Role of pine needle biochar in operation and stability of anaerobic processes.

Utility of biochar addition in anaerobic processes for promoting direct interspecies electron transfer (DIET) is demonstrated in this research. Biochar produced from pyrolysis of pine needle forest residue was used as conductive material for DIET. Three CSTRs were operated in parallel with and without biochar addition in fed-batch mode. Reactor without biochar which represented indirect interspecies electron transfer (IIET) exhibited wide variation in pH and VFA and took longer period during startup. All the rectors were operated at steady state with an OLR ranging from 0.5 to 1.75 kg-COD/m3.d. As OLR increased, performance of reactor without biochar resulted in rapid pH drop and increase in VFA, leading to its eventual failure at OLR of 1.75 kg-COD/m3.d. As against to this, performance of reactors with biochar remained robust and relatively unaffected at higher OLR values. Daily VFA accumulation from fed-batch mode always remained highest in reactor without biochar.

Facilitation of interspecies electron transfer in anaerobic processes through pine needle biochar.

Role of biochar in promoting methanogenesis during anaerobic processes was investigated in this research. Biochar produced from Himalayan pine needles was used as medium for conductive material mediated interspecies electron transfer (CM-IET) amongst the electron producing microorganisms and electron consuming methanogenic archaea. Three anaerobic continuous stirrer tank reactors (CSTRs) with 0, 5 and 10 g/L pine needle biochar (PNB) were operated at steady state organic loading rate (OLR) of 2.0-2.5 kgCOD/(m3.d). R0 (0 g/L PNB), representing indirect interspecies electron transfer (IIET), failed at an OLR of 2.0 kgCOD/(m3.d) due to the highest volatile fatty acid (VFA) concentration of 6,300 mg/L among the three CSTRs. On the other hand, at an OLR of 2.5 kgCOD/(m3.d), R2 (10 g/L PNB) showed the most superior performance with chemical oxygen demand (COD) removal of 55% and volatile fatty acid (VFA) concentration of 3,500 mg/L, while R1 (5 g/L PNB) recorded COD removal of 45% and VFA concentration of 4,400 mg/L. In comparison, fixed biofilm reactor (FBR) with 80 g/L of PNB as support material operated satisfactorily at OLR of 13.8 kgCOD/(m3.d) with 70% COD removal and VFA concentration of 1,400 mg/L. These investigations confirmed the beneficial role of biochar in anaerobic processes by promoting CM-IET amongst VFA degrading bacteria and methane producing archaea.

Copper removal from aqueous solution using chemical precipitation and adsorption by Himalayan Pine Forest Residue as Biochar.

This research deals with the use of pine residue biochar as an adsorbent for the removal of copper from aqueous solution which is a major component of printed circuit boards from E-waste. Biochar was produced from pine residue such as bark, cone and needle through pyrolysis, and the effect of temperature on biochar properties was assessed. The biochar yield of about 33% and maximum surface area of 368 m2/g was obtained at pyrolysis temperature of 650°C. FTIR analysis revealed the existence of C-O, O-H and C = C functional groups on the surface of biochars. The point of zero charge of pine biochars were in the range 5.55 to 5.75. Batch adsorption studies revealed maximum copper adsorption capacity of 60-81 mg/g at near neutral pH. The batch adsorption data fitted well with Langmuir isotherm and followed the pseudo-second order kinetics. Adsorption of copper onto the biochar surface mainly followed physisorption which was reversible in nature. Desorption study revealed that pine biochar could be reused up to three cycles. Column adsorption data fitted well with Thomas model. These investigations revealed that the pine residue, which otherwise results in adverse environmental impacts, can be converted into useful resource like biochar as a heavy metal adsorbent.

Fluoride removal from groundwater using chemically modified rice husk and corn cob activated carbon.

