Fuel Processing Technology 92 (2011) 17641775

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Fuel Processing Technology

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Enrichment of inorganic trace pollutants in re-circulated water streams from a wet limestone ue gas desulphurisation system in two coal power plants
Patricia Crdoba a,, Oriol Font a, Mara Izquierdo a, Xavier Querol a, Aurelio Tobas a, Mara Antonia Lpez-Antn b, Raquel Ochoa-Gonzalez b, Mercedes Daz-Somoano b, M. Rosa Martnez-Tarazona b, Carlos Ayora a, Carlos Leiva c, Constantino Fernndez c, Antonio Gimnez d
a

Instituto de Diagnstico Ambiental y Estudios del Agua (IDA-CSIC), Jordi Girona 18-26, E-08034-Barcelona, Spain Instituto Nacional del Carbn (INCAR-CSIC), Francisco Pintado Fe, 26-33011-Oviedo-Spain c Escuela Superior de Ingenieros de Sevilla, Departamento de Ingeniera Qumica y Ambiental, Camino de los Descubrimientos, s/n. Isla de la Cartuja, 41092 Sevilla, Spain d ENDESA GENERACIN, S.A. Ribera del Loira, 60, planta 2, sector E, 28042, Madrid, Spain
b

a r t i c l e

i n f o

a b s t r a c t
The enrichment of inorganic trace pollutants in re-circulated water streams was studied at two power plants equipped with wet limestone Flue Gas Desulphurisation (FGD) system from the rst re-circulation cycle of water up to the start of sampling campaigns. To elucidate the enrichment of inorganic trace pollutants as result of water re-circulation, a partial and total mass balances were undertaken. A t-Student analysis was performed to ascertain whether the mean contribution of ltered water affected the balance of elements and the enrichment of this water stream. The t-Student revealed the mean contribution of ltered water to total mass balance was statistically signicant (p b 0.05) for Na, Mg, Cl, B, Mn, Se, Cd, Mo, and U at rst plant, and Na, Cl, K, Mg, Hg, Li, B, F, Ni, Zn, Mn, Co Sc, Ge, Se, at the second one. High levels of inorganic trace pollutants in ltered water could be affected by limestone purity, electrostatic precipitator gas temperature, use of additives, uoride and/or sulphate complexes, and the S/F and S/Cl ratios in the scrubber, which may reduce the gaseous retention efciencies in FGD and increase the emission of metals by entraining and/or evaporation of droplets as particulate matter from gypsum slurry. 2011 Elsevier B.V. All rights reserved.

Article history: Received 22 February 2011 Received in revised form 14 April 2011 Accepted 15 April 2011 Available online 8 May 2011 Keywords: Inorganic trace pollutants Re-circulated waters FGD Mass balance Scrubber

1. Introduction The current power generation policy of the European Union (EU) promotes the implementation of co-combustion techniques and Flue Gas Desulphurisation (FGD) systems at Pulverised Coal Combustion plants (PCC). However, these techniques not only bring environmental and economic benets but could also have adverse effects on the environment. Hence, the role of the FGD systems in the abatement of trace pollutants at coal power plants has been extensively studied [111]. A number of processes have been used to prevent and remove SO2 [12]. The wet limestone based process is by far the most widely employed because of its high desulphurisation performance, reliability, and efciency [4]. In this process, SO2 is removed from ue gas combustion by absorption into the limestone in a scrubber giving rise to the formation of gypsum, which is eventually dewatered. The dissolved SO 2 2 dissociates to HSO 3 , which is subsequently oxidised to SO4 2+ 2 by injected air. Finally, SO 4 ions combine with Ca ions, originating from dissolved limestone, and crystallise as gypsum

[13]. The overall reaction in a wet limestone FGD system can be written as follow:
CaCO3 s SO2 g =2 O2 g 2H2 OlCaSO4 :2H2 Os CO2 g
1

Corresponding author. Tel.: + 34 934095410; fax: + 34 934110012. E-mail address: patricia.cordoba@idaea.csic.es (P. Crdoba). 0378-3820/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.fuproc.2011.04.025

FGD chemistry (alkaline sorbent) allows the capture of many pollutants other than sulphur, such as F, As, B, Cl, Se or Hg [1,5,8,9,14], in a gaseous form and/or as particulate matter (PM). Once captured, a certain proportion of the trace pollutants is partitioned into solid and water streams. Low proportions are released in a gaseous and/or PM form. The design of the FGD system depends on the availability of water near the power plant. Power plants with available water resources are usually designed with efuent treatment plants resulting in sludge with a high pollutant load. Where water resources are scarce, the recirculation of the water to the scrubber from gypsum slurry ltration is preferred owing to the economic and environmental benets of recycling. Enrichment of some inorganic trace pollutants in re-circulated water streams is the most important consequence of FGD systems with re-circulation of water from gypsum slurry. High levels of inorganic trace pollutants in re-circulated waters may give rise to a high ionic strength which reduces the gaseous solubility and

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probably, the retention efciencies in wet FGD. The enrichment may also increase the concentration of trace pollutants in the re-circulated waters up to very high levels compared with that of the natural fresh waters [15].This could result in environmental (pollution of soil and groundwater) and technical problems (fouling of scrubber and pipes of the FGD), especially, if the re-circulation of the water streams is interrupted and/or a water treatment is necessary for hypothetical and eventual discharges to the environment. Furthermore, the contribution of other streams (limestone) and the operational conditions of the FGD system, such as use of additives, control the speciation and the partitioning of trace pollutants into FGD streams. Earlier studies [16] reported changes on the speciation of F when Al additives are injected into the scrubber. These authors showed that the speciation of trace pollutants especially F plays a crucial role in the leaching potential of the FGD gypsum end-product. Although the solid by-products of PCC-FGD plants such as y ash (FA) and slag [1725] and FGD gypsum [13,14] have been studied and classied, less attention has been paid to the partitioning, speciation, and enrichment of inorganic trace pollutants in FGD water streams with water re-circulation. The study of FGD water streams with water re-circulation is therefore essential for determining and evaluating the partitioning and speciation of inorganic trace pollutants through FGD system. The objectives of the present work are: (a) to study the enrichment and partitioning of inorganic trace pollutants in recirculated water streams at two large power plants in Spain (PP1 and PP2) equipped with forced-oxidation wet limestone FGD system from the rst re-circulation cycle of water up to the start of sampling campaigns; and (b) to assess the contribution of the most important sources (PM incoming scrubber and limestone) to the enrichment of inorganic trace pollutants in re-circulated water streams, and the feed fuel blend estimation as crucial factor for the FA composition and the PM that escapes from the electrostatic precipitator (ESP). Our results will give rise to subsequent modelling studies of inorganic trace pollutant speciation in FGD water streams with water re-circulation and FGD gypsum and to preventive and/or corrective measures for the removal of inorganic trace pollutants in FGD water streams. 2. Materials and methods 2.1. Sampling execution The sampling campaigns at PP1 (1075 MW) and PP2 (1200 MW) were carried out at 100% MCR (maximum capacity) and 100% desulphurisation on two consecutive days in September 2007 at PP1 and in November 2007 and November 2008 at PP2. Both power plants were equipped with a wet limestone FGD system with forcedoxidation. PP1 was fed with 100% coal (60:40 blend of imported bituminous and local high sulphur sub-bituminous coal). PP2 was fed with 84:16 and 88:12 coal/petroleum coke blends for samplings conducted in 2007 and 2008, respectively. The coal at PP2 is a blend of Spanish anthracitic coals and imported South African bituminous coal. The petroleum coke is a blend of Spanish and imported petroleumcokes. The FGD system involves a number of water streams that can be separated into 2 groups: (i) water streams not involved directly in FGD (process and slag water); and (ii) FGD water streams (treated and added water, limestone and gypsum slurry waters, and ltered water). At PP1, the process water comes from a nearby ash pond overlaying of sulphate and Sr-rich sedimentary rocks, whereas at PP2, the process water is located over metamorphic and igneous rocks. In both power plants, the process water is used in slag quenching and drainage giving rise to slag water. At PP1, a fraction of process water is treated before its use to reduce the high content of salts. The resulting water (treated water) is used for limestone slurry preparation, and is then considered as FGD water stream. The added water is similar in

