Dissipation pathways of organic pollutants during the composting of organic wastes

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  • ts


    GlyphosateNon-extractable residues

    s) pntaeir ps, w-ex4-nomzati

    respectively. In the nal composts, the proportions of water soluble residues of OPs considered as readily

    h orgaaterialresid

    ther ciowastto largeed on

    During composting, OPs can be incompletely degraded bymicroorganisms into metabolites or mineralized as CO2, lixiviatedor establish sorption interactions with the composted organic mat-ter (Michel et al., 1995; Lashermes et al., 2010) culminating with

    Brndli et al., 2007). A dissipation higher than 77% of LAS has beenrecorded (Pakou et al., 2009), 87% of NP (Gibson et al., 2007) and50% for pesticides (Kupper et al., 2008). However, only very fewstudies differentiated the dissipation pathways, which requiresthe use of 14C-labeled OPs. Less than 25% of initial 14C-PAH formedNER during composting (Racke and Frink, 1989; Hartlieb et al.,2003). The formation of NER has been reported as very variablefor pesticides, from 20% of initial 14C-2,4-D to 86% for 14C-carbarylwith low mineralization in most cases (Racke and Frink, 1989;Michel et al., 1995; Hartlieb et al., 2003).

    Corresponding author. Tel.: +33 130815401; fax: +33 130815396.E-mail addresses: gwenaelle.lashermes@reims.inra.fr (G. Lashermes), enrique.

    barriuso@grignon.inra.fr (E. Barriuso), sabine.houot@grignon.inra.fr (S. Houot).1 INRA, UMR614, Fractionnement des AgroRessources et Environnement, 2

    Chemosphere 87 (2012) 137143

    Contents lists available at


    eviEsplanade Roland Garros, BP 224, F-51686 REIMS cedex 2, France.Pakou et al., 2009). In several countries, thresholds of maximumconcentrations into the compost have been dened for some ofOPs such as polycyclic aromatic hydrocarbons (PAHs), polychlori-nated biphenyls (PCBs) or polychlorinated dibenzo-p-dioxins/fur-ans (PCCDs/Fs) (Hogg et al., 2002). New regulations includinglimitation for other emergent OPs such as linear alkylbenzenesulfonates (LAS) or nonylphenol (NP) are under discussion(European Commission, 2000, 2001).

    tion risks on the short term. However, NER are susceptible to laterremobilization (Gevao et al., 2000) and have to be taken intoaccount in risk assessment over medium and long terms.

    An increasing number of references have reported the dissipa-tion of OPs during composting. In most cases the dissipation ofPAHs has been observed, with median decrease of OP concentra-tions varying from 10% for chrysene to 81% for acenaphtene(Lazzari et al., 2000; Amir et al., 2005; Oleszczuk 2006, 2007;1. Introduction

    Compost can be contaminated wittially present in organic feedstock mcan be found including pesticide(Byksnmez et al., 2000) or many osludge (Harrison et al., 2006) or in b

    Composting has been recognizedtrations in the nal composts appli0045-6535/$ - see front matter 2011 Elsevier Ltd. Adoi:10.1016/j.chemosphere.2011.12.004available were

  • ered as non directly available fraction (Benoit and Barriuso, 1997).

    phosate, LAS, uoranthene, and NP, respectively.

    the C-CO2 was measured by LSC.Sequential extraction was carried out in triplicate on fresh sam-

    osp2.2. Composting set-up

    The waste mixture and composting reactors have beendescribed in Lashermes et al. (2012). Briey, the waste mixturewas roughly ground and contained (% of DM): aerobic digestedsewage sludge (20%), branches (25%), grass clippings (15%), hedgetrimmings (20%), and leaves (20%). The composting system com-prised 4-L glass reactors supplied with warm humidied air andsurrounded by an external jacket through which water circulatedfrom a thermostatic bath. Composting was performed in triplicatefor each OP introducing into each reactor 750 g wet weight of theinitial waste mixture which corresponded to different equivalentdry weight in the two sets of composting experiments becausethe DM of organic waste evolved during storage, 250 g DM in gly-phosate and LAS experiments and 400 g DM in uoranthene andNP. The initial waste mixture was spiked with the OP solution drop2. Materials and methods