The fluoride adsorption potential of chemically modified rice husk and corn cob activated carbon was investigated in batch and column tests. The effect of pH, contact time, initial fluoride concentration and adsorbent dose on the adsorption capacity and efficiency was studied. Batch experimental results were analysed using analysis of variance. The maximum adsorption capacity of 7.9 and 5.8 mg/g and a removal efficiency of 91% and 89% were achieved in batch tests, respectively, for rice husk and corn cob activated carbon. The adsorption data and kinetic model fitted well to the Langmuir isotherm and pseudo-second-order kinetics, respectively. Fluoride adsorption was governed by both intraparticle diffusion and surface or film diffusion for both rice husk and corn cob activated carbon. Continuous tests were carried out using three columns packed with 100% rice husk activated carbon, 100% corn cob activated carbon and 50% rice husk + 50% corn cob activated carbon. The breakthrough adsorption capacities were found to be 7.9, 5.0 and 5.2 mg/g, respectively. The results were analysed using the Thomas model, which yielded adsorption capacities of 11, 8.1 and 9.4 mg/g, respectively, for the three columns investigated.

Cyanide degradation kinetics during anaerobic co-digestion of cassava pulp with pig manure.

Anaerobic co-digestion of cassava pulp (CP) and pig manure (PM) under cyanide inhibition conditions was investigated and modeled. Batch experiments were performed with initial cyanide concentrations ranging from 1.5 to 10 mg/L. Cyanide acclimatized sludge from an anaerobic co-digester treating cyanide-containing CP and PM was used as the seed sludge (inoculum). Cyanide degradation during anaerobic digestion consisted of an initial lag phase, followed by a cyanide degradation phase. After a short sludge acclimatization period of less than 3 days, the anaerobic sludge was able to degrade cyanide, indicating that the sludge inhibition due to cyanide was reversible. Cyanide degradation during anaerobic co-digestion of CP and PM followed the first-order kinetics with a rate constant of 0.094 d-1. Gas evolution during batch anaerobic degradation was modeled using the modified Monod-type kinetics to incorporate cyanide inhibition. The model predicted results yielded a satisfactory fit with the experimental data.

Anaerobic co-digestion of cyanide containing cassava pulp with pig manure.

Anaerobic co-digestion of cyanide-containing cassava pulp with pig manure was evaluated using laboratory scale mesophilic digester. The digester was operated in a semi-continuous mode with the mixed feedstock having C/N ratio of 35:1. Digester startup was accomplished in 60days with loading of 0.5-1kgVS/m(3)d. Subsequently, the loading to digester was increased step-wise from 2 to 9kgVS/m(3)d. Digester performance was stable at loading between 2 and 6kgVS/m(3)d with an average volatile solid removal and methane yield of 82% and 0.38m(3)/kgVSadded, respectively. However, beyond loading of 7kgVS/m(3)d, solubilization of particulate matter did not take place efficiently. Cyanide present in cassava pulp was successfully degraded indicating that anaerobic sludge in the digester was well acclimatized to cyanide. The results show that cassava pulp can be successfully digested anaerobically with pig manure as co-substrate without any inhibitory effect of cyanide present in the cassava pulp.

Spontaneous electrochemical treatment for sulfur recovery by a sulfide oxidation/vanadium(V) reduction galvanic cell.

Sulfide is the product of the biological sulfate reduction process which gives toxicity and odor problems. Wastewaters or bioreactor effluents containing sulfide can cause severe environmental impacts. Electrochemical treatment can be an alternative approach for sulfide removal and sulfur recovery from such sulfide rich solutions. This study aims to develop a spontaneous electrochemical sulfide oxidation/vanadium(V) reduction cell with a graphite electrode system to recover sulfide as elemental sulfur. The effects of the internal and external resistance on the sulfide removal efficiency and electrical current produced were investigated at different pH. A high surface area of the graphite electrode is required in order to have as less internal resistance as possible. In this study, graphite powder was added (contact area >633 cm(2)) in order to reduce the internal resistance. A sulfide removal efficiency up to 91% and electrical charge of more than 400 C were achieved when using five graphite rods supplemented with graphite powder as the electrode at an external resistance of 30 Ω and a sulfide concentration of 250 mg L(-1).

Chemical sulphate removal for treatment of construction and demolition debris leachate.

