PAPER

www.rsc.org/jem | Journal of Environmental Monitoring

Generation of crystalline silica from sugarcane burning

Jennifer S. Le Blond,*ab Claire J. Horwell,c Ben J. Williamsond and Clive Oppenheimera
Received 27th February 2010, Accepted 5th May 2010 First published as an Advance Article on the web 2nd June 2010 DOI: 10.1039/c0em00020e Sugarcane leaves contain amorphous silica, which may crystallise to form crystalline silica polymorphs (cristobalite or quartz), during commercial sugarcane harvesting where sugarcane plants are burned. Respirable airborne particulate containing these phases may present an occupational health hazard. Following from an earlier pilot study (J. S. Le Blond, B. J. Williamson, C. J. Horwell, A. K. Monro, C. A. Kirk and C. Oppenheimer, Atmos. Environ., 2008, 42, 55585565) in which experimental burning of sugarcane leaves yielded crystalline silica, here we report on actual conditions during sugarcane burning on commercial estates, investigate the physico-chemical properties of the cultivated leaves and ash products, and quantify the presence of crystalline silica. Commercially grown raw sugarcane leaf was found to contain up to 1.8 wt% silica, mostly in the form of amorphous silica bodies (with trace impurities e.g., Al, Na, Mg), with only a small amount of quartz. Thermal images taken during several pre-harvest burns recorded temperatures up to 1056  C, which is sufcient for metastable cristobalite formation. No crystalline silica was detected in airborne particulate from pre-harvest burning, collected using a cascade impactor. The sugarcane trash ash formed after pre-harvest burning contained between 10 and 25 wt% SiO2, mostly in an amorphous form, but with up to 3.5 wt% quartz. Both quartz and cristobalite were identied in the sugarcane bagasse ash (515 wt% and 13 wt%, respectively) formed in the processing factory. Electron microprobe analysis showed trace impurities of Mg, Al and Fe in the silica particles in the ash. The absence of crystalline silica in the airborne emissions and lack of cristobalite in trash ash suggest that high temperatures during pre-harvest burning were not sustained long enough for cristobalite to form, which is supported by the presence of low temperature sylvite and calcite in the residual ash. The occurrence of quartz and cristobalite in bagasse ash is signicant as the ash is recycled onto the elds where erosion and/or mechanical disturbance could break down the deposits and re-suspend respirable-sized particulate. Appropriate methods for treatment and disposal of bagasse ash must, therefore, be employed and adequate protection given to workers exposed to these dusts.

1. Introduction
The sugarcane industry is undergoing a period of considerable change and, as with other examples of economy-driven

a Department of Geography, University of Cambridge, Downing Site, Cambridge, CB2 3EN, UK. E-mail: jl490@cam.ac.uk; Fax: +44 (0)1223 333392; Tel: +44 (0)1223 339819 b Department of Mineralogy, Natural History Museum, Cromwell Road, London, SW7 5BD, UK c Institute of Hazard, Risk and Resilience, Department of Earth Sciences, Durham University, Science Labs, South Road, Durham, DH1 3LE, UK d Camborne School of Mines, College of Engineering, Mathematics and Physical Sciences, University of Exeter, Penryn, Cornwall, TR10 9EZ, UK

industrial change, modest consideration has been given to the potential environmental effects and impacts on human health. One particular concern is exposure to crystalline silica (SiO2) which may form during sugarcane burning,1 a practice common on many sugarcane estates (Fig. 1). Two varieties of crystalline silicacristobalite and quartzare classed as human carcinogens2 and can cause the chronic disease silicosis.3 If temperatures reached during sugarcane burning are sufciently high (i.e. $900 to 1000  C), amorphous silica in sugarcane plants could be converted into a crystalline variety and exposure to the resulting ash or particulate matter (PM) may pose a respiratory health hazard.

Environmental impact
Our research has shown, for the rst time that crystalline silica can be present in products formed from sugarcane burning at commercial sugarcane-growing estates. Crystalline silica is a known respiratory health hazard and people working on or residing near estates could be exposed to the combustion products if inadequate disposal procedures are employed. Ash formed from other biomass types frequently combusted either for fuel, such as Miscanthus grass or rice husks, or during wildres could also contain crystalline silica. The range of methods detailed in this paper, to characterize and quantify silica, could also be used to investigate other ash and dust mixtures to identify potential sources of crystalline silica or other hazardous materials in the environment.
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1.3.

Sugarcane burning

The sugarcane trash (surplus leaf matter) is removed from the sugarcane stalks, by burning, before they are crushed to extract sucrose (Fig. 1). During pre-harvest burning, a signicant amount of PM is released into the atmosphere and after the burn, thick deposits of sugarcane trash ash (SCTA) are left in the eld. The air quality measured within sugarcane growing regions of Sa o Paulo state, Brazil, has been shown to deteriorate dramatically during the burning season: ambient levels of PM can be double those measured during non-burning periods.20 Bagasse, the brous remains left after the sucrose extraction, can constitute between 20 and 30% of the harvested sugarcane,21 and is routinely combusted in the processing factory boilers to supply energy (Fig. 1).
Fig. 1 Simplied schematic of the sugar and bioethanol production process from sugarcane. SCTA sugarcane trash ash, SCBA sugarcane bagasse ash.

1.4.

Possible health implications from sugarcane burning

1.1.

