Water Air Soil Pollut (2009) 199:171182 DOI 10.

1007/s11270-008-9869-7

Ash Leaching of Forest Species Treated with Phosphate Fire Retardants

Stylianos Liodakis & Magdalini Tsoukala

Received: 15 July 2008 / Accepted: 16 September 2008 / Published online: 8 October 2008 # Springer Science + Business Media B.V. 2008

Abstract The chemical, mineralogical, and leaching behavior of three dominant Greek forest species ashes (Pinus halepensis, Pistacia lentiscus, and Olea europaea), before and after treating forest species with diammonium phosphate (DAP) 5% and 10% weight to weight, have been studied using a new five-step shake leaching method at pH=6. For the analysis of ashes (prior and after leaching) and leachants, the following analytical techniques were used: atomic absorption spectroscopy, X-ray diffraction, and scanning electron microscopy with energy dispersive X-ray fluorescence analysis. The presence of DAP obstructs the extraction process of some metal ions (i.e., Na, K) contained in ashes by converting the soluble carbonate salts to the less soluble phosphates (i.e., Na2CO3 Na3PO4). On the contrary, DAP enhances the mobility of some other metals (i.e., Ca) by forming more soluble compounds [i.e., CaCO3 Ca3(PO4)2]. In addition, the presence of DAP lowers the pH of leachates, causing dissolution of some toxic elements (i.e., Mn, Pb, Zn). Unexpectedly, DAP prevents the leachability of Cr from ash. The above study concerns the environmental effects (soil and ground and underground water
S. Liodakis (*) : M. Tsoukala Laboratory of Inorganic and Analytical Chemistry, Department of Chemical Engineering, National Technical University of Athens (N.T.U.A.), 9 Iroon Polytechniou Street, Athens 157 80, Greece e-mail: liodakis@central.ntua.gr

streams) caused by the use of chemical retardants on forest fires. Keywords P. halepensis . P. lentiscus . O. europea . Forest fires . DAP . Ash leaching

1 Introduction Wildfires burn thousands of hectares all over the world each year. The produced white ash, termed as wood ash, comprises the inorganic constituents of wood that remain after burning. The wood ash is a highly alkaline matter (pH=913.5) with high content in heavy metals, and its disposal is a growing problem as environmental regulations become more stringent (Campbell 1990). Wood ash has been used in agriculture as soil amendment because it is an excellent source of potash (potassium), lime, and other plants nutrients (Campbell 1990; Etigni and Campbell 1991; Voundi Nkana et al. 1998, 2002). A variety of chemicals have been increasingly used on wildland fire suppression. The fire suppression chemicals are classified into the long-term fire retardants, which inhibit combustion even after the loss of their watery matrix; the short-term retardants, which lose their effectiveness with the evaporation of water; the fire-fighting foams forming small bubbles when mixed with water; and the wetting agents, which reduce the surface tension of water and increase its spreading ability (Kalabokidis 2000).

172

Water Air Soil Pollut (2009) 199:171182

The active constituents in most long-term forest fire retardants are basically agricultural fertilizers (i.e., ammonium sulfates and phosphates). However, even materials of inherent low toxicity can cause adverse environmental effects when the rate or intensity of use is sufficiently great, as chemicals can enter plant organisms, soil, and ground and underground water and have toxic effects on vegetation (Bradstock et al. 1987; Gimnez et al. 2004; Pappa et al. 2006, 2008). The ammonium, phosphate, and sulfate ions are the chemicals in retardant solutions most likely to cause changes in the local environment. Ammonium ions are taken by the plants directly and/or indirectly as nitrite and nitrate ions. Some ammonium ions may be denitrified (evaporated as nitrogen gas) and some may leach away to ground water or streams. Expansive clays can also trap a portion of ammonium ion. The phosphates can be taken up directly by plants (in 20% efficiency) and indirectly (converted chemically into available forms) or be lost in soil water. The sulfate ions lower soil pH by forming sulfate acid, causing elements such as iron, copper, zinc, and manganese to become more readily soluble (Hardy 1977). The ash composition of forest species before and after treatment with (NH4)2HPO4 [diammonium phosphate (DAP)] has been previously reported (Liodakis et al. 2007; Fallman and Aurell 1996). Among the metals determined were some toxic ones (i.e., Pb, Cr, Cd, Zn). The presence of DAP alters the composition of ashes by converting, almost completely, at high temperatures the metallic oxide constituents of ash to phosphate salts. To estimate the environmental threat of ash disposal, leaching tests are indicated as an indispensable characterization tool. A number of different leaching tests have been developed (Fallman and Aurell 1996; Saikia et al. 2006). The Comit Europen de Normalisation commission developed new methods for harmonization reasons (Hage and Mulder 2004). These tests have been successfully used mainly for environmental assessments of waste disposals. A number of factors affect the composition of leachates, such as the conditions of leaching (i.e., leaching time and eluent pH) and the composition (chemical and mineralogical) of solid extracted (Demeyer et al. 2001). Thus, the release of metals from forest species ash depends on the chemical characteristics of ash in

