Phosphate and potassium recovery from source separated urine through struvite precipitation

Phosphate can be recovered as struvite or apatite in fluidised bed reactors. Urine has a much higher phosphate concentration than sludge reject water, allowing simpler (and less expensive) process for precipitation of phosphates. A stirred tank reactor with a special compartment for liquid solid separation was used to precipitate struvite from urine. Magnesium ammonium phosphate as well as potassium magnesium phosphate are two forms of struvite that were successfully precipitated. Liquid/solid separation was very effective, but the compaction of struvite was rather poor in the case of potassium struvite. Crystals did not form clusters and maintained the typical orthorhombic structure. Ammonium struvite had slightly lower effluent phosphate concentrations, but an average of 95% of influent phosphate was removed regardless of ammonium or potassium struvite precipitation. Fluid mechanics is believed to be important and should inform further work.     

A bench-scale aeration study using batch reactors on swine manure stabilization to control odour in post treatment storage

A bench-scale study on swine manure stabilization for odour control was conducted using batch aeration reactors. In trial 1, two aeration lengths, i.e., 0.5 and 4.0 day, were used under uncontrolled ambient temperature that increased gradually over the experimental period. While in trial 2, a 16.0-day aeration scheme was employed under constant 17 degrees C. An airflow rate of 1.2L/s/m(3) was used for both trials to aerate batch reactors containing finishing pig manure with initial total solids (TS) levels ranging from 0.5 to 4.0%. Manure stabilization during the 90-day post-treatment storage was evaluated by the changes in organic materials, nitrogen and volatile fatty acids (VFA). The odour generation potential in the treated manure was determined by the changes in VFA. Up to 827 mL of liquid was lost due to aeration related foaming. The reductions in total volatile solids (TVS), 5-day biochemical oxygen demand (BOD(5)), total Kjeldahl nitrogen (TKN) and VFA during storage were improved when aeration length increased. Low solids levels offered a more advantageous circumstance for manure stabilization and odour control. Biodegradation of organic matter, removal of nitrogen, and breakdown of VFA would increase with increasing ambient temperature. VFA removals in manure under 16.0-day aeration were higher than those under 0.5- and 4.0-day aeration; however, VFA regeneration started to exceed its consumption on day 20 (4 days after the aeration treatment). BOD(5) was the best estimate of VFA concentration in the aerated manure during storage. The 4.0-day aeration scheme was sufficient to stabilize manure to effectively assuage odour generation potential during the 90-day storage under increasing ambient temperature conditions.     

Modeling of ammonia speciation in anaerobic digesters

Anaerobic digestion of high-nitrogen wastes such as animal manure can be inhibited by high concentrations of un-ionized ammonia, NH₃ (aq). Understanding the toxicity of NH₃ (aq) to anaerobic digestion requires a method for determining its concentration. Previous work on ammonia toxicity in anaerobic digesters has utilized a simple equilibrium calculation for estimating NH₃ (aq) concentration from total ammonia, temperature, and pH. This approach is not appropriate for concentrated solutions. In this work, a speciation model for major solutes in anaerobic digesters, based on Pitzer's ion-interaction approach, is presented. Model simulations show that the simple equilibrium calculation (without corrections for non-ideal behavior) substantially overestimates NH₃ (aq) concentration for all but dilute digesters. This error in concentration determination increases with total solids content and is estimated to be greater than 40% for a digester fed dairy manure with 5% total solids or swine manure with 3% total solids. However, including an estimate of the activity coefficient for NH₄⁺ in the simple equilibrium calculation results in much more accurate estimates of NH₃ (aq) concentration. In this case, the estimated error is less than 10% in the absence of struvite precipitation at the highest total solids contents considered.     

