9 urine treatment methods (maurer water research paper, 2006)

16
 Available at www.sciencedirect.com  jo ur na l ho me pa ge : ww w. el se vi er .com /l oc at e/ wa tr es Review Treatment processes for source-separated urine M. Maurer , W. Pronk, T.A. Larsen Swiss Federal Institute for Aquatic Science and Technology (Eawag), 8600 Du ¨ bendorf, Switzerland a r t i c l e i n f o Article history: Received 20 December 2005 Received in revised form 7 July 2006 Accepted 11 July 2006 Available online 1 September 2006 Keywords: Urine treatment Process engineering Wastewater Source separation Sustainable wastewater treatment Struvite P-recovery N-recovery A B S T R A C T The separate collection and treatment of urine has attracted considerable attention in the enginee ring community in the last few years and is seen as a viable option for enhanci ng the exibility of wastewater treatment systems. This comprehensive review focuses on the status of current urine treatment processes and summarises the properties of collected uri ne. We distin gui sh bet wee n sev en mai n pur pos es of uri ne- tre atment proces ses: hygien isati on (stora ge), volume reduc tion (evapo ratio n, freeze- thaw , revers e osmos is), stabilisation (acidication, nitrication), P-recovery (struvite formation), N-recovery (ion- excha nge, ammon ia strippi ng, isobu tylald ehyde-d iurea (IBDU) precip itatio n), nutri ent remo val (anammox) and handli ng of micro pollutants (elec trodia lysis, nanol tratio n, ozonation). The review shows clearly that a wide range of technical options is available to treat collected urine effectively, but that none of these single options can accomplish all seven purposes. Depending on the overall goal of the treatment process, a specic technical solution or a combination of solutions can be found to meet the requirements. Such combinations are not discussed in this paper unless they are explicitly presented in the litera ture . Except for ‘evaporation’ and ‘stora ge’, none of the processes described have so far advanced beyond the laboratory stage. Considerable development work remains to be done to optimise urine-processing techniques in order to create marketable products. & 2006 Elsevier Ltd. All rights reserved. Contents 1. Introducti on . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3152 2. Composi tion of ur ine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3152 3. Tre at ment units. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3153 3. 1. Hygienisati on . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3155 3.1.1. Intr oduct ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3155 3.1.2. St or age . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3155 3. 2. Vol ume re duction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3156 3.2.1. Intr oduct ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3156 3.2.2. Ev apor ation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3156 3.2.3. Fr eeze -th aw . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3157 3.2.4. Re ve rse osmosis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3157 AR TIC LE IN PR ESS 0043-13 54/$ - see front ma tter &  2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.watres.2006.07.012 Corresponding author. Te l.: +411 8235386. E-mail address: [email protected] (M. Maurer). WAT ER RESEAR CH  40 (2006) 3151– 3166

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Urine Treatment Methods

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  • Available at www.sciencedirect.com

    Review

    M. Maurer , W. Pronk, T.A. Larsen

    8600 Dubendorf, Switzerland

    Article history:

    3152

    3153

    3155

    3.2.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3156

    ARTICLE IN PRESS

    WAT E R R E S E A R C H 40 ( 2006 ) 3151 3166Corresponding author. Tel.: +41 1 8235386.3.2.2. Evaporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3156

    3.2.3. Freeze-thaw . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3157

    3.2.4. Reverse osmosis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3157

    0043-1354/$ - see front matter & 2006 Elsevier Ltd. All rights reserved.doi:10.1016/j.watres.2006.07.012

    E-mail address: [email protected] (M. Maurer).3.1.1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3155

    3.1.2. Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3155

    3.2. Volume reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31562. Composition of urine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

    3. Treatment units. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

    3.1. Hygienisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Contents

    1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3152Received 20 December 2005

    Received in revised form

    7 July 2006

    Accepted 11 July 2006

    Available online 1 September 2006

    Keywords:

    Urine treatment

    Process engineering

    Wastewater

    Source separation

    Sustainable wastewater treatment

    Struvite

    P-recovery

    N-recoveryThe separate collection and treatment of urine has attracted considerable attention in the

    engineering community in the last few years and is seen as a viable option for enhancing

    the flexibility of wastewater treatment systems. This comprehensive review focuses on the

    status of current urine treatment processes and summarises the properties of collected

    urine. We distinguish between seven main purposes of urine-treatment processes:

    hygienisation (storage), volume reduction (evaporation, freeze-thaw, reverse osmosis),

    stabilisation (acidification, nitrification), P-recovery (struvite formation), N-recovery (ion-

    exchange, ammonia stripping, isobutylaldehyde-diurea (IBDU) precipitation), nutrient

    removal (anammox) and handling of micropollutants (electrodialysis, nanofiltration,

    ozonation). The review shows clearly that a wide range of technical options is available

    to treat collected urine effectively, but that none of these single options can accomplish all

    seven purposes. Depending on the overall goal of the treatment process, a specific technical

    solution or a combination of solutions can be found to meet the requirements. Such

    combinations are not discussed in this paper unless they are explicitly presented in the

    literature. Except for evaporation and storage, none of the processes described have so

    far advanced beyond the laboratory stage. Considerable development work remains to be

    done to optimise urine-processing techniques in order to create marketable products.

    & 2006 Elsevier Ltd. All rights reserved.a r t i c l e i n f o A B S T R A C TSwiss Federal Institute for Aquatic Science and Technology (Eawag),Treatment processes for source-separated urine

    journal homepage: www.elsevier.com/locate/watres

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    ion

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    less than one percent of the total wastewater volume.

    (Wilsenach

    Urine-sou

    leaves many

    me

    org

    lism (Esche

    wa

    ing

    2006; Medila

    flexibility a

    prototypic w

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    in this pap

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    household t

    with todays

    lon

    pro

    T

    sep

    and Gujer (1996) suggested local storage and transport in

    ARTICLE IN PRESS

    ( 2g it would take a market economy to develop smart mass-

    duced technology to do exactly that at competitive costs.

    A large amount of data for urine is available in the medical

    literature. Urine from collection systems differs from thesehere are

    aration otreatment is seldom discussed. As an example,

    reatment of urine seems inefficient and expensive

    technology, but nobody has really examined how

    2. Composition of urineycling, but the potential of mass-producing goods for

    stewatery the many different treatment options discussed

    er, ranging from nutrient removal to nutrienttions (e.g. manned space flights) as well as on experience in

    the treatment of other high-strength liquid waste products.ced market goods (Larsen and Gujer, 2001). Flexibility is well

    strated bexperience gained with urine treatment in different situa-r-scarce cities in emerging countries (Huang et al.,

    nski et al., 2006). Furthermore, it offers increased

    nd a possible shift away from investments in

    astewater treatment plants towards mass-pro-

    in agriculture is the most obvious application, but industrial

    usage or simple nutrient removal are other possible options.