terms of form and solubility: (1) metals may be present as water-soluble salts (i.e., chlorides) where dilution determines the concentrations in the solution phase and there is no pH dependency; (2) metals may be present as soluble or moderately soluble phases but trapped in materials that need dissolution (i.e., carbonates or oxides) and, when dissolved with acid, make the soluble phases free; and (3) metals occur in a form (i.e., carbonates, oxides or hydroxides) that would be released following dissolution processes (Ludwig et al. 2005). The objective of this research is to investigate the leaching properties of three dominant Greek forest species ashes before and after treating forest species with a phosphate fire retardant (DAP). Thus, we evaluate the pollution potential of leachants and solid residues on forest fires after the use of phosphate fire retardants. The chemical and mineralogical compositions of ashes (before and after leaching) and the chemical composition of leachants were determined by various analytical techniques.

2 Materials and Methods 2.1 Samples Tests were conducted on three forest species: Pinus halepensis, Olea europaea, and Pistacia lentiscus before and after treatment with DAP. The selected species are very common in the Mediterranean region and are often devastated by forest fires. The sample collection site of P. halepensis and P. lentiscus was Thracomacedones, an area in the foothills of mountain Parnitha, near Athens, with geographic coordinates 38 07 50 and 23 46 22 E, height 323 m, and average slope 10%. The dominant rocks in this area were marls and sandstone. The sample collection site of O. europaea was the mountainside Kalopoula of Imittos, near Athens, with geographic coordinates 37 58 13 and 23 48 20 E, height 487 m, and average slope 70%. The dominant rock was limestone. The collection took place in September 2007. All samples were mature foliage, collected after a long drought period in order to avoid moisture effects such as microbe growth (Nurmi and Hillebrand 2007). The samples were first dried at 105C for 24 h and then ground (Dimitrakopoulos and Panov 2001). A

Water Air Soil Pollut (2009) 199:171182

173

fraction between 100 and 200 m was separated and dry ashed at 600C, according to a standard method (ASTM 2001). The preparation of DAP-treated samples was performed by well mixing a certain quantity [5% and 10% weight to weight (w/w)] of Merck laboratory reagent DAP with the forest material powder. The uniformity of the prepared samples was checked using a reflected-light microscope. The concentration level chosen (5% and 10% w/w) was similar to that applied by Hellenic Fire Service in real forest fires. However, only a small fraction of DAP remains with ash due to the thermal decomposition of DAP during the ash preparation at 600C. 2.2 Leaching Experiments The method developed to assess the water-soluble fractions of elements in ash samples was a shake leaching test, similar to the DIN-S4 method (ASTM 2004; DIN 1984). In this test, aqueous acidic solutions were used in quantities of 20 mL per gram of ash (1.00 g of dried ash sample was mixed with 20 mL eluent of pH=6) and reaction time (shaking) of 24 h. The aqueous extracts were selected by filtration via a filter of pore size 0.45 m. This procedure was repeated five times: 20 mL was removed from the first extraction solution via filtration for analysis. In the remaining ash, 20 mL of eluent (pH=6) was added and the suspension was shaken again for 24 h (Saikia et al. 2006). The eluent of pH=6, which approximates rainwater, was prepared by acidifying demineralized (ultra pure) water with 0.10 mM HNO3. Then, the conductivity, pH, and elemental composition of leachates were determined. 2.3 Analytical Methods For the determination of electrical conductivity and pH of ash samples, 5.00 g of dried ash sample was mixed with 100 mL of deionized water. The mixture was shaken for 3 h and the electrical conductivity of the supernatant was measured. Then, the ash solution was filtered over a membrane filter of pore size 0.20 m and the pH was measured. The conductivity of the leachants was measured at 25C with a Mettler Toledo MPC227 conductivity meter and the pH was measured at 25C with a Hanna HI\8314 pH meter.