Construction and demolition debris (CDD) is a product of construction, renovation or demolition activities. It has a high gypsum content (52.4% of total gypsum), concentrated in the CDD sand (CDDS) fraction. To comply with the posed limit of the maximum amount of sulphate present in building sand, excess sulphate needs to be removed. In order to enable reuse of CDDS, a novel treatment process is developed based on washing of the CDDS to remove most of the gypsum, and subsequent sulphate removal from the sulphate-rich CDDS leachate. This study aims to assess chemical techniques, i.e. precipitation and adsorption, for sulphate removal from the CDDS leachate. Good sulphate removal efficiencies (up to 99.9%) from the CDDS leachate can be achieved by precipitation with barium chloride (BaCl2) and lead(II) nitrate (Pb(NO3)2). Precipitation with calcium chloride (CaCl2), calcium carbonate (CaCO3) and calcium oxide (CaO) gave less efficient sulphate removal. Adsorption of sulphate to aluminium oxide (Al2O3) yielded a 50% sulphate removal efficiency, whereas iron oxide-coated sand as adsorbent gave only poor (10%) sulphate removal efficiencies.

Use of organic substrates as electron donors for biological sulfate reduction in gypsiferous mine soils from Nakhon Si Thammarat (Thailand).

Soils in some mining areas contain a high gypsum content, which can give adverse effects to the environment and may cause many cultivation problems, such as a low water retention capacity and low fertility. The quality of such mine soils can be improved by reducing the soil's gypsum content. This study aims to develop an appropriate in situ bioremediation technology for abbreviating the gypsum content of mine soils by using sulfate reducing bacteria (SRB). The technology was applied to a mine soil from a gypsum mine in the southern part of Thailand which contains a high sulfate content (150 g kg(-1)). Cheap organic substrates with low or no cost, such as rice husk, pig farm wastewater treatment sludge and coconut husk chips were mixed (60:20:20 by volume) and supplied to the soil as electron donors for the SRB. The highest sulfate removal efficiency of 59% was achieved in the soil mixed with 40% organic mixture, corresponding to a reduction of the soil gypsum content from 25% to 7.5%. For economic gains, this treated soil can be further used for agriculture and the produced sulfide can be recovered as the fertilizer elemental sulfur.

Biological sulfate removal from construction and demolition debris leachate: effect of bioreactor configuration.

Due to the contamination of construction and demolition debris (CDD) by gypsum drywall, especially, its sand fraction (CDD sand, CDDS), the sulfate content in CDDS exceeds the posed limit of the maximum amount of sulfate present in building sand (1.73 g sulfate per kg of sand for the Netherlands). Therefore, the CDDS cannot be reused for construction. The CDDS has to be washed in order to remove most of the impurities and to obtain the right sulfate content, thus generating a leachate, containing high sulfate and calcium concentrations. This study aimed at developing a biological sulfate reduction system for CDDS leachate treatment and compared three different reactor configurations for the sulfate reduction step: the upflow anaerobic sludge blanket (UASB) reactor, inverse fluidized bed (IFB) reactor and gas lift anaerobic membrane bioreactor (GL-AnMBR). This investigation demonstrated that all three systems can be applied for the treatment of CDDS leachate. The highest sulfate removal efficiency of 75-85% was achieved at a hydraulic retention time (HRT) of 15.5h. A high calcium concentration up to 1,000 mg L(-1) did not give any adverse effect on the sulfate removal efficiency of the IFB and GL-AnMBR systems.

Biological sulfate removal from gypsum contaminated construction and demolition debris.

Construction and demolition debris (CDD) contains high levels of sulfate that can cause detrimental environmental impacts when disposed without adequate treatment. In landfills, sulfate can be converted to hydrogen sulfide under anaerobic conditions. CDD can thus cause health impacts or odor problems to landfill employees and surrounding residents. Reduction of the sulfate content of CDD is an option to overcome these problems. This study aimed at developing a biological sulfate removal system to reduce the sulfate content of gypsum contaminated CDD in order to decrease the amount of solid waste, to improve the quality of CDD waste for recycling purposes and to recover sulfur from CDD. The treatment leached out the gypsum contained in CDD by water in a leaching column. The sulfate loaded leachate was then treated in a biological sulfate reducing Upflow Anaerobic Sludge Blanket (UASB) reactor to convert the sulfate to sulfide. The UASB reactor was operated at 23 ± 3 °C with a hydraulic retention time and upflow velocity of 15.5 h and 0.1 m h(-1), respectively while ethanol was added as electron donor at a final organic loading rate of 3.46 g COD L(-1) reactor d(-1). The CDD leachate had a pH of 8-9 and sulfate dissolution rates of 526.4 and 609.8 mg L(-1) d(-1) were achieved in CDD gypsum and CDD sand, respectively. Besides, it was observed that the gypsum dissolution was the rate limiting step for the biological treatment of CDD. The sulfate removal efficiency of the system stabilized at around 85%, enabling the reuse of the UASB effluent for the leaching step, proving the versatility of the bioreactor for practical applications.