Temperature Effects On Pig Manure Under Low Level Batch Aeration

This project investigated the temperature effect on some chemical and biological characteristics of liquid swine manure under low level batch aeration conditions. An airflow rate of 0.129 L/min/L manure was used to aerate manure contained in reactors made of plexiglas tubes. Five temperatures, i.e. 5°C, 10°C, 15°C, 20°C, and 25°C, were examined. Data showed that manure pH would decrease with an increase in temperature. When temperature increased from 5°C to 25°C, the average oxidation-reduction potential decreased from +40 mV to m 60mV, resulting in a decrease in aerobic counts from 5.5 2 10 6 to 2.2 2 10 6 . This was accompanied by an increase in anaerobic bacterial counts (from 3.8 2 10 6 to 5.1 2 10 6 ). The increased anaerobic population produced more volatile fatty acids, leading to the decrease in pH. An inversely linear correlation was observed between pH and volatile fatty acids with a correlation coefficient of 0.8742. To prevent aerobic bacteria from decreasing and anaerobic bacteria from increasing, manure temperature should be kept under 15°C during aeration. To reduce odor generation potential (based on reduced VFA production), the oxidation-reduction potential should be maintained at +35 mV or higher.     

Effect of swine manure dilution on ammonia, hydrogen sulfide, carbon dioxide, and sulfur dioxide releases

Animal manure is a significant source of environmental pollution and manure dilution in barn cleaning and slurry storage is a common practice in animal agriculture. The effect of swine manure dilution on releases of four pollutant gases was studied in a 30-day experiment using eight manure reactors divided into two groups. One group was treated with swine manure of 6.71% dry matter and another with manure diluted with water to 3.73% dry matter. Ammonia release from the diluted manure was 3.32 mg min⁻¹ m⁻² and was 71.0% of the 4.67 mg min⁻¹ m⁻² from the undiluted manure (P < 0.01). Because the ammonia release reduction ratio was lower than the manure dilution ratio, dilution could increase the total ammonia emissions from swine manure, especially in lagoons with large liquid surface areas. Carbon dioxide release of 87.3 mg min⁻¹ m⁻² from the diluted manure was 56.4% of the 154.8 mg min⁻¹ m⁻² from the undiluted manure (P < 0.01). Manure dry matter was an important factor for carbon dioxide release from manure. No differences were observed between the treatments (P > 0.05) for both hydrogen sulfide and sulfur dioxide releases. Therefore, dilution could also significantly increase the total releases of hydrogen sulfide and sulfur dioxide to the environment because dilution adds to the total manure volume and usually also increases the total gas release surface area.     

Kinetics of struvite to newberyite transformation in the precipitation system MgCl2-NH4H2PO4NaOH-H2O

The influence of the initial reactant concentrations on the composition of the solid phases formed in the precipitation system MgCl(2)-NH(4)H(2)PO(4)-NaOH-H(2)O was investigated. The precipitation diagram constructed shows the approximate concentration regions within which struvite, newberyite, and their mixtures exist at 25 degrees C and an aging time of 60 min. It was found that immediately after mixing the reactant solutions, struvite (MgNH(4)PO(4).6H(2)O) precipitated in nearly the whole concentration area, while newberyite (MgHPO(4).3H(2)O) appeared mostly within the region of the excess of magnesium concentration. It was also found that after aging time of 60 min the precipitation domain of struvite alone is much broader than that of newberyite or the domain of their coexistence, and shows that struvite is more abundant in the systems in which the initial concentration of ammonium phosphate is higher than that of magnesium. The kinetics of struvite to newberyite transformation (conversion) was systematically studied under the conditions of different initial reactant concentrations and different initial pH in the systems in which a mixture of both phases precipitated spontaneously. The struvite to newberyite conversion period was found to be strongly related to the ratio of initial supersaturations, S(N)/S(S), rather than to the any particular physical quantity that can describe and predict the behavior of the precipitation system. Experimental data suggest a solution-mediated process as a most possible transformation mechanism. Along with a continuous monitoring of the changes in the liquid phase, the content of struvite in the solid phase was estimated by means of a Fourier transform infrared (FT-IR) method, developed for this particular precipitation system.     