    In this paper, we give an overview of the available technol-

    ogies for treating source-separated urine, drawing on thestewater management when applied in the rapidly expand-

    andwateand van Wijk-Sijbesma, 2005), the use of urine as a fertilizerropollutants originating from the human metabo-

    r et al., 2006) and new ways of more efficientBecause the composition of urine reflects the average

    requirement of nutrients for plant growth (Heinonen-Tanskintioned above, it also promises better ways of removing

    anic micengineering options.tion, denitrification and phosphorus elimination

    and Van Loosdrecht, 2004).

    rce separation presents many advantages, but also

    open questions. Besides the obvious advantages

    Frohlich, 2002) and finally, on-site treatment may be possible

    in the future, provided that the technical difficulties can be

    overcome (Wilsenach et al., subm.). In the present paper, we

    concentrate on the possibilities and difficulties of the processSubstantial separation of urine at source would thus allow

    nutrient recycling from a concentrated nutrient solution and

    at the same time obviate advanced nutrient removal, includ-

    ing nitrifica

    sewers over night; the concept developed in Sweden is long-

    term local storage followed by truck transport (Hanaeus et al.,

    1997); in some pilot projects, multiple piping is tested (Peter-3.3. Stabilisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

    3.3.1. Introduction . . . . . . . . . . . . . . . . . . . . . . .

    3.3.2. Acidification . . . . . . . . . . . . . . . . . . . . . . .

    3.3.3. Partial nutrification . . . . . . . . . . . . . . . . .

    3.4. P-recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

    3.4.1. Introduction . . . . . . . . . . . . . . . . . . . . . . .

    3.4.2. Struvite (MgNH4PO4) . . . . . . . . . . . . . . . . .

    3.5. N-recovery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

    3.5.1. Introduction . . . . . . . . . . . . . . . . . . . . . . .

    3.5.2. Ion exchange . . . . . . . . . . . . . . . . . . . . . .

    3.5.3. Ammonia stripping . . . . . . . . . . . . . . . . .

    3.5.4. Isobutylaldehyde-diurea (IBDU) precipitat

    3.6. Nutrient removal (P and N) . . . . . . . . . . . . . . . . .

    3.6.1. Introduction . . . . . . . . . . . . . . . . . . . . . . .

    3.6.2. Anammox Process . . . . . . . . . . . . . . . . . .

    3.7. Removal of micropollutants . . . . . . . . . . . . . . . . .

    3.7.1. Introduction . . . . . . . . . . . . . . . . . . . . . . .

    3.7.2. Electrodialysis. . . . . . . . . . . . . . . . . . . . . .

    3.7.3. Nanofiltration . . . . . . . . . . . . . . . . . . . . . .

    3.7.4. Ozonation and advanced oxidation . . . . .

    4. Conclusions and outlook. . . . . . . . . . . . . . . . . . . . . . . . .

    Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

    References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

    1. Introduction

    In the 1990s, various European groups began working on the

    same basic idea that separating urine at source could

    promote the sustainability of wastewater management

    (Kirchmann and Pettersson, 1995; Larsen and Gujer, 1996).

    All these approaches are based on the fact that urine contains

    most of the nutrients in domestic wastewater but makes up

    WAT E R R E S E A R C H 403152also many challenges in connection with source

    f urine. Once urine has left the body it becomes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3158

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3159

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3159

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3159

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3159

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3160

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3160

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3160

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3160

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3160

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3161

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3161

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3161

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3161

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3162

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3162

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3163

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3163

    an unpleasant, smelly and unstable solution. It is locally

    produced and the present practise of dilution with large

    amounts of water is actually a perfect way of neutralising

    many of the more unpleasant aspects of urine. Furthermore,

    centralized wastewater management is a system with inter-

    dependent actors, and changing even a small part of it is

    extremely difficult (Larsen and Lienert, 2003). Finally, the

    question of transportation has not yet been solved. Larsen. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3157

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3157

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3157

    . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3158

    006 ) 3151 3166data, because (a) the composition is averaged over time and

    user group, (b) chemical alteration occurs in a non-sterile

  • ARTICLE IN PRESS

    ste

    kpl

    H [2 CH S CH urine

    .26

    9.0

    793

    720

    76

    650

    770

    98

    837

    400

    28

    1.0

    ted

    mn

    ita

    ), [6

    (2environment, and (c) dilution with flushing water adds

    elements such as calcium and magnesium that can further

    alter the composition.

    The composition of stored urine from different collection

    Table 1 Concentration of urine from different collection sy

    Parameter Unit

    Source Household

    S [1]School S [1] Wor

    C

    Dilution[a] () 0.33 0.33 0

    pH () 9.0 8.9

    Ntot (gNm3) 1795 2610 1

    NH4++NH3 (gNm

    3) 1691 2499 1

    NO3+NO2

    (gNm3) 0.06 0.07

    Ptot (gPm3) 210 200

    COD gO2 m3 1

    K (gKm3) 875 1150

    S (gSm3) 225 175

    Na (gNam3) 982 938

    Cl (gClm3) 2500 2235 1

    Ca (gCam3) 15.75 13.34

    Mg (gMgm3) 1.63 1.50

    Mn (gMnm3) 0 0

    B (gBm3) 0.435 0.440

    The dilution[a] by the flushing water of the collection systems is extrac

    urine composition of fresh urine (non hydrolysed) is listed in colu

    (SO42S), [c]: value measured in undiluted, fresh urine, without precip

    Ronteltap et al. (2003), [4]: Jonsson et al. (1997), [5]: Udert et al. (2005a

    WATER RESEARCH 40systems is listed in Table 1. Data from a medical source (Ciba-

    Geigy, 1977; last column) is given as a comparison for fresh

    urine. During storage under non-sterile conditions, the urea

    present in urine is hydrolysed to ammonia/ammonium and

    carbonate due to microbial activity. This causes a pH increase

    from around 6 to around 9 and triggers the precipitation of

    calcium and magnesium in form of carbonates and phos-

    phates (Udert et al., 2003a/b). This is clearly visible in the low

    Ca and Mg concentrations in the stored urine. Depending on

    the urine collection system, more or less flushing water is

    present in the collected liquid. This water dilutes the overall

    concentration of the substances and is considered in Table 1

    with a dilution factor that expresses the fraction of undiluted

    urine in the collection tank. Only the composition from

    reference [5] in Table 1 presents concentrations from un-

    diluted urine and therefore deviates substantially from all the

    other concentrations.