For the elemental analysis, the leachant fractions were filtered over a membrane filter of pore size 0.20 m. For the analysis of ashes before and after treatment with DAP, 50 mg of the dried ash was dissolved in 10.0 mL hydrochloric acid 20% w/w. The solution was heated and filtered and the precipitate was washed with deionized water. The filtrate was diluted to 100.0 mL and then analyzed. The determination of elements in both leachate and ash samples was carried out using a Varian, model AA 240FS, atomic absorption spectrometer. The ash samples prior to and after leaching were analyzed in a Siemens D5000 X-ray diffractometer using a copper target to generate the X-rays (wavelength=1.5405 1010 m). The ash samples were first finely ground and then mounted on a sample holder. The powder was ground fine to ensure random orientation of the crystals so that there were a sufficient number of crystals to generate detectable signals of all angles and the background noise was kept to a minimum. The ash samples before and after leaching were examined by a FEI Quanta 200 scanning electron microscope (SEM) combined with an energy dispersive X-ray fluorescence spectrometer for determining the elemental composition at chosen points on the sample surface. The instrument was operated under low vacuum conditions (90 Pa) and a voltage of 10 kV to avoid any deterioration of ash samples. Samples were deposited on a sample holder and were secured with a conductive carbon tape. No pretreatment or coating of the samples was required. A number of 1520 analyses were performed for each class of samples, covering different magnifications and surface areas, to improve the credibility of the reported data.

3 Results and Discussion 3.1 Electrical Conductivity and pH Measurements of Ashes and Ash Leachates In Table 1 are given the conductivity and pH values of forest species ashes before and after leaching (fivestep mode, pH= 6). The ash samples were prepared from P. halepensis, P. lentiscus, and O. europaea forest species, before and after treatment with DAP. In Fig. 1 are presented the respective conductivity and

174 Table 1 Conductivity and pH values of forest species ashes before () and after (+) leaching (5-steps mode, pH=6) Forest species + DAP % Leaching state + + + + + + + + + Conductivity (mS cm1) 13.0 0.6 4.5 0.7 4.0 0.7 25.1 0.4 0.6 0.7 3.1 1.9 42.0 0.2 4.6 0.2 3.3 0.6 pH

Water Air Soil Pollut (2009) 199:171182

P. halepensis + 0 P. halepensis + 5 P. halepensis + 10 P. lentiscus + 0 P. lentiscus + 5 P. lentiscus + 10 O. europea + 0 O. europea + 5 O. europea + 10

12.1 7.6 8.3 7.5 2.8 2.7 12.7 7.9 7.9 6.6 5.3 4.7 12.8 8.9 8.1 7.4 6.1 5.3

the conductivity values of all leachate fractions of DAP-treated samples do not reveal significant changes during the leaching process (Fig. 1). Thus, DAP obstructs the extraction process of some metal ions contained in ash by forming phosphate salts, which are less soluble than the respective carbonates (i.e., Na3PO4, K3PO4) (Lide 2007). These compounds are formed via the decomposition of DAP to polyphosphates (NH4PO3)n and P2O5(g), according to the following reactions (Liodakis et al. 2007): NH4 2 HPO4 ! NH4 H2 PO4 NH3 g 150 C 1