Silica in sugarcane

Broadly speaking, plants can be classied as either Si-accumulators, or Si-non-accumulators.4 Sugarcane and other varieties of Gramineae (grasses) are Si-accumulators and, in the most extreme cases, such as the horsetail plant (Equisetum), the silica content can be up to 25% of the total dry weight of the plant.5 Silicic acid is taken up from the soil by plant roots and precipitated as distinct silica bodies called phytoliths,6 or within tissue cells such as microhairs, prickle hairs1,7 and guard cells which surround the stomata (e.g. ref. 8). They can occur as discrete shapes (e.g. dumbbell) or as fused, elongated structures, and their size typically varies between <1 and 30 mm in diameter, but can occasionally occur up to 200 mm.9 Although some plants phytoliths are composed of calcium oxylate (cystoliths),10 the phytoliths in sugarcane are amorphous silica (SiO2$nH2O), with trace amounts of crystalline quartz.1 1.2. Crystalline silica transition

The conversion of quartz to cristobalite occurs at temperatures >1300  C, but the conversion of amorphous silica to a crystalline state may occur at temperatures #1000  C.11,12 Feltl et al.13 heated samples of Porasil (amorphous silica) at various temperatures and found that partial crystallisation of amorphous silica occurs at 900  C, whereas complete crystallisation (to alpha-cristobalite) was observed at 1010  C. Cristobalite can form as a metastable phase at lower temperatures when impurities (e.g. Na, K, Al) are present in the structure.14 Similarly, the temperature at which amorphous silica converts to a crystalline state increases with increasing sample purity.15 A study of the thermal changes occurring during sugarcane bagasse burning16 attributed the distinct peak in heat ow observed (via differential scanning calorimetry) between 900 and 1000  C, to the melting of amorphous phases or a phase change in quartz. The crystallisation of amorphous silica to cristobalite has also been recorded at 1000  C in rice hulls17,18 and a mixture of y ash and burnt clay.19
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Potential exposure to crystalline silica has been investigated (in specic locations) during a number of agricultural activities, such as potato and nut farming,2225 but much of the exposure has been attributed to soil re-suspension. Although, acute symptoms such as cough, shortness of breath and aggravation of preexisting conditions (e.g. asthma) can occur after brief, highconcentration exposure to crystalline silica, silicosis is associated with chronic exposure.26 Exposure data are crucial in determining the dose, however, and it is recognised that the mineralogical characteristics of crystalline silica may act to override the dose-related health effects.27 Newman (1986)28 rst speculated that biogenic silica bres are responsible for causing mesothelioma and lung cancer in some sugarcane workers. In India, the incidence of lung cancer was elevated in long-term sugarcane workers exposed to sugarcane trash burning in the eld29 and mesothelioma has been reported in sugarcane workers in rural areas.30,31 Conversely, however, no association was found between mesothelioma and exposure to biogenic amorphous silica bres in three subsequent communitybased case-control studies.32,33 Whilst crystalline silica is not directly associated with mesothelioma, biogenic silica bres found in plants have structural similarities to asbestos minerals34 and were shown to promote mesothelial tumours in rats.35 More generally, exposure to the PM from pre-harvest burning has been associated with a variety of acute and chronic diseases of the respiratory system, such as asthma.36,37 There is little detailed information, however, on the health impacts specically from sugarcane harvesting and, in particular, sugarcane burning.38 The bagasse ash (SCBA) remaining after combustion can represent up to $0.3% of the total weight of sugarcane processed21 and is conventionally removed by ushing water through the boiler. Traditionally, the SCBA is separated from the water and retained on site and/or used as a fertiliser on elds.39 People are, therefore, at risk of exposure to the ash as it is broken down and re-suspended by wind or mechanical disturbance during removal, storage and re-distribution on elds. Although there is increasing research into alternative uses, such as the addition of SCBA to cement to improve its physical and mechanical properties,40,41 potential health hazards from frequent inhalation of SCBA PM have not been investigated.
This journal is The Royal Society of Chemistry 2010

This study investigates the properties of sugarcane combustion products from operational sugarcane estates, to identify whether silica, found naturally in the sugarcane plant, can convert to a crystalline form during agricultural burning thereby posing a potential health hazard to exposed workers. A key aim of this work is to determine whether crystalline silica is found in either the PM emission or residual ash from real-life sugarcane burning situations, in a similar way to previously reported experimental burning.1 Initially the silica in the raw sugarcane leaves and bagasse was studied to determine chemical composition and morphology in situ. Conditions during a number of pre-harvest sugarcane burning events were monitored, to establish whether temperatures during the res were sufcient to convert plant silica into crystalline silica. The presence of crystalline silica phases within SCBA SCTA and smoke from pre-harvest burning was investigated and quantied. Other crystalline phases within the ash samples were also identied to elucidate more information regarding the conditions during the burn. A preliminary assessment of associated occupational exposure is reported elsewhere.42

plot burned varied from 1217 ha. All samples were kept in dry storage until analysis. 2.1. Burn conditions

The atmospheric conditions were recorded at each of the seven burn sites studied, including ambient temperature and relative humidity (Table 2). Duration of burn was also recorded. Thermal images were acquired with a FLIR Systems ThermaCAM P25 infrared camera to track combustion temperatures. The instruments detector consists of a focal plane microbolometer array composed of 320 240 elements and is sensitive in the 7.513 mm waveband. The camera was handheld and operated at distances of a few metres from the burning sugarcane. The nominal instantaneous eld of view of the detector is 1.3 mrad, corresponding to a footprint of order 5 mm projected to the targeted burning vegetation. At such short observation distances the transmittance of the atmosphere can be neglected but the brightness temperatures were adjusted assuming an emissivity of 0.96 in the instrumental waveband based on a prior study of burning pine forest.43 2.2. Smoke collection

2. Field methodology
Samples of raw sugarcane leaves, bagasse, SCTA and SCBA and auxiliary data were collected from two commercial sugarcanegrowing estates from different South American countries (including Brazil; Table 1). The species of sugarcane grown at each of the estates was the same (Saccharum ofcinarum), although they differed in genetic variety. Five burning events were sampled in country A and two in country B. The areas of
Table 1 Sample collection and treatment details Sample type Raw leaf Bagasse SCTA Sample name Country(A/B)_leaf# A_bag Country(A/B)_ash# Collection details In each of the 7 plots the third and sixth green leaf were taken from 20 randomly selected plants before the burn. Taken from the processing factory prior to boiler combustion (in country A). Sampled from the top 4 cm of the accumulated ash (taking care not to disturb/include the underlying soil), at 12 randomly chosen sites within each of the 7 plots, immediately after the pre-harvest burn. Collected directly from the water ushed out from bagasse-burning boilers (periodically ushed out to clear the residual ash). A_ashbag1: supernatant liquid portion of the water. A_ashbag2: sediment in settlement ponds. Post-collection treatment Washed thoroughly with deionised water, oven dried (60  C for at least 24 h), cut into $1 mm sections and homogenised (within each plot). Air dried and cut into $1 mm sections and homogenised. Samples were homogenised (within each plot).