Precipitation of heavy metals from coal ash leachate using biogenic hydrogen sulfide generated from FGD gypsum.

Investigations were undertaken to utilize flue gas desulfurization (FGD) gypsum for the treatment of leachate from the coal ash (CA) dump sites. Bench-scale investigations consisted of three main steps namely hydrogen sulfide (H(2)S) production by sulfate reducing bacteria (SRB) using sulfate from solubilized FGD gypsum as the electron acceptor, followed by leaching of heavy metals (HMs) from coal bottom ash (CBA) and subsequent precipitation of HMs using biologically produced sulfide. Leaching tests of CBA carried out at acidic pH revealed the existence of several HMs such as Cd, Cr, Hg, Pb, Mn, Cu, Ni and Zn. Molasses was used as the electron donor for the biological sulfate reduction (BSR) process which produced sulfide rich effluent with concentration up to 150 mg/L. Sulfide rich effluent from the sulfate reduction process was used to precipitate HMs as metal sulfides from CBA leachate. HM removal in the range from 40 to 100% was obtained through sulfide precipitation.

Biological sulfide oxidation in an airlift bioreactor.

Biological sulfide oxidation process was investigated in an airlift reactor under oxygen-limited condition (0.2-1.0 mg l(-1)). Reactor start-up was accomplished using seed sludge from activated sludge process treating domestic wastewater. Synthetic wastewater was used as feed. Gradual increase in volumetric sulfide loading rate resulted in increase of elemental sulfur production. At sulfide loading rate of 2.2 kg S m(-3)d(-1), 50% of influent sulfide was converted to elemental sulfur. At maximum volumetric sulfide loading rate of 4.0 kg S m(-3)d(-1), sulfide consumption of 4.3 kg S kg VSS(-1)d(-1) was achieved, and over 93% of sulfide removal was observed. Investigation revealed that up to 90% of sulfide removed was converted to elemental sulfur. Addition of polyaluminium chloride as coagulant was found to be effective for sulfur-particle aggregation.

Pilot scale investigation of zinc and sulphate removal from industrial discharges by biological sulphate reduction with molasses as electron donor.

A biological sulphate reduction process, with molasses as an electron donor, was used for the removal of zinc and sulphate from Rayon industrial wastewater. The process involved reduction of sulphate to sulphide under anaerobic conditions. The sulphide-rich effluent was used to remove zinc as zinc sulphide precipitate. The investigation was conducted at pilot scale with real wastewater from the Rayon industry as feed. The effects of sulphate loading rate and temperature of feeding wastewater were evaluated. The experimental results showed that there was no significant difference in sulphide production when the reactor was operated at 50 +/- 2 degrees C and 65 +/- 2 degrees C. Sulphide production was in the range of 500-515 mg L(-1). In addition, an increase in sulphate loading rate from 6.3 +/- 0.7 kg SO4 m(-3) d(-1) to 14.9 +/- 2.4 kg SO4 m(-3) d(-1) resulted in a dramatic decrease in sulphate removal efficiency. Furthermore, zinc sulphide precipitation at pH 7 removed more than 96% of zinc.

Investigation on laboratory and pilot-scale airlift sulfide oxidation reactor under varying sulfide loading rate.