    2.1. Organic pollutants

    The [3C-ring-14C] uoranthene (specic activity:1665 MBq mmol1, 98.3% radiopurity) and the [methyl-14C] N-(phosphonomethyl)glycine (glyphosate) (specic activity: 81.4MBq mmol1, 93.8% radiopurity) were purchased from SigmaChemicals (St. Louis, USA), the [U-ring-14C] 4-n-nonylphenol (spe-cic activity: 1924 MBq mmol1, 99% radiopurity) from ARC-900(St. Louis, USA), and the [U-ring-14C] sodium linear dodecylbenzenesulfonate (specic activity: 230.9 MBq mmol1, 92.7% radiopurity)from Izotop (Budapest, Hungary). Non-labeled uoranthene (99%purity), NP (99.5% purity), and LAS (79.9% purity, containing theC10C13 homologous) were obtained from Sigma Chemicals (St.Louis, USA), Interchim (Montluon, France), and Sasol (Marl, Ger-many), respectively. The water solubilities (Sw) were 25 104,1 104, 7 and 0.26 mg L1 for LAS, glyphosate, NP and uoranthene,respectively. The octanolwater partition coefcients (Kow) were5.16, 1.23,2.73,3.4 (as logKow) forNP, uoranthene, LAS, andgly-phosate, respectively (PHYSPROP database).

    Solutions of 14C-labeled OPs were prepared in methanol for u-oranthene and NP, in MilliQ water (Millipore, Molsheim, France)for LAS and glyphosate. Isotopic dilution with non-labeled OPwas used to reach the nal concentrations of 44, 28919, 29 and700 mg L1 and 53407, 47816, 84233 and 51071 MBq L1 for gly-The objectives of this study were to assess the dissipation path-ways of OPs with contrasted characteristics during composting andtheir availability in the nal compost. A mixture of aerobically di-gested sewage sludge with green waste including branches, grassclipping, hedge trimming and leaves was spiked with 14C-OPsand composted over 83 d in triplicate, using small-scale instru-mented reactors. Four 14C-labeled OPs were studied: a PAH (uo-ranthene), two surfactants (NP and LAS) and a widely-usedherbicide (glyphosate) whose behavior during composting hasbeen poorly investigated (Byksnmez et al., 2000). The mineral-ization, volatilization and lixiviation of the OPs during compostingwere determined. The speciation of OP was also followed duringcomposting: (1) water extraction was used to estimate an easilyavailable fraction for degrading microorganisms, plant assimilationor transfer to ground water; (2) solvent extraction allowed toassess potentially available fraction; and (3) the NER was consid-

    138 G. Lashermes et al. / Chemby drop and under continuous mixing (either 20 mL of the uo-ranthene, NP and glyphosate solutions, or 25 mL of the LAS solu-tion) to reach the following initial OP concentrations (mg kg1ples of the initial waste mixture and composts. An average weightof 4.8 1.0 g DM of organic sample was placed in a glass centrifugetube. The rst extraction was performed with 75 mL of MilliQwater. After 24 h of shaking, water extracts were recovered by cen-trifugation at 2400 g for 20 min. Three successive extractions werethen performed following the same procedure but with 75 mL ofmethanol for uoranthene, NP and LAS, or 75 mL of 0.54 M ammo-nium hydroxide solution for glyphosate. The 14C-OP concentrationin all extracts was measured by LSC. After extraction, the compostresidues were dried at 40 C, ground at 200 lm and the remainingnon-extracted radioactivity (corresponding to the NER) was deter-mined by scintillation counting of the 14C-CO2 evolved after com-bustion of the solid (Sample Oxidizer 307, Packard, Meriden, CT,USA). All 14C-fractions were expressed in percentage of total recov-ered 14C (sum of the 14C-activity recovered in all the fractions min-eralized, volatilized, leached, extractable and NER) at a specicsampling date. The dissipation of OPs during composting was cal-culated (1) as the difference between the initial and nal concen-trations (in mg kg1 DM) of total extractable residues (additionof water and solvent extractable 14C-fractions) as usually measuredin composts produced on composting plants and (2) as the differ-DM): 3, 2860, 1.5 and 34, for glyphosate, LAS, uoranthene andNP, respectively. Finally, the waste mixtures were humidied with59 mL Milli-Q water for uoranthene, NP and glyphosate and54 mL for LAS experiment.