PM in the smoke was sampled during the pre-harvest burning using a Sioutas cascade impactor with Isopore polycarbonate membranes (25 mm diameter, 0.4 mm pore size, Millipore), which was attached to a Leland Legacy pump operating at a constant ow rate of 9 L min1. Under these conditions, the stages in the impactor collect particles with the following aerodynamic cut-off

SCBA

A_ashbag#

The ashwater mixture was desiccated in an oven (60  C for 7 days).

Table 2 Summary of sampling sites during pre-harvest burning and atmospheric conditions Approximate duration of re/min 43 25 53 61 42 47 62

Sample number (#) 1 2 3 4 5 6 7

Sampling site 183 083 051 052 053 107 157

Country A A A A A B B

Area burned/ha 17.09 12.22 14.87 12.30 10.70 9.49 11.36

Date 26/09/08 30/09/08 01/10/08 02/10/08 03/10/08 10/05/07 15/05/07

Local time of re 12:02 14:09 14:33 13:05 14:09 18:10 18:25

Average ambient air temperature/ C 26 26 26 25 27 18 17

Relative humidity (%) 8487 8284 8284 8083 8284 2527 2627

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diameters, D50 (where at least 50% of the material will be less than or equal to the cutoff size): <0.25, 0.250.5, 0.51.0, 1.02.5 and 2.510 mm. The workers were shadowed (closer than 1 m) and the impactor inlet was kept roughly at head height, to reproduce their exposure to PM produced during the burn.

samples were ground (as previously stated) and packed into the deep well of a circular Al mount (for further details see ref. 45). The samples were analysed on an Enraf-Nonius diffractometer with a 120 2q static position sensitive detector (PSD), using CuKa1 radiation and tube operating conditions of 45 kV and 45 mA, with ZnO as the internal attenuation standard. 3.4. Individual particle analysis

3. Analytical methodology
All of the analyses were carried out at the Natural History Museum (NHM), London, unless specied. 3.1. Total silica content For SEM studies, the SCTA and SCBA were scattered onto the surface of carbon sticky tabs which were mounted onto 12 mm diameter Al stubs. Small ($12 mm diameter) portions were cut (with PTFE scissors) from the polycarbonate lters used to collect PM from pre-harvest burns and mounted onto Al stubs using silver dag solution. All stubs were coated with $25 nm of carbon and analysed in the LEO 1455 VP SEM with EDS. Samples of ash were also mounted on resin blocks, polished to a at surface and coated with $25 nm of carbon for electron probe microanalysis (EPMA). Selected particles were analysed in a Cameca SX100 at an accelerating voltage of 10 kV, a beam current of 20 nA and a spot size of 1 mm. The instrument was calibrated using a range of natural and synthetic standards: FOR(std277) for Si and Mg, JAD3(std048) for Na, COR4(std028) for Al, WOL4(std097) for Ca, MNT(stdIC) for Ti, FAY(std278) for Fe and KBR3(std075) for K. For each ash sample, ve elds of view were imaged and approximately 8 to 12 particles in each eld of view were analysed. The aim of the EPMA studies was to acquire quantitative elemental data for individual silica particles, in order to gain an insight into whether particle purity affects conversion from amorphous silica into the crystalline forms.

The raw sugarcane leaf (air-dried), bagasse and ash samples were ground to powders in a Retsch Mill (using liquid nitrogen) at the Department of Chemistry, University of Cambridge. The bulk oxide composition of the raw leaves, bagasse, SCTA and SCBA was determined by wet chemical analysis, using an improved method of closed microwave digestion.44 Carbon, hydrogen and nitrogen (ultimate analysis) in the samples were also quantied using a Thermo Finnigan EA1112 CHN-analyser (with BBOT from FISONS Instruments: C, 72.53%; H, 6.09%; N, 6.51%, as a calibration standard). 3.2. Silica in the sugarcane plant

Sections of the raw sugarcane leaf and bagasse samples were mounted onto carbon sticky pads and coated with $25 nm of carbon. Silica-rich bodies on the epidermal layer of the sugarcane leaf were imaged in backscattered electron mode (BSE) under high vacuum in a LEO 1455 VP Scanning Electron Microscope (SEM). Elemental composition of features, such as the phytoliths and prickle hairs on the leaf, was determined using an Oxford Instruments INCA X-ray analysis system. 3.3. Crystalline composition

4. Results
4.1. Silica in the raw leaf and bagasse SiO2 was the most abundant constituent detected in the raw leaf samples, between 0.45 and 1.8 wt% SiO2 (as a total wt% of the raw leaf sample, Table 3). The raw leaf samples collected from country B (B_leaf6 and B_leaf7) contained almost one third of the amount of silica compared to raw leaf samples from country A (A_ leaf 1, A_ leaf2, A_ leaf3, A_ leaf4 and A_ leaf5). The raw bagasse (A_bag) contained 0.7 wt% SiO2. Levels of C, H and N were similar for all raw leaf samples. Carbon, however, was slightly higher in the bagasse sample (52.3 wt%) than in the raw leaf samples (average 46.2 wt%).

