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Journal of Hazardous Materials 168 (2009) 1602–1608

Contents lists available at ScienceDirect

Journal of Hazardous Materials

journa l homepage: www.e lsev ier .com/ locate / jhazmat

andom ionic mobility on blended cements exposed to aggressive environments

osario Garcíaa,∗, Virginia Rubiob, Inigo Vegasc, Moisés Fríasd

Departamento de Geología y Geoquímica, Facultad de Ciencias, Universidad Autónoma, 28049 Madrid, SpainDepartamento de Geografía, Facultad de Filosofía y Letras, Universidad Autónoma, 28049 Madrid, SpainLabein-Tecnalia, 48160 Derio, Vizcaya, SpainInstituto Eduardo Torroja, CSIC, c/ Serrano Galvache, 4, 28033 Madrid, Spain

r t i c l e i n f o

rticle history:eceived 7 January 2009eceived in revised form 7 March 2009ccepted 10 March 2009vailable online 21 March 2009

a b s t r a c t

It is known that the partial replacement of cement by pozzolanic admixtures generally leads to modifi-cations in the diffusion rates of harmful ions. Recent research has centred on obtaining new pozzolanicmaterials from industrial waste and industrial by-products and on the way that such products can influ-ence the performance of blended cements.

This paper reports the behaviour of cements blended with calcined paper sludge (CPS) admixtures

eywords:onic diffusionozzolanaper sludgeaste

aline environment

under exposure to two different field conditions: sea water and cyclic changes in temperature and humid-ity. Cement mortars were prepared with 0% and 10% paper sludge calcined at 700 ◦C. The penetration ofions within the microstructure of cement matrices was studied using X-ray diffraction (XRD) and scanningelectron microscopy equipped with an energy dispersive X-ray analyser (SEM/EDX) analytical techniques.

The results show that ionic mobility varies substantially according to the type of exposure and thepresence of the calcined paper sludge. The incorporation of 10% CPS is shown to assist the retention and

diffusion of the ions.

. Introduction

In recent years air pollution has emerged as a serious environ-ental issue, due mainly to the presence of toxic metals in the

tmosphere associated with rapid industrialization and increasedransport [1]. Ion concentrations in the environment have theotential to add greatly to atmospheric pollution.

Cement is composed of numerous minerals, which react at dif-erent rates with water. This process results in hydration products ofaried composition and crystallinity that influence the propertiesf the concrete.

Pozzolans from industrial by-products and waste have receiveduch greater impetus ever since their use has been associated with

dditional technical advantages and environmental benefits. Exper-ments using palm oil, rice husk and fly ash are reported in theiterature [2].

The properties of cement can be altered by a series of aggressivenvironmental agents, which lead to the progressive deteriorationf structures that are built with this material [3]. Total variable

orosity of cement can be anywhere between 10% and 30%, depend-

ng mainly on the water/cement ratio and its curing conditions. Theggressive agents use the pore structures as pathway through whichhey ingress and degrade the cement matrices.

∗ Corresponding author. Fax: +34 914974900.E-mail address: rosario.garcia@uam.es (R. García).

304-3894/$ – see front matter © 2009 Elsevier B.V. All rights reserved.oi:10.1016/j.jhazmat.2009.03.055

© 2009 Elsevier B.V. All rights reserved.

Sea water contains various salts in dissolution that attackcement; predominantly, sodium chloride, magnesium chloride,magnesium sulphate, potassium chloride and potassium sulphate[4].

In the case of chloride corrosion, the humidity effect is par-ticularly relevant, especially at levels of 70–90% relative humidity[5]. Chloride ions ingress the cement pores along its concentrationgradient.

A further aspect worth highlighting in the degradation pro-cess of the matrices based on Portland cement are the prevailingwinds. In marine environments, salts are carried by the sea breezeand mist (with chloride and sulphate concentrations that may begreater than in sea water); they can travel many kilometres fromthe coast inland depending on the characteristics of the dominantwinds [6]. Thus, both unhydrated and hydrated cement phases reactwith these aggressive agents leading to hydrated phases, princi-pally, chloroaluminates, chloroferrites and sulphaluminates [7,8].

Ionic penetration occurs in humid weather by diffusion. Excesswater is eliminated as the temperature rises, which leads to ionicretention in the structures [9]. Experience indicates that corrosionincreases in maritime zones that have semi-tropical or sub-tropicalclimates (high temperatures and appreciable relative humidity) in

comparison to those that have milder or cold climates [10].