2NH4 H2 PO4 ! NH4 2 H2 P2 O7 H2 O g 170 C 2 NH4 2 H2 P2 O7 ! NH4 PO3 2 H2 O g 280 C 3

NH4 PO3 2 ! P2 O5 g 2NH3 g H2 O g 660 C

pH values of leachates vs leachate fraction. The data reported in Table 1 and Fig. 1 are the average values of four replicate measurements with relative standard deviation below 10%. The low pH values recorded on the DAP-treated ash samples are due to the dissolution of the acidic products of DAP decomposition (Table 2). Thus, the presence of 10% w/w DAP decreases the pH value of ash from 12.1 to 2.8 for P. halepensis, from 12.7 to 5.3 for P. lentiscus, and from 12.8 to 6.1 for O. europaea (Table 1). As is shown in Table 1, a significant decrease in pH values of DAP-free ashes was recorded after their leaching (12.1 to 7.6 for P. halepensis, 12.7 to 7.9 for P. lentiscus, 12.8 to 8.9 for O. europaea). On the contrary, the DAP-treated samples reveal minor pH changes prior to and after leaching (Table 1). The conductivity deviation between ash leachates and pure eluent (2.64 S cm1) indicates the most efficient steps of the leaching process applied (Fig. 1). For the non-DAP-treated samples, the conductivity value of the first leachate fraction is much higher than that of the other ones (Fig. 1). Thus, the most efficient leaching step is number one, where a significant quantity of ions is released from the water soluble constituents of ash (i.e., Na2CO3, K2CO3). In contrast,

4
P2 O5 g 3Na2 CO3 ! 2Na3 PO4 3CO2 g 600 C

5 P2 O5 g 3K2 CO3 ! 2K3 PO4 3CO2 g 600 C 6 P2 O5 3H2 O ! 2H3 PO4 7

Finally, the leachates of all samples were approaching the conductivity values of pure eluent in all cases. Similarly, the pH value variations in relation to leachate fraction (Fig. 1) indicate that the most efficient leaching step is number one, and the presence of DAP obstructs the dissolution of ash constituents. The use of ammonium sulfate (NH4)2SO4 as fire retardant additive is expected to lead to similar results because of its decomposition to acidic products (Liodakis et al. 2003, 2008). On the contrary, the

Water Air Soil Pollut (2009) 199:171182 Fig. 1 Electrical conductivity and pH of ash leachates vs leachate fraction (ac): the ashes were prepared from forest species treated (or not) with DAP, the aqueous solution had pH=6

175

use of carbonate salts [i.e., Mg5(CO3)4(OH)24H2O, Mg3Ca(CO3)4] is not expected to alter the leaching properties of ash, due to the alkaline media set by their decomposition (Liodakis et al. 2007). 3.2 Elemental Analysis of Ashes and Ash Leachates Table 2 lists the concentrations of metals (K, Na, Ca, Mg, Mn, Fe, Zn, Pb, Cr, Cu, Cd) for all forest species ashes examined, before and after treatment with DAP. In the same table, the ash content (% w/w) of forest species is shown. The data reported in Table 1 are the

average values of four replicate measurements with relative standard deviation below 10%. Among the major metals determined in ash samples, Na has the lowest concentration value (0.41.7%), whereas, among the minor metals, Cr and Cd have the lowest values (1134 g g1). Olea europaea ash has the highest amounts of Ca, Fe, and Zn and the lowest amounts of Mg, Na, and Cu compared to other forest species ashes. The above results are in agreement with other works (Liodakis et al. 2005, 2007; Etigni and Campbell 1991). In general, the presence of DAP decreases the content

176

Water Air Soil Pollut (2009) 199:171182 Cr (g g1) Cd (g g1) Pb (g g1) Cu (g g1) Zn (g g1) Mn (g g1) Table 2 Ash content and ash metal composition of forest species, before and after treatment with DAP Fe (mg g1) Na (mg g1) Mg (mg g1) K (mg g1) Ca (mg g1) ash content (% w/w) Forest species + DAP % 17 16 14 14 12 10 17 13 11 P. halepensis + 0 P. halepensis + 5 P. halepensis + 10 P. lentiscus + 0 P. lentiscus +5 P. lentiscus + 10 O. europea + 0 O. europea + 5 O. europea +10 3.0 5.0 7.8 4.4 6.2 8.2 5.2 6.9 9.2 234 194 153 320 246 191 345 283 196 167 89 68 175 130 79 179 111 91 82 49 35 59 38 31 48 32 27 17 14 20 23 14 9.3 6.1 5.4 4.2 6.3 3.7 3.0 9.0 6.6 4.8 15 12 9.5 830 366 292 995 745 542 918 688 456 718 336 276 760 320 200 1320 685 310 375 236 212 360 327 300 302 295 254 184 156 97 200 186 165 191 176 135 34 24 22 50 38 29 41 26 20