    During the rst 6 d, the temperature increased by self-heating;then the temperature was modulated to mimic a typical compost-ing temperature prole. After 41 d, composts were moved to 21-Lglass cells for maturation and placed in a thermostatic room at28 1 C for additional 42 d. The composting mixtures were sam-pled three times after homogenization: at the end of the thermo-philic phase (day 13), at the end of the cooling phase (day 41)and at the end of the maturation phase (day 83). At each samplingdate, water was sprayed on the compost to maintain the moisturecontent at 5070% of wet weight. The composting mixture wascharacterized during another set of six composting experiments,with the same initial waste mixture and composting procedurebut without addition of 14C-OPs (Lashermes et al., 2012). The evo-lution of the chemical and biochemical characteristics attested of asatisfactory composting process with a decrease of C:N ratio from15.7 to 12.2 and the increase of the ratio of lignin to holocellulosefrom 0.4 to 0.9.

    2.3. Organic pollutant mineralization, volatilization, lixiviation andspeciation during composting

    During the rst 41 d of composting, the exhaust air of each reac-tor was passed through a 400-mLmethanol plug to trap volatile or-ganic compounds (VOCs) and through two successive CO2 traps,each containing 750 mL 3 M NaOH. The traps of methanol andNaOH were replaced respectively 14 and 18 times and analyzedfor 14C-VOC and 14C-CO2 concentrations by liquid scintillationcounting (LSC) with a Tri-Carb 2100 TR counter (Perkin ElmerIns., Courtabeuf, France) using Ultima Gold XR (Packard) as scintil-lation cocktail. Lixiviates were recovered at the bottom of eachreactor and were pumped out after 13 and 41 d of composting.The collected volumes were measured and their 14C content wasdetermined by LSC. During maturation (days 4183), a vial con-taining 100 mL 3 M NaOH was placed in each maturation cell totrap the 14CO2 produced. These vials were replaced 14 times and


    here 87 (2012) 137143ence between the initial and nal amount (mg) of total extractableresidues per reactor in order to assess the dissipation of OP takinginto account the compost mass reduction during the process.

  • was only detected once for LAS and accounted for 5% of recovered

    osp14C. This was unexpected since LAS is not a volatile surfactant.

    3.2. OP dissipation through mineralization during the compostingprocess

    Composting can reduce OP contamination of an initial wastemixture through its complete mineralization as observed for PAHsand pesticides (Michel et al., 1995; Hartlieb et al., 2003). In thepresent experiment, the OP mineralization at the end of compost-ing reached (in % of applied 14C): 0.3 0.2 (95% condence interval)for uoranthene, 24 8 for glyphosate, 29 2 for NP and 51 4 forLAS (Fig. 1). The mineralization of glyphosate, LAS and NP mostlyoccurred during the most biologically active composting period(days 041) (Ai, Table 1). During maturation (days 4183) muchless mineralization occurred (on average, 3%, 6% and 1% of initial14C for glyphosate, LAS and NP, respectively).

    A lag phase was observed in the mineralization of LAS, glyphos-2.4. Data analyses

    Microsoft Excel Solver was used to adjust the cumulative 14C-CO2 mineralization kinetics to distinct Gompertz sigmoid equa-tions for the thermophilic and maturation phases:

    Pt Ai exp exp lmi eAi ki t 1


    where P(t) is the total mineralized 14C-CO2 at time t, expressed as apercentage of initial 14C; Ai, the asymptote representing the maxi-mum mineralization attained; lmi, the maximum specic growthrate; ki, the lag time (Zwietering et al., 1990), and i index equaled1 or 2 for the active (thermophilic + cooling phases, 041 d) andmaturation phases(4183 d), respectively.

    Ninety-ve percent condence intervals were calculated con-sidering the three replicates of composting for mineralizationand speciation results.

    3. Results and discussion

    3.1. Overall balance of the OP behavior during composting

    The evolution of the 14C distribution for each OP and compost-ing experiment among the different analyzed fractions is shown inFig. 1. Each OP presented different behavior with a good replicationbetween the three replicated composting experiments and withcondence intervals for all fractions generally lower than 10% ofrecovered 14C. The average 14C-OP recovery considering all sam-pling dates was (in % of initially applied 14C): 96, 95, 85, and 83for uoranthene, glyphosate, LAS and NP, respectively.