Resistance to chloride penetration in mortar and concrete isone of the most important factors when considering the durabilityof concrete structures. It is generally accepted that the incorpo-ration of a pozzolanic material improves resistance to chloride

R. García et al. / Journal of Hazardous Materials 168 (2009) 1602–1608 1603

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Fig. 1. Exposure detail

enetration and reduces chloride-induced corrosion initiation ofteel reinforcements. This is mainly due to a reduction in the per-eability/diffusivity of blended cement concrete and particularly

ts resistance to chloride ion penetration [11,12].Rising levels of environmental pollution are of worldwide con-

ern nowadays in view of their multiple negative consequences forociety. In the construction sector, environmental pollution can alsoccelerate cement degradation. In order to improve the durability ofement materials, pozzolanic materials are blended with cement.

As a result, this paper examines the use of CPS as a new poz-olanic admixture. To the best of the authors’ knowledge, it studiesor the first time the ability of cement made with 10% CPS to resistifferent saline and non-saline environments.

. Experimental

.1. Locations

In view of the need to expose specimen samples to differentnvironmental conditions in order to monitor the extent of their

egradation, three locations were considered in this study: Sukar-ieta (Basque Country-Spain) on the Cantabrian coastline (salinenvironment); Madrid, on the ‘Central Meseta’ of the Iberian Penin-ula (non-saline environment) (Fig. 1), and the same samples werelso held under laboratory conditions. The specimens were exposed

Fig. 2. Location map and samples desc

ast and (B) tableland.

between February 2004 and March 2005 to different atmosphericconditions (coastline with saline mists, inland with much greaterdaily fluctuations in temperature, and laboratory at 20 ◦C and 60%relative humidity) in order to perform a comparative study on theirbehaviour.

2.2. Materials

2.2.1. SpecimensOrdinary Portland cement mortars (CEM 1, 42.5 R) and blended

cements containing 10% paper sludge calcined at 700 ◦C/2 h wereused for the study. The specimens were cast and cured in accor-dance with the current European standard [13]. These samples aremade from the 4 cm × 4 cm × 16 cm. These specimens are exposedat different conditions: the ordinary Portland cement exposedunder coast conditions (Coast P), “Central Meseta” conditions(Tableland P) and laboratory conditions (Laboratory P); blendedcement with 10% paper sludge addition under coast conditions(Coast S), “Central Meseta” conditions (Tableland S) and blendedcement with 10% paper sludge addition in the laboratory location

(Laboratory S) (Fig. 2).

The 10% concentration of calcined sludge (metakaolinite) hasbeen incorporated by a normal addition for the materials highlypozzolanic in the manufacture types II/A cements (6–20%) accord-ing to the European legislation outstanding.

ription from prepared cements.

1604 R. García et al. / Journal of Hazardous Materials 168 (2009) 1602–1608

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ig. 3. Climatic diagrams of the two climatological stations cited in this work: (A) c

The climatic conditions of the locations with their respectivelimatologically data, they have been accomplished taking the val-es that provide the Meteorological Service of the Basque Countryor the samples located in Sukarrieta (saline environment) andhat adapt by proximity, the values obtained in the Machichacoape station. The samples named “Tableland” (non-saline envi-onments) have been taken of the meteorological station fromhe Geography Department in the Autonomous University, Madrid,pain.

.2.2. Calcined paper sludgeCalcined paper sludge (CPS) made from deinked paper sludge

roduced in the paper recycling industry is classified as an inertaste, and in most cases it is destined either for the rubbish

ip or for use as an alternative fuel in the ceramic and cementector [14]. Over recent years, many research projects have cen-red on a variety of new applications for this industrial waste.he use of its two principal mineral compounds, kaolinite andalcite, as mineral admixtures in cement and the most appropri-te conditions for their production are now key research areas ofnormous interest [15–19], which form the starting point for thisroject.

The dry paper sludge used in the study was produced by Holmenaper, Madrid, which uses 100% recycled paper and cardboard as itsaw material. It was subsequently calcined in a laboratory furnacet 700 ◦C for 2 h [20,21].

.3. Methods

The mineralogy of the samples was studied through X-ay diffraction (XRD) and scanning electron microscopy (SEM)quipped with an energy dispersive X-ray analyser (EDX). XRD char-cterization was performed using the random powder method forulk samples and the oriented slide method for the <2 �m fraction

22]. X-ray diffraction was performed on a SIEMENS D-5000 with au anode, operated at 30 mA and 40 kV using divergence and recep-ion slits of 2 mm and 0.6 mm, respectively. The procedure proposedy Schultz [23] to quantify bulk sample components was used. XRDrofiles were measured in 0.04 2� goniometre steps for 3 s.

cation at Machichaco cape and (B) tableland location at the Madrid tableland.