Salinity of animal manure and potential risk of secondary soil salinization through successive manure application

To enhance animal productivity and maximize economic returns, mineral salts are routinely added to animal feed worldwide. Salinity and ionic composition of animal manure from intensive poultry and livestock farms in Guangdong province were investigated. Field experiments were conducted for six successive crops of Brassica Parachinensis to evaluate the possibility of secondary soil salinization by successive application of chicken manure (CM) and pigeon manure (PM) to a garden soil. The concentration of total soluble salts (TSS), which were mainly composed of sulfate and chloride of potassium and sodium, averaged 49.0, 20.6 and 60.3 g.kg(- 1) in chicken, pig and pigeon manure, respectively. After three crops, successive application of CM and PM increased soil concentrations of TSS, Na(+), K(+), Mg(2+), SO(4)(2-), and Cl(-) with application rate, resulting in a rise in soil salinity from low to medium levels and a slight reduction in soil pH. After heavy rains during the last three crops, soil TSS was reduced considerably and pH showed a slight increase. Concentrations of Cl(-) and Mg(2+) increased and Ca(2+) decreased at the end of the experiment, all leading to changes in the ionic composition of soil salinity. Manure with higher ion concentrations appeared to play a more important role in affecting ionic composition of soil salinity. The results further suggest that even in a region with abundant rainfall like Guangzhou, there is still potential risk for secondary soil salinization when high rates of CM and PM are applied.     

Enhancing anaerobic digestibility and phosphorus recovery of dairy manure through microwave-based thermochemical pretreatment

Anaerobic digestion and struvite precipitation are two effective ways of treating dairy manure for recovering biogas and phosphorus. Anaerobic digestion of dairy manure is commonly limited by slow fiber degradation, while struvite precipitation is limited by the availability of orthophosphate. The aim of this work is to study the possibility of using microwave-based thermochemical pretreatment to simultaneously enhance manure anaerobic digestibility (through fiber degradation) and struvite precipitation (through phosphorus solubilization). Microwave heating combined with different chemicals (NaOH, CaO, H₂SO₄, or HCl) enhanced solubilization of manure and degradation of glucan/xylan in dairy manure. However, sulfuric acid-based pretreatment resulted in a low anaerobic digestibility, probably due to the sulfur inhibition and Maillard side reaction. The pretreatments released 20-40% soluble phosphorus and 9-14% ammonium. However, CaO-based pretreatment resulted in lower orthophosphate releases and struvite precipitation efficiency as calcium interferes with phosphate to form calcium phosphate. Collectively, microwave heating combined with NaOH or HCl led to a high anaerobic digestibility and phosphorus recovery. Using these two chemicals, the performance of microwave- and conventional-heating in thermochemical pretreatment was further compared. The microwave heating resulted in a better performance in terms of COD solubilization, glucan/xylan reduction, phosphorus solubilization and anaerobic digestibility. Lastly, temperature and heating time used in microwave treatment were optimized. The optimal values of temperature and heating time were 147 °C and 25.3 min for methane production, and 135 °C and 26 min for orthophosphate release, respectively.     

Characterization of pig slurry with reference to flocculation and separation

Pig production is concentrated in large farms, increasing the need to export excess nutrients, so manure separation would be useful to concentrate the nutrients. We examined the physicochemical properties of pig manure pertinent to flocculation and separation. Manures from three farms were stored for 3 months at 13 °C. The organic pools in the manure did not vary significantly during storage, so microbial metabolism was low and storage was of minor importance to separation. The manure contained highly charged particles and surface charges did not vary between the manures. This implies that the polymer doses required for flocculation can be determined directly from the manure dry matter content and that highly charged, high-molecular-weight cationic polymers can be used. Phosphorus was mainly found in the particulate fraction as struvite and was retained in the solids fraction at high pH. Thus, pH adjustment can control the amount of dissolved phosphorus in manure.     

Phosphorus removal from a real anaerobic supernatant by struvite crystallization

In this paper the phosphorus removal from a real anaerobic supernatant through the crystallization of struvite and or hydroxyapatite was investigated. A comparison between experimental results on phosphorus crystallization carried out in a fluidized-bed reactor (FBR) on a bench-scale and on a half-scale plant is presented, together with a double saturational model able to describe all experimental results, independent of the different geometry of the reactors, the distinct contact times and the unlike products obtained. Experimental results show that removal efficiencies are very satisfactory, and the maximum phosphorus removal is of 80%.     