    The heavy metal content in urine is generally low (Kirch-

    mann and Pettersson, 1995; Jonsson et al., 1997; Ciba-Geigy,

    1977). Specific concentrations, i.e. relative to phosphorus or

    nitrogen, are relevant if we want to use urine or products

    derived from it as fertiliser. The comparison with commercial

    fertilizer shows clearly that urine is always at the low or very

    low end compared to commercially available fertilizer or

    manure. Phosphate fertiliser in particular can have a high

    heavy-metal content depending on the rock phosphate used.

    Thus, analyses performed by Rogowski et al. (1999) and

    McBride and Spiers (2001) show that agricultural bulk

    fertilizers can have cadmium concentrations of up to36gCd kgP1, which are several magnitudes higher than those

    of typical urine.

    An important excretion pathway for hormones and many

    pharmaceuticals is via urine. This is actively prepared in the

    ? 0.75 1 1

    9.0 9.1 9.1 6.2

    3631 9200 8830

    4347 3576 8100 463

    o0.1 0 154 313 540 8002000

    6000 10000

    3284 1000 2200 2737

    273[b] 331 505[b] 1315

    1495 1210 2600 3450

    2112 1768 3800 4970

    18 0 233

    11.1 0 119

    0.037 0.019

    0.97

    from the information given by the publications. For comparison, the

    [6].Legend: [a]: defined as Vurine/(Vurine+Vwater), [b]: only sulfateStion, [1]: Kirchmann and Pettersson (1995), [2]: Udert et al. (2003a), [3]:

    ]: Ciba-Geigy (1977).ms

    Concentration

    ace]

    Workplace[3]

    Household[4]

    Workplace[5]

    Fresh[6],[c]

    006) 3151 3166 3153liver by enhancing the water solubility of organic substances

    adsorbed, so that they can be removed in the kidneys and

    excreted via the urine (e.g. Ritschel and Kearns, 1999). Urine

    might therefore contain a majority of the dissolved micro-

    pollutants excreted by humans and due to their mobility also

    the one most prone to transport and relevant for aquatic

    ecosystems. However, it has to be emphasised that so far

    there are no systematic evaluation of the medical literature

    published that would back up this point statistically. Excep-

    tions are estrogens, where 80% of the natural estrogens and

    67% of the artificial hormone 17a-ethinyl estradiol areexcreted via urine (review in Christiansen et al., 2002).

    Recent research indicates that the toxic effects of pharma-

    ceuticals are additive. Silva et al. (2002) made it very clear that

    in complex mixtures, such as wastewater or urine, threshold

    values are very difficult to set. Escher et al. (2002 & 2005)

    showed that the toxic effect of a mix of pharmaceuticals,

    each without any specific mode of toxicity (baseline toxicity),

    can be estimated by adding up the toxic effects of the single

    substances.

    3. Treatment units

    The unique properties of urine mean that a wide variety of

    technologies may be used to treat it. We defined seven main

    purposes of a treatment unit: volume reduction, P-recovery,

    N-recovery, stabilisation, hygienisation, removal of micropol-

    lutants and biological nutrient removal. For practical

  • ARTICLE IN PRESS

    Ta

    ble

    2

    Overv

    iew

    of

    the

    treatm

    en

    tm

    eth

    od

    sd

    iscu

    ssed

    inth

    ep

    ap

    er

    Hygiene

    Vol.

    reduction

    Stabilisation

    P-recovery

    N-

    recovery

    MP

    elimination

    NutrientMP

    separation

    Nutrient

    elimination

    Solidification

    Needofpre/post-

    treatm

    ent

    Info

    literature

    Hygienisation

    Storage

    +o

    oo

    oo

    oo

    (+)

    -+

    Volumereduction

    Evaporation

    +++

    +++

    ++

    oo

    o++

    +o

    Freeze-thaw

    ?+

    o++

    ++

    oo

    oo

    o+

    Reverseosm

    osis

    ?+

    o++

    ++

    oo

    oo

    ++

    Stabilisation

    Acidification

    +o

    ++

    oo

    ?o

    oo

    o+

    Microfiltration

    +o

    ++

    oo

    oo

    oo

    o+

    Nitrification

    +o

    ++

    oo

    ?o

    o(+)

    o+

    P-recovery

    Struvite

    o++

    +++

    +o

    ++

    o++

    o++

    N-recovery

    Ionexch

    ange

    o+

    oo

    ++

    o+

    o++

    o+

    Struvite

    o++

    +++

    ++

    o++

    o++

    o++

    NH3stripping

    o+

    oo

    ++

    o++

    oo

    o+

    Isobutylaldehyde-

    diurea

    o+

    oo

    ++

    o+

    o+

    o+

    Nutrientremoval

    Anammox

    +o

    ++

    oo

    ?+

    ++

    (+)

    +++

    Others

    +o

    +(+)

    o?

    o+

    (+)

    (+)

    +

    Micropollutionremoval

    Electrodialysis

    ++

    ++

    ++

    o+

    oo

    o+

    Nanofiltration

    ++

    o+

    oo

    o++

    oo

    ++

    Ozo

    nation

    +o

    +o

    o++

    oo

    oo

    +

    Thecolumnsrepresentthegoals

    thatcanbeach

    ievedwithasp

    ecificprocess;therowslist

    thetech

    nologicalprocess.Legend:o:noeffect,+:positiveeffect,++:strongeffect,:

    notapplicable.

    WAT E R R E S E A R C H 40 ( 2006 ) 3151 31663154

  • ARTICLE IN PRESS

    cri

    Fig

    (2Fig. 1 General template for the des

    Fig. 2 Storage (seeWATER RESEARCH 40purposes, each treatment unit is assigned one of these seven

    main purposes and is discussed under the corresponding

    section. The assignment is somewhat arbitrary, because most

    treatments attain several goals and other purposes might

    have prevailed depending on the priorities set by the

    evaluator. Table 2 gives an overview of the treatment methods

    discussed in the paper. The efficiencies for specific goals

    (columns) are roughly characterised. In order to achieve a

    specific treatment target, it may be necessary to combine

    several unit operations. For reasons of brevity, such combina-

    tions are not discussed here unless they are explicitly

    presented in the literature.

    Each urine treatment process is roughly summarized in a

    little scheme (Figs. 214). A general explanation of these

    schemes is given in Fig. 1.

    3.1. Hygienisation

    3.1.1. IntroductionUrine from unhealthy humans may contain pathogenic

    organisms (Santos et al., 2004; Vanchiere et al., 2005) as well

    as prions (Reichl, 2002). Furthermore, faecal contamination

    can result in high counts of faecal indicator organisms

    (Hoglund et al., 2002b). Schonning et al. (2002) estimated a

    faecal contamination of 9.175.6mg lurine1 in the urine collec-

    tion system that they investigated. Although the exposition

    pathways and effects associated with these pathogens have

    not been investigated in detail, hygienic risks associated with

    source-separated urine have to be avoided.. 1 for explanation).ption of urine treatment processes.