of metals in ash due to the formation of phosphate salts. The cumulative eluted masses of metals Ca, Mg, K, Fe, Mn, Zn, Cu, Pb, and Cr per gram of ash (prepared from forest species, before and after treatment with DAP) during the leaching procedure (five-step mode at pH=6), were plotted against the cumulative volume of leachates (Figs. 2, 3, and 4). The initial leachates of untreated P. halepensis needles ash showed a sharp increase in amount released with progressive leaching for the metals Ca, K, and Cr. The amounts of Mg eluted showed a slight but steady increase in the initial leachates and a higher increase after 40 mL. The amounts of Fe, Mn, Zn, Cu, and Pb were under the detection limits (Fig. 2). As shown in Fig. 2, the presence of DAP obstructs the extraction process of some metals (i.e., Na, K, Cr) contained in ashes and facilitates the removal of others (i.e., Mg, Mn, Zn, Cu when 5% DAP was applied and Ca, Fe, Pb when 10% DAP was applied). In the first case, DAP may form sparingly soluble phosphate compounds that trap the metal ions (i.e., Na2CO3 Na3PO4), whereas in the second case, some less-soluble salts are converted to more soluble ones [i.e., CaCO3 Ca3(PO4)2] (Lide 2007). In addition, the presence of DAP lowers the pH value of leachates up to pH=2.4 because of the formation of H3PO4 (Fig. 1). Under these acidic conditions, severe amounts of toxic elements (i.e., Pb) are resolved, which may lead to a subsequent contamination of soil and ground and underground water. Unexpectedly, a lower amount of Cr was extracted when samples were treated with DAP (Figs. 2, 3 and 4). This observation is in agreement with other reports (Chirenje et al. 2002). Pistacia lentiscus and O. europaea ashes have similar behavior as P. halepensis ash (Figs. 3 and 4). Thus, the metal release from all ash samples examined is governed by the dissolution process at acidic conditions or the conversion of metal ions to soluble or nonsoluble salts. 3.3 X-ray Diffraction Analysis of Ashes Before and After Leaching Table 3 presents the crystalline compounds identified by X-ray diffraction (XRD) analysis in all examined ashes before and after leaching (five-step mode,

Water Air Soil Pollut (2009) 199:171182

177

Fig. 2 Cumulative eluted mass of metals per gram of ash vs and cumulative leachate volume: the ashes were prepared from P. halepensis treated (or not) with DAP, the aqueous solution had pH=6

aqueous eluent of pH=6.0) for samples treated and not treated with DAP. The main types of compounds identified in the forest species ashes, before treatment with DAP, were oxides of Ca and Mg; carbonates; and sulfates of Ca, Mg, and K (Table 3). The crystalline compounds were found to contain mainly Ca and Mg and, to a lesser extent, K. Calcium and magnesium were mainly in

the form of oxides, whereas potassium was mainly in the form of potassium carbonate or calciumpotassium carbonate. In O. europaea and P. lentiscus, the main potassium compound was KCl. The above results were confirmed by atomic absorption spectroscopy (AAS) elemental analysis (Table 2). MgO and CaO detected in forest ashes were probably formed via combustion of magnesia and

178

Water Air Soil Pollut (2009) 199:171182

Fig. 3 Cumulative eluted mass of metals per gram of ash vs and cumulative leachate volume: the ashes were prepared from P. lentiscus treated (or not) with DAP, the aqueous solution had pH=6

calcia organic matter rather than via decomposition of MgCO3 and CaCO3, which takes place at higher temperatures. In some cases, Ca(OH)2 was detected in the sintered products. This compound is formed after the thermal treatment through the reaction between CaO and ambient moisture (Liodakis et al. 2005). After leaching at pH=6, the metal oxides CaO and MgO, as well as K2CO3, K2SO4, MgCO3, and K2Ca

(CO3)2, have been dissolved in the eluent solution, whereas CaCO3 and (CaMg)CO3 remained. The main compounds identified in the 5% w/w DAP-treated ash samples before leaching were Ca4Mg5(PO4)6, Ca2P2O7, Mg2P2O7, and Ca3(PO4)2 for pine needle ash; CaCO3, KPO3, and KCl for P. lentiscus ash; and CaCO3, K2Ca(CO3)2, and Ca(OH)2 for O. europaea ash. After leaching, the remained