Heavy metal removal by clinoptilolite. An equilibrium study in multi-component systems

Ternary and quaternary ion-exchange equilibria have been studied between heavy metal solution (Pb(2+), Cd(2+), Cu(2+)) and Na-form of clinoptilolite. The value of the ion-exchange equilibrium constant was estimated using the Langmuir, Competitive Langmuir, and thermodynamic sorption models. For each isotherm, calculations were done taking into account the concentration of ions in both phases. Additionally, for the thermodynamic isotherm, two other cases were considered: activity of ions in the liquid phase and concentration in the solid phase; activity of ions in both phases. The activity coefficients of ions in the liquid phase were determined using Pitzer's model; activity coefficients in the solid phase were estimated by Wilson's model. It was found that the exchange capacity for a given M(2+) is not constant and differs in one- or multi-component systems. The results show that the equilibrium model based on the law of mass action, which considers nonideal behavior of both phases, allows one to achieve the best approach to the real multi-component equilibrium data in all studied systems.     

Measurements of N2O and CH4 from the aerated composting of food waste

Emissions of N2O and CH4 from an aerated composting system were investigated using small-scale simulated reactors. The results show relatively high emissions of N2O at the beginning of composting, in proportion to the application amount of food waste. After 2 days, the N2O emission decreased to 0.53 ppmv on average, near to the background level in the atmosphere (0.45 ppmv). The addition of composted cattle manure increased N2O emissions not only at the beginning of composting, but also during the later period and resulted in two peak emission curves. Good correlation was observed between the N2O concentration at the air outlet and NO2- concentration in waste, suggesting a generation pathway for N2O from NO2- to N2O. Methane was only detected in treatments containing composted cattle manure. The high emission of methane illustrates the involvement of anoxic/anaerobic microorganisms with the addition of composted manure. The result suggests the existence of anoxic or anaerobic microsite inside the waste particles even though ventilation was employed during the composting process.     

Innovative process scheme for removal of organic matter, phosphorus and nitrogen from pig manure

Disposal of pig manure often requires treatment with respect to environmental legislations. In this study different processes for reduction of the organic matter (anaerobic digestion, effluent separation by decanter centrifugation, membrane microfiltration, post-digestion in upflow anaerobic sludge blanket (UASB) reactor, partial oxidation), nitrogen (oxygen-limited autotrophic nitrification-denitrification, OLAND) and phosphorus (phosphorus removal by precipitation as struvite, PRS) from pig manure were tested. Results obtained showed that microfiltration was unsuitable for pig manure treatment. PRS treated effluent was negatively affecting the further processing of the pig manure in UASB, and was therefore not included in the final process flow scheme. In a final scheme (PIGMAN concept) combination of the following successive process steps was used: thermophilic anaerobic digestion with sequential separation by decanter centrifuge, post-digestion in UASB reactor, partial oxidation and finally OLAND process. This combination resulted in reduction of the total organic, nitrogen and phosphorus contents by 96%, 88%, and 81%, respectively.     

Phragmites australis: a novel biosorbent for the removal of heavy metals from aqueous solution

Reed (Phragmites australis), a commonly used macrophyte in the wetlands constructed for water purification, was investigated as a new biosorbent for the removal of Cu(2+), Cd(2+), Ni(2+), Pb(2+) and Zn(2+) from aqueous solution. The metal adsorption capacity of reed biomass was improved significantly by water-wash, base- and acid-treatment. The maximum sorption of NaOH-pretreated reed biomass was observed near neutral pH for Cu(2+), Cd(2+), Ni(2+) and Zn(2+), while that for Pb(2+) was from an acidic range of pH 4.0 or higher. The maximum metal adsorption capacity on a molar basis assumed by Langmuir model was in the order of Cu(2+)>Ni(2+)>Cd(2+)>Zn(2+)>Pb(2+). Reed biosorbent showed a very high adsorption affinity value, which helps predict its high ability to adsorb heavy metals at low concentration. Desorption of heavy metals and regeneration of the biosorbent was attained simultaneously by acid elution. Even after three cycles of adsorption-elution, the adsorption capacity was regained completely and the desorption efficiency of metal was maintained at around 90%.     