composition to the treated water and is used to offset the water loss because of moisture in the gypsum and in the emitted gas. The gypsum slurry water is the liquid fraction from gypsum slurry produced in the scrubber. The ltered water is the water that results from the gypsum slurry ltration. At PP1, a fraction of ltered water is re-circulated to the scrubber after a purge process, which reduces the concentrations of some elements (especially Cl); while the remaining ltered water fraction is used for limestone slurry preparation. This result in a 0.55/0.45 mixture ratio of limestone slurry water and ltered water in the scrubber (named mixture water). At PP2, all ltered water is directly re-circulated to the scrubber and the limestone slurry is only prepared with process water which results in limestone slurry water/ltered water ratio of 0.47/0.53 (mixture water). Furthermore, an aluminium additive is injected into the scrubber at PP2 to boost the reaction of F with Al in order to improve SO2 sorption by Ca. In this article, the terms gypsum slurry and limestone slurry are used for the total fraction of the slurries (solid + liquid) while gypsum slurry water and limestone slurry water are employed for the liquid fraction of the corresponding slurries. It is should be pointed out that the gypsum slurry water is the water stream where the inorganic trace pollutant can be primarily enriched by dissolution. However, given that the ltered water is the water re-circulated to the scrubber, the enrichment of inorganic trace pollutants should be referred to ltered water. A total of 13 streams, 6 solid (feed fuel blend, slag, FA, PM, limestone, and FGD gypsum) and 7 water streams (process water, slag water, treated water, added water, ltered water, and limestone and gypsum slurry waters) were sampled and analysed at PP1. At PP2, 11 streams, 6 solids (feed fuel blend, slag, FA, PM, limestone, and FGD gypsum) and 5 water streams (process water, slag water, ltered water, and limestone and gypsum slurry waters) were collected and analysed in the 2007 and 2008 sampling campaigns (Fig. 1). Isokinetic measurements of gaseous streams were performed at two sampling points (Fig. 1), IN-FGD (1) and OUT-FGD (2), simultaneously. Each sampling run lasted about 2.5 h. At each sampling point, two trains of sampling system were assembled with specic trapping solutions, one for the capture of anions and metals, and other for the capture and speciation of Hg. In the rst case, the gas sampling system was devised according to EN 1911 and EN 14385. In such a system, two impingers 100 mL of de-ionised H2O (or MilliQ grade water) and two lled with 6 wt.% HNO3 and 10 wt.% H2O2 were assembled to determine the concentrations of anions and metals, respectively, in a ice bath. The sampling and speciation of gaseous Hg (Hg0 and Hg2+) were devised according to EN 13211 and Meij and Winkel [9]. A train of dark glass impingers in an ice bath was used. The Hg sampling system consists of a rst impinger lled with 100 mL of HCl to capture Hg2+ [9], the second impinger containing 3 wt.% H2O2 for SO2 removal (150 mL at point A and 100 mL at point B), and the two last impingers containing 4 wt.% K2Cr2O7 with 20 wt.% of HNO3 for Hg0 trapping. The PM that escapes ESP and FGD is dened and termed y ash and y dust [26], respectively, although the terms PM IN and OUT-FGD are used in this article. A quartz lter was placed before the isokinetic train for PM IN and OUT-FGD collection in the Hg sampling. A Teon lter was used for the PM capture of anions and metals since HF reacts with quartz to form highly volatile SiF2 6 with a subsequent loss of uorine. 2.2. Chemical characterisation of solid, water, and gaseous streams The solid samples were acid-digested in duplicate by using a twostep digestion method devised by Querol et al. [27]. The resulting solution was then analysed by Inductively-Coupled Plasma AtomicEmission Spectrometry (ICP-AES) for major and minor elements using the Iris Advantage Radial ER/S device from Thermo Jarrell-Ash. A previous semi-quantitative analysis was carried out to identify the

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WS3 Treated water
WS4 Added water Limestone slurry (solid) Limestone slurry water WS6 Water treatment

PP1

Process water WS1

Limestone SS4

Limestone slurry

2 BOILER Air pre-heater

ESP

Scrubber
1

Air (forced oxidation)

Desulphured gas

GGH

Stack

Filtered water WS5

Mill
Coal blend SS1 Raw coal

Gypsum slurry
Filtering system

(Hydrocyclons)
Fly ash SS3 Gypsum slurry (solid) Gypsum slurry water WS7

Gypsum SS6

Dumped

Slag SS2

Slag water

WS2
WS1 Process water

PP2
SS4 Limestone Al-sulphate

Limestone slurry (solid) Limestone slurry water WS4 Limestone slurry 2

Scrubber 1
Air (forced oxidation)

BOILER

Air pre-heater

ESP

Desulphured gas

GGH

Stack

Filtered water WS3

Mill
Feed blend SS1 Slag SS2 Slag water

Feed coal

Gypsum slurry Filtering system

(Hydrocyclons) Gypsum SS6 Dumped

Feed co-matter
(petroleum coke)

Fly ash SS3

Gypsum slurry (solid) Gypsum slurry water WS5

WS2

1: Sampling point of particulate matter (PM) and gaseous stream that reach the FGD system (PM and GAS IN-FGD). 2: Sampling point of particulate matter (PM) and gaseous stream that escape the FGD system (PM and GAS OUT-FGD). SS: solid samples WS: water samples
Fig. 1. Sampling scheme of PP1 and PP2 and the corresponding samples.

range of element concentrations as well as the matrix and the possible spectral interferences. The calibration was carried out by means of the international certied standard (1000 and 10.000 ppm). Most of the trace elements were analysed by Inductively-Coupled Plasma Mass Spectrometry (ICP-MS) using the X-SERIES II device from Thermo Fisher SCIENTIFIC. The quantitative analysis was carried out using an external standard with similar matrix of the samples,

which covered concentrations range expected forming the calibration lines. The internal correction was carried out by means of an internal standard (In 10 ppb). The Fly ash and coal international reference material (NBS1633b and SARM19) were also digested to determine the accuracy of the analytical and digestion methods. Analytical precision of 4 NBS1633b samples expressed as relative error percentage (ER) were estimated at 2 to 9% for most of the elements

Table 1 Source of major, minor, and trace elements to FGD system at PP1 and PP2. PP1 2007 Limestone (64100%) Al, Ca, Fe, Na, K, Mg, Li, Sc, Ti, P, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, As, Rb, Sr, Y, Zr, Sn, Ba, Pb and U (99100%) Be, Ge, Mo, Cd, Bi, and REEs (6899%) S, Cl, F, Hg, B, and Se PP2 2007 (35100%) Ca, Fe, Mg, P, Mn, Co, Se, Sr, Y, Mo, Pb, and U PP2 2008 (6197%) Ca, Fe, Mg, Cr, Mn, Ni, Cu, Se, Sr, Y, and U

PM IN-FGD

GAS IN-FGD Al-additive

(48100%) Na, K, Li, Be, Sc, Ti, V, Cr, Ni, Cu, Zn, Ga, Ge, As, Rb, Sn, Sb, Ba, Se, and REEs (9099%) S, Cl, F, Hg, and B Al (88%) and S (9%)

(57100%) K, Li, Be, Sc, Ti, P, V, Co, As, Ba, Mo, Zn, Ga, Ge, Pb, and REEs (8099%) S, Cl, F, Hg, and B Al (77%) and S (0.7%)

PM IN-FGD: y ash that escapes from the electrostatic precipitator (ESP) and enter into the FGD system. GAS IN-FGD: gaseous stream that enter into the FGD system. Al-additive: additive of Aluminium used at PP2.