Water Air Soil Pollut (2009) 199:171182

179

Fig. 4 Cumulative eluted mass of metals per gram of ash vs and cumulative leachate volume: the ashes were prepared from O. europaea treated (or not) with DAP, the aqueous solution had pH=6

compounds were Ca 3 (PO 4 ) 2 , Ca 4 Mg 5 (PO 4 ) 6 , Mg2P2O7, and Ca2P2O7 (Table 3). The ash samples prepared after treating forest species with 10% w/w DAP have similar mineral composition with those treated with 5% w/w DAP. However, the peaks of XRD patterns of ash samples treated with 10% w/w DAP are lower than those of the ash samples treated with 5% w/w DAP.

3.4 Scanning Electron Microscopy Analysis of Ashes Before and After Leaching Pinus halepensis needles ash samples were examined with scanning electron microscopy (SEM)/energy dispersive X-ray (EDX) in order to determine the influence of DAP and leaching on their morphology and chemical composition. Prior to the DAP treatment and leaching

180

Water Air Soil Pollut (2009) 199:171182

Table 3 Crystalline compounds in forest species ashes, before () and after (+) leaching, identified by XRD analysis: the ashes were prepared from forest species treated (or not) with DAP, the eluent was aqueous solution pH=6 Forest species + DAP % Leaching state Ash composition P. halepensis + 0 P. halepensis +5 P. halepensis + 10 P. lentiscus + 0 P. lentiscus + 5 P. lentiscus + 10 O. europea + 0 O. europea + 5 O. europea + 10 + + + + + + + + + CaCO3, MgCO3, (CaMg)CO3, K2Ca(CO3)2, K2CO3, CaO, MgO, K2SO4 CaCO3, (CaMg)CO3 Ca4Mg5(PO4)6, Ca2P2O7, Mg2P2O7, Ca3(PO4)2, Ca7Mg2P6O24, P2O5, K3PO4, K4P2O7 Ca3(PO4)2, Ca4Mg5(PO4)6, Mg2P2O7, Ca2P2O7, Ca10(PO4)6(OH)2, Ca(H2PO4)2, K5P3O10 Ca7Mg2P6O24, Ca4Mg5(PO4)6, Ca2P2O7, Ca3(PO4)2, Mg2P2O7, P2O5, K3PO4, K4P2O7 Ca3(PO4)2, Ca4Mg5(PO4)6, Mg2P2O7, Ca2P2O7, P2O5, Ca10(PO4)6(OH)2, Ca(H2PO4)2, K5P3O10 KCl, Ca(OH)2, MgO, (CaMg)CO3, K2Ca(CO3)2, K2CO3, CaO, SiO2 CaCO3, K2Ca(CO3)2, Ca(OH)2, MgCO3, CaMg(CO3)2, CaO CaCO3, KPO3, KCl, Ca3(PO4)2, K2Ca(CO3)2, Ca2P2O7, Mg2P2O7, Ca4Mg5(PO4)6, P2O5 KPO3, CaCO3, KCl, Ca(OH)2, K2Ca(CO3)2, Ca2P2O7, Ca3(PO4)2, Mg2P2O7 CaCO3, KPO3, Ca2P2O7, KCl, Ca3(PO4)2, K2Ca(CO3)2, Mg2P2O7, Ca4Mg5(PO4)6, P2O5 KPO3, CaCO3, Ca(OH)2, KCl, K2Ca(CO3)2, Ca2P2O7, Ca3(PO4)2, Mg2P2O7 CaO, KCl, K2CO3 CaCO3, K2CO3, MgO, SiO2, K2SO4 CaCO3, Ca(OH)2, CaMg(CO3)2, CaO CaCO3, K2Ca(CO3)2, Ca(OH)2, MgCO3, CaMg(CO3)2, CaO,, P2O5, K3PO4 Ca3(PO4)2, Ca4Mg5(PO4)6, Mg2P2O7, Ca2P2O7, Ca10(PO4)6(OH)2, Ca(H2PO4)2, CaO CaCO3, KPO3, Ca2P2O7, KCl, Ca3(PO4)2, K2Ca(CO3)2, Mg2P2O7, CaO, P2O5 CaCO3, KPO3, Ca2P2O7, KCl, Ca3(PO4)2, K2Ca(CO3)2, Mg2P2O7, CaO, P2O5