Crystalline components of the raw bagasse and ash samples were identied using X-ray diffraction (XRD), and crystalline silica phases were quantied in ash samples using an improved methodology for mixed-dust samples.45 Raw leaf samples have previously been investigated1 and were not therefore analysed by XRD in this study. For phase identication, sections of lter membrane (from airborne PM collections) were mounted at onto quartz substrates. The bagasse, SCTA and SCBA samples were ground (grain size z5 to 20 mm) and a thin smear was placed on a quartz substrate. For phase quantication, ash

Table 3 Wet chemical bulk oxide analysis (wt%) for the raw leaf and bagasse samples, including ultimate (CHN) analysis results (excluding oxygen)a Sample A_leaf1 A_leaf2 A_leaf3 A_leaf4 A_leaf5 B_leaf6 B_leaf7 A_bag
a

Al2O3 0.18 0.22 0.20 0.14 0.22 0.23 0.26 1.14

CaO 1.31 0.76 1.24 1.14 1.03 3.22 2.89 0.32

Fe2O3 0.15 0.13 0.17 0.09 0.11 0.10 0.09 0.61

K2O 2.11 2.21 2.47 2.52 2.50 1.68 1.50 0.57

MgO 0.88 0.82 0.94 0.77 1.03 1.15 0.98 0.33

MnO 0.01 0.02 0.01 0.01 0.11 0.04 0.03 0.01

Na2O 0.16 0.11 0.09 0.10 0.09 0.09 0.08 0.22

P2O5 1.20 1.14 0.85 0.86 0.76 0.43 0.55 0.15

SiO2 1.33 1.84 1.59 1.12 1.41 0.45 0.54 0.70

TiO2 bdl bdl bdl bdl bdl 0.01 0.01 0.02

C 46.7 44.6 45.6 44.2 45.6 48.6 47.9 52.3

H 5.2 5.5 5.9 5.2 5.4 5.8 5.5 4.7

N 0.9 0.9 0.9 1.0 0.9 0.9 0.9 0.3

bdl below detection limit.

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Fig. 2 SEM (backscatter, BSE) images of the adaxial surface of a raw sugarcane leaf, with EDS analysis spots on a phytolith (Spectrum 1) and a spine near the margin of the leaf (Spectrum 2).

Fig. 4 4 FLIR images of the burning sugarcane eld, with temperature scales, a) wide angle image and b) close up of burning leaves.

4.2.

Burn conditions

Images taken with the infrared camera during pre-harvest burning are shown in Fig. 4. Generally the temperatures recorded (the brightest pixel in the image, n 174 images) ranged from <200 to a maximum of 1056  C, when 3 0.96.43 4.3. Silica in the airborne PM

Fig. 3 XRD pattern with the main crystalline peaks identied for raw bagasse (A_bag).

The amount of deposit was too small and the inuence of the polycarbonate substrate too great to ascertain any information regarding the quantity and form of the crystalline phases within the airborne PM by XRD. No further analysis of the cascade impactor samples was carried out. 4.4. Silica in the pre-harvest burning ash

The BSE images of the sugarcane leaf surface showed distinct differences in contrast according to chemical composition, facilitating identication of silica bodies (Fig. 2) on both the upper and lower surfaces of the leaf. Si and O were the main elements identied by EDS spot analysis (spectra 1 and 2, Fig. 2) within the bilobate phytoliths as well as margin hairs, prickle hairs and bulliform cells. There were other trace elements, including K (spectrum 2, Fig. 2), Al, Fe and Mg, but these were rare compared with Si and O. The XRD pattern for the raw bagasse sample suggests that it was principally composed of amorphous material (shown as the broad-angle hump), but quartz, calcite and feldspar were identied as the predominant crystalline phases (Fig. 3), although these were not present in sufcient amounts for quantication.
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The SCTA from country A (A_ash1, A_ash2, A_ash3, A_ash4 and A_ash5) contains approximately double the amount of silica (20.224.8 wt% SiO2) compared to the SCTA from country B (B_ash6 and B_ash7; 10.410.8 wt% SiO2) (Table 4). The carbon content is also noticeably different, and tends to be much higher in the SCTA samples from country B (68.969.7 wt% SiO2), when compared with country A (26.830.9 wt% SiO2). The XRD patterns for country A SCTA samples (Fig. 5a) all show a distinct hump at $20 to 21 2q, which may be due to the amorphous silica component, whereas the patterns from the country B SCTA (Fig. 5b) appear to have a broader feature (from a much lower angle 2q) indicative of amorphous carbon, with a portion of amorphous silica. Quartz was identied in all of the SCTA samples from country A, but no crystalline silica was
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Table 4 Wet chemical bulk oxide analysis (wt%) results for the SCTA and SCBA samples, including ultimate (CHN) analysis (excluding oxygen)a Sample A_ash1 A_ash2 A_ash3 A_ash4 A_ash5 B_ash6 B_ash7 A_ashbag1 A_ashbag2
a

Al2O3 3.87 5.59 3.57 4.42 4.13 1.68 6.36 10.04 9.40

CaO 1.35 1.47 1.34 1.58 1.38 3.04 2.78 9.46 10.21

Fe2O3 2.85 3.29 1.92 2.34 2.10 8.43 8.04 7.42 7.54

K2O 7.64 8.24 8.61 7.81 8.84 4.88 4.81 11.21 8.69

MgO 9.83 8.58 9.02 9.20 9.18 11.05 11.34 7.26 7.50

MnO 0.21 0.23 0.19 0.21 0.18 2.00 1.61 0.30 0.26

Na2O 1.21 1.06 0.93 1.11 0.92 0.34 0.49 4.51 5.68

P2O5 2.63 1.70 2.03 3.00 2.63 5.96 4.47 4.21 3.51

SiO2 24.30 20.20 23.06 22.85 24.77 10.38 10.81 39.23 40.05

TiO2 0.05 0.07 0.06 0.07 0.08 1.12 0.88 0.45 0.52

C 27.7 26.8 30.9 29.2 27.9 68.9 69.7 10.8 2.8

H 0.3 0.3 0.3 0.3 0.3 2.5 2.1 bdl bdl

N bdl bdl bdl bdl bdl bdl bdl bdl bdl

bdl below detection limit.