P. Crdoba et al. / Fuel Processing Technology 92 (2011) 17641775 Table 2 Mean concentration of major, minor, and trace elements in feed fuel blend, FA, slag, and FA/slag ratios at PP1 and PP2. PP1 2007 Fuel blend % dry basis (db) Al 3.5 Ca 1.1 Fe 3.7 Na 0.05 S 5.4 K 0.3 Mg 0.2 mg/kg (db) Cl 47 F 197 Hg 0.08 Li 70 Be 3 B 43 Sc 5 Ti 1420 P 566 V 57 Cr 38 Mn 82 Co 9 Ni 20 Cu 17 Zn 65 Ga 11 Ge 2 As 21 Se 3 Rb 19 Sr 258 Y 13 Zr 43 Nb 6 Mo 3 Cd b 0.2 Sn 2 Sb 1 Cs 4 Ba 166 La 15 Ce 35 Pr 3 Nd 14 Sm 3 Eu b 0.1 Gd 3 Tb b 0.1 Dy 2 Ho b 0.1 Er 1 Yb b 0.1 Hf 1 Ta 1 W 3 Tl b 0.1 Pb 13 Bi b 0.1 Th 6 U 5 FA 14 4 13 0.1 0.3 1 0.7 Slag 13 4 16 0.1 0.04 0.9 0.6 FA/slag 1.1 1.0 0.8 1.0 7.5 1.1 1.1 PP2 2007 Fuel blend 3.2 0.5 1.4 0.2 1.8 1.0 0.3 FA 13 2 5 0.5 0.2 3 1 Slag 13 2 6 0.5 b 0.1 3 1 FA/slag 1.0 1.0 0.9 1.0 N2 1.0 1.0 PP2 2008 Fuel blend 3.3 0.5 1.3 0.2 1.6 0.9 0.3 FA 14 2 5 0.6 0.1 3 1 Slag 13 2 5 0.5 0.04 3 1

1767

FA/slag 1.0 1.0 1.0 1.0 3.7 1.0 1.0

15 123 0.04 298 11 211 23 5468 2014 219 149 321 33 74 63 309 47 8 85 6 81 1001 51 197 17 14 0.9 8 3 15 683 57 133 14 56 12 2 12 2 9 2 4 5 7 2 9 2 59 2 28 22

20 7 0.002 263 9 58 19 5199 1380 162 153 340 35 74 59 174 32 5 15 8 71 947 49 204 17 5 b 0.1 4 2 13 639 56 131 13 56 11 2 12 1 8 1 4 5 6 3 5 b 0.01 30 b 0.01 25 18

0.8 18.0 20.0 1.1 1.2 3.7 1.2 1.1 1.5 1.4 0.9 0.9 0.9 1.0 1.1 1.8 1.5 1.7 5.5 0.8 1.1 1.1 1.1 0.9 1.0 2.6 N 10 2.1 1.9 1.2 1.1 1.0 1.0 1.1 1.0 1.1 1.0 1.0 1.1 1.1 1.1 1.0 1.0 1.1 0.9 1.7 N 0.01 1.9 N 0.01 1.1 1.3

54 186 0.2 56 2 32 5 1535 411 447 46 136 9 90 22 50 10 b 0.1 24 2 45 87 10 36 9 7 b 0.1 1 4 6 292 13 32 3 14 3 b 0.1 3 b 0.1 2 b 0.1 1 b 0.1 1 1 2 b 0.1 20 b 0.1 7 2

26 135 0.09 197 6 70 22 5819 1644 1414 149 516 30 288 81 184 36 3 94 4 162 381 37 159 32 23 0.7 7 17 22 1111 48 119 12 52 11 2 10 1 7 1 3 4 5 4 8 2 83 1 27 7

28 14 0.01 197 6 22 22 6042 1011 1157 150 558 27 227 68 87 22 1 9 3 165 368 38 177 33 8 b 0.1 2 7 21 1118 48 125 12 53 11 2 10 1 7 1 4 4 5 5 5 b 0.01 34 b 0.01 28 7

0.9 10.0 13.0 1.0 1.0 3.2 1.0 1.0 1.6 1.2 1.0 0.9 1.1 1.3 1.2 2.1 1.7 2.6 10.0 1.4 1.0 1.0 1.0 0.9 1.0 2.9 N7 3.3 2.5 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 0.9 1.0 1.0 0.8 1.8 N 0.01 2.4 N 0.01 1.0 1.0

50 229 0.2 54 1 39 5 1271 494 285 32 115 9 64 25 49 9 b 0.1 23 2 41 82 9 30 9 6 b 0.1 2 5 6 246 11 28 3 12 3 b 0.1 b 0.1 2 b 0.1 0.4 b 0.1 b 0.1 1 2 2 b 0.1 23 b 0.1 6 2

157 0.082 212 5 92 23 5526 1780 1194 170 566 35 229 102 192 38 3 90 5 173 293 38 158 37 22 1 7 23 25 1125 47 117 11 50 11 2 10 1 7 1 3 4 5 2 11 1.6 102 2 26 8

b 40 14 0.001 204 5 49 23 5498 1217 941 157 589 31 184 83 104 26 1 9 5 171 290 37 168 40 8 b 0.1 3 10 24 1086 46 115 11 49 11 2 10 1 7 1 3 4 5 5 7 b 0.01 42 b 0.01 25 8

11.0 62.0 1.0 1.0 1.9 1.0 1.0 1.5 1.3 1.1 1.0 1.1 1.2 1.2 1.8 1.5 2.6 9.8 1.0 1.0 1.0 1.0 0.9 0.9 2.7 N 10 2.5 2.3 1.1 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 0.5 1.6 N1 2.4 N1 1.0 1.0

FA: y ash. FA/slag: y ash/slag concentration ratios.

and around 18% for Cd with respect to certied values, while the analytical precision of 4 SARM 19 samples were estimated at 2 to 9% for most of the elements with the exception of B, Zn, Ti, Rb, Ge, Sr, Cs, and La (9% b ER b 20%). Chlorine contents in solid samples were determined by ASTM D4208, and F was determined according to the pyro-hydrolitic extraction method described in the ISO 11724 standard. The reference materials SARM 19 and NIST 1635 were also measured by oxidative and

pyro-hydrolysis digestion for subsequent determination of Cl and F, respectively by selective electrode. Water streams and trapping solutions from ue gas sampling were directly analysed by ICP-AES and ICP-MS for major and trace elements, respectively. Chloride contents were measured by means of high performance ion chromatography (HPIC), whereas uoride was determined by ion selective electrode. Levels of NH+ 4 in water streams and trapping solutions were analysed using a selective electrode. Mercury

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analyses were carried out directly on solid, water, and lter samples using a LECO AMA 254 gold amalgam atomic absorption spectrometer, after pyrolysis of each sample in combustion tube approximately at 750 C under an oxygen-rich atmosphere, and collection on a gold amalgamator. The analysed and certied values of Hg (NBS 1633 b (N 0.01) and SARM 20) were also measured to determine the accuracy of the results. Accuracies determined by comparing results on NBS 1633 b and SARM 20 with certied values, were within 7%. The levels of PM IN and OUT-FGD were obtained using standard gravimetric methods. The contents of major and trace elements in the lters were determined by ICP-AES and ICP-MS, respectively, after a lter digestion. Particulate Hg was directly determined by GA-AAS on lter samples. 2.3. Mass balances for trace pollutants in FGD water streams The mass balances of FGD water streams operating at PP1 and PP2 during samplings (considering the re-circulation of water streams) were closed without/in ratios close to 1. Therefore, two mass balances, partial and total mass balances (PMB and TMB) were performed to determine the potential enrichment of inorganic trace pollutants in recirculated water streams from the rst re-circulation cycle of water up to the start of sampling campaigns by normalising the concentration of each element in a given stream with the corresponding sampling ow. Owing to the impossibility of determining the analytical composition of the FGD waters streams in the rst operating cycle of the water re-circulation, an estimation of this cycle was carried out. The rst operating cycle estimation was performed by considering the process/treated water as the only water stream for limestone slurry preparation, and by including limestone, gas, PM, and gypsum as inputs and outputs streams. The rst operating cycle estimation was performed considering the following ows:
PMB =    h FlowGypsum Ci Gypsum + FlowPM OUTFGD Ci PM OUTFGD 2 i h   FlowLimestone Ci Limestone + FlowGAS OUTFGD Ci GAS OUTFGD     + FlowMixture water Ci Process = treated water + FlowPM INFGD Ci PM INFGD

IN and OUT-FGD. The ows of mixture water are 80.1 and 52.5 g/h for PP1 and PP2, respectively. A number of species were omitted from + PMB and TMB (NO 3 and NH4 ) given the low concentrations and their partial secondary origin. Combining information from PMB and TMB will allow us to determine the behaviour and watersolid partitioning of elements in