Compounds in italics are the main constituents of the ash examined

test, the morphological analysis of the ash samples shows large porous fibrous particles with holes and voids (Fig. 5a). The respective EDX elemental analysis reveals that the main elements are Ca, Mg, K, P, C, and O (Fig. 5a). After treating P. halepensis needles with 5% w/w DAP, the particles in the ash samples appear to be attached to each other, forming large aggregates with smooth glassy surfaces. By raising the percentage of DAP added up to 10% w/w, amorphous glassy shards are developed (Fig. 5c). The EDX analyses of the DAP-treated samples suggest the decrement of Ca and Mg concentration as the DAP concentration increases. The SEM/EDX analyses of the ash samples after the five-step leaching method revealed a significant change in the morphology (Fig. 5b,d). A partially glassy surface was observed due to the presence of glassy oxides of Si. The main elements of pine ash after leaching are O, Mg, P, Si, and Ca (Fig. 5b). After leaching, the treatment with 10% w/w DAP samples showed large porous particles attached to each other. The respective EDX analysis reveals that the main elements are O, P, K, and Ca (Fig. 5d). Similar results were obtained for the P. lentsicus and O. europaea samples. The above findings are in agreement with those of AAS and XRD analysis (Sections 3.2 and 3.3).

4 Conclusions In conclusion, the leaching properties of ashes of P. halepensis, P. lentiscus, and O. europaea, before and after treatment with DAP, have been evaluated by various analytical techniques (AAS, XRD, and SEM) using a five-step shake leaching test with an aqueous eluent of pH=6. The most interesting conclusions are: 1. Among the leaching steps operated, number one is the most efficient. 2. The presence of DAP obstructs the extraction process of some metals (i.e., K, Na) by transforming carbonate salts to less-soluble phosphates. 3. DAP facilitates the extraction of some toxic metals (i.e., Zn, Mn, Cu) due to the acidic conditions set by the DAP decomposition to phosphate acid. Unexpectedly, DAP prevents the removal of Cr. 4. The leachability properties of forest ash depend on DAP concentration applied on forest species. Thus, with 5% DAP, the maximum quantity of Mg, Zn, Cu, and Mn was eluted, whereas the maximum eluted amount of Fe and Pb was recorded with 10% DAP application.

Water Air Soil Pollut (2009) 199:171182 Fig. 5 Morphological features of P. halepensis needle ashes (treated or not with DAP), prior to and after leaching (five-step mode at pH=6) (ad)