Zinc-induced antibiotic resistance in activated sludge bioreactors

Increased levels of bacterial resistance to antibiotics noted in recent decades poses a significant obstacle to the effective treatment and prevention of disease. Although overuse of antibiotics in agriculture and medicine is partially responsible, environmental exposure to heavy metals may also contribute to antibiotic resistance, even in the absence of antibiotics themselves. In this study, a series of eight lab-scale activated-sludge reactors were amended with Zn and/or a suite of three antibiotics (oxytetracycline, ciprofloxacin, and tylosin), in parallel with unamended controls. Classical spread-plating methods were used to assess resistance to these compounds in culturable bacteria over 21 weeks. After seven weeks of general acclimation and development of baseline resistance levels (phase 1), 5.0 mg/L Zn was added to half of the reactors, which were then operated for an additional 7 weeks (phase 2). For the final seven weeks (phase 3), two of the Zn-amended reactors and two of the control reactors were amended with all three antibiotics, each at 0.2 mg/L. Zn amendment alone did not significantly change resistance levels at the 95% confidence level in phase 2. However, tylosin resistance increased significantly during phase 3 in the Zn-only reactors and resistance to all three antibiotics significantly increased as a consequence of combined Zn+antibiotic amendments. Ambient dissolved Zn levels in the reactors were only 12% of added levels, indicating substantial Zn removal by adsorption and/or precipitation. These results show that sub-toxic levels of Zn can cause increased antibiotic resistance in waste treatment microbial communities at comparatively low antibiotic levels, probably due to developed cross-resistance resulting from pre-exposure to Zn.     

Modelling multiple mineral precipitation in anaerobic digester liquor

Mineral precipitation problems have been experienced with the conveyance and treatment of anaerobically digested primary and waste activated sludge blends. This paper describes an experimental investigation into mineral precipitation in anaerobic digester liquor (ADL) from the Cape Flats (CF) Wastewater Treatment Plant (WWTP) (Cape Town, South Africa), and application of the three-phase (aqueous/solid/gas) physical and chemical processes kinetic model developed by Musvoto et al. (Water Res. 34 (2000) 1857; Water Res. 34 (2000) 1868; Water SA 26(4) (2000) 417) to the experimental data. From the experimental investigation and theoretical modelling, it is concluded inter alia that: (i) there is a close correlation between experimental measured and theoretically predicted data, (ii) the dominating mineral that precipitates is struvite, with small amounts of amorphous calcium phosphate and negligible newberyite, calcite and magnesite, (iii) the precipitation of struvite is governed by the increase in pH when CO2 is lost from the ADL, (iv) the ADL is initially undersaturated with respect to struvite, but becomes supersaturated at pH > 7.3-7.7, (v) the rate and mass of struvite precipitation are controlled by the rate of pH increase and the initial Mg concentration and (vi) the three-phase kinetic model is able to simulate accurately the time dependent precipitation data for multiple minerals competing for the same species and allows determination of specific precipitation rates for a number of minerals simultaneously in an integrated manner from a single batch test. Some operational strategies to minimise struvite precipitation are proposed.     

The behaviour of pharmaceuticals and heavy metals during struvite precipitation in urine

Separating urine from wastewater at the source reduces the costs of extensive wastewater treatment. Recovering the nutrients from urine and reusing them for agricultural purposes adds resource saving to the benefits. Phosphate can be recovered in the form of struvite (magnesium ammonium phosphate). In this paper, the behaviour of pharmaceuticals and heavy metals during the precipitation of struvite in urine is studied.When precipitating struvite in urine spiked with hormones and non-ionic, acidic and basic pharmaceuticals, the hormones and pharmaceuticals remain in solution for more than 98%.For heavy metals, initial experiments were performed to study metal solubility in urine. Solubility is shown to be affected by the chemical conditions of stored and therefore hydrolysed urine. Thermodynamic modelling reveals low or very low equilibrium solute concentrations for cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), nickel (Ni) and lead (Pb). Experiments confirmed Cd, Cu and Pb carbonate and hydroxide precipitation upon metal addition in stored urine with a reaction half-life of ca. 7 days.For all metals considered, the maximum specific metal concentrations per gram phosphate or nitrogen showed to be typically several orders of magnitudes lower in urine than in commercially available fertilizers and manure. Heavy metals in struvite precipitated from normal stored urine could not be detected.Phosphate recovery from urine over struvite precipitation is shown to render a product free from most organic micropollutants and containing only a fraction of the already low amounts of heavy metals in urine.     