Table 3 Mean concentration of major, minor, and trace elements in limestone and gypsum at PP1 and PP2. PP1 2007 Limestone % dry basis (db) Al 0.5 Ca 37 Fe 0.3 Na 0.01 S 0.03 K 0.2 Mg 0.5 mg/kg Cl F Hg Li Be B Sc Ti P V Cr Mn Co Ni Cu Zn Ga Ge As Se Rb Sr Y Zr Nb Mo Cd Sn Sb Cs Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta W Tl Pb Bi Th U (db) 24 217 0.003 8 b 0.1 8 1 293 178 11 8 86 2 8 3 18 1 b 0.01 2 b 0.01 9 161 2 8 1 b 0.01 b 0.2 0.1 b 0.1 0.9 22 2 5 b 0.1 3 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 2 b 0.1 1 3 Gypsum 0.3 23 0.2 0.02 18 0.1 0.4 PP2 2007 Limestone b 0.1 39 0.1 b 0.1 b 0.1 b 0.1 0.3 Gypsum 0.1 25 0.1 b 0.1 15 b 0.1 0.2 PP2 2008 Limestone b 0.1 39 0.0 b 0.1 b 0.1 b 0.1 0.2 Gypsum 0.1 25 0.05 b 0.01 15 b 0.01 0.2

 i + FlowGAS INFGD Ci GAS INFGD

Given the ows considered for this estimation, PMB values 1 indicate the partial dissolution of a given element in the gypsum slurry water. Two important factors should be borne in mind when considering PMB: a) the solid by-products are produced under re-circulation of water streams. Hence, a number of elements are retained in gypsum by precipitation if saturation or equilibrium is reached in the water stream; and b) adsorption processes may account for the retention in gypsum of certain highly soluble elements (such as Cl, B, and Hg). TMB was performed by considering the process/treated water as the only water stream for limestone slurry preparation and the ltered water as water output stream. TMB values N 1 will therefore suggest elements enriched by re-circulation of ltered water after a number of re-circulations. The ows considered for TMB calculations are detailed as follow:
TMB =    h FlowGypsum Ci Gypsum + FlowPM OUTFGD Ci PM OUTFGD 3    i + FlowGAS OUTFGD Ci GAS OUTFGD + FlowFiltered water Ci Filtered water    h = FlowLimestone Ci Limestone + FlowMixture water Ci Process = treated water   i  + FlowPM INFGD Ci PM INFGD + FlowGAS INFGD Ci GAS INFGD

Where the output and input ows (Flowx) are the ows for a given stream (x) IN and OUT-FGD for mass balance calculations; and Ci is the mean concentration of a certain element in the corresponding stream

297 931 0.154 5 b 0.1 14 1 201 136 7 5 56 1 4 2 b 0.01 1 b 0.01 2 2 5 113 1 5 1 b 0.01 b 0.2 0.1 b 0.01 b 0.01 16 2 3 b 0.01 2 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 1 b 0.01 b 0.01 2

22 14 0.0002 b 0.01 b 0.01 b 0.01 b 0.01 8 b 0.01 1 1 142 1 5 1 b 0.01 b 0.01 b 0.01 b 0.01 1 b 0.01 186 5 b 0.01 b 0.01 2 b 0.01 b 0.01 b 0.01 b 0.01 2 2 3 b 0.001 2 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 2 b 0.01 b 0.01 1

556 904 0.3 1.4 b 0.1 7.7 b 0.1 22 b 0.01 7 1 93 b 0.1 5 1 1 b 0.1 b 0.1 1 1 b 0.1 115 3 b 0.1 b 0.1 b 0.1 b 0.1 1 b 0.1 b 0.1 5 1 3 b 0.1 2 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 1 b 0.01 b 0.01 1

b 40 16 0.002 b 0.01 b 0.01 14 b 0.001 11 b 0.01 3 1 121 b 0.01 6 1 b 0.01 b 0.01 b 0.01 1 2 b 0.01 188 3 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 4 b 0.001 2 b 0.001 1 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 0.4 b 0.01 b 0.01 1

478 2286 0.3 1 b 0.01 31 b 0.01 24 b 0.01 6 2 67 b 0.01 5 1 5 b 0.01 b 0.01 1 3 1 120 2.4 1 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 5 1 2 b 0.001 1 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 b 0.01 1 b 0.01 b 0.01 1

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the wet limestone FGD system with re-circulation of ltered water, and their enrichment or depletion in ltered water. 2.4. Statistical analysis A t-Student statistical test was performed to determine the accuracy of the results and to ascertain statistically whether the differences between PMB and TMB (out/in ratios) were due to an enrichment of inorganic trace pollutants in ltered water. We ascertained whether the mean contribution of ltered water for a given element to TMB was signicant (p b 0.05) and whether the differences between PMB and TMB were attributable to the enrichment of the element in ltered water. The t-Student was applied to mean ow (g/h) from 4 and 6 subsamples of the ltered water, for each element, at PP1 and PP2, respectively. The t-Student was applied to the elements with differences 0.2 out/in ratios between PMB and TMB. 3. Results and discussion The solid (limestone), water (process water/treated water and limestone slurry water), and gaseous streams IN-FGD (including PM) are the sources of trace pollutants in the FGD system (Table 1). Nevertheless, the characteristics of the feed fuel blend are crucial for the FA composition and also of PM that escapes from the ESP. 3.1. Characterisation of solid streams 3.1.1. Feed fuel blend The feed fuel blends at PP1 and PP2 are characterised by high ash (2829%, dry basis (db)). The feed fuel blend at PP1 is characterised by high to moderate contents of S, Fe, and Ca with respect to feed fuel blend at the PP2, and by a number of trace elements such as Sr and U. The feed fuel blend has higher contents of Na, K, Rb, Sb, and Hg at PP2 than at PP1. The petroleum coke co-ring at PP2 gives rise to high contents of V and Ni in the feed fuel blend (Table 2). Both the organic afnity and high contents of V and Ni in the petroleum coke may promote the condensation of these elements in FA and a subsequent higher contribution as PM IN-FGD at PP2 than at PP1. 3.1.2. Fly ash and slag In line with the observations on the feed fuel blend chemistry, FA at PP1 is enriched in Ca (by a factor of 2), in B (3), Ge (3), and U (3) with respect to FA at PP2. By contrast, the FA at PP2 is enriched in Na (5), K (3), V (6), Ni (4), Rb (2), Sb (7), and Ba (2) (Table 2). The FA/slag concentration ratio determined for FA at PP2 is similar to that at PP1 despite the use different feed fuel blends. Nevertheless, it should be noted that the FA/slag ratio for elements with a high condensation potential is higher for Ni (1.3), Ge (1.5), As (1.8), Se (1.8), Sn (1.6), Sb (1.3), Zn (1.1), and Pb (1.3) at PP2 than that at PP1 (Table 2). In spite of the volatized proportion of the elements during combustion at PP1 and PP2, the lower ESP gas temperatures at PP2

(149 C) with respect those at PP1 (170180 C) may also account for enhancing condensation during (co)combustion and a higher PM contribution to FGD at PP2 than at PP1. 3.1.3. Limestone The limestone used in the FGD system at PP1 has relatively high contents of Mn and Sr (Table 3). The PP1 limestone also contains signicant concentrations of Al, F, Ti, P and minor contents of Cl and U. Conversely, the limestone used at PP2 (Table 3) has a high purity (99% Ca-carbonate), with only Sr and Mn being present in signicant levels. 3.1.4. Gypsum FGD gypsum at PP1 has signicant proportions of Ca, S, Mg, Al, and Fe. Gypsum at PP1 also contains high concentrations of F, Cl, Ti, P, Sr, and minor contents of Mn and U. FGD gypsum at PP2 shows a similar composition with slight differences in some elements (Table 3). Gypsum at PP2 is enriched in Cl, F, Mn, and Hg, and depleted in S, Mg, Al, Fe, and Ti. 3.2. Characterisation of gaseous streams and particulate matter 3.2.1. Gaseous streams Signicant differences in the gaseous streams are observed for S, Hg, F, Cl, B, Se, and As IN-FGD at the two power plants. SO2 is the dominant specie IN-FGD reaching levels around 14500 mg/m3N at PP1, and 40005000 mg/m3N at PP2. These levels are drastically decreased after FGD (Table 4), which indicate that SO2 emissions are successfully reduced. The levels of B, Se, and As are also higher at PP1 than those in 2007 and in 2008 at PP2. These levels decrease after FGD, yielding reduction rates N 89% at PP1, and 6792% in 2007 and N 91% in 2008 with the exception of Se reduction rate (37%) at PP2. By contrast, the Cl and F levels IN-FGD are higher in 20072008 at PP2 than those at PP1 (Table 4). Fluorine and Cl levels decrease markedly after FGD (retention rate N 97%) at two power plants. In line with the higher Hg concentration in the feed fuel blend at PP2, the concentration of total Hg IN-FGD is markedly higher in the two campaigns at PP2 than at PP1, attaining reduction levels of 21% and 65% at PP2, and 72% at PP1.The detailed behaviour of gases IN and OUT-FGD and the emissions from PP1 and PP2 are reported elsewhere [14]. 3.2.2. Particulate matter The higher inputs of most condensing elements in PM at PP2 (Table 5) should be pointed out. At PP2, the content of Cu is higher in 2007 PM (by a factor of 10), in Sb (9), Ni (8), Hg (6), V (5), Pb (5), Se (4), Mo (4), Rb (4), As (3), Ba (3), and.Zn (2), with respect to PM INFGD at PP1 given the aforementioned higher enrichment of the condensing elements in FA at PP2 than those at PP1. It is also worth mentioning the higher contribution of PM in 2007 than in 2008 at PP2. The results on chemical characterisation of PM (Table 5) reveals that the contents of most elements tend to decrease in PM OUT-FGD with the exception of S, Se, and Hg. The concentrations of S, Se, and