Table 5 XRD analysis of the SCTA and SCBA. There is an approximate 13 wt% error in the XRD of the calculations (Le Blond et al. 2009), n6 Crystalline silica identied in XRD patterns Sample A_ash1 A_ash2 A_ash3 A_ash4 A_ash5 B_ash6 B_ash7 A_ashbag1 A_ashbag2 Quartz 3 3 3 3 3 3 3 Cristobalite 3 3

XRD crystalline silica quantication (wt%) Quartz 0.2 3.5 2.3 1.4 3.3 0.4 0.6 5.0 15.0 Cristobalite 1.2 3.0

Fig. 5 XRD patterns with the main crystalline peaks identied for a) SCTA samples from country A, b) country B, and c) SCBA samples (A_ashbag1 and 2).

recognized in the XRD patterns for country B. The other main crystalline components in the XRD patterns were calcite (CaCO3) and feldspar (Na/Ca/Al silicates) from country A (Fig. 5a), whereas calcite, sylvite (KCl) and pyroxene (Ca/Mg/Fe
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silicates) were identied in country B samples (Fig. 5b). The quantitative XRD analyses conrmed that SCTA samples from country A contained quartz (Table 5), even at relatively low levels (0.2 to 3.5 wt%). SCTA ash samples from country B had very little quartz, $0.5 wt% (average), which was not identied in the initial XRD pattern. Cristobalite was not identied in any SCTA samples. On rst observation, SCTA from country B (B_ash6 and B_ash7) contained abundant woody structures and unburned leaf material, while samples from country A were dominated by black ash and entirely lacking material that resembled the original sugarcane plant. SEM images of the SCTA (Fig. 6a and b), however, show many features such as phytoliths, long silica cells and stomata that are still intact in the SCTA samples from both countries. The ash commonly had a uffy and often brous texture, and much of the material was aggregated together in a fused mass. The individual particles were irregular in shape with rough surfaces and many have a spongy appearance. SEMEDS analysis identied that carbon was the main component in all SCTA samples, with occasional, irregular-shaped particles of pure-phase silica and mixed-phase silicates, including fused bodies (forming elongated lengths of silica; Fig. 6a), carbon bres and bundles (Fig. 6b), and individual crystals of calcite and sylvite. EPMA on sectioned blocks enabled imaging and analysis of particle cross-sections, rather than mass aggregations as viewed under the SEM. Chain-structures common in leaf epidermis were
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Fig. 6 SEM (BSE) images of the ash samples; SCTA a) A_ash1 from country A (silica trilobite phytoliths circled, arrow points to elongated silica cells), and b) B_ash7 from country B (silicaedged stomata circles, arrow points to carbonaceous bre bundle), and SCBA samples c) A_ashbag2 (spherical silicate and prismatic silica particles circled) and d) A_ashbag1 (two phytoliths bodies circled).

seen in BSE images of SCTA (A_ash1; Fig. 7a). EPMA analysis was selective and only lighter contrast, individual particles were analysed to investigate whether the silica was pure phase or contained impurities. Approximately half ($52%) of the 281 particles selected for EPMA were predominantly silica (i.e. >96 wt% SiO2), with trace amounts of Ca, Al, Mg, Fe and Na. These selected silica particles, averaged for each sample, are shown in Table 6.

4.5.

Silica in the bagasse ash

Fig. 7 Electron microprobe images (BSE) of a) SCTA sample A_ash3 (all probe spots were predominantly silica with trace amounts of Mg, Ca and very low Fe. The exception was spot number 8, which had a very low count level) and b) SCBA sample A_ashbag1 (all probe spots were also predominantly silica, with the following trace elements; Fe, Na, Mg and Mg. The exceptions were spots 6 that had a low count level, and 8 which was an Al+Ca+Mg silicate).

The SCBA samples (A_ashbag1 and A_ashbag2) contained similar levels of silica (39.240.0 wt% SiO2; Table 4) and there was a greater proportion of carbon in A_ashbag1 (10.8 wt%), when compared with A_ashbag2 (2.8 wt%). XRD analysis revealed quartz and cristobalite in both SCBA samples, and quartz was particularly noticeable in A_ashbag2 (Fig. 5c). Other crystalline phases included anhydrite, calcite and silicate minerals (feldspar and pyroxene). The crystalline silica quantication showed that SCBA samples contained between 5 and 15 wt% quartz and 1.2 and 3.0 wt% cristobalite (Table 5). Distinctive morphologies can be seen in A_ashbag2, including spheres, prismatic particles, blocky and brous structures (Fig. 6c). SCBA sample A_ashbag1 also contains relics of the parent material, such as phytoliths, or components from the leaf structure (Fig. 6d), as with the SCTA but with lower abundances. SEM-EDS showed that the prismatic particles were predominantly Si- and O-bearing, blocky particles contained Al, Ca, K, Mg and Na, as well as Si and O, and the spherical forms were mostly silicates, containing Mg, Al and Fe. All brous particles analysed were carbon-rich. Although residual plant-like structures were present in the SCBA, the majority of EPMA images show rounded, vesiculated particles (Fig. 7b), which predominantly consisted of SiO2 with
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Table 6 EPMA results for the SCTA and SCBA samplesa wt% Sample A_ash1 A_ash2 A_ash3 A_ash4 A_ash5 A_ashbag1 A_ashbag2
a

mg g1 SiO2 99.4 99.2 99.5 99.6 99.4 99.2 97.4 Na bdl 136 487 554 353 768 2286 Mg 496 535 bdl 2160 1321 619 157 Al 134 bdl 757 bdl bdl 464 9598 Ca 1962 1445 bdl 2285 1985 bdl 2206 Ti bdl bdl bdl bdl bdl 933.2 bdl Fe bdl bdl 2056 bdl bdl 2315 bdl

No. of analyses 28 16 17 21 28 23 28

Total 99.9 99.9 99.9 99.9 99.9 99.9 99.9

bdlbelow calculated detection limit.

trace Al, Na, Ca, Ti and Fe. The SCBA particles tended to have higher levels of Na, Al, Ti and Fe compared to SCTA samples (Table 6).