Nitrogen and water recovery from animal slurries by a new integrated ultrafiltration,reverse osmosis and cold stripping process: A case study

The correct management of livestock manure represents one of the major challenge for the agricultural sector development, as it may ensure environmental and economic sustainability of livestock farming. In this work, a new treatment process called N-Free^®, was monitored on two plants treating digested cattle manure (DCM) and digested swine manure (DSM). The process is characterized by sequential integration of solid/liquid separations, ultrafiltration, reverse osmosis and cold ammonia stripping. Solid and liquid streams were characterized regarding TS, TKN, N–NH₄⁺, P and K content allowing to draw a complete mass balance. The main results were a substantial reduction of initial digestate volume (38 and 51% in DCM and DSM respectively) as clean water and a high N–NH₄⁺ removal percentage (47 and 71% in DCM and DSM respectively), through cold ammonia stripping, allowing the production of up to 1.8 m³ concentrated ammonium sulfate, every 100 m³ of treated digestate. The concentrated streams, rich in either organic or mineral N, P and K, can be efficiently used for land application. The N-Free^® technology demonstrated to be a valuable candidate for the path toward nutrient and water recycle, in a new sustainable agriculture and farming concept.     

Metal supplementation to UASB bioreactors: from cell-metal interactions to full-scale application

Upflow anaerobic sludge bed (UASB) bioreactors are commonly used for anaerobic wastewater treatment. Trace metals need to be dosed to these bioreactors to maintain microbial metabolism and growth. The dosing needs to balance the supply of a minimum amount of micronutrients to support a desired microbial activity or growth rate with a maximum level of micronutrient supply above which the trace metals become inhibitory or toxic. In studies on granular sludge reactors, the required micronutrients are undefined and different metal formulations with differences in composition, concentration and species are used. Moreover, an appropriate quantification of the required nutrient dosing and suitable ranges during the entire operational period has been given little attention. This review summarizes the state-of-the-art knowledge of the interactions between trace metals and cells growing in anaerobic granules, which is the main type of biomass retention in anaerobic wastewater treatment reactors. The impact of trace metal limitation as well as overdosing (toxicity) on the biomass is overviewed and the consequences for reactor performance are detailed. Special attention is given to the influence of metal speciation in the liquid and solid phase on bioavailability. The currently used methods for trace metal dosing into wastewater treatment reactors are overviewed and ways of optimization are suggested.     

Evaluation of heavy metal removal from aqueous solution onto scolecite

Scolecite is a zeolite associated to basalts of the Parana Continental Igneous Province (PCIP South America). The potential of scolecite as a new material for heavy metal removal (Pb2+ Cu2+, Zn2+, Ni2+, Co2+ and Cd2+) from aqueous solutions is evaluated. The experiments were carried out by immersion of 0.5 g of sample in solutions containing the metal ions, and kept under constant agitation for 24h, at ambient temperature. The meq of cations retained per mass of scolecite was evaluated as a function of: initial concentration (5-60 mg L(-1)), pH (4-6), liquid/solid ratio (200, 1000 and 2000) and particle size. The results indicated a great affinity of scolecite for Cu2+ with a retention value of 130 microeq g(-1) at pH 6, Ci = 30 mg L(-1) and liquid/solid ratio of 200. In the same conditions, the maximum retention measured for the other ions were 64 microeq g(-1) (Zn2+), 56 microeq g(-1) (Pb2+), 31 microeq g(-1) (Ni2+), 7.8 microeq g(-1) (Co2+) and 3.2 microeq g(-1) (Cd2+). These values increase substantially when the L/S ratio is increased. The affinity of copper and lead for scolecite is discussed based on their free ionic forms (i.e., their hydrated bivalent ions) and their hydrolysis products. The remaining ions are retained as free ions.