181

182

Water Air Soil Pollut (2009) 199:171182 Hage, J. L. T., & Mulder, E. (2004). Preliminary assessment of three new European leaching tests. Waste Management (New York, N.Y.), 24, 165172. doi:10.1016/S0956053X (03)001296. Hardy, C. E. (1977). Chemicals for forest fire fighting. Boston: National Fire Protection Association. Kalabokidis, K. (2000). Effects of wildfire suppression chemicals on people and the environmenta review. Global Nest. International Journal, 2, 129137. Lide, D. R. (2007). Handbook of chemistry and physics (88th ed.). Boca Raton: CRC/Taylor & Francis. Liodakis, S., Antonopoulos, I., Agiovlasitis, I. P., & Kakardakis, T. (2008). Testing the fire retardancy of Greek minerals hydromagnesite and huntite on WUI forest species Phillyrea latifolia L. Thermochimica Acta, 469, 4351. doi:10.1016/j. tca.2007.12.010. Liodakis, S., Bakirtzis, D., & Dimitrakopoulos, A. P. (2003). Autoignition and thermogravimetric analysis of forest species treated with fire retardants. Thermochimica Acta, 399, 3142. doi:10.1016/S00406031(02)004008. Liodakis, S., Katsigiannis, G., & Kakali, G. (2005). Ash properties of some dominant Greek forest species. Thermochimica Acta, 437, 158167. doi:10.1016/j.tca.2005. 06.041. Liodakis, S., Katsigiannis, G., & Lymperopoulou, T. (2007). Ash properties of Pinus halepensis needles treated with diammonium phosphate. Thermochimica Acta, 453, 136 146. doi:10.1016/j.tca.2006.11.022. Ludwig, B., Khanna, P., Prenzel, J., & Beese, F. (2005). Heavy metal release from different ashes during serial batch tests using water and acid. Waste Management (New York, N.Y.), 25, 10551066. doi:10.1016/j.wasman.2005.01.007. Nurmi, J., & Hillebrand, K. (2007). The characteristics of wholetree fuel stocks from silvicultural cleanings and thinnings. Biomass and Bioenergy, 31(6), 381392. doi:10. 1016/j.biombioe.2007.01.010. Pappa, A., Tzamtzis, N., & Koufopoulou, S. (2006). Effect of fire retardant application on phosphorus leaching from Mediterranean forest soil: short-term laboratory-scale study. International Journal of Wildland Fire, 15, 287 292. doi:10.1071/WF05002. Pappa, A. A., Tzamtzis, N. E., & Koufopoulou, S. E. (2008). Nitrogen leaching from a forest soil exposed to fire retardant with and without fire: A laboratory study. Annals of Forest Science, 65, 210. doi:10.1051/forest:2007093. Saikia, N., Sakaguchi, Y., Kato, S., & Kojima, T. (2006). Composition and leaching behaviours of combustion residues. Fuel, 85, 264271. doi:10.1016/j.fuel.2005. 03.035. Voundi Nkana, J. C., Demeyer, A., & Verloo, M. G. (1998). Chemical effects of wood ash on plant growth in tropical acid soils. Bioresource Technology, 63, 251260. doi:10. 1016/S09608524(97)00134-X. Voundi Nkana, J. C., Demeyer, A., & Verloo, M. G. (2002). Effect of wood ash application on soil solution chemistry. Bioresource Technology, 85, 323325. doi:10.1016/ S09608524(02)001402.

5. Overall, the metal ions extraction from ash samples are governed by their dissolution process at acidic conditions or their transformation to soluble or nonsoluble salts caused by the chemical retardants. 6. High-volume application of wood ash on the ground after forest fire events using chemical retardants may introduce severe quantities of some toxic elements (i.e., Zn, Mn, Cu) to the ecosystem (soil, streams, and ground and underground water).

References
ASTM D110284. (2001). Standard test method for ash in wood. ASTM D 3987 85. (2004). Standard test method for shake extraction of solid wastes with water. Bradstock, R., Sanders, J., & Tegart, A. (1987). Short-term effects on the foliage of a eucalypt forest after an aerial application of a chemical fire retardant. Australian Forestry, 50(2), 7180. Campbell, A. G. (1990). Recycling and disposing of wood ash. Tappi Journal, 73, 141145. Chirenje, T., Rivero, C., & Ma, L. Q. (2002). Leaching of As and Cr in wood-ash-amended soil columns. Soil and Sediment Contamination, 11(3), 359375. doi:10.1080/ 20025891106790. Demeyer, A., Voundi Nkana, J. C., & Verloo, M. G. (2001). Characteristics of wood ash and influence on soil properties and nutrient uptake: an overview. Bioresource Technology, 77, 287295. doi:10.1016/S09608524(00) 000432. Dimitrakopoulos, A. P., & Panov, P. I. (2001). Pyric properties of some Mediterranean vegetation species. International Journal of Wildland Fire, 10, 2327. doi:10.1071/WF01003. DIN 38 414, Teil 4. (1984). Bestimmung der Eluierbarkeit mit Wasser (S4). Deutsch Einheitsverfahren zur Wasser-, Abwasser- und Schlammuntersuchung. Schlamm und Sedimente (Gruppe S.). Etigni, L., & Campbell, G. (1991). Physical and chemical characteristics of wood ash. Bioresource Technology, 37, 173178. doi:10.1016/09608524(91)90207-Z. Fallman, A. M., & Aurell, B. (1986). Leaching tests for environmental assessment of inorganic substances in wastes. The Science of the Total Environment, 178, 71 84. doi:10.1016/00489697(95)047999. Gimnez, A., Pastor, E., Zrate, L., Planas, E., & Arnaldos, J. (2004). Long-term forest fire retardants: a review of quality, effectiveness, application and environmental considerations. International Journal of Wildland Fire, 13, 1 15. doi:10.1071/WF03001.