5. Discussion
5.1. Silica in the raw leaf and bagasse The average amount of SiO2 in the whole, raw sugarcane leaves was $1.5 and 0.5 wt% in countries A and B (respectively). Previous studies quantied silica as a portion of the dried material combusted (as part of the analysis), whereas we have determined the silica by digesting the whole leaf without combustion. Patel and Kumari46 determined that ashed (at 350 400  C) sugarcane leaf from an estate in India contained 7.0 wt% SiO2, which indicates that either combustion acts to concentrate the silica or that these Indian sugarcane leaves are much more SiO2 rich. A previous study by the present authors showed that the tips of sugarcane leaves cultivated in Kew Gardens, London contained from $2.5 to 6.5 wt% SiO2,1 but the tips are known to concentrate silica to a greater extent than the rest of the leaf. The CHN total can be used to show that results here are comparable with previous literature values. The CHN totals determined in raw leaves in our investigation (an average of $46.2 wt%) are consistent with the 45.4 wt% reported by Jorapur and Rajvanshi.47 The CHN totals for raw bagasse samples have been reported as between 49.4 and 64.9 wt%,4854 and are comparable to the value obtained for raw bagasse in this study (52.3 wt%). The general differences in chemical composition of sugarcane amongst samples can be attributed to sugarcane variety, growth conditions,55 fertilisers and climate and the inherent heterogeneity of composition resulting from sampling organic material which consists of a mixture of brous bundles and structural elements (such as parenchyma/epithelial cells and vessels). Our SEM analyses revealed that some of the phytoliths and other silica bodies in sugarcane leaves contained trace elements. This is consistent with ndings of Carnelli et al.56 who reported small amounts of Al in the phytoliths of other Gramineae species. Trace impurities within the silica bodies may provide a source of ions that inuence (potentially reduce) the temperature at which the amorphous to crystalline silica phase transition occurs and may also alter the toxicity of any emitted PM. Trace carbon has also been identied in phytoliths by Parr and Sullivan57 at levels of up to 5% of the total weight. Carbon was difcult to determine
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in this investigation as the samples were carbon coated before they were analysed in the SEM to reduce charging effects. The XRD pattern of raw bagasse shows that it is largely amorphous, containing only a low level of quartz. This compares with other studies that have found that the phytoliths in other Gramineae are mainly composed of amorphous silica.58 The raw leaf was not analysed by XRD, but Le Blond et al.1 have previously identied both quartz and calcite in the XRD patterns of raw sugarcane leaf samples. Sapei et al.59 speculated that the quartz may originate from soil contamination, but the leaves were thoroughly washed during the cited study, so it is unlikely that the quartz is from soil adhering to the leaf. It is possible that there is soil (including silicate) contamination in the bagasse samples analysed in the present study as, although the sugarcane stalks would have been washed (at the processing factory before they are crushed to release the sucrose), soil would inevitably still be present in the mixture and may be incorporated into the bagasse. This may explain the presence of feldspar in the XRD patterns for the bagasse, and might also indicate that there are two sources of silica entering into the boiler: the (mainly) amorphous silica in the plant and the crystalline silica associated with particles of soil. 5.2. Burn conditions

We found that the temperatures achieved during commercial sugarcane burning are substantial (up to 1056  C) and reach the range required for conversion of amorphous silica in the sugarcane leaf to crystalline forms such as cristobalite. It is hard to judge the duration of these high temperatures during pre-harvest burns, as it seemed dependent on the antecedent and prevailing meteorological conditions and vegetation conditions at the time of the burn. It is possible that very high burn temperatures are only ephemerally maintained on a particular stem or leaf limiting generation of crystalline silica. The laboratory experiments of Le Blond et al.,1 however, indicated that only 3 min are necessary for cristobalite to be formed in the ash and smokes from burning sugarcane leaves at 1100  C. We note also that, for obvious reasons, the temperatures were measured at the periphery of the burned plots when it was feasible to make a close approach. The re intensity in the interior of the plots was surely greater. Typically the burning of the 1217 ha plots lasted around 20 min. There are limited examples in the literature of the temperatures obtained in other types of biomass burning. Typically, the peak
This journal is The Royal Society of Chemistry 2010

temperatures are $500 to 700  C during smouldering and much higher for the aming phase at $1500  C.60 Maximum temperatures recorded during savannah res have been measured as 8001200  C, during the aming phase.61 Infrared and thermocouple monitoring of burns of piles of hazel logs have recorded maximum temperatures of 643  C, and up to 750  C with added wind.62 Although the temperature of combustion in the boilers was not measured during this study (due to health and safety restrictions), operating temperatures have been stated to range from 700900  C in sugar-producing factories in Rio de Janiero, Brazil.63 An indirect way to assess the maximum temperatures reached during the burn in the ash itself is to determine the presence of certain temperature-sensitive phases. For example, crystalline KCl (sylvite) has been identied in some biomass boiler deposits where rice and wheat straws have been combusted at 525  C,64 and when woody and herbaceous biomass samples were red at 500  C.65 Other biomass combustion experiments have revealed the breakdown of sylvite and the release of Cl at approximately 700800  C, which also plays a role in the rate of K-release,16 and sylvite was found to disappear from wheat straw completely at 1000  C.64 Thy et al.64 also suggested that the release of K may be due to dehydration, re-crystallisation and partial melting of amorphous silica. Calcite (CaCO3) is also known to begin to break down at around 500  C, and disappears if combustion temperatures exceed 1100  C.64 The presence of sylvite and calcite in the ash samples in this study indicates that temperatures did not regularly exceed $1000  C and therefore may not have been sufcient for the large-scale formation of cristobalite. 5.3. Silica formation during pre-harvest burning

The concentration of crystalline silica in the airborne PM was too low to be detected by XRD on the cascade impactor substrates. It was, therefore, surmised that there was a low risk from crystalline silica exposure in smoke of the pre-harvest burning events monitored here. This is also consistent with the nding that burn temperatures were not sustained at temperatures high enough to enable the amorphous silica to convert to a crystalline form. During pyrolysis (chemical decomposition during burning, leaving a solid residue), much of the carbon will be lost, leaving a mineral-rich ash deposit. The average amount of silica measured in SCTA from country A and country B (23.0 and 10.6 wt% SiO2, respectively) was much lower than previously reported, XRF-determined, values for silica in sugarcane mate~a et al.66 found that ash from rial. For example, Villar-Cocin burning sugarcane straw (i.e. leaves) in a furnace at 800  C and 1000  C for 20 min, had 70.2 wt% and 71.0 wt% SiO2, respectively. Similarly, Martirena Hern andez et al.67 found 59.1 wt% SiO2 in the ash from open-air burning of sugarcane straw. In both experiments, XRF was used to determine the SiO2, and the duration of combustion was most probably longer than that undergone by the sugarcane leaves analysed here. For example, ~a et al.66 incinerated samples for 20 min in a furnace Villar-Cocin and Martirena Hern andez et al.67 sampled ash material from heaps of open-air burnt [sugarcane] straw which would be allowed to burn until completely ashed. The total silica content in the SCTA from country B, however, was an order of magnitude less than that in samples from country
This journal is The Royal Society of Chemistry 2010