    006) 3151 3166 3155Technically, there are many ways of pasteurising or

    sterilising any solution (heat, pressure, UV, etc.), but none of

    these methods have been tested for urine. Only storage has

    been explicitly investigated for its ability to reduce the

    amount of pathogens in source-separated urine, although

    many of the treatment steps discussed in this paper are

    expected to have an influence on its hygienic properties

    (see Table 2).

    3.1.2. StorageStorage (Fig. 2) offers a possible way of reducing the potential

    health risks from faecal pathogens (See Fig. 1 for explana-

    tion). Three storage parameters influence this process:

    storage time, temperature and pH. Hoglund et al. (1998,

    1999, 2000, 2002a/b) investigated the decay rates of bacterial

    and viral indicator organisms in stored urine collected from

    households. From the inactivation curves for rhesus rota-

    virus, Campylobacter jejuni and Cryptosporidium parvum, the

    authors concluded that if stored at 20 1C for at least 6

    months, urine may be considered safe to use as a fertilizer for

    any crop (Hoglund et al., 2002b). Their experiments showed

    that temperature was the most crucial parameter influencing

    the inactivation rates. Without pH control (pH49), 90% of the

    rhesus rotavirus were inactivated after 35 days at 20 1C, but no

    significant decrease could be detected at 4 1C. Combined with

    pH control (see Fig. 3), pH values below 4 seem to result in

    additional reduction in the number of pathogens (Hellstrom,

    1999). Important side-effects of storing raw source-separated

    urine are the precipitation of phosphorus compounds (Udert

  • ARTICLE IN PRESS

    e F

    e Fig.

    ( 231Fig. 3 Evaporation (se

    Fig. 4 Freeze-thaw (seet

    tha

    3.2

    3.2Fro

    con

    wo

    tio

    ha

    spa

    3.2Ev

    rem

    the

    Th

    ap

    su

    WAT E R R E S E A R C H 4056al., 2003b) and possible evaporation of ammonia from tanks

    t are not sufficiently sealed (Udert et al., 2005a).

    . Volume reduction

    .1. Introductionm the perspective of commercial fertilisers, the nutrient

    tent in urine is small: N: 0.9%, P: 0.06%, K: 0.3% (Table 1). It

    uld be beneficial to concentrate the nutrients for transporta-

    n and storage purposes. Various water extraction techniques

    ve been investigated and developed for long-term manned

    ce flights (seeWieland, 1994 for an overview and references).

    .2. Evaporationaporation is the most straightforward technology for

    oving water from urine (Fig. 3). For space applications,

    focus is on recycling water of the best possible quality.

    e following list gives a condensed overview of the

    proaches reported in the literature. Most of them are

    mmarised and referenced in Wieland (1994):

    Vapour compression distillation (VCD) recovers more than

    96% of the water content and the energy requirement for a

    T

    los

    can

    tio

    by

    us

    sp

    Fig. 5 Reverse osmosis (see F1 for explanation).1 for explanation).ig.006 ) 3151 3166small-scale unit is 277396MJm3. NASA plans to install

    this unit for processing urine in the international space

    station in 2005.

    Thermoelectric integrated membrane evaporation sys-

    tems (TIMES). The urine is pre-treated with ozone (or

    ideally UV) and sulphuric acid. It is then heated, pumped

    through hollow fibre membranes and exposed to reduced

    pressure so that it evaporates.

    Air evaporation systems (AES). Pre-treated urine is

    pumped through a particulate filter to a wick package.

    Heated air is used to evaporate the water from the wick,

    leaving the solids.

    Lyophilization (Holland et al., 1992). Frozen urine sub-

    limates under vacuum and is recovered at 90 1C toproduce ice with a total solid content of 51mgTSl

    1.

    he evaporation of urine presents two major challenges: (i)

    s of ammonia and (ii) energy consumption. Ammonia loss

    be avoided by using non-hydrolysed urine or by acidifica-

    n (see below). The energy consumption can be minimised

    energy recovery. Large-scale thermal desalination plants

    e vapour compression distillation (VCD) and can reach

    ecific energy requirements of 150180MJm3 distiled water

    ig. 1 for explanation).

  • (Wood, 1982) compared to 2600MJm3 without any energy

    recovery. The small-scale space VCD system for about four

    adults requires less than 400MJm3, which is equivalent to an

    energy recovery of 85%.

    In our own laboratory-scale experiments (Mayer, 2002),

    non-hydrolysed urine was evaporated at 200mbar and 78 1C.

    A tenfold volume reduction was possible without any crystal-

    lisation problems, producing a viscous liquid that contained

    2000). The required dosages of these agents must be

    determined experimentally as a function of the concentration

    factor.

    3.3. Stabilisation

    3.3.1. Introduction

    3.3.2. Acidification

    ARTICLE IN PRESS

    WATER RESEARCH 40 (2006) 3151 3166 31579.7% nitrogen by weight.

    3.2.3. Freeze-thawLind et al. (2001) showed that by freezing urine at a

    temperature of 14 1C, approximately 80% of the nutrientscan be concentrated in 25% of the original volume (Fig. 4).

    Gulyas et al. (2004) confirmed these results by using falling-

    film and stirred-vessel freeze concentrators. Using data from

    commercial freeze concentrators, they calculated an energy

    consumption of 1100MJm3 for a fivefold volume reduction.

    These data indicate that evaporation is more efficient with

    respect to energy efficiency and that the freeze-thaw process

    will be an option only in places with cheap freezing energy

    (a cold climate).

    3.2.4. Reverse osmosisIn reverse osmosis membranes, the retention of ammonium

    is better than its uncharged form (ammonia) and therefore

    the retention performance depends strongly on the pH (Fig. 5).

    Dalhammar (1997) acidified stored urine to pH 7.1 in order to

    prevent permeation of ammonia. At a pressure of 50bar, a

    maximum concentration factor of 5 could be achieved,

    resulting in the following recoveries of nutrients in the

    retentate: ammonium: 70%; phosphate: 73%; potassium:

    71%. Similar results were achieved by Thorneby et al. (1999)

    in reducing the volume of manure with reverse osmosis.

    Fluxes in the range of 2025 lm2h1 could be obtained at

    30bar (25 1C). The retention was greater than 98%, except for

    ammonia, which was between 93% and 97%. Reverse osmosis

    membranes have a high retention for micropollutants (Hof-

    man et al., 1997) so that no separation between nutrients and

    micropollutants can be expected in this process. The energy

    consumption depends on operational and technical para-

    meters and energy recovery systems can be installed in large-

    scale applications (Avlonitis et al., 2003).