Table 4 Concentration of gaseous components IN and OUT-FGD and gaseous retention efciencies at PP1 and PP2. mg/m3N SO2 PP1 2007 IN-FGD OUT-FGD % retention IN-FGD OUT-FGD % retention IN-FGD OUT-FGD % retention 14595 989 94 4319 779 82 4746 555 88 Cl 6212 202 97 7191 51 99 6148 93 98 F 23019 370 99 14357 78 99 31296 147 100 B 385 16 96 187 15 92 310 26 91 g/m3N Se 88 5.2 94 1.0 0.2 80 1.8 1.2 37 As 1.2 0.1 89 0.3 0.1 67 0.8 0.01 98 Hg tot 7.8 2.2 72 21 7.4 65 19 15 21 Hg2+ 5.8 0.7 89 18 4.9 73 17 13 24 Hg0 2.0 1.6 26 3.0 2.5 17 2.2 2.0 9.1

PP2 2007

PP2 2008

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Table 5 Mean concentrations of PM IN and OUT-FGD at PP1 and PP2. PP1 2007 mg/m3N Al Ca Fe K Mg Na P S g/m3N Li Be B Sc Ti V Cr Mn Co Ni Cu Zn Ga Ge As Se Rb Sr Y Zr Nb Mo Cd Sn Sb Cs Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Yb Hf Ta W Tl Pb Bi Th U Hg (ng/m3N) IN-FGD 5.2 2.2 4.7 0.3 0.2 0.01 0.2 0.9 16 0.6 4.3 1.3 313 26 20 24 1.9 27 5.7 29 3.0 0.5 7.9 3.6 2.2 62 2.0 10 1.2 3.3 0.2 1.8 0.4 0.4 31 2.9 7.1 0.6 2.3 0.5 0.1 0.4 0.1 0.3 0.1 0.2 0.2 0.2 0.3 1.2 0.2 4.2 0.2 1.3 1.0 1.3 OUT-FGD 1.2 0.5 1.0 0.1 0.1 0.01 0.1 4.1 3 0.1 0.1 0.3 57 4.7 12 6.7 0.4 8.4 4.3 8.3 0.6 0.2 2.3 27 0.7 12 0.5 1.9 0.3 1.6 0.3 0.3 0.1 0.1 6.9 0.6 1.3 0.1 0.6 0.1 0.02 0.1 0.01 0.1 0.02 0.04 0.04 0.1 0.04 0.3 0.1 0.8 0.04 0.3 0.2 8.8 PP2 2007 IN-FGD 7.6 2.0 5.3 2.0 0.9 0.4 0.4 5.1 13 0.4 1.9 1.5 395 133 406 76 4.2 220 57 55 4.5 1.0 21 14 9.7 27 2.9 13 2.5 13 0.6 3.0 3.4 1.3 89 4.5 8.9 1.1 4.7 1.0 0.1 0.8 0.1 0.6 0.1 0.3 0.3 0.5 0.3 2.3 0.7 21 0.7 2.3 0.8 7.3 OUT-FGD 3.1 2.1 1.2 0.7 0.6 0.2 0.1 3.5 6.3 0.2 0.6 0.6 150 54 4.9 26 1.0 10.6 7.7 39 1.8 0.7 12 17 3.1 21 1.6 6.4 0.8 4.3 0.3 0.7 1.4 0.5 38 2.3 3.8 0.6 2.4 0.5 0.1 0.4 0.1 0.3 0.1 0.1 0.2 0.3 0.04 0.6 0.4 5.8 0.2 1.1 0.6 9.4 PP2 2008 IN-FGD 2.9 0.4 1.1 0.6 0.3 0.1 0.1 0.5 4.7 0.1 b 0.001 0.6 138 37 3.9 16 0.9 6.5 2.7 12 1.3 0.3 6.0 1.3 3.4 7.3 1.0 4.9 1.1 2.0 0.1 0.4 1.3 0.5 29 1.4 2.9 0.3 1.5 0.3 0.05 0.3 0.03 0.2 0.04 0.1 0.1 0.2 0.4 0.6 0.1 3.8 0.1 0.8 0.2 0.7 OUT-FGD 0.7 0.3 0.3 0.2 0.2 0.1 0.02 0.6 1.1 0.04 b 0.001 0.1 52 11 1.7 10 0.3 3.1 1.2 5.7 0.4 0.1 3.3 0.9 0.7 2.4 0.3 1.9 0.3 b 0.001 0.1 0.2 0.4 0.1 5.4 0.5 0.7 0.1 0.5 0.1 0.02 0.1 0.01 0.1 0.01 0.03 0.04 0.1 0.01 0.3 0.02 1.2 0.1 0.3 0.1 1.8

3.3. Characterisation of water streams 3.3.1. Treated and process water streams The treated water is characterised by remarkable concentrations of Sr, B, Li, Ca, U, Cl, and S at PP1; probably attributable to aforementioned source of process water. At PP2, the process water shows low concentration of most elements, only B, Sr, and Mn are slightly enriched in this water stream in the two sampling campaigns (Table 6).

PM IN-FGD: y ash that escapes from the ESP and enter into the FGD system. PM OUT-FGD: y dust that escapes from FGD system.

especially Hg (at PP2) in PM increased OUT-FGD with respect those IN-FGD probably due to the entraining of gypsum slurry particles by the gas OUT-FGD and/or evaporation of gypsum slurry droplets subsequently condensed on lters. PM levels fell considerably (45%) at PP1 and (6978%) at PP2 after FGD.
Notes to Table 6: PW: process water. TW: treated water. a LSW: limestone slurry water. b GSW: gypsum slurry water. c FW: ltered water.

3.3.2. Limestone and gypsum slurry waters and ltered waters The limestone and gypsum slurry waters at PP1 have very high concentrations of S, Mg, Ca, and Cl (Table 6), followed by B, Li, Se, Ba, Mo, and especially Ni, Zn, Co and U in the gypsum slurry water. This could be related with the relatively high mobility of oxy-anionic species (i.e. As, B, Cr, Mo, Se, and V) and the slightly alkaline pH (7.47.6) of limestone and gypsum slurry waters. In the case of the limestone slurry water, the high contents of the above elements are attributed to the re-circulation of a fraction of ltered water for limestone slurry preparation. Furthermore, U may form soluble uranyl complexes with carbonates that may promote presence of U bearing complexes in the gypsum slurry water [28]. The leaching of y ash particles reaching FGD system may also account for the high concentration of abovementioned oxy-anionic species and U complexes in limestone and gypsum slurry waters. At PP2, the limestone and gypsum slurry waters have high concentrations of elements associated with soluble salts (Ca, K, Mg, Na, S, Sr, and Cl) and major and minor elements (B, Mn, Cu, Se, Cu Ba, and U), which give rise a high ionic strength in these water streams. The high concentration of these elements in the limestone and gypsum slurry water may be ascribed to the dissolution of limestone components and to the complete re-circulation of the ltered water to the scrubber, respectively. The re-circulation of the ltered water also accounts for the increase in B, Sr, Se, and Ba in the 2008 gypsum slurry water given the similar contribution of these elements by gaseous and PM streams in 2007 and 2008. The decrease in Ni, Co, Be, Cu, and Th in the 2008 gypsum slurry is due to the aforementioned lower PM contribution in 2008. It is worth mentioning that the high Ni concentration in the petroleum coke is in line with the acidic-natured gypsum slurry at PP2 (pH b 5) that increases its solubility with respect to alkaline wastes. Petroleum coke is also an important source of V, but this element reveals a different response and remains highly immobile under slightly acidic conditions. Other differences between sampling campaigns are the higher contents of Mg, S, and Al in the 2007 gypsum slurry water than those in 2008 owing to the high dosages of the Al additive (68 and 14 kg/h, respectively) and to the addition of MgO during the operational period of 20062007 (Table 6). The differences between PP1 and PP2 in FGD waters are those due to the higher concentrations of some elements in the limestone slurry water at PP1 owing to the use of a fraction of ltered water for limestone slurry preparation, and the different contents of Al (by a factor of 20 to 40) and of F (by a factor of 2 to 20) in the gypsum slurry at PP2 with respect to those at PP1 (Table 6). The addition of Al to the scrubber at the PP2 modies the partitioning of these elements, promoting the presence of soluble Al-uoride complexes and reducing the fraction in gypsum. In addition, a highly acid insoluble Al-uoride ralstonite (NaMgAlF6.H2O) [16] is formed instead of uorite (CaF2), probably because ralstonite forms an iso-structural