Airlift bioreactor was established for recovering sulfur from synthetic sulfide wastewater under controlled dissolved oxygen condition. The maximum recovered sulfur was 14.49 g/day when sulfide loading rate, dissolved oxygen (DO) and pH values were 2.97 kgHS(-)/m(3)-day, 0.2-1.0 mg/L and 7.2-7.8, respectively. On the other hand, the increase in recovered sulfur reduced the contact surface of sulfide oxidizing bacteria which affects the recovery process. This effect caused to reduce the conversion of sulfide to sulfur. More recovered sulfur was produced at high sulfide loading rate due to the change of metabolic pathway of sulfide-oxidizing bacteria which prevented the toxicity of sulfide in the culture. The maximum activity in this system was recorded to be about 3.28 kgS/kgVSS-day. The recovered sulfur contained organic compounds which were confirmed by the results from XRD and CHN analyzer. Afterwards, by annealing the recovered sulfur at 120 degrees C for 24 hrs under ambient Argon, the percentage of carbon reduced from 4.44% to 0.30%. Furthermore, the percentage of nitrogen and hydrogen decreased from 0.79% and 0.48% to 0.00% and 0.14%, respectively. This result showed the success in increasing the purity of recovered sulfur by using the annealing technique. The pilot-scale biological sulfide oxidation process was carried out using real wastewater from Thai Rayon Industry in Thailand. The airlift reactor successfully removed sulfide more than 90% of the influent sulfide at DO concentration of less than 0.1 mg/L, whereas the elementary sulfur production was 2.37 kgS/m(3)-day at sulfide loading rate of 2.14 kgHS(-)/m(3)-day. The sulfur production was still increasing as the reactor had not yet reached its maximum sulfide loading rate.

Lead removal and toxicity reduction from industrial wastewater through biological sulfate reduction process.

The practicability of lead removal from sulfate-rich wastewater through biological sulfate reduction process with hydrogen as electron donor was investigated. Sulfide, which was converted from sulfate by a sulfate-reducing bacteria (SRB) in a gas-lift reactor, was used to remove lead as lead sulfide precipitate. Furthermore, the toxicity of wastewater in terms of whole effluent toxicity (WET) before and after treatment was analyzed by using Microtox analyzer. The experiment was divided into three stages as follows: Stage I, startup and operation of sulfidogenic process fed with synthetic wastewater in a gas-lift reactor; Stage II, operation of sulfidogenic process fed with real wastewater in the same reactor and analysis of toxicity; and Stage III, separation of lead from wastewater. In stage I, the volumetric sulfate-sulfur loading rate was gradually increased from 1.0 g/L.d until no improvement of sulfide-sulfur production efficiency was evident at 2.58 g/L.d and maximum sulfide-sulfur concentration was set to 340 mg/L. In stage II, the results showed that the laboratory scale reactor could treat a real wastewater without inhibition or any remarkable problem. The produced sulfide-sulfur, 200 mg/L, was a little less in comparison with that of the previous stage. It could be due to the higher concentration of total dissolved solid (TDS). However, the sulfate concentration was still reduced by approximately 30%. The WET test by Microtox showed that toxicity was reduced more than 13 times. In stage III, the effluent from the reactor containing sulfide-sulfur of about 200 mg/L and lead-containing solution of 20 mg/L were fed with sulfide to lead ratio 3 moles: 1 mole into the precipitation chamber in which the optimum pH for lead sulfide precipitation of 8.0 was maintained. It was found that lead removal of 99% was attained.

Combined activated sludge with partial nitrification (AS/PN) and anammox processes for treatment of seafood processing wastewater.

An activated sludge process with partial nitrification (AS/PN) in combination with anaerobic ammonium oxidation (Anammox) process for treatment of seafood processing wastewater was developed and investigated in this research. Operating conditions of AS/PN process for coupling with Anammox process were identified as pH between 7.7-8.2 and DO as 0.5-0.9 mg L(-1) to achieve over 85% COD removal as well as partial nitrification. The developed AS/PN process could produce almost equal concentration of ammonium and nitrite nitrogen in the effluent which was highly suitable for the Anammox process. Near complete removal of ammonium and nitrite was achieved during steady state Anammox process operation. Maximum nitrogen removal rate for the Anammox process was found to be 0.6 kg N m(- 3) d(-1). Microorganisms involved in both AS/PN and Anammox processes were identified using in situ hybridization and polymerase chain reaction techniques. The result 16S rDNA revealed 94% homology to Candidatus "Brocadia fulgida."

Electron donors for biological sulfate reduction.