    A limiting factor for the application may be the precipita-

    tion of salts on or in the membrane, a phenomenon known as

    scaling (Migliorini and Luzzo, 2004). In order to control

    scaling, chemical formulations based on acids, surfactants or

    combinations of both can be added (Jaffer, 1994; Al-Rammah,Fig. 6 Acidification (see FA way of preventing urea hydrolysis is to keep the pH in the

    collection tank below 4 (Hellstrom, 1999). Experiments

    showed that 60mmolH l1urine of a strong acid (e.g. 2:9g l

    1urine

    of concentrated sulphuric acid) successfully keeps the pH

    below 4 for more then 250 days and prevents hydrolysis of

    urea (Fig. 6).

    The side effects of acidification are positive with respect to

    hygiene due to detrimental effects on pathogenic organisms

    at pH values below 4 (Hellstrom, 1999). Low pH values can also

    have an impact on pharmaceuticals present in the urine. At

    pH 2, an inactivation level of between 50% and 95% could be

    found for antibiotics (sulfamethazin, sulfamethoxazol, tetra-

    cyclin) and the anti-inflammatory drug diclofenac (Butzen et

    al., 2005).

    The prevention of urine hydrolysis is muchmore economic-

    al than subsequent neutralisation. The neutralisation of

    already hydrolysed urine requires 230mmolH l1urine (e.g.11:3g l1urine of concentrated sulphuric acid), approximatelyfour times more than preventive acid addition.Fresh urine contains salts, soluble organic matter and

    ammonia bound in urea (Table 1). After microbial contamina-

    tion, organic matter is degraded and urea hydrolysed.

    Hydrolysis of urea releases ammonia and causes a pH

    increase to about 9.2, resulting in more volatile NH3 and

    precipitation of compounds with low solubility. True stabili-

    sation of urine would thus prevent (i) degradation of organic

    matter (causing odour), (ii) precipitation processes (clogging

    pipes) and (iii) volatilisation of NH3 (with a number of

    negative effects on air quality during storage, transport and

    application of liquid fertilizer). Since microbial activity

    triggers all these processes, prevention of microbial growth

    would be the ultimate stabilisation process. Acidification,

    microfiltration and ultrafiltration have been suggested to

    achieve this, but only acidification has been studied in detail.

    Information is available from the literature on urease

    inhibitors to prevent urea hydrolysis, but Benini et al. (1999)

    found that the reported efficiencies are low and negative side

    effects have to be considered.ig. 1 for explanation).

  • ARTICLE IN PRESS

    4) (s

    (s

    ( 23.3.3. Partial nutrificationNitrification is a suitable method for lowering the pH. Since

    no other relevant buffers are present in urine in significant

    concentrations, nitrification of urine can only oxidise half the

    available ammonium until nitrification stops due to low pH

    conditions. High nitrite concentrations and low pH have a

    specific detrimental effect on nitrite oxidisers, due to their

    sensitivity to nitrous oxide (e.g. Hunik et al., 1993). Complete

    Fig. 8 Struvite (MgNH4PO

    Fig. 7 Partial nitrification

    WAT E R R E S E A R C H 403158conversion of ammonia to nitrite is therefore often inhibited,

    depending on the operational conditions. Experimental

    results by Johansson and Hellstrom (1999) and Udert et al.

    (2003c) confirm that the product of urine nitrification is either

    an ammonium-nitrate or ammonium-nitrite solution with an

    approximate 1:1 composition (Fig. 7).

    Due to high concentrations in urine (mainly of salt,

    ammonia and nitrous acid, see Udert et al., 2003c for a

    detailed discussion), inhibition affects nitrification andmakes

    a continuously operated technical process sensitive to

    instabilities. A more detailed overview of the nitrifier kinetics

    can be found in Hellinga et al. (1999) and Van Hulle (2005). An

    attractive alternative for converting nitrite to nitrate is by

    chemical oxidation with oxygen at low pH values (Udert et al.,

    2005b).

    Udert et al. (2003c) operated three continuous laboratory

    systems: A moving-bed biological reactor (MBBR), a sequen-

    cing batch reactor (SBR) and a continuously stirred reactor

    (CSTR). Only the MBBR system was capable of producing

    ammonium nitrate as a final product. The measured conver-

    sion rates were 380gNm3 d1 (25.3 1C) at steady state. The

    other two systems produced stable ammonium nitrite even at

    high sludge ages or hydraulic residence times respectively.

    The measured nitrite formation rates were 790gNm3 d1

    (30 1C; HRT 4.8d) for the CSTR and 280gNm3 d1 (24.5 1C;HRT 4d; SRT430d) for the SBR. Because the inhibitionkinetics are not yet fully understood, it is important forpractical purposes to monitor the nitrification process care-

    fully. This can easily be done in technical systems by feeding

    the system in such a way that the pH does not get too high or

    too low. The product of these efforts is a stable solution

    without the typical urine smell and with no easily degradable

    substances.

    3.4. P-recovery

    ee Fig. 1 for explanation).

    ee Fig. 1 for explanation).

    006 ) 3151 31663.4.1. IntroductionPhosphate is produced from phosphate rock, a limited

    resource. The estimated worldwide reserves range from 1.2

    to 5 1010 tons, which would suffice for 50300 years (Steenand Steen, 1998; results also in Driver et al., 1999; Zapata and

    Roy, 2005), depending on the assumed consumption scenario.

    At the moment, the depletion of phosphorus reserves is less

    of a concern than the decrease in their quality (and therefore

    increase in price) and the strategic considerations of the

    worlds phosphorus producers. If no new sources of high-

    quality phosphate are identified, future phosphorus reserves

    will contain less phosphate and higher levels of enrichment

    by heavy metals, principally cadmium (Driver et al., 1999;

    Smil, 2000; Isherwood, 2000).

    Extensive reviews of phosphorus removal and recovery

    technologies from liquid wastes are given in Brett et al. (1997),

    Wilsenach and Van Loosdrecht (2002), Valsami-Jones (2004),

    and De-Bashan and Bashan (2004). Many of the processes

    described, especially those for the treatment of digester

    supernatant, are also applicable to urine.