P. Crdoba et al. / Fuel Processing Technology 92 (2011) 17641775 Table 6 Mean concentration of major, minor, and trace elements in treated/process waters, limestone and gypsum slurry waters, and ltered water at PP1 and PP2. PP1 2007 TW pH K (S/cm) Flow (t/h) mg/L Al Ca Fe K Mg Na Mn P S Si F Cl B Sr NO 3 2 SO4 NH4 Hg g/L Li Be Sc Ti V Cr Co Ni Cu Zn Ga Ge As Se Rb g/L Y Zr Nb Mo Cd Sn Sb Cs Ba La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta W Tl Pb Bi Th U 7.3 875 24 b 0.4 151 b 0.05 3 36 10 0.006 b 0.2 117 3 0.4 55 0.1 3 ND 351 ND 0.001 LSW
a

1771

PP2 2007 GSW

b

PP2 2008 LSW 7.0 1807 24.5 b2 294 b 0.5 5 322 7 0.6 b1 667 4 12 144 4 0.4 307 1247 ND 0.05
a

FW

PW 5.6 14915 54 b 0.2 18 b 0.1 1 8 4 0.03 b 0.1 12 2 0.1 2 0.4 0.07 0.5 44 ND 0.002

GSW

FW

PW 7.7 150 52 b 0.2 16 0.1 0.8 8 4 0.1 b 0.1 13 0.7 0.2 5 0.02 0.06 2 40 0.2 0.004

LSW

GSW

FW

7.5 10400 87 b5 795 b 0.1 61 1643 173 3 b 2.5 3048 11 14 797 25 5 598 9129 1 0.001

7.6 17830 71.6 b 10 807 b 0.1 113 3414 300 103 b5 5725 63 87 841 48 3 1239 17118 1 0.01

7.4 11663 71.6 b 10 763 b1 65 1871 185 54 b5 3419 29 54 664 28 4 594 10223 0.7 0.002

5.0 24932 28 642 781 14 97 10394 17 510 b 10 17551 104 1273 3675 126 2 8675 45740 ND 2

5.3 22484 28 581 728 11 87 9584 16 470 b 10 15947 95 1055 3369 116 2 ND 47760 ND 2

9.0 3947 20.2 0.2 365 b 0.1 8 306 9.3 0.5 b 2.5 857 11 7 176 8 0.7 29 2570 0.7 0.02

4.6 39853 28 38 950 6 102 5638 79 416 b5 12123 77 185 3420 145 4 1201 36370 15 2

5.1 42175 28 27 828 3 73 4240 58 321 b 0.1 9165 62 169 3059 117 3 932 27495 15 2

19 b 0.8 6 2 5 1 b 0.8 3 11 b 0.8 b 0.8 b 0.8 2 1 1

619 b1 24 10 72 3 11 68 20 b1 b1 b1 29 145 30

1231 2 63 31 168 5 201 514 53 346 3 3 52 470 72

705 b1 31 14 94 4 85 236 27 22 1 2 28 262 41

4 b 0.8 24 5 1 1 b 0.8 1 6 7 1 b 0.8 1 3 1

56 b1 44 12 11 5 4 52 11 46 2 1 4 38 5

1537 12 166 86 395 15 827 5214 319 4776 18 17 67 405 14

1501 13 214 85 356 14 815 5303 337 4777 28 22 76 646 15

2 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 2 1 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8

88 b 0.1 1 1 18 7 2 29 7 b 0.1 b 0.1 b 0.1 3 82 15

1468 b 0.1 22 49 158 10 505 2779 196 4824 4 15 53 1496 71

1159 b1 18 29 104 7 382 2099 126 3567 3 14 38 1956 56

b 0.8 b 0.8 b 0.8 1 b 0.8 b 0.8 b 0.8 b 0.8 40 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 2

b1 b 0.1 b1 79 b 0.1 b 0.1 1 b 0.1 59 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 99

3 b 0.1 b 0.1 65 25 b 0.1 2 1 188 1 2 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 330

b1 b 0.1 b 0.1 51 8 b 0.1 1 b 0.1 131 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 219

b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 2 b 0.8 b 0.8 b 0.8

b1 b 0.1 b 0.1 4 b1 b 0.1 1 b 0.1 9 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 12

77 8 2 56 162 b 0.1 14 b 0.1 149 17 18 2 9 2 b 0.1 5 b 0.1 4 1 3 b 0.1 4 1 1 10 2 5 2 b 0.1 6 654

76 7 1.3 53 163 b 0.1 14 b 0.1 154 17 18 2 9 2 b 0.1 6 b 0.1 3 b 0.1 3 b 0.1 4 b 0.1 b 0.1 5 b 0.1 4 2 b 0.1 5 568

b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 7 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8 b 0.8

b 0.1 b 0.1 b 0.1 4 b 0.1 b 0.1 3 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 b 0.1 2 b 0.1 b 0.1 b 0.1 b 0.1 8

28 18 b 0.1 30 204 b 0.1 29 b 0.1 295 7 8 b 0.1 5 b 0.1 b 0.1 3 b 0.1 3 b 0.1 3 b 0.1 4 b 0.1 b 0.1 b 0.1 3 5 3 b 0.1 b 0.1 667

21 12 b1 21 159 b1 23 b 0.1 236 5 7 b 0.1 4 b 0.1 b 0.1 3 b 0.1 3 b 0.1 2 b 0.1 3 b 0.1 b 0.1 b 0.1 b 0.1 4 2 b 0.1 b 0.1 494

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solid solution between hydrated Al-uoride complexes rich in Na and Mg compounds [29]. Filtered water shows a composition similar to that of the corresponding gypsum slurry waters. However, the highly efcient purge at PP1 increases the differences between ltered water and gypsum slurry water in terms of element concentration. These differences are especially signicant for Ni, Zn, and Cd with concentrations over 2 orders of magnitude higher in ltered water at PP2 than at PP1 (Table 6). For mass balance calculations it is necessary to normalise the concentration of each element in a given stream with the corresponding stream ow. Low concentrations of a given element together with a high ow rates result in high net inputs into FGD. Nevertheless, a high concentration of a given element and a low ow rate may also take place. Owing to the high S of the feed fuel at PP1, the limestone and gypsum slurry ows (Table 6) considerably exceeds those at PP2. 3.4. FGD mass balances and enrichment of inorganic trace pollutants PMB and TMB and the t-Student of inorganic trace pollutants in FGD at PP1 and PP2 are shown in Tables 7 and 8, respectively. Based on the results of the mass balances, the elements in the FGD waters at PP1 and PP2 may be classied as follows (Table 9): a) Elements enriched in ltered water (0.7 PMB 1.2 and TMB 1.2) b) Elements not enriched in ltered water (PMB 1.0 and TMB 1.2). c) Elements with uncertain behaviour (PMB 0.8 and TMB 0.8). Although t-Student was only performed in case of differences 0.2 in the out/in ratios between PMB and TMB, it was also applied to a few additional elements at each power plant to verify the aforementioned classication based on the mass balances in FGD waters. 3.4.1. Elements enriched in ltered water The elements enriched in ltered water (0.7 PMB 1.2 and TMB 1.2) are: Na, Mg, Cl, B, Mn, Se, Cd, Mo, and U (PP1), and Na, Cl, K, Mg, F, Hg, Li, B, Mn, Sc, Co, Ni, Cu, Ge, Zn, Se, Cd, and U (PP2). The enrichment of these elements is attributed to the following factors: Dissolution of carbonate-bearing elements from limestone and formation of soluble sulphate complexes in the scrubber: Na, Mg, Mn, and U (99%, PP1) and Mg, Mn, and U (8995%, PP2), and also Cu, Ni, and Co (PP2 in 2008) are supplied by limestone (Table 1). Their probable carbonate afnity in limestone accounts for a relatively rapid dissolution in limestone slurry which reacts with SO2 to form the corresponding soluble sulphate complexes. Dissolution of elements in gaseous phase in the gypsum slurry water: Cl, B, and Se (6899%, PP1) and Cl, F, B, and Hg (8099%, PP2) enter the scrubber in a gaseous form (Table 1). The high solubility of Cl, B, [30] and Se and Hg salts promotes the partial dissolution in the gypsum slurry water and a high enrichment in the ltered water as a result of continuous water re-circulations. Dissolution of elements with high condensation potential on y ash: Mo and Cd (99100%, PP1) and K, Zn, Ge, and Cd (70100%, PP2) enter the scrubber as PM (Table 1. The alkaline pH of y ash and the nearneutral pH of the limestone slurry promote the dissolution of these elements and other (i.e. Se, As, Sb or V) in their oxy-anionic form when ue gas passes through the sprayers. Contribution of elements by several sources: Na, Sc, and Se (PP2). The process water supplies relatively high contributions of Na (3050%) and Sc (51%, in 2007 sampling), whereas the remaining fraction enters FGD as PM. Limestone (3560%), PM (4816-%), and gaseous