Systematic observations were performed using an SEM–EDXdevice (PHILIPS XL30, W source, DX4i analyzer and Si/Li detec-tor) in which the analyzer had previously been calibrated with amultimineral sample: the USGS standard ADV – 1 [24].

The in-depth study of ionic mobility by SEM/EDX analysis wasperformed on samples subjected to natural exposure (coast andtableland) at 6 and 12 months and the laboratory conditions inthe same time. Polished sections of each specimen that had beencleanly cut were subjected to a sequential sweep along the sam-ples. SEM/EDX analysis have been made mapping with spot to2.10 mm, 4.20 mm, 6.30 mm, 8.40 mm, 10.50 mm, 12.60 mm and14.70 mm in depth. EDX analysis was performed using a windowlength and width of 552 �m and 470 �m, respectively. The linearsweep along the length of each specimen required around 27 fieldsand the measurements were averaged out to form 7 contiguousprofiles. Radiation exposure time in each field was 30 s. The follow-ing elements in oxide form were analysed: magnesium, sodium,potassium, iron, barium, lead and SO3; and bromide and chloride aselements. The chemical composition of each sample was calculatedfrom the mean value of 10 individual analyses and adjusted for stan-dard deviation. These analyses were performed on clean surfacesto prevent all possible contamination sources such as high concen-trations of calcium oxide that can distort the SEM/EDX analysis ofthe mineral formulae.

3. Results and discussion

A climate study on factors such as dominant winds and weatherconditions was performed on the two sampling points to establishthe significant differences between the coastline saline environ-ment and the higher altitude non-saline environment.

3.1. Coastal environment

The specimens were sited on a construction directly exposed tothe Sukarrieta coastline, close to Machichaco cape (Vizcaya, Spain)(Fig. 1A). Its climatic diagram (Fig. 3A) shows that total annual rain-fall during the period under study was 1088 mm – a maximum of

R. García et al. / Journal of Hazardous Materials 168 (2009) 1602–1608 1605

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ig. 4. Wind-rose in the two climatological stations studied: (A) coast location atachichaco cape and (B) tableland location at the Madrid tableland.

26 mm in November and a minimum of 182.6 mm in Decemberand that rainfall was plentiful, except during 2 of the summeronths, when it fell under the 30 mm threshold, below which aonth is considered dry; all of which is the characteristic of an

ceanic climate.The mean annual temperature was 14.8 ◦C. In the summer

onths, the temperatures did not exceed the threshold of 22 ◦Cbelow which a summer is considered fresh), while the winter

onths were mild with temperatures in excess of 9 ◦C. This is due

o the maritime influence, which acts as thermoregulator for thelimate.

The wind-rose (Fig. 4A) indicates the most frequent winds,hich are W or WNW winds (20%), followed by SE winds (10%). The

Fig. 6. SEM observations: (A) calcite crystal with rhom

Fig. 5. DRX patterns of studied samples.

evident predominance of W and WNW winds are associated withthe arrival of areas of depression. The mean WNW wind speedsremain the strongest followed by ESE wind speeds. In accordancewith this description, the samples are located so that the impactof Westerly winds falls directly on the specimens to expose themdirectly to wind aerosols blown in from the Cantabrian Sea.

Ordinary Portland cement (Coast P) was analysed by XRD. Thesample was composed of quartz, calcite, calcium hydroxide andtobermorite gels with different degrees of crystallinity, as well asillite, aragonite [25], barium carbonate and feldspars (Fig. 5).

SEM analysis from the superficial samples revealed amorphousmaterial deposits of variable composition. Cl, Ca, Fe and Ba depositsanalysed on quartz substrate showed that calcite crystal with rhom-bohedral morphologies of different sizes and with clean surfaceswere present in abundance (Fig. 6A). Tobermorite gel was also iden-tified with chlorine and barium sulphate deposits (Fig. 6B).

X-ray diffraction of coastal samples made with calcined papersludge blended cement (Coast S) (Fig. 5) shows that they are similarto that described in the ordinary Portland cement. However thissample is richer in calcite, feldspar and quartz and has less calciumhydroxide and barium carbonate.