    In the literature on phosphate recovery, precipitation of

    struvite seems to be the predominant product, followed by

    calcium phosphate. Udert et al. (2003b) investigated scales in

    urine collection systems and reported struvite, calcium

    phosphate (hydroxyapatite) and calcite as the predominant

    forms of precipitation. Despite the many P-recovery options,

  • known as struvite, MAP or AMP, is an attractive precipitate

    ARTICLE IN PRESS

    ee

    g (

    (2because it conveys two dominant wastewater nutrients in

    solid form (Fig. 8). Additionally, the product can be used as a

    slow-release fertiliser (Bridger et al., 1961; Johnston andonly struvite precipitation can be found in the literature on

    P-recovery from urine.

    3.4.2. Struvite (MgNH4PO4)Magnesium ammonium phosphate (MgNH4PO4 6H2O), also

    Fig. 9 Ion exchange (s

    Fig. 10 Ammonia strippin

    WATER RESEARCH 40Richards, 2003). Gaterell et al. (2000) suggest the conversion

    of struvite into an enhanced struvite that contains two parts

    of a slow-release fertiliser (magnesium phosphate, MgHPO4)

    and one part of the easily soluble ammonium phosphate

    ((NH4)2HPO4): this product is claimed to have good market

    potential. Technical struvite precipitation was extensively

    investigated for the removal of N and P from digester

    supernatant (e.g. Wu and Bishop, 2005), animal waste slurries

    (e.g. Suzuki et al., 2002) and for the treatment of wastewater,

    landfill leachate and abattoir effluent.

    The pH of hydrolysed urine is optimal for struvite pre-

    cipitation (Buchanan et al., 1994) and therefore no pH

    adjustment is required. The precipitation is triggered by the

    addition of magnesium, usually in the form of MgO, Mg(OH)2,

    MgCl2 or bittern (the magnesium-rich brine from table-salt

    production). As shown in Table 1, there is much more

    ammonium than phosphate present in urine on a molar

    basis. As a consequence, about 3% of the nitrogen can be

    eliminated by magnesium addition only so that the effect on

    the pH value is small. Ronteltap et al. (2006) investigated the

    conditional solubility product and the equilibrium reactions

    for urine. The simplified solubility product was determined

    with [Mg] [NH4++NH3] [Portho] 107.6 M3 (pH 9 and a ionicstrength 0.68), where [Mg] is the concentration of dissolvedmagnesium, [NH4

    ++NH3] the measured ammonium+ammo-

    nia, and [Portho] the dissolved ortho-phosphate. See alsoRonteltap et al. (2003) for an overview of the published

    solubility products for struvite.

    No relevant information is given about the kinetics of

    struvite precipitation in urine. From the fact that stored urine

    contains a plethora of fine particles such as micro-organisms

    and precipitation products (Hoglund et al., 1998; Udert et al.,

    2003b), it can be concluded that heterogeneous nucleation

    could play a dominant role in the formation of struvite

    crystals. Our own experience with urine shows that pre-

    cipitation in batch experiments is fast and without any

    Fig. 1 for explanation).

    see Fig. 1 for explanation).

    006) 3151 3166 3159perceivable lag.

    3.5. N-recovery

    3.5.1. IntroductionProcesses for the production of nitrogen fertiliser are based

    on the fixation of atmospheric nitrogen in the Haber-Bosch

    process. Depletion of resources does not therefore play a

    major role in evaluating the environmental benefits of

    nitrogen recovery processes, energy consumption being the

    main parameter. An overview of current nitrogen recycling

    technologies in general wastewater treatment is given in

    Rulkens et al. (1998) and Maurer et al. (2002); corresponding

    energy consumptions are summarised in Maurer et al. (2003).

    3.5.2. Ion exchangeAn ion exchanger with a high affinity for ammonium is

    clinoptilolite, a naturally occurring zeolite, and polymeric

    macronet exchangers have recently also become available

    which are suitable for this purpose (Jorgensen and Weath-

    erley, 2003) (Fig. 9). Both materials as well as other zeolites

    have been tested for the treatment of waste water effluents

    (Liberti et al., 1981), and zeolites have been tested for the

    removal of ammonia from urine, also combined with the

    addition of MgO for recovering phosphate in the form of

    struvite (Lind et al., 2000; Ban and Dave, 2004). The highest

  • If the aim of urine treatment is improved control of water

    ARTICLE IN PRESS

    see

    s (s

    ( 23.5.3. Ammonia strippingStored urine was stripped under vacuum (0.4 bar, 40 1C) and

    the gas stream was adsorbed in water at a pressure of 5 bar

    and 20 1C (Behrendt et al., 2001). The resulting productrecovery rates were obtained at an MgO dosage of 0.5mg/l and

    a zeolite dosage of 15g/l. The remaining supernatant

    concentrations for P and N were 10gPm3 and 1000gNm

    3,

    respectively.

    Fig. 12 Electrodialysis (Fig. 11 Anammox proces

    WAT E R R E S E A R C H 403160contains 10% ammonia and is unstable at normal pressure.

    No information is provided on the concentration of ammonia

    remaining in the urine solution after stripping (Fig. 10).

    Energy consumptions can be estimated from experiments

    with digester supernatant (Siegrist, 1996). At 20 1C and 95%

    ammonia removal, the energy consumption was reported to

    be around 7kWhm3treated liquid. Vapour Phase Catalytic Am-

    monia Removal (VAPCAR) combines vaporisation with high-

    temperature catalytic oxidation of ammonia and other

    volatile compounds. A two-step catalytic process is used to

    produce nitrogen gas, carbon dioxide and water (Slavin and

    Oleson, 1991).

    3.5.4. Isobutylaldehyde-diurea (IBDU) precipitationIn fresh, non-hydrolysed urine, nitrogen is mainly present in

    the form of urea. Urea forms a complex with isobutyralde-

    hyde (IBU), resulting in the precipitation of isobutylaldehyde-

    diurea (IBDU), a commercially available slow-release fertilizer.

    Its industrial production requires a high urea concentration

    (Behrendt et al. 2001, Reinhart, 2002) and even at these

    concentrations an excess of urea or IBU results only in partial

    complexation, so that relatively high fractions of urea remain

    in the liquid phase after treatment. Production at the urea

    concentration of approximately 1% present in urine is there-

    fore not feasible (Reinhart, 2002). Experimental results with

    urine confirm this statement (Behrendt et al. 2001). At a five-pollution, it may be desirable to remove N and P without

    recovering them. Whereas biological P-removal has neverfold stoichiometric excess of IBU, about 75% conversion of

    urea was obtained.

    3.6. Nutrient removal (P and N)

    3.6.1. Introduction

    Fig. 1 for explanation).ee Fig. 1 for explanation).