(1723%) streams are the main inputs of Se in the scrubber at PP2 in the two sampling campaigns. These elements are enriched in the ltered water after a number of re-circulations. The enrichment of Na, Se, and Cd in the ltered water at PP1 should be pointed out. These elements show PMB values that are slightly higher than 1.2, which it is not consistent with the theoretical values of this PMB, which is usually closed to out/in ratios 1 (Table 7). This may be due to the crucial factors considered in the PMB calculations discussed in the 2.3 section above. However, the enrichment of these elements is clearly patent when comparing the complementary PMB and TMB, which is supported by the statistically signicant difference (p b 0.05). Consequently, the comparison between PMB and TMB suggests the enrichment of these elements in ltered water after a number of re-circulations. At PP2, F displays potential enrichment in the 2007 sampling because of the high dosages of Al additive, which gives rise to high soluble proportions of this element as AlF aqueous complexes. Sodium, Ni, Zn, Mn, and Co show potential enrichment in the 2008 sampling. The elements that display a particular enrichment pattern with PMB values N 1.2 but notably high values of TMB (2.3 b TMB b 12.8) are Mg, Li, and U in the 2007 campaign; and K, Li, Zn, Zr, Se, and Rb in the 2008 campaign. Comparison of PMB and TMB supported by the statistically signicant difference (p b 0.05), suggests the enrichment of these elements after re-circulations of the ltered water (Table 8). 3.4.2. Elements not enriched in ltered water The elements not enriched in ltered water (PMB 1.0 and TMB 1.2) are: Al, Fe, K, S, F, Hg, Li, Sc, Ti, V, Cr, Ba, Ga, Ge, Sr, and Zr (PP1) and Ca, Ti, S, Fe, V, Sr, and Ba (PP2). These elements are not enriched in ltered water due to the following factors: Elements supplied by the highly insoluble AlSi fraction of limestone: Al, Fe, K, Li, Sc, Ti, V, Cr, Ga, and Zr (PP1). Titanium, Fe, and V (PP2). Elements associated with the carbonate fraction of limestone that reacts with S to form low soluble sulphate species: Ba and Sr (PP1), and Ca, Ba, and Sr (PP2). Elements in gaseous phase that react with limestone components and are retained in gypsum as sulphate or uoride species: S, F, and Hg (PP1). Sulphur (PP2 2007). PM IN-FGD elements not dissolved in gypsum slurry water and ltered water: Ge (PP1). 3.4.3. Elements with uncertain behaviour The elements with uncertain behaviour (PMB 0.8 and TMB 0.8) are: Ni (PP1), and Al, Ga, Mo, and Sb (PP2) and Ni, Cu, and Pb (2007, PP2). These values suggest a rapid dissolution, reaching equilibrium or saturation with subsequent precipitation in the FGD gypsum. At PP1, Ni supplied by limestone (92%, Table 1) adopts a behaviour similar to that of Na, Mg, and Mn. However, the reason for the limited presence of this soluble complex in the ltered water remains unclear and will be investigated in subsequent works. At PP2, Ga, Sb, Mo, Ni, Cu, and Pb enter the scrubber as PM (54 100%), but limestone is also an important source of Mo (46%) and Pb (35%) in the 2007 sampling (Table 1). Most of the above elements condense as ne sulphate and/or chloride species after combustion. The solubility of these salts [31] under slightly acidic pH (4.65.0) in the scrubber would give rise to enrichment of these elements in recirculated waters. For Al, the use of highly soluble Al-additives explains the high solubility of this metal in gypsum slurry water. However, the highly acid insoluble ralstonite formation [16] may also give rise to high fractions (4581%, depending on Al dosages) of Al trapping, thus avoiding a signicant Al enrichment in ltered water. As aforementioned for Ni, the reason for the uncertain behaviour of

P. Crdoba et al. / Fuel Processing Technology 92 (2011) 17641775 Table 7 PMB and TMB and t-Student of major, minor, and trace elements at PP1. PP1 2007 (n = 4) Element Al Fe K Mg Na S F Cl Hg Li B Sc Ti V Cr Zr Mn Ni Ga Ge Se Sr Mo Cd Ba U FWAF a (g/h) 0 0 4686.8 1.3 13303.4 2.5 3898.3 47614.9 0.1 50.6 1983.6 2.2 1.0 6.8 0.3 0 3846.9 16.9 0.1 0.1 18.8 315.4 3.7 0.6 9.4 15.7 SDb 0 0 140.7 2436.0 403.5 4915.2 774.2 27656.2 0.01 0.8 29.0 0.2 0.1 0.2 0.0 0 177.4 0.7 0.01 0.04 3.8 0.1 14.1 0.1 0.2 1.7 t 110 66.95 3.44 136.59 43.36 48.54 6.96 9.83 24.06 14.73 18.01 p-value (p b 0.005) b 0.001 b 0.001 0.041 b 0.001 b 0.001 b 0.001 0.006 0.002 b 0.001 0.001 b 0.001 PMB 1.0 1.0 0.8 1.1 N 1.2 0.9 1.0 1.0 1.0 0.9 0.8 0.9 1.0 0.9 0.9 1.0 1.0 0.7 0.9 0.9 N 1.2 1.0 0.7 N 1.2 1.0 1.2 TMB 1.0 1.0 0.9 2.1 6.2 0.9 1.2 4.2 1.0 1.1 3.4 1.0 1.0 0.9 0.9 1.0 2.4 0.8 0.9 1.1 6.3 1.1 1.9 15.0 1.0 1.4

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these species remains unclear and will be investigated in subsequent works. 3.5. Comparison of PP1 and PP2 Comparison of the results of the PMB and TMB and the enrichment of inorganic trace pollutants at PP1 and PP2 reveal signicant differences between PP1 and PP2 subjected mainly to operational conditions. A larger number of elements are enriched in the ltered water at PP2 than at PP1. This is attributed to the following causes: a) The higher input of soluble PM at PP2 than at PP1 because of the lower ESP gas temperatures at PP2 that may favour the occurrence of ne condensed species that escapes from the ESP subsequently dissolved in the FGD system. This together the lower acidic pH of the gypsum slurry (4.65.0) at PP2 than pH (7.6) at PP1 may also favour the presence of metal complexes at PP2. b) A greater occurrence of uoride and/or sulphate complexes and the lower S/F (52140) and S/Cl (2837) ratios in the scrubber at PP2 than at PP1 (251 and 137 for S/F and S/Cl ratios, respectively) give rise to these enrichment factors for Na, F, Cl, Li, Zn, Ni, Cd, Ge, and Hg in the scrubber at PP2 than at PP1. The rapid dissolution of these elements as soluble sulphate and uoride complexes promotes their enrichment after water re-circulations. c) The differential behaviour and enrichment of Hg between PP1 and PP2. The different Hg enrichment is probably due to the higher Cl content and the lower S/Cl ratio at PP2 than those at PP1. This promotes the occurrence of highly soluble HgCl2 complexes in ltered water at PP2. d) The differential behaviour and enrichment of F and Al is controlled by the use of additives. At both plants, gaseous HF is the major input of F. However, the Al additives at PP2 promote the

PMB: partial mass balance. TMB: total mass balance. n = degrees of freedom. : no signicant differences. a FWAF: ltered water mean ows. b SD: standard deviation.