A. This can, in part, be explained by the original silica content of the leaves from country B being almost half that of the leaves from country A (indicating that silica did not concentrate to the same extent). Combustion dynamics will also be affected by burn conditions. For example, in country B the average ambient temperature and relative humidity during the burn were lower (1718  C and 2527%, respectively), compared with the eld conditions encountered in country A (2527  C and 8087%, respectively). The amount of carbon in SCTA from the two different countries also shows that burn conditions were different, as samples from country A had far less carbon ($28.5 wt%), compared to those from country B ($69.3 wt%), consistent with a hotter burn in country A with loss of C as CO2. Cristobalite was not identied in any SCTA samples. Cristobalite has been identied in SCTA produced at 1000  C (20 min) in an electric furnace, but was not present in SCTA produced at 800  C for the same period of time.68 Martirena et al.69 showed that cristobalite was present in SCTA burned in an uncontrolled (outdoor) environment, but was not present when the furnace was kept below 600  C. The SCTA analysed in this study lacks cristobalite, perhaps because burn temperatures only occasionally reached temperatures necessary for cristobalite formation in isolated locations (as indicated by the infrared camera results and the presence of calcite and sylvite). An alternative suggestion is that the cristobalite was preferentially released as airborne particles instead of remaining in the ash deposits,1 however, this is not supported by our (limited) analysis of PM from pre-harvest burning here. Quartz was present at concentrations between 0.2 and 3.5 wt% in SCTA samples from country A, but was absent in SCTA from country B. Although care was taken to exclude soil in the ash collection, quartz and other complex silicate (feldspar/pyroxene) mineral contamination from soil adhering to sugarcane leaves during combustion may have occurred. Temperatures of the preharvest burning were suitable for formation of quartz from amorphous silica in the sugarcane. Silica-rich elongated structures were seen in SCTA, which could result from the fusion (either naturally or via burning) of silica phytoliths. The elongated bres (observed in $30% of the SEM images of SCTA) were carbonaceous. Biogenic bres are well known in many cultivated plants, such as sugarcane, ax and rice.70 Whilst these biogenic bres are not crystalline silica, they must still be considered in health and exposure assessments as they have been implicated as a causal factor in mesothelioma occurrence in exposed populations30,31 and in vivo.35 EPMA results showed that silica particles in SCTA contain up to $2300 mg g1 ($0.23 elemental wt%) of impurities such as Al, Fe, Ca and Mg. Although aluminium may be present in concentrations from <0.0013 to 1.5 wt% in natural quartz samples,71 compared with cristobalite and tridymite, quartz has a closed atomic structure; thus the relatively large quantity of impurities in biogenic (amorphous) silica may impede formation of quartz. 5.4. Silica in the bagasse ash

SCBA contained 39.240.0 wt% SiO2, which is below the range of previously reported values ($58 to 86 wt% SiO2),7275 from XRF analysis. Again, the variability may reect the differences in
J. Environ. Monit., 2010, 12, 14591470 | 1467

techniques used to quantify silica and the fact that the silica determined in this study is for the whole material and does not, therefore, need to account for loss on ignition. Raw bagasse has a similar level of silica compared to raw leaf, and so the higher level of silica in SCBA compared with SCTA samples is likely to be due to different combustion conditions within the processing factory. Bagasse fed into the combustion furnaces is potentially subject to conditions that encourage a more complete combustion, and therefore the amount of carbon remaining in SCBA will be reduced, when compared to SCTA from (uncontrolled) open air burning. Due to the demand for SCBA as an additive in cements,40,63,67,76,77 its chemical composition has been exhaustively studied. We found a CaO-content in SCBA of $9.8 wt%, comparable to that reported for samples by Chusilp et al.41 and Fr as et al.,68 at 11 and 12 wt% respectively, but greater than the $2 wt% reported by Cordeiro et al.63 Our SCBA samples, however, had $9.8 wt% Al2O3, which is similar to the $9 wt% reported for other samples by Cordeiro et al.63 but higher than values reported by Fr as et al.68 (2 wt%) and Chusilp et al.41 (6 wt%). The differences in SCBA composition compared with previous studies show that bagasse preparation techniques and combustion conditions vary signicantly, as does the starting composition of the sugarcane. The crystallinity of biomass ash samples should increase with increasing temperature and duration of combustion. For example, Fr as et al.68 found that at temperatures $1000  C, the crystallinity of SCBA increased, and there was a commensurate decrease in the amount of vitreous material associated with lower temperatures. Increased crystallinity was also observed in the XRD patterns of sugarcane ash formed at 1100  C after 10 min when compared with ash formed after just 3 min in a laboratory furnace.1 The SCBA samples in this study were more crystalline than the SCTA, apparent from the less pronounced hump at $15 to 35 2q in the associated XRD patterns (Fig. 5c). Cristobalite was identied in both SCBA samples, at 1.2 and 3.0 wt% in A_ashbag1 and A_ashbag2, respectively, in addition to quartz (5 and 15 wt% for A_ashbag1 and A_ashbag2). Although cristobalite has previously been recognized in SCBA,63,66,78 it is not always observed.74,79 Quartz has been also identied in SCBA after bagasse was heated at 450  C.16 The cristobalite identied here may have been converted from either the amorphous silica within the sugarcane or the soil quartz particles adhered to the sugarcane. It is likely, however, that if boiler temperatures do not exceed 900  C, then the source of the silica for cristobalite formation is the silica in the leaf, since the temperature for the transition from quartz to cristobalite (>1300  C) exceeds that required to alter amorphous silica to cristobalite ($900 to 1000  C). The absence of sylvite and calcite in SCBA samples also suggests that temperatures in the boilers exceed $700  C (above the temperature needed for the breakdown of sylvite). Prismatic particles in the SCBA were identied as silica (by SEM), but it is unlikely that these structures are composed entirely of crystalline silica, as their abundance (observed in $20% of all SEM images taken of SCTA) would have increased the crystalline silica quantity detected by XRD. The EPMA results show that SCBA contains silica-dominated particles, with minor amounts of Na, Mg, Al, Fe, Ca, Ti and Fe in their
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structure. When compared to SCTA, the total amount of SiO2 is slightly less in both A_ashbag1 and A_ashbag2 and correspondingly, the amount of impurities (Na, Al, Ti and Fe) is increased. This increase in the impurities within the silica structure may be due to the presence of cristobalite in the SCBA, which was also detected by XRD. The impurities, measured by EPMA, may be held in the atomic structure of cristobalite, enabling cristobalite to form outside of its stability eld, and possibly also stabilising it so this form of cristobalite can persist. Elevated quartz in both of the SCBA samples may effectively disguise the inuence of cristobalite on the EPMA results. The observation that some SCBA particles were porous suggests that they may have been in a molten state,77 and can be compared with some examples of carbon y ash.79 Erlich et al.80 also found that melting occurred when bagasse pellets were heated at 900  C in a furnace, although Cetin et al.52 noted that the bagasse samples were much less susceptible to melting, when compared with soft/hard wood species, at high temperatures and pressures. 5.5. Silica in other biomass fuels