    The 14C-uoranthene behavior showed little changes duringcomposting maintaining a high solvent extractable fraction. Inthe case of glyphosate, the proportion of NER increased but a largepart remained extractable with an equal distribution between thewater and solvent extracts. LAS behavior was characterized by a ra-pid mineralization whereas the NP mineralization was balanced bya rapid formation of NER which remained at high level during theentire composting process.

    The volumes of leachates recovered were on average 450 mL,820 mL, 620 mL and 520 mL for uoranthene, glyphosate, LAS andNP experiments, respectively. The highest 14C-lixiviated fractionsrecovered were found for the glyphosate and LAS, representing5 3% of recovered 14C for both OPs after 41 d of composting. The14C lixiviationwas negligible for uoranthene andNP. Volatilization

    G. Lashermes et al. / Chemate and NP at the beginning of composting, corresponding to thetime required for the degrading microorganisms to reach an ef-cient level (Drer et al., 1996). The mineralization kinetics werewell described by the Gompertz equation (R2 > 0.98) (Table 1). Therst lag phase (k1) was on average 3, 5, 8 d for glyphosate, NP, andLAS, respectively, corresponding to the self-heating period duringthe thermophilic step. Then mineralization rate of these OPsreached the highest values when the temperature increased until60 C on days 811. During the maturation phase, after homogeni-zation and rewetting, a second lag phase (k2) was on average 7and 8 d for LAS and glyphosate, respectively; while the mineraliza-tion of NP remained very low and nearly linear. The lag phase for NPmineralization was signicantly and negatively correlated with themaximum temperature observed during composting (P > 0.001).The microorganisms responsible for NP mineralization may indeedbe less efcient at thermophilic than at mesophilic temperatures(Moeller and Reeh, 2003a).

    The variability observed in glyphosate mineralization kineticscould be explained by temperature and moisture limitations whichoccasionally occurred because of aeration and high temperaturesin some reactors. Indeed, the asymptotes of mineralization kinetics(A1 of Gompertz equation, Table 1) were negatively correlated withthe moisture content of the compost sampled after 13 d (P > 0.001)and 41 d (P > 0.01) and positively correlated with the mean tem-perature during the rst 6 d (P > 0.001).

    The proportions of 14C-OP mineralized at the end of compostingin the present study decreased in the same order as found duringincubation with composts sampled at different composting stages(Lashermes et al., 2010): LAS > NP > glyphosate > uroanthene.However, the extent of 14C-OP mineralization was lower duringcomposting than compost incubations. In particular, NP and uo-ranthene showed respectively a high potential of mineralizationduring incubation with compost sampled during the cooling phase(56% of initial 14C) and with mature compost (21% of initial 14C).For uoranthene, the differences may be explained by a durationof composting (83 d) not long enough to allow the compost coloni-zation by microorganisms capable of degrading aromatic struc-tures, such as white-rot fungi (Hammel, 1995) or prokaryotes(Haderlein et al., 2006) which could have developed during theadditional incubation time (92 d). Moreover, the mineralizationof NP could have been limited by the high temperature duringthe thermophilic phase while the mineralization of NP in incuba-tion took place at a lower temperature (28 C) probably closer tothe optimal conditions for NP degradation.

    In soils, the potentials of mineralization also decrease in thesame order among the four OPs. However, the extent of minerali-zation during composting was always lower than found in soils:for LAS (Drer et al., 1996), NP (Gejlsbjerg et al., 2003) or glyphos-ate (Mamy et al., 2005), while the mineralization of 14C-uoranth-ene can reach 25% of initial 14C in agricultural soil (Vessigaud et al.,2007). The presence of specic microora, in particular for uo-ranthene, and differences in sorption on soil and compost matrixlimiting the fraction available for degradation can explain thedifference.

