was dripped uniformly onto the surface of each column. Then water was infiltrated and breakthrough times of leachates were recorded. Atrazine concentration in the leachates was determined by means of HPLC Waters. Macro-porosity and percolation rate were higher in OR than CT soil. Cumulative recovery % of the atrazine applied was 1.267% for OR and approximately one third more from the CT soil but the rate of leaching (per unit of time) was greater from the OR soil. The lower leaching under OR than CT can be due to a greater SOM and the presence of earthworm burrows with organic burrow linings that could adsorb atrazine and contribute to preferential flow allowing solutes to bypass parts whereas the greater rate of leaching due to a greater infiltration rate.The results indicate potential of management practices for minimizing atrazine leaching.     

Biosorption of reactive black 5 by Corynebacterium glutamicum biomass immobilized in alginate and polysulfone matrices

Corynebacterium glutamicum, a lysine fermentation industry waste, showed promise for the removal of Reactive black 5 (RB5). Due to practical difficulties in solid-liquid separation, the free biomass was immobilized in two polymer matrices: calcium alginate and polysulfone. Initially, the optimization of biomass loading in polymeric beads and bead dosage were examined. Of the different combinations examined, 4% (with bead dosage of 2 g per 40 ml) and 14% (with bead dosage of 1 g per 40 ml) in the case of alginate and polysulfone beads, respectively, were identified as the optimal conditions. According to the Langmuir model, at pH 1, the maximum RB5 uptakes of 352, 282 and 291 mg g(-1) were observed for free, alginate and polysulfone-immobilized biomass, respectively. According to the Weber-Morris model, intraparticle diffusion was found to be the potential rate limiting step for the immobilized beads. Regeneration experiments, with 0.01 M NaOH and Na(2)CO(3) as eluents, revealed that polysulfone beads exhibited invariable RB5 uptake capacity and very high mechanical stability even at the end of twentieth cycle, confirming the technical feasibility of the biosorption process for industrial applications.     

Continuous time random walk model better describes the tailing of atrazine transport in soil

Contaminant transport in soils is complicated and involves some physical and chemical nonequilibrium processes. In this research, the soil column displacement experiments of Cl⁻ and atrazine under different flow velocities were carried out. The data sets of Cl⁻ transport in sandy loam fitted to the convection dispersion equation (CDE) and the two-region model (TRM) indicated that the effects of physical nonequilibrium process produced by immobile water on the breakthrough curves (BTCs) of Cl⁻ and atrazine transport through the repacking soil columns were negligible. The two-site model (TSM) and the continuous time random walk (CTRW) were also used to fit atrazine transport behavior at the flow rate of 19.86 cm h⁻¹. The CTRW convincingly captured the full evolution of atrazine BTC in the soil column, especially for the part of long tailing. However, the TSM failed to characterize the tailing of atrazine BTC in the soil column. The calculated fraction of equilibrium sorption sites, F, ranging from 0.78 to 0.80 for all flow rates suggested the contribution of nonequilibrium sorption sites to the asymmetry of atrazine BTCs. Furthermore, the data sets for the flow rates of 6.68 cm h⁻¹ and 32.81 cm h⁻¹ were predicted by the TSM and the CTRW. As to the flow rate of 6.68 cm h⁻¹, the CTRW predicted the entire BTC of atrazine transport better than the TSM did. For the flow rate of 32.81 cm h⁻¹, the CTRW characterized the late part of the tail better, while the TSM failed to predict the tailings of atrazine BTC.     

Oily wastewater treatment using a novel hybrid PBR-UASB system

In this study, anaerobic treatability of oily wastewater was investigated in a hybrid reactor system consisting of a packed bed reactor (PBR) followed by an upflow anaerobic sludge blanket (UASB) reactor at 35 degrees C. The system was operated using real pet food wastewater at different hydraulic retention times and loading rates for 165 d. The PBR was packed with sol-gel/alginate beads containing immobilized enzyme which hydrolyzed the oil and grease (O&G) into free long chain fatty acids, that were biodegraded by the UASB. The hybrid system was operated up to an oil loading rate of 4.9 kg O&Gm(-3)d(-1) (to the PBR) without any operational problems for a period of 100 d, with COD and O&G removal efficiencies above 90% and no sludge flotation was observed in the UASB. Beads supplement to the PBR was less than 2 g d(-1) and the relative activity was about 70%. Further increment in O&G loading to 18.7 kg O&Gm(-3)d(-1) caused destabilization of the system with 0.35% (v float/v feed) sludge float removed from the UASB.     