Table 8 PMB and TMB and t-Student of major, minor, and trace elements at PP2 in 2007 and 2008. PP2 2007 (n = 6) Element Al Ca Fe S K Mg Cl F Hg Li B Sc Ti V Mn Co Ni Cu Zn Ga Ge Mo Se Cd Sb Ba Pb U FWAF a (g/h) 16276.9 20384.5 311.8 4.5 2438.5 2.7 94341.3 29540 52.6 42 3244.7 6 2.4 10 13156.7 22.8 148.5 9.4 133.8 0.8 0.6 1.5 18.1 4.6 0.4 4.3 0 15.9 SDb 1881.6 3805.8 166.9 48252.3 146 13375.2 4503.8 3116 11.2 2.6 141.9 1.5 0.2 6.4 599.4 1.4 10.2 0.4 7.4 0.3 0.2 0.1 10.2 0.5 0.1 0.4 0.03 1 t 40.92 49.14 51.31 23.22 11.55 40.18 56 9.8 53.76 40 43.99 6.39 8.62 4.37 21.63 1.58 40.04 p-value b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 0.176 b 0.001 PMB 0.3 1.0 0.9 1.0 0.7 N 1.2 1.0 0.8 0.7 N 1.2 0.9 0.7 1.0 0.9 0.8 0.1 0.3 0.3 0.9 0.4 0.8 0.2 1.2 0.8 0.4 0.9 0.6 N 1.2 TMB 0.5 1.2 0.9 1.2 1.3 12.8 11.0 2.5 2.6 4.6 15.0 2.2 1.0 1.0 4.1 1.0 0.8 0.5 2.9 0.6 1.3 0.2 1.8 7.1 0.5 0.9 0.6 3.0 Element Al Ca Fe Na K Mg Cl F Hg Li B Ti V Mn Co Ni Cu Zn Se Rb Sr Zr Mo Cd Sb Ba Tl U FWAF a (g/h) 744.6 23174.7 86.6 1613.6 2046.3 119000 85638 4736.7 41.4 32.5 3277.1 0.8 2.9 8982.9 10.7 58.8 3.5 99.9 54.8 1.6 91.1 0.3 0.6 4.4 0.6 6.6 0.1 13.8 PP2 2008 (n = 6) SDb 554 3216.7 42.6 360.4 385.8 26580.8 1856.7 880 3.1 5.4 487.7 0.6 0.5 1579.1 1.9 10 0.5 20 13.5 0.8 12 0.1 0.1 0.6 0.1 1.2 0.02 13.8 t 10.97 12.99 10.39 112.98 13.18 32.56 14.75 16.46 13.94 13.84 14.44 18.43 12.26 9.95 5.13 9.98 16.9 15.08 16.84 p-value b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 b 0.001 PMB 0.6 0.9 1.0 0.8 N 1.2 0.9 0.8 1.2 1.0 N 1.2 0.7 1.0 1.0 0.8 0.8 1.0 1.2 N 1.2 N 1.2 N 1.2 0.9 N 1.2 0.0 0.9 0.4 0.8 0.3 1.0 TMB 0.6 0.9 1.0 4.9 4.2 6.7 10.0 1.6 2.5 6.2 6.8 1.2 1.1 10 8.0 2.0 1.5 8.0 7.8 2.2 0.9 2.3 0.2 52 0.7 0.9 1.5 2.2

PMB: partial mass balance. TMB: total mass balance. n = degrees of freedom. : no signicant difference. a FWAF: ltered water mean ows. b SD: standard deviation.

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Table 9 Classication of elements based on mass balances at PP1 and PP2. Source Elements enriched in ltered water (0.7 PMB 1.2 and TMB 1.2) As soluble sulphate complexes Dissolution of elements in gaseous phase Dissolution of elements as PM IN-FGD Elements supplied by several sources Supplied by the insoluble AlSi fraction of limestone As low soluble sulphate species Retained in gypsum as sulphate and uoride species PM IN-FGD not dissolved in gypsum slurry water PP1 2007 Na, Mg, Mn, and U Cl, B, and Se Mo and Cd Al, Fe, K, Li, Sc, Ti, V, Cr, Ga, and Zr Ba and Sr S, F, and Hg Ge Ni PP2 2007 Mg, Mn, and U Cl, F, B, and Hg K, Zn, Ge, and Cd Ti, Fe, and V Ca, Ba, and Sr S Al, Ga, Sb, Mo, Ni, Cu, and Pb PP2 2008 Mg, Mn, U, Cu, Ni, and Co Cl, F, B, and Hg K, Zn, Ge, and Cd Na, Sc, and Se Ti, Fe, and V Ca, Ba, and Sr Al, Mo, Ga, and Sb

Elements not enriched in ltered water (PMB 1.0 and TMB 1.2)

Elements with uncertain behaviour (PMB 0.8 and TMB 0.8)

occurrence of stable AlF aqueous complexes that increase F concentrations in ltered water. In the absence of additives (PP1), HF reacts with Ca to form insoluble uorite, which is partially retained in the FGD gypsum. The use of highly soluble Al-additives at PP2 explains the high solubility of this metal in gypsum slurry water. However, the highly acid insoluble ralstonite may also give rise to high fractions (4581%, depending on Al dosages) of Al trapping, thus avoiding a signicant Al enrichment in ltered water. In equilibrium with ralstonite, low Mg levels and acidic conditions (pH b 5) may lead to precipitation of sulphate complexes such as balsaluminite (Al4 (SO4)(OH)10.4H2O) [32]. 4. Conclusions The results reveal that re-circulation of ltered water at PP1 and PP2 gives rise to unusually high concentrations of some elements of major environmental concern such as, Cd, B, Se, Sc, Ni, Zn, and especially Hg and U. The elements in FGD waters may be classied as: (a) elements enriched in ltered water at PP1 and PP2: Na, Cl, Mn, B, Se, Mg, Cd, and U. Furthermore, Mo is enriched at PP1, and K, Hg, Li, Sc, Ge, F, Ni, Zn, Rb, Zr, and Co at PP2; (b) elements not enriched in ltered water at PP1 and PP2: Ca, Fe, Ti, V, Ti, S, Sr, and Ba. This group of elements also includes Al, K, Li, F, Hg, Cr, Zr, Ga, Ge, and Sc at PP1; and (c) elements displaying an uncertain behaviour at PP1 and PP2: Al, Ga, Cu, Mo, Sb, Pb (PP2), and Ni (PP1). The enrichment of inorganic trace pollutants in re-circulated waters in wet limestone based FGD systems is heavily dependent on: a) the low purity of limestone may result in high inputs of elements occurring in soluble carbonates promoting the formation of soluble sulphate complexes, which may be crucial at power plants that use fuels with a high S content since increased limestone ows are required for the abatement of SO2 emissions; b) the uoride and sulphate complexes and the S/F and S/Cl ratios of the scrubber. Low S/F and S/Cl ratios in the scrubber promote the presence of soluble metal chloride complexes. A high PM contribution to the FGD system may increase the amount and the presence of metal chloride complexes in re-circulated waters; c) the ESP gas temperature. Low ESP gas temperature may favour the occurrence of metal condensation on PM, which is subsequently dissolved in the FGD system; and d) the use of additives in the scrubber. Additives may modify the speciation and partitioning of some elements. Thus, high Al dosages enhance the formation of water soluble AlF complexes leading to Frich FGD waters. In the absence of additives, HF reacts with Ca to form uorite which is retained in the FGD gypsum, with the subsequent increase in the leachable potential of this by-product. Our ndings demonstrate that the re-circulation of ltered water from the rst operation cycle up to the start of sampling campaigns

increases the concentration of some elements of major concern such as U and Hg in FGD waters. High levels of these metals and other pollutants in ltered water give rise to a high ionic strength which may reduce the gaseous retention efciencies and also increase the emission of metals by entraining and/or evaporation of droplets as PM from gypsum slurry. Owing to the strong inuence of the operational factors in this enrichment, an in-depth knowledge of such factors is crucial for implementing preventive or remediation measures to reduce the levels of these elements in ltered waters. The application of these measures may be of paramount importance for maintaining a high retention of gaseous pollutants and for reducing the element contents should the re-circulation system be interrupted since the waters would require a decontamination treatment. Subsequent studies will be focused on the speciation of inorganic trace pollutants in FGD water streams with water re-circulation, the modelling of the FGD solidliquid processes (sorption, co-precipitation, etc.), and on preventive and/or corrective measures. Acknowledgements This work was carried out with a grant from the Research Fund for Coal and Steel (Contract Number: RFCR-CT-2006-00006). The authors would like to thank the staff of the Spanish power plants for their support, help and assistance during and after the sampling campaigns. The corresponding author gratefully acknowledges the Institute of Environmental Assessment and Water Research (IDAEA), Spanish Research Council (CSIC) for awarding, a JAE-pre-doctoral fellowship to Ms. Patricia Crdoba. References
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