    3.3. OP stabilization as non extractable residues during composting

    The NER formation participates in the OP apparent dissipationestimated through classical OP extraction. The NER were detectedas soon as NP was applied (35% of 14C recovered at the beginning ofthe composting process), whereas the NER proportions at thebeginning of composting reached only 7%, 4% and 3% for uoranth-ene, LAS and glyphosate, respectively (Fig. 1). The NER formationmainly occurred during the early phases of composting, as previ-ously observed for pyrene by Hartlieb et al. (2003). The NER fromNP tended to slightly decrease during maturation, with a decrease


    here 87 (2012) 137143 139of 4% of recovered C. At the end of composting, NER proportionsrepresented (in % of recovered 14C): 45 2 for NP, 37 3 for gly-phosate, 24 7 for uoranthene, and 14 3 for LAS (Fig. 1).

  • osp140 G. Lashermes et al. / ChemThe NER formation during composting has been less studiedthan in soil but the mechanisms described for NER formation insoils are likely to be transposable. The NER can be formed throughphysical entrapment in the nanoporosity of the humic compounds

    Fig. 1. Variation during composting of the distribution (as a % of recovered 14C) ofextractable residues, from 14C-labeled glyphosate, LAS, uoranthene and NP applied at theLAS-3, FLT-1 to FLT-3 and NP-1 to NP-3, respectively. The percentage of recovered 14C coactivity recovered in all the fractions at a specic sampling date. Bar errors represent thhere 87 (2012) 137143or through chemical stabilization with the establishment of cross-linking reactions with compounds in the organic matrix (Kstneret al., 1999; Barriuso et al., 2008). Non humied organic mattermay display great afnity to form NER with some OPs (Barriuso

    mineralized, volatilized, leached, water-extractable, solvent-extractable and non-beginning of the three replicated composting experiments GLY-1 to GLY-3, LAS-1 to

    rresponded to the 14C-activity in a given fraction compared with the sum of the 14C-e condence intervals of analytical replicates (n = 3).

  • LAS 45 10 5.8 1.4 8.0 3.0 0.997 0.001NP 28 2 4.3 1.7 4.7 2.7 0.998 0.003

    ospet al., 2008). Initial waste mixtures have been found to have high-er sorption capacities than mature compost (Lashermes et al.,2010). The organic matter may be more reactive at the beginningof composting than in mature compost possibly because of higherlevels of aliphatic components. Moreover, the formation of NERduring the early stages of composting might also be related to in-tense microbial activity (Benoit and Barriuso, 1997; Vessigaudet al., 2007), thus the OPs and metabolites may be incorporatedinto growing biomass (Barriuso et al., 2008) or linked to organicmatter after oxidation reactions catalyzed by extracellular en-zymes (Gevao et al., 2000). The high level of NER formation fromNP throughout composting was probably related to its highlyreactive phenolic structure (Gevao et al., 2000; Dec et al., 2003).Nevertheless, the immediate formation of NER after NP applica-tion could also be partly attributed to a lack of efciency in thesequential water/methanol extraction technique employed, evenif methanol has previously been shown to be an efcient extrac-tive of NP from compost material, reaching 90% recoveries (Pakouet al., 2009). The proportion of NER with glyphosate was also highand could be explained by the chemical reactivity of functionalgroups such as carboxylic, amino and phosphate groups in itschemical structure (Kstner et al., 1999). The level of NER forma-tion during composting with uoranthene was relatively low andsimilar to that found for pyrene (Hartlieb et al., 2003). The fused

    4183 d periodA2 lm2 k2 R2

    % of initial 14C d1 dGLY 3 1 0.1 0.0 8.2 2.1 0.996 0.004LAS 6 5 0.3 0.3 7.4 4.1 0.999 0.001NP 1 0 0.1 0.0 0.0 0 0.983 0.005

    a Mean 95% condence intervals of three composting replicates.b Coefcient of determination of linear regression.Table 1Values of Ai, lmi and ki parameters obtained by tting the 14C-CO2 evolution kineticsto the Gompertz equation on the 041 (i = 1) and 4183 (i = 2) day periods forglyphosate, LAS and NP composting experiments.