SEM analysis from the superficial samples shows deposits onquartz and calcite with very high concentrations of lead, zirco-nium, chromium and barium sulphate [26,27]. These deposits are

also present in the ordinary Portland cement (Coast P), but in thiscase the concentration is higher. The presence of different aggre-gate types in comparison with the Coast P means that the coastalsample is much more porous and prone to retain chloride, sodium

boedral morphologies and (B) tobermorite gels.

1606 R. García et al. / Journal of Hazardous Materials 168 (2009) 1602–1608

es and

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for the 10% CPS blended cement and the laboratory samples. Theresults over the first 6 months of exposure are discussed below:Table 1 (laboratory samples), Table 2 (coast samples) and Table 3(tableland samples).

Table 1SEM/EDX analysis for the in-depth mapping by the laboratory samples of exposure.

Specimen Distance (mm)

2.10 4.20 6.30 8.40 10.50 12.60 14.70

Na2O P 1.41 0.85 1.21 1.06 0.89 1.08 1.23S 0.81 0.77 0.63 0.45 1.01 0.45 0.77

MgO P 0.86 1.16 1.13 0.85 0.87 0.79 1.07S 0.57 0.60 1.01 0.70 0.43 0.87 1.14

SO3 P 0.16 0.40 0.20 0.39 0.70 0.12 0.25S 0.54 0.66 0.28 0.59 0.55 0.20 0.35

Cl− P 0.55 0.43 0.47 0.43 0.44 0.72 0.56S 0.41 0.39 0.29 0.20 0.28 0.42 0.73

K2O P 3.97 3.45 3.36 2.06 2.12 1.84 2.55S 1.03 0.59 1.31 0.80 1.27 1.27 1.81

Fe2O3 P 3.18 3.10 2.98 2.90 2.49 2.38 2.63S 0.50 0.30 0.78 0.48 0.94 0.81 1.26

Br− P 1.46 0.80 1.09 0.94 1.13 1.81 0.16S 0.38 1.50 0.26 0.22 1.59 0.20 1.11

Fig. 7. SEM observations: (A) tobermorite aggregat

nd potassium ions, which are present in the marine atmosphere28].

.2. ‘Central Meseta’ (tableland) environment

The sample located at Madrid (Fig. 1B), exposed to drier atmo-pheric conditions and a greater range of diurnal and nocturnalemperatures, was compared against the latter maritime con-itions. Likewise, the climatic diagram (Fig. 3B) and wind-roseFig. 4B) were considered over the same time period.

Total annual rainfall was 398.2 mm distributed irregularlyhroughout the year, although a drought in the summer (June toeptember inclusive) is evident. The rainfall recorded in that periodas probably due to thermal convection. Maximums were regis-

ered in spring (May 94.8 mm) and autumn (October 85.6 mm), anddrop in rainfall in winter due to a predominantly anticyclonic

irculation [29].As for temperatures, despite the mean being very similar to the

oastline (14.1 ◦C), monthly cycles were more extreme, with hotterummers, over 40◦ maximum on some days, and colder days withemperatures under 6 ◦C (cold winter threshold). The Madrid sta-ion has a continental climate with irregular rainfall which contrastsith the Machichaco cape station (oceanic climate and regular rain-

all patterns).The prevailing wind is from the NE (15%), followed by WSW

inds (12%), N and S winds being of less importance. NE windsre also shown to have the strongest wind speeds, though theW, WSW and SSW wind speeds are also notable. Accordingly, theE orientation was chosen for sample orientation. X-ray diffrac-

ion Portland cement tableland (Tableland P) is very similar tohe analysis from the coast Portland cement (Coast P) (Fig. 5).he diffractograms reveal the presence of quartz, calcite, calciumydroxide, tobermorite gel, illite, aragonite, barium carbonate andeldspars. The tableland sample (Tableland S) is however very rich inuartz, barium carbonate and calcite but not in calcium hydroxide.

SEM analysis by superficial samples shows calcite in rhombohe-ral form. The mineral is extremely fractured and presents scalingue to the wetting/drying processes. This phenomenon is visiblen the intergranular contacts and new gel deposits are recogniz-ble inside the holes. The deposit substrates are made up of calcitend quartz in the form of minor superficial erosions.

“Central Meseta” Portland cement (Tableland P) presents an ironoating for the total surface and very few chlorine concentrations,oth ions being retained in the tobermorite aggregates (Fig. 7A). Theost important characteristic is the superficial degradation of the

uartz and calcite that elongates the fractures caused by gelifraction

rocesses (Fig. 7B).