As well as sugarcane burning, consideration must also be given to the potential for crystalline silica formation and exposure from combustion of other silica-rich biomass. Agricultural burning is a widespread issue that affects ambient air quality over vast areas. A link has already been suggested between rising hospital admissions for childhood asthma during the rice burning months in California and Japan.81,82 Another situation in which silica-rich biomass is burned is the generation of energy from certain renewable fuels, and this might also represent a hazard especially where the practice occurs in conned areas, such as indoor domestic combustion ovens or poorly ventilated rooms. Many biomass types commonly used as fuels are known to contain relatively large amounts of silica in their ash products, for example, wheat straw (48.0 wt% SiO2), olive husk (32.7 wt% SiO2) and red oak wood (49.0 wt% SiO2) by XRF.83 In the UK, Miscanthus grass is currently grown as a fuel crop, as it provides an annual harvest, is relatively easy to cultivate/harvest and gives a reasonable high dry-matter yield.84 The silica content in ash from Miscanthus has been reported as $70 wt%85 and it is likely that crystalline silica is formed during combustion if temperatures exceed $700  C, which would be typical in biomass boiler furnaces that operate at 800900  C.86 Although renewable fuel crops are not burned in the eld, as with sugarcane, exposure to crystalline silica could occur during removal of ash from the combustion furnaces/boilers or re-suspension from stored deposits of ash.

6. Conclusions
The sugar-producing industry is undergoing a noticeable shift towards encouraging the utilisation of its waste products, for use in bioethanol generation and co-generation to provide energy for the sugar-extraction process. Pre-harvest burning is, however, still common in many sugar-producing countries and workers exposed to the ash formed during burning are potentially at risk from developing respiratory and related problems. Identifying the presence and conditions under which crystalline silica can
This journal is The Royal Society of Chemistry 2010

form in the ash created during sugar production is important in determining the potential risk from silicosis and other silicainduced diseases, which may take years to manifest symptoms that can be attributed to crystalline silica exposure. Our studies have shown that temperatures during pre-harvest burning of sugarcane are within the range required for the formation of crystalline silica. However, no cristobalite and only trace amounts of quartz were found in the residual ash from sugarcane burning. It is not clear if the quartz was generated as a result of combustion or incorporation of soil particles. The lack of crystalline silica in the ash is likely due to the fact most of the burning occurred at temperatures <800  C, as evident from the presence of sylvite in the ash. Fibrous material was present in the sugarcane ash samples, and should be taken into account in any risk assessment studying the potential effects from exposure. Further investigation is also warranted to determine the extent to which crystalline silica could be emitted in the pre-harvest burning smoke, especially as sampling only took place at ground level in this study, rather than in the lofting smoke plumes. The bagasse ash, however, contained both cristobalite (up to 15 wt%) and quartz (up to 3 wt%). Bagasse ash is an inevitable and abundant waste product from sugar production,87,88 and although the amount of cristobalite it contains is relatively low, when taken together with quartz, its total crystalline silica content is up to 18 wt%. It may therefore pose a signicant health hazard, especially if the ash is broken down further and re-suspended into the atmosphere. Adequate disposal of bagasse ash should become an important consideration, and routine monitoring of the products formed after the combustion of bagasse should be in place to identify and reduce possible crystalline silica release and exposure. Gaining access to commercial sugarcane estates for such experimental work is not straightforward (reected in the relatively small number of samples obtained and analysed here), thus we are duly cautious in generalising from our results. While we did identify crystalline silica in the trash and bagasse ash products from sugarcane burning, we could not identify crystalline silica in the airborne particulate matter. Clearly, burning conditions, antecedent meteorology, sugarcane species, soils and harvesting practice vary widely between commercial sugarcane estates creating very different exposure characteristics. Future work might also be directed to investigating this variability in order to determine typical concentrations of crystalline silica that result from sugarcane burning, and to identify best practice.

both at the NHM, London. We would also like to acknowledge comments from two anonymous reviewers, which greatly improved the manuscript.

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Acknowledgements
JSLs work was supported by a NERC studentship (Grant No. NER/S/A/2006/14107) with the University of Cambridge and the Natural History Museum, London. CJH acknowledges a NERC Postdoctoral Research Fellowship (Grant No. NE/C518081/2), and CJH and CO acknowledge support from the NERC Environment and Health Programme. We thank A. Cardoso, at UNESP, Brazil for eldwork assistance and guidance. Thanks also to the Farm Managers, who allowed me to collect data and samples on their land. Thanks also to T. Friscic at the Department of Chemistry, University of Cambridge for access to the Reisch Mill. We acknowledge the help of J. Spratt during the EPMA and G. Cressey for assistance with the XRD analysis,
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