    OP 041 d period

    A1 lm1 k1 R2

    % of initial 14C d1 dGLY 21 8a 1.4 0.7a 3.1 0.4a 0.998 0.001b

    G. Lashermes et al. / Chemaromatic ring structure of uoranthene (without any reactivefunctional groups) has a low potential for coupling with organicmatter. And nally, the low NER with LAS revealed the weak reac-tivity of the molecule to binding with organic matter. The forma-tion of NER leads to a decrease in the toxicity and bioavailabilityof OPs (Barriuso et al., 2008). However, the formed NER can besubsequently released through microbial degradation, being thenpotentially available. The environmental impact of NER and theirecological signicance thus depends on the reversibility of theirstabilization (Gevao et al., 2000).

    3.4. OP availability and estimation of dissipation parameters for riskassessment

    The OP fraction easily available for the degrading microora orfor leaching is usually assessed by water extraction (Benoit andBarriuso, 1997), whereas the use of other solvents can estimatethe overall potentially available residues. The water extractablefractions were related to the water solubility of the different OPs(glyphosate > LAS > NP > uoranthene). This fraction for all OPsdecreased during the more active thermophilic step of composting,remaining at relatively constant levels thereafter. The 14C-uo-ranthene was characterized by a high solvent extractable fractioncorresponding to 72 8% of recovered 14C at the end of compost-ing; thus, uoranthene could be potentially available in soil aftercompost application. For glyphosate, 47% and 50% of recovered14C were in the water and solvent extractable fractions at thebeginning of composting, respectively, and only 11 5 and18 5% at the end of composting. The proportion of 14C-LAS and14C-NP in the water extracts were low throughout compostingwith 9 1% of recovered 14C for LAS, and 5 1% for NP at the endof composting (Fig. 1). The solvent extractable fractions of LASand NP were very high at the beginning of composting (respec-tively 89% and 60% of recovered 14C) and decreased quickly to6 2% and 7 1% at the end of composting. Concerning uoranth-ene, due to its low solubility and high hydrophobicity, its waterextractable fraction remained very low during composting thatcould explain its poor availability for degrading microorganisms(Katayama et al., 2010).

    At the end of composting, the proportion of water soluble resi-dues considered to be directly available was generally small, sug-gesting a low risk linked to direct OP assimilation by plants ortransfer to soil water (Benoit and Barriuso, 1997). For glyphosate,the water extractable fraction was higher during composting thanin soil (Mamy et al., 2005). Thus, glyphosate mineralization duringcomposting was probably not limited by sorption on compost or-ganic matter, but rather related to a less active glyphosate degrad-ing microora in compost than in soil. On the contrary, althoughLAS and NP are soluble compounds, the small quantities of waterextractable residues may have limited the extent of theirmineralization.

    The dissipation of an OP is classically calculated from the de-crease in its concentration analyzed after extraction between twosampling dates. We used here the results of the water and solventextractions to assess the dissipation kinetics of the different OPs,supposing that the measured 14C in the extracts correspond tothe initial non degraded OP. This hypothesis implies an overesti-mation of OP persistence since probably a part of measured 14Ccorresponded to metabolites formed during composting. Total dis-sipation over 83 d of composting was calculated from the differ-ence between the initial and nal amount of extractable OP perreactor taking into account the mass loss of wastes during com-posting. The dissipation results expressed in % of initial amountof OP applied were: 84 4 for LAS, 82 4 for NP, 70 10 for gly-phosate and 18 8 for uoranthene. Based on dissipation results,half-life duration (in days) were approached supposing rst-orderkinetics: 22 8 for LAS, 15 4 for NP, 31 19 for glyphosate and286 188 for uoranthene. These values were in the ranges ofhalf-lives reported in soil for uoranthene (150300 d, Van Brum-melen et al., 1996) and LAS (727 d, Jensen, 1999), in biosolid-amended soil for NP (719 d, Hseu, 2006) but were higher thanthe ranges reported in soil for glyphosate (14 d, Mamy et al.,2005).