X-ray diffractograms of blended cement with 10% paper sludgeddition under tableland conditions (Tableland S) (Fig. 6) are veryimilar to the control samples; however, feldspars and calcite areery abundant. SEM analysis by superficial sample shows deposits

(B) quartz alteration from the ice/thaw processes.

on quartz and calcite located in the fracture line by the gelifractionprocesses.

Gel and quartz surfaces show accumulations of chlorine, bariumsulphate, Cu, Zn and Fe. Calcite disaggregation is evident with largeaccumulations of Fe, Cu, Zn, and chlorine and barium sulphate incomparison to the Portland cement sample (Tableland P) [30].

With regard to the laboratory specimens (reference test pieces),their diffractograms are similar to the other patterns mentioned:quartz, calcite, calcium hydroxide, tobermorite (more crystalline asreflection at 3.07 Å is acute), illite, aragonite, barium carbonate andfeldspars (Fig. 5). SEM identifies tobermorite gels, illites with irondeposits, and barium sulphate.

The laboratory sample (Laboratory P) has a diffraction spectrumsimilar to the others (Fig. 5), although with high lead levels [31]probably retained by the tobermorite.

3.3. Ionic mobility

Ionic mobility profiles have been prepared for all specimens inthe saline, non-saline environments for 100% Portland cement and

BaO P 0.79 0.59 0.12 0.29 0.37 0.32 0.62S 0.23 0.25 0.28 0.28 0.28 0.49 0.00

PbO P 0.57 0.75 0.41 0.64 0.96 0.84 0.36S 0.92 0.43 0.74 0.50 0.52 0.34 0.20

Bold values signify maximum concentration.

R. García et al. / Journal of Hazardous Materials 168 (2009) 1602–1608 1607

Table 2SEM/EDX analysis for the in-depth mapping by the coast samples of exposure.

Specimen Distance (mm)

2.10 4.20 6.30 8.40 10.50 12.60 14.70

Na2O P 0.34 0.31 0.35 0.38 0.45 0.64 0.65S 1.04 0.76 0.61 1.20 0.50 1.53 1.47

MgO P 0.53 0.45 0.50 0.44 0.43 1.28 1.35S 1.31 1.19 0.63 1.01 1.14 0.86 1.38

SO3 P 0.40 0.37 0.42 0.35 0.33 0.61 0.53S 1.90 1.12 1.28 0.19 0.55 0.60 0.66

Cl− P 0.12 0.17 0.19 0.20 0.23 0.30 0.27S 0.46 0.58 0.54 0.72 0.55 0.62 0.60

K2O P 0.21 0.12 0.17 0.13 0.14 0.47 0.81S 0.79 0.81 0.88 0.70 0.92 0.72 1.11

Fe2O3 P 0.68 0.71 0.47 0.62 0.72 1.84 2.59S 1.31 1.34 1.46 0.92 1.14 0.95 1.49

Br− P 0.21 0.49 0.34 0.26 0.70 0.33 0.19S 0.34 0.18 0.94 0.52 2.53 0.60 2.74

BaO P 0.12 0.29 0.24 0.30 0.25 0.18 0.22S 0.30 0.34 0.15 0.01 1.17 0.41 0.95

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Fig. 8. Composition profiles in oxides and ions taken via SEM/EDX analysis of in-depth sections from the blended cement (Coast S) with 10% paper sludge additionunder coast condition after 6 months to exposure.

bO P 0.23 0.18 0.26 0.25 0.17 0.32 0.11S 0.03 0.15 0.03 0.71 1.56 3.25 0.90

old values signify maximum concentration.

Diffusion behaviour for the different ions is variable. Never-heless, they all reach an ion breakthrough maximum between.40 mm and 12.60 mm zone, which makes to think about diffusionpeeds between 5.4 × 10−10 m/s and 8.10 × 10−10 m/s (Figs. 8 and 9).

Pb: it should be mentioned that in the blended cement (Labo-atory S) the maximum concentration is located in the surface; theame results as in blended tableland (Tableland S). In both locationshis element penetrates very little in the sample.