Biological sulfate reduction is widely used for treating sulfate-containing wastewaters from industries such as mining, tannery, pulp and paper, and textiles. In biological reduction, sulfate is converted to hydrogen sulfide as the end product. The process is, therefore, ideally suited for treating metal-containing wastewater from which heavy metals are simultaneously removed through the formation of metal sulfides. Metal sulfide precipitates are more stable than metal hydroxides that are sensitive to pH change. Theoretically, conversion of 1 mol of sulfate requires 0.67 mol of chemical oxygen demand or electron donors. Sulfate rich wastewaters are usually deficient in electron donors and require external addition of electron donors in order to achieve complete sulfate reduction. This paper reviews various electron donors employed in biological sulfate reduction. Widely used electron donors include hydrogen, methanol, ethanol, acetate, lactate, propionate, butyrate, sugar, and molasses. The selection criteria for suitable electron donors are discussed.

Influence of anaerobic co-digestion of sewage and brewery sludges on biogas production and sludge quality.

This research investigated operating parameters and treatment efficiency for the digestion of sewage and brewery sludge. The prime objective of this study was to enhance the quality of treated sludge for use as agriculture fertilizer and to enhance biogas production, a by-product that can be used as an energy source. Three bench-scale completely stirred tank reactor (CSTR) anaerobic digesters were operated at mesophilic condition (36+/-0.2 degrees C). A mixture of sewage and brewery sludge were used as substrates at ratios of 100:0, 75:25, 50:50, 25:75 and 0:100, based on wet weight basis (w/w). For each digester, the solids retention times (SRT) were 20 days. The organic loading and volatile solids loading were between 1.3-2.2 kg chemical oxygen demand (COD)/m3/day and 0.9-1.5 kg/m3/day, respectively. The digester fed with brewery sludge as co-substrate yielded higher treatment efficiency than sewage sludge alone. The removal efficiencies measured in terms of soluble chemical oxygen demand (SCOD) and total chemical oxygen demands (TCOD) ranged from 40% to 75% and 22% to 35%, respectively. Higher SCOD and TCOD removal efficiencies were obtained when higher fractions of brewery sludge was added to the substrate mixture. Removal efficiency was lowest for sewage sludge alone. Measured volatile solid (VS) reduction ranged from 15% to 20%. Adding a higher fraction of brewery sludge to the mixture increased the VS reduction percentage. The biogas production and methane yield also increased with increase in brewery sludge addition to the digester mixture. The methane content present in biogas of each digester exceeded 70% indicating the system was functioning as an anaerobic process. Likewise the ratio of brewery sewage influenced not only the treatment efficiency but also improved quality of treated sludge by lowering number of pathogen (less than 2 MPN/g of dried sludge) and maintaining a high nutrient concentration of nitrogen (N) 3.2-4.2%, phosphorus (P) 1.9-3.2% and potassium (K) 0.95-0.96%. The heavy metals, chromium (Cr) and copper (Cu) remaining in digested sludge were present at relatively high levels (Cr 1,849-4,230 and Cu 930-2,526 mg/kg dried sludge). The metals were present as organic matter-bound and sulfide-bound fractions that are not soluble and available. The digested sludge could be safely applied to soil as a plant nutrient source, without fecal coliforms or heavy metals risk. A sludge mixture ratio of 25:75 (sewage:brewery), which generated the higher nutrient concentrations (N=4.22%, P=3.20% and K=0.95%), biogas production and treatment efficiency meet the Bangkok Metropolitan Administration (BMA) safety guidelines required for agricultural application. Biogas production and methane at the 25:75 ratio (sewage:brewery) yielded highest amount of VSremoved (0.65 m3/kg) and CODremoved (220 L/kg), respectively.

Lead removal through biological sulfate reduction process.

The feasibility of lead removal through biological sulfate reduction process with ethanol as electron donor was investigated. Sulfide-rich effluent from biological process was used to remove lead as lead sulfide precipitate. The experiments were divided into two stages; Stage I startup and operation of sulfidogenic process in a UASB reactor and Stage II lead sulfide precipitation. In Stage I, the COD:S ratio was gradually reduced from 15:1 to 2:1. At the COD:S ratio of 2:1, sulfidogenic condition was achieved as identified by 80-85% of electron flow by sulfate reducing bacteria (SRB). COD and sulfate removal efficiency were approximately 78% and 50%, respectively. In Stage II, the effluent from UASB reactor containing sulfide in the range of 30-50 mg/L and lead-containing solution of 45-50 mg/L were fed continuously into the precipitation chamber in which the optimum pH for lead sulfide precipitation of 7.5-8.5 was maintained. It was found that lead removal of 85-95% was attained.