    It is important to point out that very often in the literature theestimation of OP dissipation does not take into account the massloss during composting, comparing directly the OP concentrationexpressed in mg kg1 DM between two sampling dates. That caninduce an overestimation of the persistence. In our experiment,dry matter losses related to organic matter mineralization duringcomposting mainly occurred during the thermophilic phase, andreached on average 41%, 43% and 52% of the initial DM after 13,41, and 83 d of composting, respectively. As a consequence, the u-oranthene concentration (in mg kg1 DM) increased during com-posting meaning that the compost organic matter was degradedmore rapidly than the uoranthene disappeared.

    here 87 (2012) 137143 141The percentages of OP dissipation found in the present study atthe end of composting were within the 25th and 75th percentileranges of the dissipation reported in the literature for LAS (Moeller

  • ospand Reeh, 2003b; Sanz et al., 2006; Pakou et al., 2009) and NP(Jones and Westmoreland, 1998; Gibson et al., 2007; Das and Xia,

    Percentage of dissipation (%)

    -100 -50 0 50 100

    Dissipation (decrease in OP concentration) in the literatureDissipation (decrease in OP concentration) in this studyDissipation (decrease in OP amount) in this study Disapearance (mineralization as CO2) in this study





    7 referencesn = 19

    4 referencesn = 12

    4 referencesn = 7

    0 reference

    Fig. 2. Distribution of the percentages of dissipation of uoranthene, LAS, NP andglyphosate at the end of composting reported in the literature (box) and from thisstudy (symbols). The dissipation percentages were calculated from the initial (Ci)and nal (Cf) concentrations in extractable OP (mg kg1 DM) as Ci Cf =Ci 100or from the initial (Qi) and nal (Qf) amount in extractable OP (mg) per reactor asQi Qf =Qi 100. The percentages of OP mineralization measured in the presentstudy are also shown. The boxes correspond to the 25th and 75th percentiles; thebars correspond to the 10th and 90th percentiles. The vertical continuous line in thebox is the median and closed circles are the extreme experimental data reported inthe literature.

    142 G. Lashermes et al. / Chem2008; Pakou et al., 2009) during composting whose duration variedfrom 14 to 60 d for LAS, and from 49 to 70 d for NP (Fig. 2). Nostudy on the evolution of glyphosate concentrations has beenfound. On the other hand, composting appeared to be inefcientto signicantly reduce uoranthene contamination, even with sim-ilar duration of composting in this study than in the literature(from 50 to 112 d) (Lazzari et al., 2000; Amir et al., 2005;Oleszczuk, 2006; Brndli et al., 2007; Oleszczuk, 2007; Hadiet al., 2008; Hua et al., 2008).

    4. Conclusion

    The dissipation pathways of 14C-labeled uoranthene, NP, LASand glyphosate and their availability in nal composts were as-sessed during the composting of sewage sludge and green waste.Dissipation mainly occurred during the early stages of compostingduring which both mineralization and NER formation mainly oc-curred while both volatilization and lixiviation were negligible.The dissipation of LAS was largely due to mineralization. For NPand glyphosate, both mineralization and NER formation equallycontributed to dissipation. The low dissipation of uoranthenewas only related to NER formation. In all cases, OP availability, esti-mated by the proportion of water soluble 14C-residues, was low inthe nal compost, whereas the proportion of solvent extractableOPs considered to be potentially available, was very small for NPand LAS, and intermediate for glyphosate. Composting appearedto be ineffective at degrading uoranthene and decreasing itsavailability, with no mineralization and most 14C-uorantheneremaining solvent extractable in the nal compost and thereforepotentially available.

    Such procedure to evaluate the evolution of OP availabilityduring composting could be used to optimize the process anddetermine the best conditions to reduce OP availability in nal

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    We would like to thank ADEME (French Environment and En-ergy Management Agency), INRA (French National Institute forAgricultural Research) for the grant, and Veolia Environment, Re-search and Development, for their nancial support for theseexperiments. We thank Valrie Bergheaud and Valrie Dumenyfor their assistance with experiments using 14C-labeled pollutantsand Maelenn Le Villio-Poitrenaud for her constructive comments.


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    G. Lashermes et al. / Chemosphere 87 (2012) 137143 143

    Dissipation pathways of organic pollutants during the composting of organic wastes1 Introduction2 Materials and methods2.1 Organic pollutants2.2 Composting set-up2.3 Organic pollutant mineralization, volatilization, lixiviation and speciation during composting2.4 Data analyses

    3 Results and discussion3.1 Overall balance of the OP behavior during composting3.2 OP dissipation through mineralization during the composting process3.3 OP stabilization as non extractable residues during composting3.4 OP availability and estimation of dissipation parameters for risk assessment

    4 ConclusionAcknowledgmentsReferences


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