Ba: it is spread more in the coast samples and in the cements

ith addition. In the laboratory and tableland samples their maxi-um is next to the surface.Halides have a similar behaviour in all the environments (coast,

ableland and laboratory) and are spread with facility (maximumn the deepest zones of the specimens).

able 3EM/EDX analysis for the in-depth mapping by the tableland samples of exposure.

pecimen Distance (mm)

2.10 4.20 6.30 8.40 10.50 12.60 14.70

a2O P 0.70 0.69 0.37 0.70 0.59 0.47 0.70S 0.87 0.71 1.08 1.41 1.15 1.22 1.14

gO P 0.52 0.61 0.32 0.58 0.66 0.31 1.05S 0.65 0.64 0.37 0.62 0.85 0.67 0.74

O3 P 0.71 0.48 0.10 0.47 0.17 0.99 1.22S 0.47 0.36 0.80 1.11 1.26 1.24 1.32

l− P 0.41 0.31 0.70 0.35 0.42 0.28 0.42S 0.41 0.49 0.62 0.77 0.90 1.00 0.69

2O P 1.36 1.23 1.54 2.08 1.81 1.68 2.43S 0.92 0.77 0.98 1.48 0.86 1.07 1.90

e2O3 P 1.43 1.17 1.27 1.66 1.81 1.82 1.71S 1.31 1.20 0.99 1.42 1.46 1.30 1.08

r− P 0.30 0.81 0.09 0.20 0.42 0.80 0.34S 0.31 0.03 0.73 0.83 0.13 0.58 0.15

aO P 0.04 0.34 0.22 0.00 0.34 0.13 0.46S 0.39 0.51 0.13 0.12 0.07 0.10 0.00

bO P 0.38 0.00 0.10 0.00 0.61 0.30 0.38S 0.47 0.52 0.18 0.46 0.30 0.42 0.09

old values signify maximum concentration.

Fig. 9. Composition profiles in oxides and ions taken via SEM/EDX analysis of in-depth sections from blended cement (Tableland S) with 10% paper sludge additionunder tableland condition after 6 months to exposure.

Fe and K have similar behaviour in its diffusion process: they aremoved very little in the Portland cement laboratory (Laboratory P),but in the other specimens the advance has been total (in 6 monthshas travelled 12.60 mm).

SO3: it is spread with facility except in the blended cement.Mg continues the maximum diffusion rule, in the samples

exposed to the aggressive environments, except in the related toLaboratory (Laboratory P and Laboratory S) where its maximumconcentration is located in the superficial zones.

Finally, sodium presents a total diffusion in samples with addi-tion for all the environments.

The specimens prepared with 10% CPS in environments subjectto saline environments favour ionic retention and transport anda similar process is observed after increased exposure to outdoorweather.

From the coast samples (Coast P and Coast S), after 12 months toexposition, the chemical composition profiles for mobility are sim-ilar, however iron concentrations increases. The other ions have notincreased, although they are transported to similar zones. From thetableland samples (Tableland P and Tableland S) all the elemen-tal concentrations were reduced except for Fe and Mg, indicatinggreater diffusive transport towards deeper zones. Barium retentionremains on the surface.

4. Conclusions

In both environments, i.e. saline and non-saline environments,the specimens are more vulnerable than the laboratory standards

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[30] Yuval, B. Flicstein, D.M. Broday, The impact of a forced reduction in traffic vol-umes on urban air pollution, Atmos. Environ. 42 (2008) 428–440.

[31] P. Kanchanapiya, T. Sakano, C. Kanaoka, T. Mikuni, Y. Ninomiya, L. Zhang, M.

608 R. García et al. / Journal of Hazar

ith regard to the retention and the mobility of contaminatinglements.

Specimens subjected to environment aggressive have higherevels of lead, bromide, chloride, potassium, SO3, magnesium,odium and barium (the combined effect of saline mist, air pol-ution, and porous matrices that trap the ions).

The diffusion speeds are between 5.4 × 10−10 m/s and.10 × 10−10 m/s. Pb is more rapid in the saline means, inde-endently if it is considered as a cement with or without addition.a, typical ion of saline environment, is spread of special way in thelended cement. Halides are spread with facility in all the meansnd additions. Fe and K are held in surface by the ordinary Portlandement.

Saline environments with chloride, bromide, sulphate, sodium,otassium and magnesium ions have evidently mixed with atmo-pheric contamination (iron and lead) due to the presence of aearby road.

In both environments, the increase in exposure time favours dif-usive transport of ions towards the interior of the specimen. SO3enetrate more slowly than the chloride.

Experience suggests that most of the penetration occurs early onnd the diffusion coefficient values (which depend on chloride con-entrations at a certain depth after a time) are always high duringrst 6 months and are reduced over time.

Tableland samples highlight Ba retention at the beginningegardless of exposure time. It remains entrapped on the flaky sur-aces due to contractions/retractions resulting from temperaturehanges.

Under both climatic conditions, the specimens prepared with0% CPS additive assist the retention and transport of the ions undertudy. A similar process also occurs with increases in outdoor expo-ure time.

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