    006 ) 3151 3166been considered for the treatment of source-separated urine,

    full nitrification can easily be achieved with an extension to

    partial nitrification (see above). Denitrification (resulting in

    N2) may be achieved in a number of ways: biological reduction

    of nitrate with organic matter as the electron donor; biological

    oxidation of ammonia with nitrite as the electron acceptor

    (the anammox process) or electrochemical oxidation of

    ammonia (NASA 1977). Of these technologies, the anammox

    process has been studied in detail for urine.

    3.6.2. Anammox ProcessAnaerobic ammonium oxidation (Anammox) is a biological

    process designed to eliminate nitrogen independently of a

    carbon source (Strous et al., 1998) (Fig. 11). Under anaerobic

    conditions, ammonium and nitrite are converted mainly to

    nitrogen gas. As reported in Fig. 7, the formation of nitrite

    stops halfway through the process, producing a 1:1 ammo-

    nium/nitrite solution. Udert et al. (2003c) added this solution

    to anammox sludge from a pilot plant treating digester

    supernatant. At 30 1C they measured a denitrification rate of

    1000gNm3d1 and the ratio of total ammonia to nitrite

    elimination was 1:1.1870.07. The results of these experi-

    ments show that nitrogen can be removed from source-

    separated urine with anammox. A combination of nitrifica-

    tion and anammox reactors could eliminate 7585% of the

    nitrogen, leaving an ammonium nitrate solution.

  • 3.7. Removal of micropollutants

    3.7.1. IntroductionIncreasingly powerful analytical methods mean that a large

    number of pharmaceuticals and natural hormones from the

    human metabolism are now detected in the aquatic environ-

    ment, but their environmental relevance is currently unclear.

    Most of the effects that can be observed, e.g. the formation of

    vitellogenin (a precursor of egg yolk proteins) in male trout

    (Harries et al., 1997), are chronic effects without clear

    consequences for the affected organism. It is generally

    recognised that urine contains a significant amount of

    excreted micropollutants. In general, a distinction must be

    made between separation and elimination processes. The

    separation of nutrients and micropollutants is relevant to the

    production of a urine-based fertilizer, whereas the micro-

    pollutants must be eliminated for water-pollution control.

    Separation processes are primarily based on membranes or

    precipitation whereas removal processes are based on oxida-

    tion or adsorption (Larsen et al., 2004).

    out (Pronk et al. 2006b) in order to manipulate the pH.

    Ammonia was transferred across a hydrophobic membrane

    from the basic into the acid concentrate. Batch experiments

    confirmed that a pH decrease occurred in the acid concen-

    trate, also known as the product compartment. However, at

    higher conversions the pH rose again to its original value.

    This pH increase can be attributed to carbon dioxide

    transported from the basic concentrate across the gas-filled

    membrane into the acid concentrate (Pronk et al. 2006b). The

    use of an ammonium-selective gas-transfer membrane

    instead of a hydrophobic gas-transfer membrane should in

    principle solve this problem, but this has not yet been

    investigated.

    3.7.3. NanofiltrationNanofiltration (Fig. 13) has been tested for the retention of a

    range of environmentally relevant compounds such as

    pesticides (Van der Bruggen et al., 2001), disinfection by-

    products and pharmaceutical compounds (Kimura et al.,

    2004), phthalates (Kiso et al. 2001) and natural steroid

    ARTICLE IN PRESS

    see

    WATER RESEARCH 40 (2006) 3151 3166 3161In addition to the processes presented here, it is possible in

    principle to remove micropollutants by adsorption to active

    carbon or other adsorbents. It can be expected that the

    presence of high amounts of COD in urine strongly interfere

    with the adsorption process (Quinlivan et al., 2005).

    3.7.2. ElectrodialysisElectrodialysis membranes are ion-exchange membranes

    made of functionalised polymers with a dense structure

    (Strathmann 1992) enabling salts to be extracted and con-

    centrated (Fig. 12). The apparent pore size is typically around

    200Da (Kim et al. 2003) so that these membranes can

    potentially retain micropollutants. Investigations showed

    that electrodialysis may be used to selectively extract the

    nutrients into a concentrated product stream while retaining

    the micropollutants (pharmaceuticals) in the diluate (Pronk et

    al., 2006a). Experiments with bipolar membranes were carried

    Fig. 13 Nanofiltration (Fig. 14 Ozonation andhormones (Nghiem et al. 2004). For production of a urine-

    based fertilizer, it is important for the micropollutants to be

    retained and for mineral salts to be permeated in order to

    obtain a product free of micropollutants. The removal of

    micropollutants was tested with different nanofiltration

    membranes (Pronk et al. 2006c). The efficiency of the

    separation process depends strongly on the pH, demonstrat-

    ing that electrostatic interactions with the membrane play

    an important role in the separation of micropollutants.

    Under optimised conditions, the removal rate of a set of

    hormones and pharmaceutical compounds in urine exceeds

    92% (Pronk et al. 2006c). Furthermore, it was shown that the

    permeation of urea is almost complete, while 5080% of

    the ammonia was retained, depending on the pH (Fig. 13). In

    order to obtain high nitrogen recoveries, therefore, it is

    important to use non-hydrolysed urine (see also Section

    Urine Stabilisation).

    Fig. 1 for explanation).advanced oxidation.

  • micropollutants from urine.

    ARTICLE IN PRESS

    ( 24. Conclusions and outlook

    In this paper, we have reviewed a number of unit processes

    for treating human urine with respect to seven different

    purposes: hygienisation, volume reduction, stabilisation, P-

    recovery, N-recovery, nutrient removal and handling of

    micropollutants. The review concentrates on processes that

    have actually been tested with human urine at least on a

    laboratory scale. Most of the urine treatment options found in

    the literature are adapted from existing technologies and

    have also been applied to other waste streams. However, the

    unique chemical properties of urine make adaptation of

    existing processes almost always inevitable. An example is

    nitrification, where the conversion of nitrite to nitrate is

    mostly inhibited and therefore makes the application of the

    anammox process relatively simple.

    Our evaluation made clear that a very large number of

    technical options are available, with different strengths and

    weaknesses. However, all seven purposes cannot be achieved

    with a single unit process. Whether the aim is to concentrate

    on a specific purpose such as nutrient removal or to combine

    different process units to achieve a more comprehensive goal

    depends on the circumstances and is not discussed in this

    paper.

    Hygienisation: Since actual effectiveness has only been

    shown for storage, it is difficult to draw any final conclusions.