Atrazine sorption and fate in a Ultisol from humid tropical Brazil

This study combined laboratory based microcosm systems as well as field experiments to evaluate the mobility of atrazine on a Ultisol under humid tropical conditions in Brazil. Results from sorption experiments fit to the Freundlich isotherm model [K(f) 0.99 mg kg(-1)/(mg l(-1))(1/n)], and indicate a low sorption capacity for atrazine in this soil and consequently large potential for movement by leaching and runoff. Microcosm systems using (14)C-atrazine to trace the fate of the applied herbicide, showed that 0.33% of the atrazine was volatilized, 0.25% mineralized and 6.89% was recorded in the leachate. After 60 d in the microcosms, 75% of the (14)C remained in the upper 5 cm soil layer indicating atrazine or its metabolites remained close to the soil surface. In field experiments, after 60 d, only 5% of the atrazine applied was recovered in the upper soil layers. In the field experiments atrazine was detected at a depth of 50 cm indicating leaching. Simulating tropical rain in field experiments resulted in 2.1% loss of atrazine in runoff of which 0.5% was adsorbed onto transported soil particles and 1.6% was in solution. Atrazine runoff was greatest two days after herbicide application and decreased 10 fold after 15 d. The use of atrazine on Ultisols, in the humid tropics, constitutes a threat to water quality, causing surface water and ground water pollution.     

Load maximization of a liquid-solid circulating fluidized bed bioreactor for nitrogen removal from synthetic municipal wastewater

A novel liquid-solid circulating fluidized bed bioreactor (LSCFB) configured with anoxic and aerobic columns and lava rock as the biofilm carrier was used to treat synthetic municipal wastewater. Four different empty bed contact times (EBCTs) of 0.82, 0.65, 0.55, and 0.44 h were examined to optimize nutrient removal capability of the system. The LSCFB demonstrated tertiary effluent quality organic and nitrogen removal efficiencies. Effluent characteristics of the LSCFB were soluble biological oxygen demand (SBOD)10 mg l(-1) and total nitrogen (TN)<10 mg l(-1) at organic loading rate (OLR) of 5.3 kg m(-3)d(-1) and nitrogen loading rate of 0.54 kg Nm(-3)d(-1). Remarkably low yields of 0.14, 0.17, 0.19, and 0.21 g VSS g(-1)COD were observed at OLR of 2.6, 3.2, 4.1 and 5.3 kg COD m(-3)d(-1), where increment of biomass growth and detachment rate were also experienced with increasing OLR. However the system demonstrated only 30% phosphorus removal, and mass balances along the anoxic and aerobic columns showed biological phosphorus removal in the system. Organic mass balance showed that approximately 40% of the influent COD was utilized in the anoxic column and the remaining COD was oxidized in the aerobic column. The system is very efficient in nitrification-denitrification, with more than 90% nitrification of ammonium and overall nitrogen removal in the LSCFB was 70+/-11% even at an EBCT of 0.44 h.     

Application of the method of temporal moments to interpret solute transport with sorption and degradation