    However, other processes will also be effective: membrane3.7.4. Ozonation and advanced oxidationMicropollutants can be oxidised with chlorine, chlorine

    dioxide, ozone (O3), or OH radicals (advanced oxidation

    processes, AOPs, see Prousek, 1996). In the case of ozone,

    the reaction can take place directly with ozone or with the

    secondary oxidants (e.g. OH-radicals) formed during ozona-

    tion (Von Gunten 2003a; Von Gunten 2003b). In view of the

    high COD content of urine (210g/l, see Table 1), oxidants

    reacting specifically with micropollutants are preferred. As

    most of the compounds tested show enhanced reactivity

    towards ozone (Huber et al. 2003), use of ozone seems to be

    preferable to advanced oxidation processes because a larger

    fraction of the oxidant (OH radical) is lost to the matrix in the

    latter (Fig. 14). From recent investigations with urine, it was

    concluded that complete oxidation of a representative set of

    micropollutants including pharmaceuticals and synthetic

    hormones may be achieved (Pronk et al., 2006d). Despite the

    quenching of oxidants by the organic matrix in urine, it was

    shown that all the tested compounds could be transformed

    completely. At an ozone dose of 1.1 g/l, fast-reacting com-

    pounds such as ethinylestradiol were completely removed,

    while removal of more recalcitrant compound such as

    ibuprofen was 80% (Pronk et al, 2006d). Analysis of the results

    showed that oxidation took place directly by ozone as well as

    by OH radicals. Considering the high reactivity of the OH

    radicals with most organic micropollutants, ozonation can be

    regarded as a suitable method for removing a wide range of

    WAT E R R E S E A R C H 403162processes (except for reverse osmosis), evaporation at high

    temperature, acidification and biological processes all havethe potential to produce a hygienic product, but further

    studies are required.

    Volume reduction: Precipitation processes obviously repre-

    sent the most efficient measures of volume reduction,

    reducing the water content to a few percent. Evaporation is

    almost as effective, resulting in a water content of 510%,

    whereas freeze-thaw, electrodialysis and reverse osmosis are

    considerably less effective.

    Stabilisation: The most effective stabilisation processes are

    acidification and biological processes: they prevent not only

    ammonia evaporation but also the typical urine odour.

    Struvite precipitation is quite efficient because it produces a

    mineral product with little water and a low content of organic

    material. Membrane processes (micro and nanofiltration plus

    electrodialysis) are effective in preventing further microbial

    growth, but require additional measures to prevent odour and

    urea hydrolysis by the hydrolysing enzymes already present

    in the dissolved urea.

    P-recovery: We define a process as a P-recovery technique if

    (a) a volume reduction has taken place and (b) the phos-

    phorus is concentrated in a small volume. Consequently, the

    relevant processes are struvite precipitation, the processes

    recorded under volume reduction and electrodialysis, all of

    them with a phosphorus recovery rate of between 90% and

    100%.

    N-recovery: We define N-recovery in an equivalent way to P-

    recovery. N-recovery actually takes place in a large number of

    processes, but with different yields. At least 90% recovery is

    achieved with evaporation, electrodialysis, reverse osmosis

    and struvite precipitation (with stoichiometric phosphate

    addition). Between 80% and 90% recovery is achieved with

    the freeze-thaw process and most likely with ammonia

    stripping. An N-recovery of between 60% and 80% is achieved

    with reverse osmosis, ion exchange with zeolite and IBDU

    precipitation with a five-fold excess of IBU.

    Nutrient removal: Only biological processes have been tested

    for nutrient elimination. A nitrogen removal efficiency of

    7580% is obtained with a combination of partial nitrification

    and the annamox process.

    Handling of micropollutants: separation from nutrients and

    removal: Only chemical oxidation has so far proved effective

    for the actual removal of micropollutants from urine, and this

    is not entirely beyond doubt. Much work remains to be done.

    Results from biological oxidation are still outstanding.

    Struvite precipitation, ammonia stripping and nanofiltration

    have proved to be highly effective for the separation of

    micropollutants and nutrients. IBDU precipitation and elec-

    trodialysis are only partially effective; electrodialysis optimi-

    sation is proceeding.

    Energy consumption: Besides the technical description of the

    various options, we also estimated the effectiveness and

    energy consumption of these processes. It is obvious that we

    had to make a number of assumptions because very few of

    these processes have actually been optimised for full-scale

    application. As an example, we assumed realistic but

    challenging energy recovery schemes resulting in estimated

    energy requirements mostly in the order of 20100MJm3

    (without the energy used to construct the treatment device),

    006 ) 3151 3166with a few exceptions. If we assume a production of 2 l

    urine per day and person (including flushing water), this

  • the job in a realistic urine source-separation scenario. Many

    of the techniques described in this paper need some sort of

    pre-treatment (e.g. evaporation) or only deal with a specific

    for substituting phosphorus recovered from wastewater

    ARTICLE IN PRESS

    (2problematic fraction in the urine (e.g. struvite precipitation).

    Urine treatment solutions will most probably consist of a

    combination of treatment processes. An example is the

    recovery of phosphate by struvite precipitation followed by

    a biological process designed to eliminate the organic

    pollutants and nitrogen. This enhanced flexibility for urban

    wastewater treatment is one of the great benefits of urine

    source separation and makes the development of processes

    for urine treatment attractive. However, it is impossible to

    discuss process combinations without a scenario as context

    and since an explicit discussion of scenarios would go way

    beyond the scope of this review, a second publication dealing

    with this issue is in preparation.

    A general assessment of NoMix technology is not possible

    on the basis of process engineering technology alone.

    However, as we have shown in this paper, the limitations

    for NoMix technology will not be found in a lack of NoMix

    process engineering options. In most cases, our expectation

    that such technologies might be too energy intensive has not

    come true either. Although other problems connected to

    NoMix technology may be more difficult to solve, one should

    not underestimate the efforts of research and development of

    NoMix process engineering technologies. Except for evapora-

    tion and storage, none of the processes described have yet

    advanced beyond the laboratory stage. Considerable develop-

    ment work remains to be done in order to enhance urine-

    processing techniques into marketable products.

    Acknowledgements

    The authors wish to thank Urs von Gunten and Detleff

    Knappe for their input with respect to the unit operations of

    oxidation and activated carbon.

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    ARTICLE IN PRESS

    WAT E R R E S E A R C H 40 ( 2006 ) 3151 31663166

    Treatment processes for source-separated urineIntroductionComposition of urineTreatment unitsHygienisationIntroductionStorage

    Volume reductionIntroductionEvaporationFreeze-thawReverse osmosis

    StabilisationIntroductionAcidificationPartial nutrification

    P-recoveryIntroductionStruvite (MgNH4PO4)

    N-recoveryIntroductionIon exchangeAmmonia strippingIsobutylaldehyde-diurea (IBDU) precipitation

    Nutrient removal (P and N)IntroductionAnammox Process

    Removal of micropollutantsIntroductionElectrodialysisNanofiltrationOzonation and advanced oxidation

    Conclusions and outlookAcknowledgementsReferences