In this note, we applied the temporal moment solutions of [Das and Kluitenberg, 1996. Soil Sci. Am. J. 60, 1724] for one-dimensional advective-dispersive solute transport with linear equilibrium sorption and first-order degradation for time pulse sources to analyse soil column experimental data. Unlike most other moment solutions, these solutions consider the interplay of degradation and sorption. This permits estimation of a first-order degradation rate constant using the zeroth moment of column breakthrough data, as well as estimation of the retardation factor or sorption distribution coefficient of a degrading solute using the first moment. The method of temporal moment (MOM) formulae was applied to analyse breakthrough data from a laboratory column study of atrazine, hexazinone and rhodamine WT transport in volcanic pumice sand, as well as experimental data from the literature. Transport and degradation parameters obtained using the MOM were compared to parameters obtained by fitting breakthrough data from an advective-dispersive transport model with equilibrium sorption and first-order degradation, using the nonlinear least-square curve-fitting program CXTFIT. The results derived from using the literature data were also compared with estimates reported in the literature using different equilibrium models. The good agreement suggests that the MOM could provide an additional useful means of parameter estimation for transport involving equilibrium sorption and first-order degradation. We found that the MOM fitted breakthrough curves with tailing better than curve fitting. However, the MOM analysis requires complete breakthrough curves and relatively frequent data collection to ensure the accuracy of the moments obtained from the breakthrough data.     

Experimental in situ chemical peroxidation of atrazine in contaminated soil

Lab-scale experiments of in situ chemical oxidation (ISCO), were performed on soil contaminated with 100 mg kg(-1) of atrazine (CIET). The oxidant used was hydrogen peroxide catalysed by naturally occurring minerals or by soluble Fe(II) sulphate, added in aqueous solution. The oxidation conditions were: CIET:H2O2=1:1100, 2 PV or 3 PV reaction volume, Fe(II):H2O2=0, 1:22, 1:11. Stabilized (with KH2PO4 at a concentration of 16 g l(-1)) or non-stabilized hydrogen peroxide was used. The pH of the reagents was adjusted to pH=1 with sulphuric acid, or was not altered. Results showed that the addition of soluble Fe(II) increased the temperature of the soil slurry and the use of stabilized hydrogen peroxide resulted in a lower heat generation. The treatment reduced the COD of the soil of about 40%, pH was lowered and natural organic matter became less hydrophobic. The highest atrazine conversion (89%) was obtained in the conditions: 3 PV, Fe(II):H2O2=1:11 with stabilized hydrogen peroxide added in two steps. The stabilizer only increased H2O2 life-time significantly when soluble Fe(II) was added. Results indicate as preferential degradation pathway of atrazine in soil dechlorination instead of dealkylation.     

Bioaugmentation with a Bacillus sp. to reduce the phytoavailable Cd of an agricultural soil: comparison of free and immobilized microbial inocula

In order to reduce the cadmium potentially available for plants, soil bioaugmentation was performed by using a Bacillus sp. In a pot experimentation, sterilized and non-sterilized soils were inoculated using free or immobilized cells entrapped in alginate beads. This test was carried out with different inoculum sizes (2 x 10(10) and 2 x 10(11)CFU kg(-1) dw of soil) and alginate bead compositions (10 and 15 g of both alginate and CaCl(2) l(-1)). Then, the soil pots were incubated at 20 degrees C and the soil humidity was kept at a level of 20%. After 3 weeks of a batch incubation, the potentially phytoavailable Cd was reduced up to a factor of 14. The bioaugmentation resulted in the soil colonization by Bacillus sp. thanks to an increase of the cell concentration up to 1.8 log units. However, in comparison to the cells being inoculated in a free mode, the immobilization of the cells did not significantly improve the survival of the cells in the soil. Although the resulting effect not being highly pronounced, the potentially phytoavailable Cd correlated with the cell concentration in a surprisingly positive way. What is more, the Bacillus concentrations in the soil were positively correlated with the inoculum, too.     

Kinetics of ammonium removal with suspended and immobilized nitrifying bacteria in different reactor systems

The degradation of ammonium by free and immobilized bacteria in different reactor systems was investigated. It was found that the start-up of a nitrifying system is enhanced if a reservoir of immobilized bacteria is present. It was also found that in a single stage system with suspended nitrifying bacteria a stable ammonium removal > 95 % could be established up to an influent ammonium concentration of 1000 mg/1 and a volumetric loading rate (VLR) of 2.3 kg NH₄⁺ m⁻³ d⁻¹. The oxygen uptake rate (OUR) due to nitrification processes was greatly enhanced with increasing volumetric loading rates. Using nitrifying bacteria immobilized on Siran material it was demonstrated that the ammonium degradation rate was directly proportional to the initial ammonium concentration.